TW201202175A - Polyamide curing agent composition - Google Patents

Abstract

Disclosed is a polyamide curing agent composition which is not derived from triethylenetetramine and can be used as an alternative for the most commonly used polyamide curing agent that is derived from triethylenetetramine. Specifically, a reaction product of (A) a compound selected from the group consisting of (a1) diethylenetriamine and (a2) amine compounds represented by formula (1) and having five or more nitrogen atoms in each molecule, (B) an amine compound having four or less nitrogen atoms and two or three active hydrogen atoms in each molecule and (C) a component containing a dimer acid is used as a polyamide curing agent composition, said reaction product having a value of (total mole number of compound (A) and compound (B))/(mole number of component (C) in terms of dimer acid) within the range from 2/1 to 4/3. (In formula (1), n represents a number of not less than 3.)

Description

201202175 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical that best shows the characteristics of the invention. WORKING STATEMENT: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyamine hardener composition. The polystyrene curing agent composition of the present invention is a curable composition of an epoxy resin used as a coating material, a binder, a floor material or the like. [Prior Art] The polyacrylamide resin composition is generally obtained by using a polybasic acid and a polyamine compound as a raw material 'dehydration condensation between an amine group and a carboxyl group under heating to form a guanamine bond and a polymer chain. Extend and synthesize. Specifically, it has been known that a dibasic acid or a polybasic acid such as adipic acid or a dimer acid, and a polyamine such as ethylene diamine or diethylene triamine are used as a starting material by a guanamine bond. A resin or the like that connects the two constituent units (for example, refer to Patent Document 1). Here, the dimer acid has a rich reactivity and is a dibasic acid having the highest molecular weight which is industrially obtained. In these polyamide resin compositions, '201202175-derived amine derived from a dimer acid becomes strong and exhibits flexibility' and has good adhesion properties, and therefore, as an adhesive, ink, surface coating The agent or the epoxy resin hardener is applied to an epoxy resin, or is used as a two-liquid reaction type adhesive for surface coating such as metal, (4), or ceramics. In the manufacture of the polyamide resin composition, I use diethylenetriamine (_', triethylenetetramine (-, tetraethylene pentamine (oxime), pentaethylene hexamine, oxime), etc., but Polyvinylamine-based oxime which is the most commonly used commercially. 4 醯 Polyamide curing agent derived from & known diethylenetetramine has a problem in low-temperature curability, and has been used in recent years for wind power generation. In the field of coatings such as turbines, it is more desirable to use a polyamide hardener which is more flexible than a base rubber. This is because in the same field, the curvature of the turbine becomes larger, and the fly is The problem of contact, etc., is remarkable, and it is required to use a coating film which does not peel more. Therefore, it is proposed to use a polyamine hardener which is a mixed composition of triethylenetetramine and a polyamine having a piperazine ring (for example, refer to Patent Document 2) According to the same publication, the obtained polyamine hardener can reduce the amount of epoxy resin relative to the polyamide hardener, thereby reducing the viscosity of the system, and obtaining a shorter film hardening time and impact resistance. Sex A good coating film. The polybenzamine hardener which is contained in the same publication has a tendency to decrease more than the tensile strength of the coating film using triethylenetetramine alone. It is suitable for the field which is equivalent to the same performance as triethylenetetramine. In addition, the equivalent of active hydrogen becomes large, and polyamine/ring 201202175 is difficult to say that it is suitable for the requirement that the ratio of highly water-resistant oxygen resin becomes high, and therefore it is used. Triethylenetetramine (TETA) is a limited supply of raw materials, which is relatively expensive compared to other polyethylene polyamines. Therefore, in the manufacture of polyamine hardeners, it is required to be relatively stable and more stable. An economical alternative ingredient. Thus, as a substitute for triethylenetetramine (TETA) 2 polyamine component is proposed. Use 3 N-3 aminopropyl ethylene diamine, ν, ν, - bis (3-amine Propyldiamine, hydrazine, hydrazine, hydrazine, tris(3-aminopropyl)ethylenediamine, hydrazine, hydrazine, hydrazine, hydrazine-tetrakis(3-aminopropyl)ethylenediamine A polyamine hardener of a mixture (for example, refer to Patent Document 3). According to the same publication, a shorter film hardening time is obtained than ΤΕΤΑ'. However, the epoxy resin cured by the polyamine hardener described in the same publication is harder than the conventional polyamine. The agent is more inferior in flexibility. Therefore, it is not particularly easy to replace the ruthenium in the case of a coating material requiring flexibility. [Prior Art Document] [Patent Document] [Patent Document 1] US Patent No. 2,450,940 [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2-7-76. [Invention] [Problems to be Solved by the Invention] 4 201202175 The present invention has been made in view of the foregoing. The object of the prior art is to provide a polyamine hardener composition which can be substituted for the polystyrene hardener from the most commonly used triethylenetetramine and which is not derived from triethylenetetramine. Specifically, φ ζ (1) is a polyamine sclerosant composition which is not derived from triethylenetetramine, which exhibits good flexibility and storage stability compared to a polyamine-derived melamine curing agent derived from triethylenetetramine. Or (2) shows the flexibility and water resistance equivalent to the polyamine amine hardener from triethylenetetramine and shows better hardening properties and storage safety; t is not derived from triethylenetetramine A polyamine hardener composition. [Means for Solving the Problem] The inventors of the present invention thoroughly reviewed the 'results' with respect to the polyamine hardener composition to complete the present invention. That is, the present invention relates to a polyamine hardener composition as shown below and an epoxy resin cured product obtained by using the polyamine hardener composition. [Π·- a polybenzamine hardener composition characterized by containing: diethylamine (al) and the following chemical formula: H2N^^P NH2 (1) (in the chemical formula, η represents 3 or more The number 〇 represents the group of amine compounds (a2) having a nitrogen atom number of 5 or more per molecule: the compound is obtained, the nitrogen atom of each molecule is below 4 and the active hydrogen number is 201202175 The reaction product of the amine compound (B) of 2 or 3 and the component (c) containing the dimer acid and [the total number of moles of the compound (A) and the compound (B)] / [component (c) The molar number in terms of polymer acid] is in the range of 2/1 to 4/3 and the molar ratio of the compound (A) to the compound (B) (a/^ is in the range of 9 〇/1 〇 15 15 /85) [2] The polyamine hardener composition according to the above [1], wherein the compound (A) is tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, polyethylene polyamine, or It is a mixture of these. [3]. The polyamine hardener composition according to [1] or [2] is a compound (8) which is a part of N-aminoethyl azine, a noise, and a di-baked triamine. N A The carbamide hardening agent group according to any one of [1] to [3], wherein the polyamine amine hardener group according to any one of [1] to [3]. The molar ratio (a/b) of the compound (A) and the compound (8) is in the range of 9 Å / 1 Torr to 40 / 60. The molar ratio of the polyamine hardener group described in the item (A/B) And 85/15 [5]: the range of the compound (A) and the compound (B) to 50/50 of any one of the above [1] to [3]. The polyamine-containing hardener group described above contains the entire amount. 70 to 95 weight [6]: The component (c) according to any one of the above [1] to [5] is a dimer acid in an amount of % relative to the component (c). ▲ [7]. The oxy-hardened resin is obtained by reacting the α-form and the bad-oxygen resin in the polyamine curing agent cylinder according to any one of the above [1] to [6]. [7] ° 5/1〜1 The ratio of the molar ratio of the epoxy group of the epoxy resin to the epoxy group in the % oxygen resin 6 201202175 is 1. 5/1~1 [1]: The hardened epoxy resin described in [7] or [8] above is a double-aged type A epoxy tree. a fat, a double-confident F-type epoxy resin, a double-hearted ring type resin, a double-stranded epoxy resin, a nail-type epoxy resin, or a mixture of these. [Effect of the invention] The polyamine hardening of the present invention The composition exhibits good performance compared to a polyamine hardener derived from triethylenetetramine which is generally used in general. For example, the polyamine of the present invention containing diethylenetriamine (al) as the compound (A) The hardener composition exhibits good flexibility and storage stability compared to the polyamine hardener from the conventional triethylenetetramine. Thus, it is suitable for use in the field of coatings which require a high degree of flexibility. In addition, the polyamine lubricant hardener composition of the present invention containing the amine compound (32) having a nitrogen atom number of 5 or more per molecule represented by the above chemical formula (1) is equivalent to the compound (A). The flexibility and water resistance of the polyamidamine hardener from the conventional triethylenetetramine show more excellent hardening properties and storage stability. In addition, it can also be improved as a blend of ethylene glycol from S. Low temperature hardenability of the disadvantages of amine hardeners. [Embodiment] The polyamine hardener composition of the present invention is characterized by containing a diethylenetriamine (al) and by the following chemical formula (丨): 201202175 1)

NH (in the chemical formula, n is a number of 3 or more.) The compound U), each of which is selected from the group consisting of an amine compound having a nitrogen atom number of 5 or more. An amine compound (B) having a molecular number of nitrogen atoms of 4 or less and an active hydrogen number of 2 or 3, and a reaction product of the component (c) containing a dimer acid and [the total of the compound (A) and the compound ((7)) The number of moles] / [the number of moles of the dimer acid of the component (c)] is in the range of 2/1 to 4/3 and the molar ratio of the compound (A) to the compound (B) (A/B) a reaction product in the range of 9 〇/ι〇~ΐ5 /85. In the present invention, the diethylenetriamine (al) used in the compound (1) can be, for example, a 1,2-chloroethane and Ammonia is reacted and synthesized, and it can be obtained as a single compound by steaming. Further, a commercially available product can be used. The material is used in the compound (1) and the mother 1 molecule represented by the above chemical formula (1) The amine compound U2) having a nitrogen atom number of 5 or more is synthesized by, for example, reacting with 1,2-dioxaethane and ammonia. Specific examples of such an amine compound include tetraethylene pentamine, pentaethylene hexamine, ethylene heptaamine, and polyethylene polyamine.

As the compound (A), it is possible to use these compounds in advance, and it is also possible to use these compounds as a compound of σ, and it is preferable to use diethylenetriamine, ', An amine, hexaethylene heptaamine, or a mixture of these. Base: The compound (8) is not particularly limited. However, it is an alkylaminoethyl azine. Table, part of guanidine, diethylenetriamine Ν-methylation 8 201202175, or A N' methyl ethylene diamine, N-ethyl ethylene diamine, N-isopropyl ethylene diamine, N-A Aminopropylamine, n,n-dimethylaminopropylamine N'N-ethylaminopropylamine, ethylenediamine (EDA) monomer or -N methylate, tallow amine (For example, 3, 3 _ diaminopropyl propyl as an alkali amine 'in the amino group at the 1-position, two alkyl groups of Ci6 or Ci8 are bonded to form a tertiary amino group, etc.). These compounds can be used singly as the compound (B), and can be used in combination. Among these, 'preferably, a part of diethylenetriamine, N-methylate, N-aminoethylpyrene&quot; chen, dimethyl-dimethylaminopropylamine, or a mixture thereof. The method for partially performing N-methylation of diethylenetriamine is not particularly limited, and 'for example, a method for producing an N-methylating agent is exemplified. In the case of the N-methylated body thus obtained, it becomes a precursor of diethylene = the active hydrogen group bonded to the nitrogen atom in the amine (hereinafter, there is an active hydrogen atom which bonds the nitrogen atom bonded to the molecule) The term "amino-based hydrogen atom" also occurs. The ratio of methylation is preferably in the range of 4% by weight. In the present invention, the mixing ratio (A/b) of the compound (A) and the compound (B) is in the range of ΘΟ/ΙΟ, "/85 (moire ratio), but preferably (four) /10 to 40/60 The range of (the molar ratio) is more preferably in the range of 85/15 to 5 〇/50 (moire ratio). In the present invention, the so-called "dimer acid" used in the component (C) means polymerization. An acid that is dimerized with an unsaturated fatty acid, including its vinegar. As a series of unsaturated fatty acids used in the synthesis of dimer acids, 201202175, for example, monofunctional unsaturated fatty acids. Specifically, it is preferably exemplified by stearic acid, palmitic acid, oleic acid, linoleic acid, linonic acid or a mixture thereof, or a tall oil fatty acid, a soybean fatty acid, a vegetable oil fatty acid, a cottonseed fatty acid or the like. The most preferred unsaturated fatty acid is tall oil fatty acid (using oleic acid and linoleic acid as the main component ^). Further, as the raw material of the dimer acid, in addition to the aforementioned unsaturated fatty acid, an ester thereof can also be used. As the ester of the unsaturated fatty acid, for example, a lower alkyl ester of the above-mentioned monofunctional unsaturated fatty acid is exemplified. Specific examples thereof include methyl esters of the above-mentioned monofunctional unsaturated fatty acids, ethyl vinegar, η-propyl ester, tert-butyl ester and the like. These systems may be used singly or in combination of two or more. As a raw material of the dimer acid, an ester of a dimer acid is obtained in a state in which an ester of an unsaturated fatty acid is used in combination. The dimer acid system is generally prepared by polymerizing the aforementioned raw materials under pressure. Here, the polymerization reaction is preferably carried out in the presence of a Lewis acid type or a Bronsted acid type catalyst having a high acid strength. Further, in the state in which an ester of an unsaturated fatty acid is used as a raw material, a dimer acid is obtained by a hydrolysis process. The reaction liquid system containing the dimer acid obtained in this manner as a main component usually contains a dimer acid or an acid having a higher degree of polymerization, and further contains an unreacted unsaturated fatty acid or a by-produced branched fatty acid. The monomer component. Therefore, most of these monomer components are removed by distillation. There is no special job as a steaming hall, but it is best to carry out decompression (4). It is also possible to hydrogenate the reaction liquid, thereby reducing the degree of unsaturation and coloration of the product. In addition, it is also possible to carry out the purification of 10 201202175 by performing molecular vaporization on the residue (four) of the steaming hall. Further, the ratio of the dimer acid and the trimer acid in the reaction liquid and the acid having a higher degree of polymerization are varied depending on the polymerization conditions, the purification conditions, and the unsaturated fatty acid which is a raw material. In the present invention, the reaction product obtained in this manner can be used as the forming tool (c). The component (the oxime system usually contains a polyfunctional fatty acid such as a dimer acid or a trimer acid having a higher degree of polymerization, or an ester thereof. The total amount of the component (C) is preferably 70% by weight to 95% by weight. A dimer acid. Further, it is preferable to contain 3% by weight to 3% by weight of a trimer acid and an acid having a higher degree of polymerization (including these three). Further, the residue may contain raw materials. Saturated fatty acids or other monofunctional (tetra) or polyfunctional _ as needed for the compounding. As component (c), it is particularly suitable for people to use oleic acid containing 70% by weight or more of oleic acid or its lower sulphur base. The unsaturated fatty acid is used as a raw material. In order to function as a hardener for epoxy resin, the terminal (tetra) group is required. Therefore, the compound (1), the compound (8), and the component (c) are The total number of moles of (8) is changed, and the number of moles of the dimer acid in the component (C) is usually 2/1 to 4/3, and the reaction is carried out at a ratio of '4'3. It is possible to adjust the reaction by using these ratios to be 4/3 or more and the south itch sleeve θ Μ The molecular enthalpy of the object can be obtained as the target poly-slurry liquid material tL MW, and the upper D object is made into a liquid substance. Further, the amine compound which is prevented from reacting by the ratio of 2/! In addition, as the compound (B) is used in M-Tangan, the group of the amine compound is partially N-methylated, and the amine compound 11 201202175 is combined with the Mohr number. The diethylenetriamine is calculated by partially calculating the average molecular weight of the composition obtained by N-thiolation. In addition, the molar number of the dimer acid converted to the component (c) is calculated from the acid value of the component. Calculated as an average bifunctional acid. The reaction system of the compound (A), the compound (B) and the component (C) is usually heated under normal pressure at a temperature of from 120 to 280 Torr, preferably from 18 Torr to 250 Torr. In addition, A prevents the formation of the color of the product, and therefore it is advantageous to carry out the reaction in an inert gas atmosphere such as nitrogen gas. The reaction time is affected by the reaction temperature or the type of the raw material to be used, and it cannot be determined generally. Usually, the knife is filled for 2 to 5 hours. In addition, it is preferable to carry out the curing in a reduced pressure state before the end of the reaction. The reaction liquid is increased as the reaction proceeds, but 疋Even after the completion of the reaction, there is no curing reaction product, and even at room temperature, it is easily transferred from the reaction container to the storage container. Further, it can be cut in the reaction as needed, and toluene is added. The polyamine hardener composition of the present invention contains the product to be obtained as described above. The polyamine hardener composition of the present invention may contain an aromatic compound and an aliphatic hydrocarbon compound. Solvents such as hydrazine, ketone, ether, alcohol, etc.: The solvent system is preferably a stupid, - 甲甘' Ben-A. The solvent content of the polyamine hardener composition is preferably in the range of 〇 〇 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Further, in the present invention, the polyamine hardener composition of t Λ , 73 may be further contained, and 12 201202175 other polyfunctional amines are further contained. The polyfunctional amine system is not particularly limited, but includes, for example, ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, a higher molecular weight polyamine, and a pyridinium. Benzene dimethyl diamine, isophorone diamine, 3, 3' _ dimethyl-4, 4' monodiaminodicyclohexylmethane, 4,4, monodiaminodicyclohexylmethane, 2, 4, monoaminodicyclohexylmethyl, U-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, diaminopentane, 16_ Diaminohexane, bis(3-aminopropyl)amine, N,N,_bis-(3-aminopropyl)-1,2-diaminoethane, 1,2-diamine Cyclohexane, 1,3-diaminocyclohexane, 1'4-diaminocyclohexane, polyoxyalkylene polyamine (eg Jef "(1) 丨 (10) D-230 ^ Jeffamine D-400 &gt; Jeffamine D-2000 ^ Jeffamine D-4000 ' jeffamine T_4 〇 3), etc. is provided, the present invention is inverted π 1 . Initial wu ^ u The epoxy resin cured according to the present invention is reacted by the present invention Formed by a polyamine modifier composition and an epoxy resin. The reaction between the brewing amine hardener composition and the epoxy resin is not particularly limited, and the cured product is formed by mixing and contacting them. The heat treatment may be carried out as necessary, and the curing may be forcibly performed. In particular, the epoxy resin used in the cured epoxy resin of the present invention is: = ... However, for example, 12 or more cyclized polyepoxy compounds are contained per molecule, and specifically, (4) &quot; Oxygen resin: Multi-static two-ring: resin, epoxy (tetra) resin, alicyclic ring resin can use 匕^, evolved epoxy resin, etc. These epoxys use no solvent, can also be diluted by solvent h 13 201202175 in this According to the invention, the "polyamine hardener composition and the epoxy system [the amine hydrogen atom in the polyamine hardener composition of the present invention] / the epoxy group in the resin) are usually U/1~ The range of 1 8.5 (Mohr number ratio:) is preferably in the range of [2/b (moire ratio). It is possible to exert good cured properties of the epoxy resin by this. Invention, in addition to the present invention, in forming an epoxy resin cured product In addition to the guanamine hardener composition, a conventional hardening accelerator may be used in combination. The curing accelerator is not particularly limited, but examples of the organic acid compound, the alcohol compound, the phenol, the tertiary amine, and the hydroxylamine are also listed. Compounds similar to these. Even among these, particularly useful hardening accelerators are benzene 33, mercapto _ H, bis, A, salicylic acid, dimethylaminomethyl benzoquinone, bis ( Further, in the present invention, in the case of forming an epoxy resin cured product, a plasticizer known per se can be used. The plasticizer is not particularly limited, but is exemplified by various types of phenolic alcohols and sulfhydryl phenols. Further, in the present invention, a solvent, a filler, a pigment, a pigment dispersant, a rheology modifier, a thixotropic agent, a fluidization and smoothing aid, an antifoaming agent, etc. may be used in forming the cured epoxy resin. . Examples of suitable solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, and alcohols. EXAMPLES The present invention will be described in more detail by the following Reference Examples and Examples. However, the present invention is not limited thereto. Further, the analysis of the reaction product was carried out by the following method. &lt;Analysis of reaction product&gt; (1) Gas chromatography analysis column: DB-5 (manufactured by Agilent Technology Co., Ltd., length 30 m 'film thickness 2.5 em, inner diameter 0.32 mm) Column temperature: 6 (TC + 1 ( TC/min temperature rise + 280 ° C / 15 minutes. (2) Nuclear magnetic resonance (NMR) analysis (4-NMR) was carried out using a Gemini-200 nuclear magnetic resonance apparatus (manufactured by Varian Co., Ltd.). 'Evaluation of the hardening speed and physical property measurement of the coating film was carried out as follows. &lt;Evaluation of film hardening time&gt; For the epoxy resin composition, a wet film thickness of 76 μm was used using an inch coater. The coating film is applied to a glass panel (25 cm x 2 cm x 〇. 2 cm). Using a low temperature constant temperature and humidity machine (manufactured by Espec, trade name: pL_3κ), after a certain temperature of 25t and a relative humidity of 50%, after curing, RC is used. The measurement was carried out by a dry-time coating applicator (manufactured by Coating Tester Co., Ltd.), and the curability was evaluated by the secondary linear disappearance time (Hr.) displayed by the measurement. <The tensile strength of the coating film. And evaluation of flexibility&gt; for the epoxy resin composition, A doctor blade having a gap of 2 μm was uniformly applied to a polypropylene film (2〇cmx4〇cmx〇. 2), and a low temperature constant temperature and humidity machine (manufactured by Espec Co., Ltd., trade name: pL_ 15 201202175) was used. Perform 48 small 3 Κ ) ' Drying and hardening at a temperature of 2 5 C and a relative humidity of 50%. Then, use a dull-type die-cutting device for tensile test (JISK 6259 No. 2 dumb type) A test piece was prepared. The test piece was attached to a TENSILON universal testing machine (manufactured by 〇rientec Co., Ltd., name: RTM500) using a parallel clamping lock to pull at a speed of 30 mm/min to measure the sample. The maximum tensile strength (kgf/mm2) of the sheet. At the same time, the distance between the markings at the time of breaking of the test piece (initial 4 〇mm) was measured by a gauge, and the tensile elongation at break was determined. The tensile elongation (%) is larger and the flexibility of the coating film is higher. &lt;Evaluation of water resistance of the cured coating film&gt; After the temperature is 40 ° C, the sink is immersed for 1 day and 7 days after hardening. After 24 hours of coating, the state change of the coating film was evaluated by visual observation. Evaluation was carried out in the following four stages: ◎: Excellent (no change); 〇: Good; △: Slightly poor; χ: Poor (expansion and deformation of the surface of the coating film, discoloration of the coating film). Evaluation of storage stability &gt; 50% of the dimer acid/polyamine amine condensate was placed in a thermostat (manufactured by Kanamoto Kasei Co., Ltd., trade name: HIFLEX FL4050), and cooled to 20 C for > hour. Then, the temperature of the thermostat was raised until the state of the dimer acid/polyamidoamine condensate was investigated by visual observation after maintaining for 1 hour. Similarly, the temperature was raised to 20, 25, 30, 35, 40, 50, 60' 70 '80, i 〇〇 °c, and after holding for i hours, the state of the polyamide was investigated by visual observation. The dimer acid. Polyamine amine condensate is defined as the liquid temperature of 16 201202175, and is defined as "liquid sturdy, ra ώ 收 体 temperature". The lower the liquidification temperature and the lower the crystallinity of the dimer acid/polyamine amine condensate, the better the storage stability of the polyamine hardener composition was judged. Production Example 1 Part of the ethylene diamine - thiol group was placed in a high pressure pin of a 1 〇 〇 ml with a blender, and charged with diethylenetriamine 2 〇〇g (manufactured by TGSGH Co., Ltd., trade name : 顺), water iQQg and catalyst pd -C (with 5%) 2 G G. After the high-pressure steel was sealed and replaced with hydrogen, the mixture was heated to (10). Next, in the high-pressure steel, hydrogen was introduced at a pressure of 3 MPa, and 妓7. After 7 hours, 314 g of a 37% aqueous solution of furfural was supplied by a pump. In advance! After the aging reaction of 丨, 拄 热 / / / 仃 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时After distilling off water from the reaction liquid using a distillation apparatus, 236 g of a product was obtained under reduced pressure. Gas chromatographic analysis and 1H-NMR analysis of the product were carried out, and as a result, 40% was converted to a methyl group ([methyl]/[hydrogen atom] with respect to a hydrogen group bonded to a gas atom of diethylenetriamine. ]=4〇/ 60 (Mor number ratio)). Thus, the average number of active hydrogens per molecule of the product is 3. Further, the composition of the obtained amine compound is DETA / monomethyl / dimethyl / tetramethyl / pentamethyl = 7 7 / 25 MM 7 / 231 / 7.6 / l. 〇 (GC area ratio) . In the following, the composition obtained by partially N-methylating the diethylenetriamine obtained in the present production example is referred to as "DETA-2M". Production Example 2 Part 3 of ethylene diamine - Aminopropylation In 236 liters of a reaction vessel, 236 g of ethylene diamine was added and heated to 17 201202175 6 0 C. In the mixture, 41 7 g of acrylonitrile was added over 2 hours. After the addition of acrylonitrile was completed, the reaction was maintained at 6 ° C for 2 hours. In a 1 liter batch reactor, 500 g of the product formed by the previous process was added, and 100 g of isopropyl alcohol and 7 58 of Raney C catalyst were further charged. After nitrogen substitution in the reaction vessel to expel the air, it was filled with 5. 5 MPa of hydrogen, and then heated to. The pressure of the reactor was maintained at 5. 5 MPa. The temperature was maintained at 12 ° C for 1 hour. The reactor was cooled to room temperature, and a reaction liquid for removing a solid component was obtained by filtration. Isopropanol and a low boiling point component were distilled off under reduced pressure from the reaction liquid to obtain 682 g of a product. Gas chromatography analysis and 1 NMR analysis of the product showed that 50% of the hydrogen groups bonded to the nitrogen atom of the ethylene diamine were substituted with an aminopropyl group. Further, the composition of the obtained product is a monoaminopropyl substituent/diaminopropyl substituent/triaminopropyl substituent/tetraaminopropyl substituent = 7/8〇/11//2 (gc area ratio). In the following, a composition obtained by partially performing 3-aminopropylation of the ethylene diamine obtained in the present production example is referred to as "apeda". Example 1. A composition of a dimer acid containing 5% by weight of a monomeric acid and 14% by weight of a trimeric acid of a Cu-unsaturated fatty acid in a 1000 ml glass container [manufactured by Nagano Food Industry Co., Ltd., trade name: Tsunodime 216, acid value: 193. 6 mgKOH / g, suitable for the component (C). l之g, and, while stirring, slowly added 21. 4 g of diethylenetriamine (manufactured by TOSOH Co., Ltd.) and 6.7 g of N-aminoethylamine (TOSOH); suitable for compounds 18 201202175 (B). ] [Mor number of the total of the compound (A) and the compound (B)] / [the number of moles of the dimer acid of the component (C)] is 3/2. The stirring speed was increased to 150 rpm, and 6.2 g of water was removed by distillation under nitrogen atmosphere for 2 hours (TC, heating for 4 hours. Further, at 2 Torr. (:, 10 mmHg, the reaction was carried out for 1 hour. Next, The reactor for the reaction was cooled to 1 Torr (rc), and the mixture was stirred and added as a homogeneous solution to a solid concentration of 7 〇% by weight, and then cooled to room temperature. (Dimer acid/polyamidoamine condensate) is amber, and does not contain the active argon equivalent system 227. , Field AX ~ rice pore blush (oiled SHELL epoxy company, trade name: postal (10) ι 〇〇ι, Epoxy 474 (4) A type epoxy resin) and become a heavy epoxy resin: liquid 32 reread, u 68 parts by weight, to add the obtained dimer acid · polyamine amine condensate The toluene solution was cut and mixed at room temperature for 5 minutes using a spatula. Here, [the amine hydrogen atom in the hardening of the polyamine of the present invention [epoxy group in the epoxy resin] is l/ i (moire ratio). It will be displayed in the table according to the above evaluation method and the result of the measurement. Film hardening arrest and physical properties Example 2 to Example 9 and Comparative Example 1 to Comparative Example 15 Other than the materials of the types and amounts shown in the remaining 1 and Table 2, and Table 2, Example 1 was carried out. Results—and shown in Table i 19 201202175 [I&lt;] Comparative Example 5 〇〇1 1 &lt;N1 CO CO 00 s' ί 1 \ CO σ&gt; eo (Nl CO CO CD 00 iri t- 〇ssi Comparative Example 4 § 1 1 Bub·1 CO ύ 1 1 CO C&lt;1 CO σ&gt; CO ΙΛ LT) oo ci CO oo s |Comparative Example 3 | g 1 1 Ο 1 呀1 1 (Μ \ ΙΓ&gt;C&lt;i CO CO CO Oo CO in* t- to ΟΪ g I Comparative Example 2 | ο ο 1 1 CO ΟΟ 1 oo s 1 1 c&lt;j \ CO 呀 CO &quot;•CP CO CO CO m in CO o* og Comparative Example 1 ο 1 1 1 t t- 03 CO 1 1 CO CvJ c3 CO CO Lfi s Example 9 ο cd 1 cd CO LTJ 1 1 1 60/40 1 CM \ CO £ &lt;NI oo CO CM CO 卜Λ so CO : Example 8 g Γ ΟΟ 1 CO LD -1 1 1 70/30 1 &lt;M CO 寸 CO CO CO ο cd CM oo σ&gt; Another Example 71 g 1 1 LT5 1 1 1 80/20 1 ζα CO CO &lt ;&gt;a C&lt;l C&lt;1 eo oo CO 呀CO CO oo o CO Example 6 ο ο cd 1 CO 1 1 1 1 60/40 1 CO \ &lt;N 1 CO CO ο CO c=&gt; CM o Another embodiment 5 | ο ο οοό 1 »-Η ο 1 1 1 1 70/30 1 CN1 \ 00 兮CO CO CO CO 05 ιτί o σ&gt; o ΙΛ οα Li Example 4 I g Ξ CO CO 1 1 1 1 1 60/40 1 CM \ CO CO CM Cvl (NI CO oo ς〇CO in og ΙΛ eo | Example 3 I g 〇 d CO o 1 1 1 1 1 70/30 1 CO \ ΙΛ c3 CO 05 o 05 ID* CNI LT5 00 Example 2 I ο ο 03 00 CO 1 1 1 1 1 80/20 1 \ CO o CO oo oo 宕 Example 1 | g inch C&lt; 1 1 cd 1 1 1 1 80/20 1 C&lt;I c- C〇3 CvJ &lt;N1 CO oo CO CD ς〇(Nl o 05 LT3 CM 3 Ί Diethylenetriamine DETA-2M N-Amino B Piperazine-specific triethylenetetramine APEDA Amine A/amine B (moire ratio) Amine (A+B)/dimer acid (C) (Mohr number ratio) Active hydrogen equivalent polyamine amine hardener added Parts by weight (pbw) Epoxy resin added parts by weight (pbw) Hardenability (Hr.) Film strength [tensile strength (kgf/mm2)] Flexibility [tensile elongation 00] Liquidification temperature (° c) c CQ S /&lt;**N ^ 3 s physical property evaluation

05.哒&lt;!=:(雄4龙0^硪«硪维—9令我)23专 05.哒&lt;&quot;: (sfT^oMql-^B-^slgoHZ-vlg l*tg&lt;-lHosoi Book gamma: sis*ow, ♦«,^«»ήο^«-Ν ,隹T^OM(z 铋Tg&lt;&lt;Secondary HOS. Umbrella ftri??: (HSSS9CO61: 筚湓, 913⁄4曰ipouasl: practice 3T05. Box) German «铋M(I 201202175

[{NIS CD &lt;〇T—^ 1 1 1 1 1 38.2 1 3/2 〇〇LO Μ &lt; LTD Csl LO 卜 CD oi 〇〇LO C&lt;l ο ◦ ,丨— 1 &lt; cd 1 1 1 Oa cd 1 1 3/2 CO 03 CO 1 LO c&gt;a cd LO —called ο 〇&gt; τTM4 18.7 1 1 1 Bu inch · 1 1 3/2 CNI Bu CO CO CO CNI cd LO Ί 1 i ◦ CO CD o τ·· &lt; oa 1 1 1 τ^Η CO 1 1 3/2 CO oo 呀CO CD CO CO cd LO t—H oo LO oo 1 1 o CNI 〇6 1 1 0/100 3/2 CNI σ&gt; CO LO 1 1 &lt; CO 呀τ—Η oo 1 1 33.5 1 1 1 0/100 3/2 CT) t—H 卜 Q CO inch CZ5 οο Τ 1 &lt; 〇CO o cz&gt; 1 i 1 〇CNI cd 1 1 10/90 3/2 CO LO LO 呀LO CO P ( LO CO Q· ο ο ι 1 i 〇CO Q o 卜CN) 1 oa cz&gt; CO 1 1 1 10/90 3/2 CD CO LO 呀LO 1 OO 呀o LO ο CD CO oo τ_·Η Bu oi CD o CO 1 1 1 1 10/90 3/2 CO o- 〇〇 CO CO CO CO as inch o CD CNI Guide o CZ5 i丨丨H oo ζό CNI 1 1 1 1 1 100/0 3/2 05 cx&gt; CNI rH 卜 LO cd LO tH LO LO LO CNI Dimer acid (C) n (g) Diethylene triamine DETA -2M N-Aminoethylpiperazine 1 pilazine triethylenetetramine APEDA A/Amine B (Mohr number ratio) Amine (A+B)/dimer acid (C) (Mohr number ratio) Active hydrogen equivalent polyamine amine hardener Adding parts by weight (pbw) Epoxy resin addition Parts by weight (pbw) Hardenability (Hr.) 1-1 /*&gt;&lt;M ε ε \ &lt;+H b〇娥4 缌Μ Flexibility [Tensile elongation 00] Liquidification temperature (° c) PO material physical property evaluation ^^φ: (雄q 装〇^硪肊^铤|〇〇令命)¥013^ 咔哒 umbrella: (锲Μ 装roMqY&lt;M®-&lt;^^)w2-VI3a ^ ^々/ηοβοι^^ι^θ^ο'^,^^,^^^ο^^-ν,^'ξ-^ομ^ ϋ^&lt;&lt;#Η05. For example: (HO^E9.CO6I: 蛱 bond, 9I33.spocnsi: 镩砰05. 柩) 荽铋 4 (1 201202175 As clearly shown from Example 1 to Example 9: by the present invention The tensile elongation and tensile strength of the coating film tuned by the guanamine hardener composition are also about 2 times higher than the state of using the hardener composition derived from triethylenetetramine (Comparative Example 1). ~ about 3 times tensile elongation. It is known that in the state of using the polyamine hardener composition of the present invention, compared with the hardener composition derived from ethylenetetramine (Comparative Example 1), It exhibits more excellent flexibility and can be suitably used for applications in which a coating material requiring flexibility (for example, a coating for a wind turbine) is used. Further, the polyamine hardener composition of the present invention is derived from three A hardener composition of ethylene tetraamine (comparatively, it has a better storage stability. Further, the polyamine hardener composition of the present invention uses diethylenetriamine as a polyvinylamine, and therefore, Triethylenetetramine, also has a better supply of safety On the other hand, as shown in Comparative Example 2 to Comparative Example 5, in the state in which triethylenetetramine and a compound having a piperazine ring are used in combination, the obtained coating film system remarkably lowers the tensile strength, and therefore, it is not easy. On the other hand, as shown in Comparative Example 6, in the state where the reaction product of the compound (Β) is not contained, the tensile elongation of the obtained coating film is increased only by triethylenetetramine. It is not easy to say that it is sufficient flexibility. On the other hand, as shown in Comparative Example 7 to Comparative Example 11, the molar ratio of the compound (Α) and the compound (Β) is separated by 15/. In the state of 85 and containing excess compound (Β), even if the tensile elongation is about 2 to 3 times, the tensile strength is extremely lowered, so it is not easy to say that it has the practicality of 22 201202175. As shown in Comparative Example 12 to Comparative Example 14, in the state in which the compound (B) was replaced with the triethylenetetramine having an active hydrogen number of 6 per knive, the tensile elongation was increased only by comparison with Comparative Example i. About 1.5 times, it is not easy to say that it is given adequately Further, the molar ratios of diethylenetriamine/triethylenetetramine of Comparative Example 12 to Comparative Example 14 were (10) / 20, 70 / 30, and 60 / 40, respectively. It is shown that in the state in which apeda is used, the coating film becomes brittle and loses flexibility, and as a result, it is compared with a polyamine hardener composition derived from triethylenetetramine (Comparative Example n, tensile elongation and tensile strength) It is not easy to say that it is practical. Example 10 A 1000 ml glass container was charged with a composition of a dimer acid containing 7% by weight of a monomeric acid and 14% by weight of a terpolymer I of a Cu-unsaturated fatty acid. Manufactured by the company, the product name: acid value: 193.6mgKOH/g, suitable for the component (Ch) of 1〇〇g, and, while stirring, slowly adding 41.8g of tetraethylenepentamine (T〇) s〇H company

() is suitable for compound (A). And N. Aminoethylpiperazine (manufactured by T〇s〇H △) of 〇g [suitable for compound (B). ] [Mor number of the compound (9) and the compound (B) in total] / [the number of moles of the dimer acid in the component (c)] is 3/2. The mixture was heated at 120 C and stirred until it became completely uniform. Ask the stirring speed to 15 rpm and 2 在 under a nitrogen atmosphere. 2克的水。 By 匸, the water was removed by distillation to remove 6. 2g of water. Also, at 2 〇〇. 〇, 23 201202175 lOmmHg, the reaction for i hours. Then, the reaction vessel was cooled to ι ° C, and toluene was added thereto, followed by stirring to obtain a homogeneous toluene solution to have a solid concentration of 70% by weight. /. Thereafter, the reaction product (dimer acid/polyammine amine condensate) obtained here is cooled to room temperature, and the active hydrogen equivalent system 167 in the state in which amber is not contained is amber. It is 7 with respect to an epoxy resin (an oil-made SHELL epoxy company, trade name: Epik〇te 1〇〇1, epoxy rice amount (4) A-type epoxy resin) diluted with toluene. 74% by weight of the epoxy tree liquid 74 parts by weight, added in a ratio of 26 parts by weight 'to the obtained toluene solution of the dimer acid · polyamine amine condensate, as a polyamine hardened" and used by the character The spatula is subjected to shearing and mixing for 5 minutes at room temperature. Here, the amine hydrogen atom in the polyamine hardener composition of the present invention] / [cyclo-epoxy group] is 1 / 1 (Mo尔数比). The evaluation of the curing speed and physical properties of the coating film in the evaluation of the liver 筏 ' f 〜 〜 〜 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ 16~Comparative Example 35 ° Except that the materials shown in Tables 1 and 2 are used, and the raw materials of the reference examples and amounts are the same as in Example i, the results are as follows. 4. In addition, it is shown in Table 3 and Table. ', No; Table 3 and Table 4, the so-called "S-ρΕΗΑ refers to the manufacture of ethylene amines. To obtain "system (ΡΕΗΑ) distillation residue, a seal alkenyl Hall G hexamine butoxy Shang of heavy distillate obtained (T0S0H Corporation). It is characterized by a large number of gas atoms in the slave. The amount of knife is greater than peha, w 24 201202175 [5 Reference example 1LO 1 CO oa 1 inch c&lt;i 1 50/50 I 3/2 C&lt;1 CvJ C&lt;1 eo 〇〇C£) CO LO* C^ o ΙΛ 05 △/〇5 -£ g 1 1 1 1 cvi CO CD oo a C&lt;1 1 Lj/2. 05 CO CN3 呀CO CO CO OO LO c- c&gt; CO ο △/〇g -£ g ^-1 1 1 1 1 Bub·1 CD Male' 1 1 3/2 1 g CO CO 03⁄4 CO LO LO 00 o CO 00 〇/◎ S Comparative Example 18 Ο Ο 1 1 1 1 inch ο 1 s' 1 L.3 /2 1 ΙΛ OJ &lt;NI (SI CO 00 CO inch LO c- o ΙΛ Cft △/〇g Ο ο 1 1 1 1 CD oi 1 oo 々· (NJ 1 L3/2 1 but C&lt;J inch CO CO CO LO in CO o △ △/〇Comparative example 16 g 1 1 1 1 1 Bu 03 CO 1 |—3^2 一” CO 1 LD* 卜©/© s ο ο 1 1 t- cd 卜 cd 1 1 50 /50 1 _3—/2” s 05 CO 〇ΙΛ 05 05 CO s Example; 17 i § *~Η 1 CO inch ' 1 1 呀 CO CO LO 1 1 70/30 1 丨——3/2— — | O CO (N1 inch OO inch* L〇CO ο 呀 province 2 Ο ο »«Η 00 1 1 1 o 1 1 85/15 1 .3/2_| CO CO CD &lt;N1 inch Inch · in CO inch ο c&lt;] ίΚ ο ο 1 呀[&gt;· CO t- ~ to 1 1 1 50/50 1 3/2 1 s Csl CT5 (Nl port C- 呀 ' OO oo CO ο ο ο 1 CO 1 o .' 1 1 1 70/30 1 3/2 CO CT) One CO Write 43 2 43⁄4 g 1 ai 4 CO CO l 1 1 1 60/40 1 3/2 LO ς〇CO C&lt;1 CO in in oo ο 苳%: Ο ο 1 〇〇1 CNI ο 1 1 70/30 1丨3/2 1 in LO 1Λ CO LO OO ΙΛ ο Example 11 ο ο 00 1 in .丨I 1 85/15 1 1 3/2 1 05 ΙΛ UO C&lt;J LO 03⁄4 — CO 5 遨2 ο ο 〇 〇1 o Ln 1 1 1 85/15 1 1 3/2 1 £ CO C&lt;J i inch o LT) Bu 5 Dimer acid (C) u(g) Tetraethylene pentamine pentaethylene hexamine S-PEHA DETA-2M N-Aminoethylpiperazine piperazine I triethylenetetramine A/amine B (moire ratio) amine (A + B) / dimer acid (C) (moire ratio) Φ1 Polyammine amine hardener added parts by weight (pbw) Epoxy resin added parts by weight (pbw) Hardenability (Hr.) 1 1 ΐ ε \ Ml &amp; 〇 4 4 娥 可 可 可 [ [ tensile elongation «)] Water resistance of hardened film (1/7 day hardening) Liquidification temperature rc) -&lt; CO S /-s 1 Material property evaluation

Ηο-^φ:(筚川发o-rqKfB-φ命)wz-g3a5t{I!?&lt;-3Hosol 嫦*I: sis«:loM ,#«,^«^10^®-N,VH3d— s,slHC$10^-,^T«-10B(z ΪΙΙ!?·&lt;3輙τηε=Umbrella: (Hop曰9_ε6Ι :蛱湓' 9T&lt;NliIP0cnsE-: Practice 05&lt; cabinet) Magnetic 铋U(I 201202175 [i] £ 〇I 1 1 1 1 | 38.2 | 1 1 3/2 1 〇〇ΙΛ Η ΙΛ (Μ CO οό o O 1 〇/◎ 1 in C&lt;1 〇◦ 05 1 1 |13 , 4 J 1 1 1 3/2 1 〇CO (Μ CO CO £ 00 oo 寸 (Nl Δ/Ο ο Comparative Example 33 〇〇1 CO 1 1 1 〇〇〇* 1 t 1 3/2 呀 OO 00 Csl Gv3 ο ιή 05 »—1 CO CO 1〇/◎ Write g oo 1 1 1 1 〇1 1 丨3/2 1 CO CO LO LO Oi oo 03 〇/◎ 1 ο Comparative Example 31 ο ο 1 ! 1 σ&gt; 〇〇1 1 I o/ioo | 1 3/2 I Cvj 05 CO Oi m CO oo »—H Χ/Δ jj g Τ«·Η 1 1 LD c6 CO 1 1 1 | o/ioo | 丨3/2 I 05 § og Χ/Δ Another comparative example 29 g 1 1 Bu CO 03⁄4 eo 1 t 1 1 5/95 | 1 3/2 I Oi ς〇in LO ΙΛ lD 守卜 CO og ^4 1 χ/Δ 1 5 Λ3 ο 1 CsJ CO 1 Oi ψ—^ CO 1 1 1 I 5/95 1 3/2 | in 00 m ΙΛ un Lf5 ς〇 O χ/Δ 1 宕 comparison Example 27 ο ΙΛ oi 1 1 σ&gt; eo 1 1 1 1 5/95 | 1 3/2 1 g CD in CO mos χ/Δ 1 5 £ g 1 mouth 1 1 1 1 95/5 | 1 3/2 o OJ sg ο Lft 03 ς〇1 ◎/◎ 1 ο A3 g 1 gt 卜 f 1 1 1 95/5 | 1 3/2 | Inch CO Cv〇CNi CD L〇05 1 ◎/◎ ι ο £ g R- co 兮1 卜1 1 1 1 95/5 | 1 3/3 | CO in ^J· CO CO LiS 05 Lft CNi 丨◎/◎ I Write Comparative Example 23 o 1 1 OO 1 1 i 1 | 100/ 0 | 1 3/2 I m *-« s § 05 CO t- oi 呀 1 ◎/◎ I ο 5 £ g 1 1 63.3 1 1 1 1 1 1 | 100/0 | 1 3/2 | 03 C&lt; I C&lt;i 05 卜CO &lt;N1 (NI CM 1 ◎/◎ 1 5 g σι 1 1 l 1 1 | loo/o | 1 3/2 | &lt;NI CO CSJ LTS 〇oi &lt;M CM 1 ◎ /◎ I Ο Dimer acid (C)" (g) Tetraethylene pentamine pentaethylene hexamine S-PEHA N-aminoethyl piperazine bridging Qin diethylene triamine APEDA Amine A / amine B (Mo _ Amount ratio) Amine (A+B)/dimer acid (C) (Mohr number ratio) Active gas equivalent polyamine amine hardener Adding parts by weight (pbw) Epoxy resin added parts by weight (pbw) Hardening (Hr.) ΐ \ Mh b〇m 娥n flexibility [tensile elongation 00] water resistance of hardened film (1/7 Daily hardening) liquefaction temperature (°c) *&lt; CQ 铤 ^ Material Physical property evaluation 05.哒^: (siM#foqJ.硪 ¢^淫— εφ^)να3α.ν

i^I!r&lt;&lt;Hosol _ 伽: 淫W爱ΟΜ,#«,#.杳硪Ot^-N , VH30.—S , si^^lolr , 甾叫费Ο0(ζ «π&lt;·4嫉TOSB as &amp;-test: (Η38®9Έ61: 筚, 9IZ3.SPO 目si: 铢W05·柩)^«ftiM(I 201202175 as shown by Example 10 to Example J 18 The hardening time of the coating film obtained by the polyamine hardener composition of the present invention is more rapid than that of the polyamidamine hardener composition which is one of the ethylene tetraamines which is used in standard use (Comparative Example 16). Therefore, it is known that it can be rapidly low-temperature hardenability and improve the productivity of the coating film by the present invention. Further, the coating film tensile elongation prepared by the polyamine amine hardener composition of the present invention is obtained. And the tensile strength, the % of the polyamidamine hardener composition of the diethylenetetramine. Thus, J can provide the coating equivalent to the flexibility of the triethylenetetramine by the present invention, and the coating film strength can be provided. The required coating film is flexible. In addition, the polyamine hardener site of the present invention can maintain the same concentration as that from triethylenetetramine. The equivalent water resistance of the amine hardener. Further, it is known that the polystyrene hardener composition of the present invention has a better storage stability than the hardener composition derived from triethylenetetramine (Comparative Example 16). On the other hand, as shown in Comparative Example 17 to Comparative Example 20, the curing time of the coating film was further longer than that of the present invention in the state in which triethyltetramine and a compound having a ring of a gynecological ring were used in combination. In addition, the obtained coating film is reduced in tensile strength, and the water resistance is further inferior to that of the present invention. Further, as shown in Comparative Example 21 to Comparative Example 26, the reaction product is not contained in the compound (B) or In the state in which the molar ratio of the compound (1) and the compound (8) is 90/10 or more and the excess compound (1) is contained, the obtained coating medium tensile elongation becomes small, and the flexibility is derived from triethylenetetramine. The polyamine hardener composition (comparative example) was even worse. 27 201202175 Further, as shown in Comparative Example 2 7 to Comparative Example 31, the molar ratio of the compound (a) and the compound (B) was 15 /85 and contains excess compound (B) In the state of the reaction product which does not contain the reaction product of the compound (A), the tensile strength of the coating film is more than that of the polystyrene hardener composition (Comparative Example 1) derived from triethylenetetramine. In the state which does not contain the reaction product of the compound (B), it is compared with the polyamine which is derived from triethylenetetramine, as shown in the comparative example 32 to the comparative example 34. In the hardener composition, the tensile elongation of the obtained coating film was small, and the flexibility was deteriorated. Further, as shown in Comparative Example 35, in the state in which APEDA was used, the coating film became brittle and lost flexibility, and as a result, Compared with the polyamine hardener composition (comparative example) derived from triethylenetetramine, the tensile elongation and the tensile strength are deteriorated together, and it is not easy to say that it is practical. Further, in the reference example, tetraethylenepentamine (manufactured by T〇s〇H Co., Ltd.) was used as the compound (A)' using N-aminoethylpiperazine (manufactured by T〇s〇H Co., Ltd.) as the compound (B). The reaction product of Tsunodime 216 (trade name, manufactured by Chikuno Food Industry Co., Ltd.) and triethylenetetramine (manufactured by Tosoh Corporation) was used as an example of the component (C). It is understood that the reaction product of the reference example, the addition of a large amount of triethylenetetramine as a raw material does not contribute to the shortening of the hardening time of the coating film or the improvement of the tensile strength and water resistance of the coating film. [Industrial Applicability] The polyamine hardener composition of the present invention exhibits better performance than the polyamine hardener derived from triethylenetetramine which is generally used in 201202175. Used in the field of coatings. In addition, the description and application of Japanese Patent Application No. 2〇10_082!42, which was filed on March 31, 2010, and the Japanese Patent Application No. 2010-082141, filed on March 31, 2010 The entire scope of the patent and the summary of the invention are incorporated in the specification of the present invention. [Main component symbol description] None. 29

Claims (1)

201202175 VII. Patent application scope: 1. A polyamine hardener composition characterized by containing a diethylenetriamine (al) and by the following chemical formula q): H2N^M&quot;NN^iiNH2 (1) In the chemical formula, the η system is a group of the amine compound (&amp;2) having a nitrogen atom number of 5 or more per molecule represented by 3 or more, and the selected compound (Α), nitrogen per molecule An amine compound having an atomic number of 4 or less and having an active hydrogen number of 2 or 3 and a reaction product containing the component (c) of the dimer acid and [the total number of moles of the compound (Α) and the compound (Β) [Mor number in terms of dimer acid of the component (C)] is in the range of 2/m to 4/3 and the molar ratio (human/8) of the compound (Α) and the compound (Β) is 9〇/ A reaction product in the range of 1 〇 15 15 / 85. 2. The polyamine hardener composition of claim 1, wherein the compound (Α) is tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, polyethylene polyamine, or a mixture thereof. 3. The polyamine hardener composition as described in claim 1 or 2 of the 'in which compound (anthraquinone-aminoethylpiperazine, piperidine, diethylenediamine, part of ruthenium-methide, ν, Ν-dimethylaminopropylamine, or a mixture of these. 4. The polyamine hardener composition according to any one of claims 1 to 3, wherein the compound (Α) and The molar ratio (a/ Β) of the compound (Β) is in the range of 90/10 to 40/60. 30 201202175 5. The polyamine hardener composition of any one of claims 1 to 3 Wherein, the molar ratio (A/B) of the compound m (A) and the compound (B) is in the range of 85/15 to 50/50. 6. As in any one of claims 1 to 5 of the patent application. The polyamine hardener composition, wherein the component m 4 tapping (C) contains 70 to 95% by weight of a dimer acid with respect to the total amount of the component (c). And the gossip is obtained by the reaction of any of the first to sixth patents in the patent application range. 8. The range of the molar ratio of the amine hydrogen atom in the (4) amine hardener composition to the ring base in the epoxy resin as in the hardened epoxy resin of claim 7 in the pot. 9. The hardened epoxy resin according to item 8 of the patent application, wherein, the oxygen resin is a double bismuth A type epoxy resin, a double age F type epoxy resin, a double age AD type epoxy resin, and a bisphenol combination. The type is broken, the resin is pressed, the phenolic phenolic resin, or a mixture of these. 31 201202175 IV. Designation of the representative figure: (1) The representative figure of the case is: No. (2) The symbol of the representative figure Brief Description: None. 5. If there is a chemical formula in this case, please disclose the chemical chemistry that best shows the characteristics of the invention. PARTICLE 6: INSTRUCTION DESCRIPTION OF THE INVENTION: The present invention relates to a polyamide hardener composition The polyamine hardener composition of the present invention is a curable composition of an epoxy resin used as a coating material, an adhesive, a floor material or the like. [Prior Art] A polyamine resin composition is generally used. A polybasic acid and a polyamine compound are synthesized as a raw material by dehydration condensation between an amine group and a carboxyl group under heating, and formation of a guanamine bond and extension of a polymer chain. Specifically, it has been known A dibasic acid or a polybasic acid such as adipic acid or a dimer acid, and a polyamine such as ethylenediamine or diethylenetriamine, which are used as a starting material to bond two constituent units of a resin or the like by a guanamine bond ( For example, refer to Patent Document 1). Here, the 'dimer acid type has rich reactivity and becomes the highest molecular weight dibasic acid obtained in the industry. In these polyamide resin compositions, 'by a dimer acid Derived poly