CN102822236A - Polyamide curing agent composition - Google Patents

Abstract

The present invention provides a polyamide curing agent composition not derived from triethylenetetramine which can replace the most commonly used polyamide curing agent derived from triethylenetetramine. The polyamide curing agent composition uses the following reaction product, the reaction product is a compound (A), an amine compound (B) with 4 or less nitrogen atoms per molecule and 2 or 3 active hydrogens, and A reaction product of a component (C) of a dimer acid, wherein the compound (A) is selected from diethylenetriamine (a1) and an amine compound having 5 or more nitrogen atoms per molecule represented by the following formula (1) (a2) The group consisting of [the total number of moles of the compound (A) and the compound (B)]/[the number of moles of the component (C) in terms of dimer acid] is in the range of 2/1 to 4/3. (In the formula, n represents a number of 3 or more).

Description

polyamide curing agent composition

technical field

The present invention relates to polyamide curing agent compositions.

The polyamide curing agent composition of the present invention is used as a curable composition of epoxy resins used in coatings, adhesives, floor applications, and the like.

Background technique

The polyamide resin composition is generally synthesized by using polybasic acid and polyamine compound as raw materials, dehydrating and condensing amino groups and carboxyl groups under heating to form amide bonds, and extending polymer chains. Specifically, it has been known so far that a dibasic acid such as adipic acid or a dimer acid or a polybasic acid and a polyamine such as ethylenediamine or diethylenetriamine are used as starting materials, and two structural units are linked by an amide bond. resin (for example, refer to Patent Document 1). Here, dimer acids are highly reactive and are the highest molecular weight dibasic acids available in the industry.

Among these polyamide resin compositions, since polyamide derived from dimer acid is tough, exhibits flexibility, and has good adhesive properties, it is used in adhesives, inks, surface coating agents, or As an epoxy resin curing agent compounded with epoxy resin, it is used for surface coating of metals, plastics, ceramics, etc., or for two-component reactive adhesives, etc.

Polyethyleneamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) are used in the manufacture of polyamide resin compositions, but are the most common commercially The polyvinylamine used was TETA.

However, conventional polyamide curing agents derived from triethylenetetramine have problems in their low-temperature curability.

In addition, in recent years, in the field of coatings for wind power generation turbines and the like, polyamide curing agents having higher flexibility than TETA-based polyamide curing agents have been demanded. This is because, in this field, problems such as large curvature of the turbine and contact with flying objects are prominent, and a coating film that is more difficult to peel off is required.

Therefore, a polyamide curing agent using a mixed composition of triethylenetetramine and a polyamine having a piperazine ring has been proposed (for example, refer to Patent Document 2). According to Patent Document 2, the obtained polyamide curing agent can reduce the amount of epoxy resin relative to the polyamide curing agent, thereby reducing the viscosity of the system, and obtaining a coating film with shorter curing time and excellent impact resistance.

However, the polyamide curing agent described in Patent Document 2 tends to lower the tensile strength of the coating film than when triethylenetetramine is used alone, and it is difficult to say that it will not necessarily be used in fields requiring performance equivalent to triethylenetetramine. Be applicable. In addition, since the active hydrogen equivalent becomes large and the ratio of polyamide/epoxy resin becomes high, it is difficult to say that it is suitable for applications requiring high water resistance.

In addition, since the raw material supply of triethylenetetramine (TETA) is limited and its price is higher than that of other polyethylene polyamines, there is a need for a more stable and economical alternative to TETA in the manufacture of polyamide curing agents.

Therefore, it is proposed to use N-3-aminopropylethylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N,N'-tris(3-aminopropyl)ethylenediamine A mixture of diamine, N,N,N',N'-tetrakis(3-aminopropyl)ethylenediamine as a polyamide curing agent for the polyamine component instead of triethylenetetramine (TETA) (for example, see patent literature 3). According to Patent Document 3, a coating film curing time shorter than that of TETA can be obtained.

However, since the cured epoxy resin based on the polyamide curing agent described in Patent Document 3 is less flexible than conventional polyamide curing agents, it cannot be said that TETA can be easily replaced in coating applications that particularly require flexibility. .

prior art literature

patent documents

Patent Document 1: Specification of US Patent No. 2450940

Patent Document 2: Japanese Patent Application Laid-Open No. 11-228672

Patent Document 3: Japanese Patent Laid-Open No. 2008-7776

Contents of the invention

The problem to be solved by the invention

The present invention was made in view of the above-mentioned background, and an object of the present invention is to provide a polyamide curing agent composition not derived from triethylenetetramine that can replace the most commonly used polyamide curing agent derived from triethylenetetramine.

Specifically, (1) provide a polyamide curing agent composition not derived from triethylenetetramine, which exhibits good flexibility and storage stability compared with polyamide curing agents derived from triethylenetetramine , or (2) provide a polyamide curing agent composition not derived from triethylenetetramine, which exhibits the same flexibility and water resistance as the polyamide curing agent derived from triethylenetetramine, and exhibits more Good curing properties and storage stability.

solutions to problems

The inventors of the present invention conducted intensive studies on polyamide curing agent compositions and completed the present invention.

That is, this invention relates to the polyamide hardening|curing agent composition shown below, and the epoxy resin hardened|cured material obtained using it.

[1] A polyamide curing agent composition characterized in that it contains the following reaction product, the reaction product is compound (A), the number of nitrogen atoms per molecule is 4 or less and the number of active hydrogen is 2 or 3 A reaction product of an amine compound (B) and a component (C) containing a dimer acid, the compound (A) being selected from nitrogen per molecule represented by diethylenetriamine (a1) and the following formula (1) A group consisting of amine compounds (a2) having 5 or more atoms,

[chemical formula 1]

(In the formula, n represents a number of 3 or more.)

Wherein, [the total number of moles of the compound (A) and the compound (B)]/[the number of moles of the component (C) in terms of dimer acid] is in the range of 2/1 to 4/3, and

The molar ratio (A/B) of the compound (A) to the compound (B) is in the range of 90/10 to 15/85.

[2] The polyamide curing agent composition according to [1] above, wherein the compound (A) is tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethylenepolyamine, or a mixture thereof.

[3] The polyamide curing agent composition according to the above [1] or [2], wherein the compound (B) is a partial N-methyl group of N-aminoethylpiperazine, piperazine, or diethylenetriamine compound, N,N-dimethylaminopropylamine, or a mixture thereof.

[4] The polyamide curing agent composition according to any one of the above [1] to [3], wherein the molar ratio (A/B) of the compound (A) to the compound (B) is 90/10~ 40/60 range.

[5] The polyamide curing agent composition according to any one of the above [1] to [3], wherein the molar ratio (A/B) of the compound (A) to the compound (B) is 85/15~ 50/50 range.

[6] The polyamide curing agent composition according to any one of the above-mentioned [1] to [5], wherein the component (C) contains 70 to 95% by weight of bismuth based on the total amount of the component (C). Polyacid.

[7] A cured epoxy resin obtained by reacting the polyamide curing agent composition described in any one of [1] to [6] above with an epoxy resin.

[8] The cured epoxy resin according to [7] above, wherein the molar ratio of the amine hydrogen atoms in the polyamide curing agent composition to the epoxy groups in the epoxy resin is 1.5/1 to 1/1.5 range.

[9] The cured epoxy resin according to [7] or [8] above, wherein the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol AD type epoxy resin , a phenol novolak type epoxy resin, a cresol novolac type epoxy resin, or a mixture thereof.

The effect of the invention

The polyamide curing agent composition of the present invention exhibits better performance than the generally widely used polyamide curing agent derived from triethylenetetramine.

For example, the polyamide curing agent composition of the present invention containing diethylenetriamine (a1) as compound (A) exhibits better flexibility and storage stability than existing polyamide curing agents derived from triethylenetetramine sex. Therefore, it can be suitably applied to the coating field which requires high flexibility.

In addition, the polyamide curing agent composition of the present invention containing an amine compound (a2) represented by the above formula (1) having 5 or more nitrogen atoms per molecule (a2) as a compound (A) is different from the conventional polyamide-derived curing agent composition. Triethylenetetramine-based polyamide curing agents are equally flexible, water-resistant, and exhibit better curing performance and storage stability. Furthermore, it is also possible to improve low-temperature curability, which is a disadvantage of conventional triethylenetetramine-derived polyamide curing agents.

Detailed ways

The present invention will be described in detail below.

The polyamide curing agent composition of the present invention is characterized in that it contains the following reaction product, the reaction product is compound (A), an amine compound with 4 or less nitrogen atoms per molecule and 2 or 3 active hydrogens ( B), and the reaction product of component (C) comprising dimer acid,

The compound (A) is selected from the group consisting of diethylenetriamine (a1) and an amine compound (a2) represented by the following formula (1) having 5 or more nitrogen atoms per molecule,

[chemical formula 2]

(In the formula, n represents a number of 3 or more.)

Wherein, [the total number of moles of the compound (A) and the compound (B)]/[the number of moles of the component (C) in terms of dimer acid] is in the range of 2/1 to 4/3, and

The molar ratio (A/B) of the compound (A) to the compound (B) is in the range of 90/10 to 15/85.

In the present invention, diethylenetriamine (a1) used in the compound (A) can be synthesized, for example, by reacting 1,2-dichloroethane and ammonia, and can be purified as a single compound by distillation. In addition, commercially available items can also be used.

In addition, the amine compound (a2) represented by the above formula (1) used in the compound (A) and having 5 or more nitrogen atoms per molecule can be synthesized, for example, by reacting 1,2-dichloroethane and ammonia. . Specific examples of such amine compounds include tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethylenepolyamine, and the like.

As the compound (A), the above compounds may be used alone or in combination. Among them, diethylenetriamine, pentaethylenehexamine, hexaethyleneheptamine, or mixtures thereof are preferred.

In the present invention, the compound (B) is not particularly limited, and examples include N-aminoethylpiperazine, piperazine, partial N-methylated products of diethylenetriamine, N-methylethylenediamine, N- Ethylethylenediamine, N-isopropylethylenediamine, N-methylaminopropylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, one or two- N-methylated compounds, tallow amines (for example, using 1,3-diaminopropane as the base amine, the amino group at position 1 is bonded to two C ₁₆ or C ₁₈ alkyl groups to form tertiary amino groups, etc.) wait.

As the compound (B), the above compounds may be used alone or in combination. Among them, partial N-methylated products of diethylenetriamine, N-aminoethylpiperazine, piperazine, N,N-dimethylaminopropylamine, or mixtures thereof are preferred.

The method of N-methylating the diethylenetriamine moiety is not particularly limited, and for example, a method using formaldehyde as an N-methylating agent is mentioned as a suitable method.

In the N-methylated form obtained in this way, the active hydrogen atom bonded to the nitrogen atom in the precursor diethylenetriamine (hereinafter, the active hydrogen atom bonded to the nitrogen atom in the molecule is sometimes referred to as "amine hydrogen atom") is preferably in the range of 40% to 60%.

In the present invention, the mixing ratio (A/B) of compound (A) and compound (B) is in the range of 90/10 to 15/85 (molar ratio), preferably in the range of 90/10 to 40/60 (molar ratio) , more preferably in the range of 85/15 to 50/50 (molar ratio).

In this invention, the "dimer acid" used for a component (C) means the acid which polymerized and dimerized unsaturated fatty acid, and includes the ester.

As an unsaturated fatty acid used for synthesis|combination of a dimer acid, a monofunctional unsaturated fatty acid is mentioned, for example. Specific examples of suitable unsaturated fatty acids include stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, or mixtures thereof, tall oil fatty acid, soybean fatty acid, rapeseed oil fatty acid, cottonseed fatty acid, and the like. The most preferred unsaturated fatty acid is tall oil fatty acid (mainly composed of oleic acid and linoleic acid).

In addition, as a raw material of the dimer acid, other than the above-mentioned unsaturated fatty acids, esters thereof can also be used. As esters of unsaturated fatty acids, for example, the lower alkyl esters of the monofunctional unsaturated fatty acids mentioned above are suitable esters of unsaturated fatty acids. Specifically, methyl ester, ethyl ester, n-propyl ester, tert-butyl ester, etc. of the said monofunctional unsaturated fatty acid can be illustrated. These may be used alone or in combination of two or more. When esters of unsaturated fatty acids are used in combination as a raw material of dimer acid, esters of dimer acid are obtained.

Dimer acids are usually prepared by polymerizing the above-mentioned raw materials under pressure. Here, the polymerization reaction is preferably carried out in the presence of a highly acidic Lewis acid type or Bronsted acid type catalyst. In addition, when an ester of an unsaturated fatty acid is used as a raw material, a dimer acid is obtained by further passing through a hydrolysis step.

The reaction solution mainly composed of dimer acid obtained in this way usually contains trimer acid and acid with a higher degree of polymerization, and monomer components such as unreacted unsaturated fatty acid and by-product branched chain fatty acid. Therefore, most of these monomer components are removed by distillation. The distillation is not particularly limited, but usually, distillation under reduced pressure is preferred. The reaction solution can be further hydrogenated, thereby reducing the unsaturation and coloration of the product. In addition, the distillation residue can also be further refined by molecular distillation. It should be noted that the ratio of dimer acid, trimer acid, and acid with a higher degree of polymerization in the reaction liquid varies depending on polymerization conditions, purification conditions, and unsaturated fatty acids used as raw materials.

In this invention, the reaction product obtained in this way can be used as a component (C). Component (C) usually contains polyfunctional fatty acid, such as a dimer acid, a trimer acid, and the acid with a higher degree of polymerization, and its ester.

The composition of the component (C) is not particularly limited, but it is preferable to contain dimer acid in an amount of 70% by weight to 95% by weight based on the total amount of the component (C). Moreover, it is preferable to contain 3 weight% - 30 weight% of trimer acid and the acid with a higher degree of polymerization (including these esters). Furthermore, the raw material unsaturated fatty acid, and other monofunctional carboxylic acid or polyfunctional carboxylic acid contained as needed may be contained as a remainder. As a component (C), the thing obtained using the monofunctional unsaturated fatty acid containing 70 weight% or more of oleic acid and its lower alkyl ester as a raw material is used especially suitably.

In order to function as a curing agent for epoxy resins, there must be terminal amino groups, so compound (A), compound (B) and component (C) are usually calculated as [total moles of compound (A) and compound (B)]/[ Component (C) is reacted at a ratio of 2/1 to 4/3 in terms of the number of moles of dimer acid. By making these ratios 4/3 or more, the molecular weight of a reactant can be moderately adjusted, and the objective polyamide curing agent composition can be obtained in the form of a liquid. In addition, by making the ratio 2/1 or less, it is possible to prevent the raw material amine compound from remaining unreacted.

In addition, when a composition obtained by N-methylating a part of diethylenetriamine is used as the compound (B), the total number of moles of the amine compound depends on the composition obtained by N-methylating a part of diethylenetriamine. Calculate the average molecular weight.

In addition, the number of moles in terms of dimer acid of the component (C) was calculated from the acid value of the component (C), and calculated as an average bifunctional acid.

The reaction of the compound (A), the compound (B) and the component (C) is usually carried out by heating in a temperature range of 120 to 280° C., preferably 180 to 250° C., under normal pressure. In addition, in order to prevent coloring of the product, it is advantageous to carry out the reaction under an inert gas atmosphere such as nitrogen.

The reaction time is affected by the reaction temperature and the types of raw materials used, and cannot be determined uniformly, but usually about 2 to 5 hours is enough. In addition, it is desirable to ripen under reduced pressure for an appropriate time before the end of the reaction. As the reaction progresses, the viscosity of the reaction liquid increases, but the reaction product does not solidify even after the reaction is completed, and can be easily transferred from the reaction container to the storage container even at room temperature. In addition, solvents such as toluene, xylene, and alcohol may be added at the end of the reaction if necessary.

The polyamide curing agent composition of the present invention contains the reaction product thus obtained.

The polyamide curing agent composition of the present invention may contain solvents such as aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, ethers, and alcohols. As the solvent, toluene, xylene and the like are preferable. The content of the solvent in the polyamide curing agent composition is preferably in the range of 0 to 60% by weight, more preferably in the range of 0 to 40% by weight.

In addition, the polyamide curing agent composition of the present invention may further contain other polyfunctional amines. Such polyfunctional amines are not particularly limited, and examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneamine with a higher molecular weight, piperazine, m-phthalylene Amine, isophorone diamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 2,4'-diaminobicyclo Hexylmethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, bis-(3 -aminopropyl)amine, N,N'-bis(3-aminopropyl)-1,2-diaminoethane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-Diaminocyclohexane, polyoxyalkylene polyamines (e.g., Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-403), etc.

Next, the epoxy resin cured product of the present invention will be described.

The cured epoxy resin of the present invention is formed by reacting the polyamide curing agent composition of the present invention with an epoxy resin. The reaction between the polyamide curing agent composition of the present invention and the epoxy resin is not particularly limited, and for example, a cured product can be formed by mixing and contacting them. If necessary, heat treatment may be performed to forcibly cure it.

The epoxy resin used for the epoxy resin cured product of the present invention is not particularly limited, and examples thereof include uncured polyepoxides containing two or more 1,2-epoxy groups per molecule, specifically Bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy novolac resin, alicyclic epoxy resin, polyfunctional epoxy resin, brominated epoxy resin etc. can be illustrated. These epoxy resins can be used solvent-free or diluted with solvents.

In the present invention, the polyamide curing agent composition of the present invention and the epoxy resin are usually 1.5/1 with [the amine hydrogen atom in the polyamide curing agent composition of the present invention]/[epoxy group in the epoxy resin] ~1/1.5 (molar ratio), preferably 1.2/1~1/1.2 (molar ratio) range. Thereby, favorable hardened|cured material property of an epoxy resin can be exhibited.

In the present invention, when forming a cured epoxy resin, a conventionally known curing accelerator may be used in combination in addition to the polyamide curing agent composition of the present invention. Such a curing accelerator is not particularly limited, and examples thereof include organic acid compounds, alcohol compounds, phenols, tertiary amines, hydroxylamine, and compounds similar to these. Among them, examples of particularly effective curing accelerators include phenol, nonylphenol, cresol, bisphenol A, salicylic acid, dimethylaminomethylphenol, bis(dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, methylaminomethyl) phenol, etc.

In addition, in the present invention, when forming a cured epoxy resin, conventionally known plasticizers can be used. Such a plasticizer is not particularly limited, and suitable plasticizers include benzyl alcohol, nonylphenol, various phthalates, and the like.

Furthermore, in the present invention, when forming a cured epoxy resin, solvents, fillers, pigments, pigment dispersants, rheology modifiers, thixotropic agents, flow aids, smoothing aids, defoamers, and the like can be used. Examples of suitable solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, ethers, alcohols and the like.

Example

The present invention is further described in detail by the following reference examples and examples, but the present invention is not limited by the reference examples and examples.

In addition, the analysis of the reaction product was performed by the following method.

＜Analysis of reaction products＞

(1) Gas chromatography analysis

Analytical column: DB-5 (manufactured by Agilent Technologies Co., Ltd., length 30m, film thickness 2.5μm, inner diameter 0.32mm),

Column temperature: 60°C + 10°C/minute temperature rise + 280°C/15 minutes.

(2) Nuclear Magnetic Resonance (NMR) Analysis ( ¹ H-NMR)

It was carried out using a Gemini-200 nuclear magnetic resonance apparatus (manufactured by Varian Inc.).

For the epoxy resin cured product, the evaluation of the curing speed and physical property measurement of the coating film was carried out as follows.

＜Evaluation of film curing time＞

The epoxy resin composition was applied to a glass panel (25 cm x 2 cm x 0.2 cm) with an inch applicator to form a coating film with a wet film thickness of 76 microns. After curing with a low temperature constant temperature and humidity device (manufactured by ESPEC Corp., trade name: PL-3K) under constant conditions of a temperature of 25°C and a relative humidity of 50%, it was carried out using an RC type drying time recorder [manufactured by Coating Tester Inc.]. Determination. The curability was evaluated according to the time (Hr.) until the stylus no longer pierced the film as indicated by this measurement.

<Evaluation of tensile strength and flexibility of coating film>

The epoxy resin composition was uniformly coated on a polypropylene film (20cm x 40cm x 0.2mm) with a doctor blade with a gap adjusted to 200 micrometers, and a low temperature constant temperature and humidity device (manufactured by ESPEC Corp., trade name: PL-3K) ) was dried for 48 hours at a constant temperature of 25°C and a relative humidity of 50% to cure.

Then, a test piece was produced using a dumbbell-shaped punch for tensile testing (JIS K62592 type dumbbell shape). Install the test piece on the Tensilon universal testing machine (Orientec Co., Ltd, trade name: RTM500) with a parallel fastening lock, stretch it at a speed of 30mm/min, and measure the maximum tensile strength of the test piece (kgf/mm ² ). At the same time, measure the distance between the marked lines (initially 40 mm) when the test piece breaks with a ruler, and measure the tensile elongation (%) at break. The larger the tensile elongation (%), the higher the flexibility of the coating film can be judged.

＜Water resistance evaluation of cured coating film＞

The coating films cured on the 1st and 7th days were immersed in a water tank whose temperature was adjusted to 40° C. for 24 hours, and then evaluated by visual observation of the state changes of the coating films. The results were evaluated on the following four scales.

◎: Excellent (no change), ○: Good, △: Slightly poor, ×: Poor (swelling and deformation of the coating film surface, discoloration of the coating film).

<Evaluation of storage stability>

The synthesized dimer acid polyamide-amine condensate was placed in a thermostat (Kusumoto Chemicals, Ltd., trade name: HIFLEX FL4050), cooled to -20°C, and kept for 1 hour. Then, after raising the temperature of the thermostat to 0° C. and maintaining it for 1 hour, the state of the dimer acid polyamide-amine condensate was visually observed. Similarly, after raising the temperature to 20, 25, 30, 35, 40, 50, 60, 70, 80, and 100° C. and maintaining each for 1 hour, the state of the polyamide was visually observed. The temperature at which the dimer acid polyamide-amine condensate becomes liquid is defined as "liquefaction temperature". The lower the liquefaction temperature, the lower the crystallinity of the dimer acid polyamide-amine condensate, and it can be judged that the storage stability of the polyamide curing agent composition is better.

Production Example 1 Partial N-methylation of diethylenetriamine

200 g of diethylenetriamine (manufactured by Tosoh Corporation, trade name: DETA), 100 g of water, and 2.0 g of catalyst Pd—C (5% loading) were charged in a 1000 ml autoclave with a stirrer. The autoclave was sealed, and after hydrogen substitution, the temperature was raised to 130°C with stirring. Then, hydrogen was introduced into the autoclave at a pressure of 3 MPa, and 314 g of a 37% formalin aqueous solution was supplied by a pump over 7 hours. After performing the aging reaction for 1 hour, it was cooled, and the reaction solution was taken out.

After distilling off water from the reaction liquid with a distillation apparatus, 236 g of a product were obtained under reduced pressure. Gas chromatography analysis and ¹ H-NMR analysis of this product showed that 40% of the hydrogen groups bonded to the nitrogen atom of diethylenetriamine were methyl groups ([methyl]/[hydrogen atom] = 40/60 (molar ratio).Therefore, the average number of active hydrogen per 1 molecule of this product is 3.

In addition, the composition of the obtained amine compound was DETA/monomethylated form/dimethylated form/trimethylated form/tetramethylated form/pentamethylated form=7.7/25.9/34.7/23.1 /7.6/1.0 (GC area ratio).

Hereinafter, the composition obtained by partially N-methylating diethylenetriamine obtained in this production example is referred to as "DETA-2M".

Production Example 2 Partial 3-aminopropylation of ethylenediamine

236 g of ethylenediamine was added to 1 liter of reaction container 1, and it heated to 60 degreeC. To this mixture was added 417 g of acrylonitrile over 2 hours. After the acrylonitrile addition was complete, the reaction was maintained at 60°C for an additional 2 hours.

Into a 1 liter batch reactor was added 500 g of the product 1 obtained in the previous process, and then filled with 100 g of isopropanol and 7.5 g of RaneyCo catalyst. After replacing the inside of the reaction vessel with nitrogen and removing the air, it was filled with 5.5 MPa of hydrogen, and then heated to 120°C. The reactor pressure was maintained at 5.5 MPa and the temperature at 120° C., and the reaction was carried out for 1 hour.

The reactor was cooled to room temperature, and the reaction liquid from which the solid content was removed was obtained by filtration. Isopropanol and low-boiling point components were distilled off from the reaction liquid under reduced pressure to obtain 682 g of a product. Gas chromatography analysis and ¹ H-NMR analysis of this product revealed that 50% of the hydrogen groups bonded to the nitrogen atom of ethylenediamine were substituted with aminopropyl groups. In addition, the composition of the obtained product is, monoaminopropyl substituent/bisaminopropyl substituent/triaminopropyl substituent/tetraaminopropyl substituent=7/80/11/2 (GC area ratio) .

Hereinafter, the composition obtained by partially 3-aminopropylating ethylenediamine obtained in this production example is referred to as "APEDA".

Example 1

In a glass container of 1000 ml, a composition [TSUNOFoods Industrial Co., Ltd. manufacture, trade name: Tsunodyme 216 containing 7% by weight of monomeric acid and 14% by weight of trimer acid of C ₁₈ dimer acid of unsaturated fatty acid was added. , acid value: 193.6mg KOH/g, equivalent to component (C)] 100g, then slowly add 21.4g of diethylenetriamine (manufactured by Tosoh Corporation) and 6.7g of N-aminoethylpiperazine while stirring [ Manufactured by Tosoh Corporation, it corresponds to the compound (B)] where [the total number of moles of the compound (A) and the compound (B)]/[the number of moles of the component (C) in terms of dimer acid] is 3/2. Increase the stirring speed to 150 rpm, heat at 200° C. for 4 hours under a nitrogen atmosphere, and remove 6.2 g of water by distillation. Further, the reaction was carried out for 1 hour under the conditions of 200° C. and 10 mmHg.

Next, the reaction container was cooled to 100° C., toluene was added so that the solid content concentration became 70% by weight, stirred to form a uniform toluene solution, and then cooled to room temperature. The reaction product (dimer acid polyamide-amine condensate) obtained here was amber in color and had an active hydrogen equivalent of 227 in a state without toluene.

Compared to the epoxy resin with an epoxy equivalent of 474 [manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epikote1001, bisphenol A epoxy resin with an epoxy equivalent of 474] diluted to 70% by weight with toluene 32 parts by weight of the epoxy resin solution and the toluene solution of the obtained dimer acid polyamide-amine condensate were added in a ratio of 68 parts by weight, and shear stirring was performed at room temperature for 5 minutes with a spatula. Here, [the amine hydrogen atom in the polyamide curing agent composition of the present invention]/[the epoxy group in the epoxy resin] is 1/1 (molar ratio). Table 1 shows the results obtained by measuring the curing rate and physical properties of the coating film according to the evaluation method described above.

Embodiment 2～Example 9 and Comparative Example 1～Comparative Example 15

Except having used the raw material of the kind and quantity shown in Table 1 and Table 2, it carried out similarly to Example 1. The results are shown in Table 1 and Table 2 in combination.

[Table 1]

[Table 2]

It can be known from Examples 1 to 9 that the tensile elongation and tensile strength of the coating film prepared from the polyamide curing agent composition of the present invention are the same as when using the curing agent composition derived from triethylenetetramine ( Compared with Comparative Example 1), the tensile elongation was about 2 times to 3 times higher. Therefore, it can be seen that when the polyamide curing agent composition of the present invention is used, it exhibits more excellent flexibility than the curing agent composition derived from triethylenetetramine (Comparative Example 1), and can be suitably applied to coatings in which flexibility is particularly required ( For example, coatings for wind turbines). In addition, the polyamide curing agent composition of the present invention is more excellent in storage stability than the curing agent composition derived from triethylenetetramine (Comparative Example 1). Furthermore, since the polyamide curing agent composition of the present invention uses diethylenetriamine as the polyethyleneamine, it is more excellent in supply stability than triethylenetetramine.

On the other hand, as shown in Comparative Examples 2 to 5, when triethylenetetramine and a compound having a piperazine ring are used in combination, the tensile strength of the obtained coating film is significantly lowered, so it is difficult to say that it is practical.

On the other hand, as shown in Comparative Example 6, when the reaction product of compound (B) was not included, the tensile elongation of the obtained coating film was only increased by about 1.5 times compared with triethylenetetramine, which was very low. It is difficult to say that sufficient flexibility is imparted.

On the other hand, as shown in Comparative Examples 7 to 11, when the molar ratio (A/B) of the compound (A) to the compound (B) deviates from 15/85, and the compound (B) is contained in excess, even if stretched The elongation is about 2 to 3 times the tensile strength and the tensile strength is extremely low, so it is difficult to say that it is practical.

On the other hand, as shown in Comparative Examples 12 to 14, when triethylenetetramine having 6 active hydrogens per molecule was used instead of compound (B), the tensile elongation was only increased compared to Comparative Example 1. By about 1.5 times, it is difficult to say that sufficient flexibility is imparted. It should be noted that, in Comparative Examples 12 to 14, the molar ratios of diethylenetriamine/triethylenetetramine were 80/20, 70/30, and 60/40, respectively.

In addition, as shown in Comparative Example 15, when APEDA was used, the coating film became brittle and lost flexibility, so the tensile elongation was lower than that of the polyamide curing agent composition derived from triethylenetetramine (Comparative Example 1). and tensile strength are degraded, it is hard to say that it is practical.

Example 10

In a glass container of 1000 ml, a composition [TSUNOFoods Industrial Co., Ltd. manufacture, trade name: Tsunodyme 216 containing 7% by weight of monomeric acid and 14% by weight of trimer acid of C ₁₈ dimer acid of unsaturated fatty acid was added. , acid value: 193.6mg KOH/g, equivalent to component (C)] 100g, then slowly add 41.8g of tetraethylenepentamine (manufactured by Tosoh Corporation) and 5.0g of N-aminoethylpiperazine while stirring [ Manufactured by Tosoh Corporation, it corresponds to the compound (B)] where [the total number of moles of the compound (A) and the compound (B)]/[the number of moles of the component (C) in terms of dimer acid] is 3/2.

Heat at 120°C, stirring until completely homogeneous. The stirring speed was raised to 150 rpm, heated at 200° C. for 4 hours under a nitrogen atmosphere, and 6.2 g of water was removed by distillation. Further, it was reacted for 1 hour under the conditions of 200° C. and 10 mmHg. Next, the reaction container was cooled to 100° C., toluene was added so that the solid content concentration became 70% by weight, stirred to form a uniform toluene solution, and cooled to room temperature. The reaction product (dimer acid polyamide-amine condensate) obtained here was amber in color and had an active hydrogen equivalent of 167 in a state without toluene.

Compared to the epoxy resin with an epoxy equivalent of 474 [manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epikote1001, bisphenol A epoxy resin with an epoxy equivalent of 474] diluted to 70% by weight with toluene 74 parts by weight of epoxy resin solution, as a polyamide curing agent composition, add the toluene solution of the obtained dimer acid polyamide-amine condensate in a ratio of 26 parts by weight, and cut it at room temperature for 5 minutes with a spatula. Cut and stir. Here, [the amine hydrogen atom in the polyamide curing agent composition of the present invention]/[the epoxy group in the epoxy resin] is 1/1 (molar ratio). Table 3 shows the results obtained by measuring the curing rate and physical properties of the coating film according to the evaluation method described above.

Embodiment 10～Example 18, Comparative Example 16～Comparative Example 35, and Reference Example

Except having used the raw material of the kind and quantity shown in Table 1 and Table 2, it carried out similarly to Example 1. The results are shown in Table 3 and Table 4 together. In addition, "S-PEHA" shown in Table 3 and Table 4 refers to heavy ethylene obtained by further distilling the distillation residue of pentaethylenehexamine (PEHA) obtained in the production process of ethylene amines. Amine mixture (manufactured by Tosoh Corporation). It is characterized in that it has a larger molecular weight than PEHA and has a larger number of nitrogen atoms per molecule.

[table 3]

[Table 4]

From Examples 10 to 18, it can be seen that the curing time of the coating film based on the polyamide curing agent composition of the present invention is faster than that of the commonly used polyamide curing agent composition derived from triethylenetetramine (Comparative Example 16). Therefore, it can be seen that the present invention enables rapid low-temperature curability and improves the productivity of coating.

In addition, the coating film prepared with the polyamide curing agent composition of the present invention has the same tensile elongation and tensile strength as the polyamide curing agent composition derived from triethylenetetramine. Therefore, according to the present invention, flexibility and coating film strength equivalent to those of triethylenetetramine can be realized, and sufficient coating film flexibility required for paints can be provided.

Furthermore, the polyamide curing agent composition of the present invention can maintain water resistance equivalent to that of a triethylenetetramine-derived polyamide curing agent. In addition, it can be seen that the polyamide curing agent composition of the present invention has better storage stability than the curing agent composition derived from triethylenetetramine (Comparative Example 16).

On the other hand, as shown in Comparative Examples 17 to 20, when triethylenetetramine and a compound having a piperazine ring were used in combination, the curing time of the coating film was longer than that of the present invention. Moreover, the tensile strength of the obtained coating film was low, and water resistance was inferior to this invention.

In addition, as shown in Comparative Example 21 to Comparative Example 26, when the reaction product of compound (B) is not contained, the molar ratio of compound (A) to compound (B) deviates from 90/10 and contains excessive compound (A) In the case of , the tensile elongation of the obtained coating film was small, and the flexibility was inferior to the polyamide curing agent composition derived from triethylenetetramine (Comparative Example 1).

In addition, as shown in Comparative Example 27 to Comparative Example 31, when the molar ratio of compound (A) to compound (B) deviated from 15/85 and excessive compound (B) was contained, the reaction product of compound (A) was not contained In the case of , the tensile strength of the coating film was extremely low compared with the polyamide curing agent composition derived from triethylenetetramine (Comparative Example 1), and sufficient strength could not be obtained.

In addition, as shown in Comparative Example 32 to Comparative Example 34, when the reaction product of the compound (B) was not included, the coating film obtained was less stretchy than the polyamide curing agent composition derived from triethylenetetramine. Small elongation and poor flexibility.

In addition, as shown in Comparative Example 35, when APEDA was used, the coating film became brittle and lost flexibility, so the tensile elongation was lower than that of the polyamide curing agent composition derived from triethylenetetramine (Comparative Example 1). and tensile strength have deteriorated, it is difficult to say that it is practical.

In addition, as a reference example, tetraethylenepentamine (manufactured by Tosoh Corporation) as compound (A), N-aminoethylpiperazine (manufactured by Tosoh Corporation) as compound (B), and Tsunodyme 216 (trade name, TSUNO Foods Industrial Co., Ltd.), and an example of a reaction product of triethylenetetramine (manufactured by Tosoh Corporation). It can be seen that in the reaction product of the reference example, a large amount of triethylenetetramine added as a raw material did not contribute to shortening of the curing time of the coating film, and improvement of the tensile strength and water resistance of the obtained coating film.

Industrial availability

The polyamide curing agent composition of the present invention shows better performance than the generally widely used polyamide curing agent derived from triethylenetetramine, and can be suitably used, for example, in the field of coatings.

It should be noted that the specifications, claims, and abstracts of Japanese Patent Application No. 2010-082141 filed on March 31, 2010 and Japanese Patent Application No. 2010-082142 filed on March 31, 2010 are cited here. The entire content is incorporated as the disclosure content of the specification of the present invention.

Claims (9)

1. polyamide curing agent compositions; It is characterized in that; Contain following reaction product, this reaction product is that the nitrogen-atoms number is below 4 and the active hydrogen number is 2 or 3 amine compound (B) and the reaction product that comprises the composition (C) of dimeracid in compound (A), per 1 molecule

It is the group that the amine compound (a2) more than 5 is formed that said compound (A) is selected from by nitrogen-atoms number in per 1 molecule of diethylenetriamine (a1) and following formula (1) expression,

[Chemical formula 1]

In the formula, n representes the number more than 3,

Wherein, [total mole number of compound (A) and compound (B)]/[mole number that the dimeracid of composition (C) converts] is 2/1 ~ 4/3 scope, and

The mol ratio (A/B) of compound (A) and compound (B) is 90/10 ~ 15/85 scope.

2. polyamide curing agent compositions according to claim 1, wherein, compound (A) is TEPA, five ethene hexamines, six ethene, seven amine, polyethylene polyamine or their mixture.

3. polyamide curing agent compositions according to claim 1 and 2, wherein, compound (B) is part N-methide, the N of N-aminoethyl piperazine, piperazine, diethylenetriamine, N-dimethylaminopropylamine or their mixture.

4. according to each described polyamide curing agent compositions of claim 1 ~ 3, wherein, the mol ratio (A/B) of compound (A) and compound (B) is 90/10 ~ 40/60 scope.

5. according to each described polyamide curing agent compositions of claim 1 ~ 3, wherein, the mol ratio (A/B) of compound (A) and compound (B) is 85/15 ~ 50/50 scope.

6. according to each described polyamide curing agent compositions of claim 1 ~ 5, wherein, the total amount that composition (C) contains with respect to composition (C) is the dimeracid of 70 ~ 95 weight %.

7. epoxy resin cured product, it obtains each described polyamide curing agent compositions of claim 1 ~ 6 and epoxy resin reaction.

8. epoxy resin cured product according to claim 7, wherein, the amine hydrogen atom in the polyamide curing agent compositions and the mol ratio of the epoxy group(ing) in the epoxy resin are 1.5/1 ~ 1/1.5 scope.

9. according to claim 7 or the described epoxy resin cured product of claim 8; Wherein, epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin or their mixture.