JP2012121997A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having more excellent flexibility than a polyamide curing agent originated in triethylenetetramine which is most generally often used.SOLUTION: This polyamide resin composition is obtained by mixing an amine component (A) containing polyamine having one or more hydroxy groups and two or more active hydrogens per molecule with a dimer acid component (B) comprising a dimer acid, dimer acid ester or both of them, and by causing a condensation reaction thereof, wherein the ratio of [amine component (A)]/[dimer acid component (B)] is in the range of 2/1-4/3 (mole ratio).

Description

  The present invention relates to a polyamide resin composition.

  The polyamide resin composition of the present invention is used, for example, as a curing agent composition for epoxy resins used for paints, adhesives, flooring applications and the like.

  Polyamide resin compositions are generally synthesized by using polybasic acid and polyamine compound as raw materials, dehydrating and condensing between amino groups and carboxyl groups under heating, forming amide bonds and stretching polymer chains. Specifically, a resin in which both structural units are linked by an amide bond using a dibasic acid or polybasic acid such as adipic acid or dimer acid and a polyamine such as ethylenediamine or diethylenetriamine as a starting material has been conventionally known. (For example, refer to Patent Document 1).

  Among these, the polyamide resin composition derived from dimer acid is tough and flexible, and has good adhesion performance. Therefore, it can be used as an adhesive, ink, surface coating agent, and epoxy resin curing agent as an epoxy resin. It is compounded and used for surface coating of metals, plastics, ceramics, etc., or for two-component reaction type adhesives.

  For the production of the polyamide resin composition, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N- (2-aminoethyl) piperazine (polyamine compound) Polyethyleneamines such as N-AEP) are commonly used, of which triethylenetetramine is most commonly used commercially.

  Here, the polyamide resin composition obtained by the method described in Patent Document 1 has low volatility compared to the low molecular weight curing agent at that time, and was excellent in flexibility and durability when blended with an epoxy resin. It is said that a cured product can be obtained.

  However, in recent years, higher flexibility than the triethylenetetramine-based polyamide resin composition has been demanded in fields such as wind turbine paints. This is because, in the same field, problems such as large deflection of the turbine and contact with flying objects are manifested, and a coating film that does not peel more is desired.

  In Patent Document 2, N-3-aminopropylethylenediamine, N, N′-bis (3-aminopropyl) ethylenediamine, N, N, N′-tris (3-amino) are used as polyamines to replace triethylenetetramine. Propyl) ethylenediamine, N, N, N ′, N′-tetrakis (3-aminopropyl) polyethyleneamine using a mixture containing ethylenediamine has been proposed. However, the epoxy resin cured product by the polyamide curing agent described in the publication is inferior in flexibility as compared with the conventional polyamide curing agent, and is therefore suitable for the above-described coating application requiring flexibility. hard.

  Further, Patent Document 3 proposes an aminoalkylpiperazine as a polyamine that replaces triethylenetetramine. The epoxy resin cured product by the polyamide curing agent described in the publication is superior to the conventional polyamide curing agent in flexibility, but in the above-described coating applications requiring flexibility, the flexibility is further increased. Improvement is desired.

U.S. Pat. No. 2,450,940 JP 2008-7776 A Japanese translation of PCT publication No. 2002-532591

  The present invention has been made in view of the above-described background art, and its purpose is to provide a polyamide resin composition that is superior in flexibility to the most commonly used polyamide curing agent derived from triethylenetetramine. It is to be.

  As a result of intensive studies on the polyamide resin composition, the present inventors have completed the present invention.

  That is, this invention relates to the polyamide resin composition as shown below.

  [1] An amine component (A) containing a polyamine having one or more hydroxyl groups and two or more active hydrogens in the molecule, and a dimer acid component (B) comprising a dimer acid, a dimer acid ester, or both In the range of 2/1 to 4/3 (molar ratio) [amine component (A)] / [dimer acid component (B)] A polyamide resin composition characterized by being.

  [2] The polyamide resin as described in [1] above, wherein the polyamine having one or more hydroxyl groups and at least two or more active hydrogens in the molecule is a polyamine represented by the following formula (1): Composition.

［上記式（１）中、Ｒ_１〜Ｒ_８は各々独立して、水素原子、炭素数１〜１６のアルキル基、炭素数６〜１６のアリール基、炭素数２〜６のヒドロキシアルキル基、炭素数２〜６のアミノアルキル基、炭素数２〜６のモノメチルアミノアルキル基、炭素数２〜６のジメチルアミノアルキル基で示される置換基を表し、ｎ、ｍは各々独立して１〜１１の整数を表し、ａ、ｂは各々独立して０〜１０の整数を表す。但し、Ｒ_７とＲ_１又はＲ_２とが結合して環状化合物となっても良い。］
［３］分子中に１個以上の水酸基と少なくとも２個以上の活性水素とを有するポリアミンが、２−（２−アミノエチルアミノ）エタノール、１−［（２−アミノエチル）アミノ］−２−プロパノール、１，１’［（１，２−エタンジイル）ビスイミノ］ビス（２−プロパノール）、１−［２−［（２−アミノエチル）アミノ］エチル］アミノ−２−プロパノール、１，１’−［イミノビス（２，１−エタンジイルイミノ）］ビス（２−プロパノール）又はこれらの混合物であることを特徴とする［１］に記載のポリアミド樹脂組成物。

[In the formula (1), R _{1 to} R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, It represents a substituent represented by a C2-C6 aminoalkyl group, C2-C6 monomethylaminoalkyl group, C2-C6 dimethylaminoalkyl group, and n and m are each independently 1-11. And a and b each independently represent an integer of 0 to 10. However, R ₇ and R ₁ or R ₂ may be bonded to form a cyclic compound. ]
[3] A polyamine having one or more hydroxyl groups and at least two active hydrogens in the molecule is 2- (2-aminoethylamino) ethanol, 1-[(2-aminoethyl) amino] -2- Propanol, 1,1 ′ [(1,2-ethanediyl) bisimino] bis (2-propanol), 1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol, 1,1′- The polyamide resin composition according to [1], which is [iminobis (2,1-ethanediylimino)] bis (2-propanol) or a mixture thereof.

  [4] The dimer acid component (B) contains 70 to 95% by weight of dimer acid with respect to the whole component (B), and contains trimer acid and an acid having a higher degree of polymerization in the range of 0 to 30% by weight. And the remainder is monomeric fatty acid, the polyamide resin composition according to any one of [1] to [3] above.

  [5] A curing agent composition for an epoxy resin, comprising the polyamide resin composition according to any one of [1] to [4].

  [6] A cured epoxy resin obtained by bringing the polyamide resin composition according to any one of [1] to [5] above into contact with an epoxy resin.

  [7] The epoxy according to the above [6], wherein the stoichiometric ratio of the polyamide resin composition amine hydrogen to the amine hydrogen in the epoxy resin is in the range of 1.5: 1 to 1: 1.5. Resin cured product.

  [8] The above [6] or [7], wherein the epoxy resin is glycidyl ether of bisphenol A, improved glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, epoxy novolac resin, or a mixture thereof. ] The epoxy resin hardened | cured material of description.

  When the polyamide resin composition of the present invention is used as a curing agent composition for epoxy resins, it exhibits a higher flexibility than a commonly used triethylenetetramine-derived polyamide curing agent, and thus high flexibility is required. It can be suitably used in the paint field.

  Hereinafter, the present invention will be described in detail.

  In the present invention, the polyamine having one or more hydroxyl groups and at least two active hydrogens in the molecule used as the amine component (A) is not particularly limited, and examples thereof include ethylene oxide and propylene. Examples thereof include compounds obtained by adding oxides or both of them to polyamines. Examples of polyamines used herein include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneamine having a higher molecular weight, meta-xylylenediamine, isophoronediamine, 3,3′-dimethyl-4 , 4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, 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, -Of diaminocyclohexane, N- (2-aminoethyl) piperazine, N- (2-aminobutyl) piperazine, N, N-bis (2-aminoethyl) piperazine and N, N-bis (3-aminopropyl) piperazine In addition, a composition obtained by partially N-methylating diethylenetriamine may be used. These may be used alone or in combination.

  Thus, as a compound obtained by adding ethylene oxide, propylene oxide, or both to polyamines, for example, 2- (2-aminoethylamino) ethanol, 2,2 ′-(ethylenebisimino) ) Bisethanol, 1-[(2-aminoethyl) amino] -2-propanol, 1,1 ′ [(1,2-ethanediyl) bisimino] bis (2-propanol), 2-[[2-[(2 -Aminoethyl) amino] ethyl] amino] ethanol, 1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol, 2,2 '[iminobis (2,1-ethanediylimino] bis And ethanol, 1,1 ′-[iminobis (2,1-ethanediylimino)] bis (2-propanol), etc. These are used alone. Also may be, it may be used in combination.

  Of these, 2- (2-aminoethylamino) ethanol, 1-[(2-aminoethyl) amino] -2-propanol, 1,1 ′ [(1,2-ethanediyl) bisimino] bis ( 2-propanol), 1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol, 1,1 ′-[iminobis (2,1-ethanediylimino)] bis (2-propanol) It is.

  When the active hydrogen in the polyamine molecule is 1 or less, the polyamide obtained by the reaction with the dimer acid component does not contain a primary amine and a secondary amine, and the reactivity with the epoxy resin disappears. It becomes difficult to use. On the other hand, by including one or more hydroxyl groups in the polyamine molecule, the flexibility of the cured epoxy resin is improved. Although this is not desired to be bound by a specific theory, it is speculated that a part of the hydroxyl group reacts with dimer acid at the time of polyamide formation, and high flexibility is developed because an ester bond is formed. .

  As the amine component (A) of the present invention, in addition to polyamines having one or more hydroxyl groups and at least two active hydrogens in the molecule, polyamines generally used in polyamide resin compositions (hereinafter, "Other polyamines") can be included as long as the effects of the present invention are not impaired. Examples of such other polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, higher molecular weight polyethyleneamine, meta-xylylenediamine, isophoronediamine, 3,3′-dimethyl-4, 4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 2,4'-diaminodicyclohexylmethane, 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, -Of diaminocyclohexane, N- (2-aminoethyl) piperazine, N- (2-aminobutyl) piperazine, N, N-bis (2-aminoethyl) piperazine and N, N-bis (3-aminopropyl) piperazine In addition, a composition obtained by partially N-methylating diethylenetriamine, N, N-dimethylaminopropylamine, polyoxyalkylene polyamine (for example, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D) -4000, Jeffamine T-403) and the like. These may be used alone or in combination.

  Of these, N- (2-aminoethyl) piperazine, N- (2-aminobutyl) piperazine, N, N-bis (2-aminoethyl) piperazine and N, N-bis (3-aminopropyl) are preferred. In addition to piperazine, N, N-dimethylaminopropylamine is a composition obtained by partially N-methylating diethylenetriamine.

  The dimer acid component (B) used in the present invention contains dimer acid, dimer acid ester, or both.

  Here, in the present invention, “dimer acid” refers to an unsaturated dicarboxylic acid obtained by polymerizing an unsaturated carboxylic acid such as oleic acid, linolenic acid, linoleic acid or the like. Any material can be used as long as it is made of unsaturated carboxylic acid, and is not particularly limited.

  Examples of unsaturated carboxylic acids used in the synthesis of dimer acids include monofunctional unsaturated fatty acids, specifically stearic acid, palmitic acid, oleic acid, linoleic acid, linacic acid, or their A mixture (for example, tall oil fatty acid, soybean fatty acid, rapeseed oil fatty acid, cottonseed fatty acid, linseed fatty acid, etc.) can be mentioned.

  Moreover, as a raw material of the dimer acid, an ester thereof may be used instead of or in addition to the above unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid ester include lower alkyl esters of the monofunctional unsaturated fatty acids described above, and specifically, methyl esters and ethyl esters of the monofunctional unsaturated fatty acids described above. , N-propyl ester, tert-butyl ester and the like. These may be used alone or in combination of two or more. In addition, when the ester of unsaturated carboxylic acid is used together as a raw material of dimer acid, ester of dimer acid is obtained.

  The dimer acid is generally prepared by polymerizing the above raw materials under pressure. Here, the polymerization reaction is preferably performed in the presence of a high acid strength Lewis acid type or Bronsted acid type catalyst. In addition, when an unsaturated fatty acid ester is used as a raw material, dimer acid can be obtained through a hydrolysis step.

  The reaction liquid mainly composed of the dimer acid thus obtained usually contains trimer acid or an acid having a higher degree of polymerization, and further monomer components such as unreacted unsaturated fatty acid and by-product branched fatty acid. Contains. For this reason, most of these monomer components are removed by distillation. Although it does not specifically limit as distillation, It is preferable to carry out pressure reduction and normal pressure. This reaction may be further hydrogenated, which reduces the degree of unsaturation and coloration of the product. Further, the distillation residue may be further purified by molecular distillation. In addition, the ratio of the dimer acid in a reaction liquid, trimer acid, and an acid with a higher polymerization degree fluctuates according to polymerization conditions, purification conditions, unsaturated fatty acid acid as a raw material, and the like.

  In the present invention, the dimer acid component (B) contains 70 to 95% by weight of dimer acid with respect to the whole component (B), and the trimer acid and the acid having a higher degree of polymerization are in the range of 0 to 30% by weight. It is preferable that the remainder be monomeric fatty acid. Other monofunctional and polyfunctional carboxylic acids may be incorporated into the dimer acid component as required.

  The commercially available dimer acid used in the present invention includes, for example, Tsunodim 216, Tsunodim 228 (Tsukino Food Industries, Amani fatty acid dimer acid), Rusty Dime DA-200 (Kaneda, soybean oil fatty acid dimer). Acid) and the like.

  In order to act as a curing agent for an epoxy resin, the presence of a terminal amino group is required, so the ratio of the number of moles of the amine component (A) to the number of moles of the dimer acid component (B) (mol / mol) is 4/3 or more and 2/1 or less. By setting the ratio to 4/3 or more, the molecular weight of the reaction product can be appropriately adjusted, and the target polyamide resin composition can be obtained as a liquid material. Moreover, raw material amine can be prevented from remaining unreacted by setting the ratio to 2/1 or less. At this time, the number of moles of the amine component (A) is calculated from the average molecular weight. Further, the number of moles of the dimer acid component (B) is calculated from the acid value, and is calculated as an average bifunctional acid.

  The condensation reaction of the amine component (A) and the dimer acid component (B) is usually performed by heating these mixtures at a temperature range of 120 to 280 ° C, preferably 180 to 250 ° C under normal pressure. This reaction is advantageously carried out in an inert gas atmosphere such as nitrogen gas in order to prevent the product from being colored. The reaction time depends on the reaction temperature and the type of raw material to be used, and cannot be determined in general, but about 2 to 5 hours is sufficient. In addition, it is desirable to age for a suitable time in a reduced pressure state before the end of the reaction. As the reaction proceeds, the viscosity of the reaction solution increases, but the reaction product does not solidify even after the reaction is completed, and transfer from the reaction vessel to the storage vessel is easy even at room temperature. Moreover, you may add solvents, such as toluene, xylene, alcohol, like the conventional product at the time of completion | finish of reaction as needed.

  The polyamide resin composition of the present invention contains the reaction product thus obtained. When some or all of the amino groups in the polyamine having one or more hydroxyl groups and at least two or more active hydrogens in the molecule are secondary amino groups, tertiary amino groups, or both Since the portion does not have a primary amino group that is highly reactive with the epoxy resin, the reaction rate between the polyamide resin composition and the epoxy resin is reduced, and the resin is gradually cured. As a result, a sufficient pot life can be ensured, which is advantageous when uniformly bonding larger application areas.

  The polyamide resin composition of the present invention is used as a curing agent composition for epoxy resins.

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

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

  Although it does not specifically limit as an epoxy resin used for the epoxy resin hardened | cured material of this invention, For example, the uncured polyepoxy compound containing 2 or more 1, 2- epoxy groups per molecule is mentioned, Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy novolac resin, alicyclic epoxy resin, polyfunctional epoxy resin, brominated epoxy resin and the like are exemplified. These epoxy resins can be used either without solvent or diluted with a solvent.

  In the present invention, the polyamide resin composition of the present invention and the epoxy resin are generally [amine hydrogen atom in the polyamide resin composition of the present invention] / [epoxy group in the epoxy resin] is usually 1.5 / 1 to 1. /1.5 (molar ratio), preferably 1.2 / 1 to 1 / 1.2 (molar ratio). By doing in this way, the cured | curing material property of a favorable epoxy resin can be exhibited.

  In the present invention, when a cured epoxy resin is formed, a conventionally known curing accelerator can be used in combination with the polyamide resin 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, hydroxylamines, and similar compounds. Among these, particularly useful curing accelerators include phenol, nonylphenol, cresol, bisphenol A, salicylic acid, dimethylaminomethylphenol, bis (dimethylaminomethyl) phenol, and tris (dimethylaminomethyl) phenol. .

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

  Furthermore, in the present invention, when the epoxy resin cured product is formed, a solvent, a filler, a pigment, a pigment dispersant, a rheology modifier, a thixotropic agent, a fluidization and smoothing aid, an antifoaming agent, and the like are used. Also good. Suitable solvents include, for example, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, ethers, alcohols and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not this limited to these.

<Evaluation of thin film curing time>
The epoxy resin composition was applied to a glass panel (25 cm × 2 cm × 0.2 cm) with a wet film thickness of 76 micrometers using an inch applicator. After curing at a constant temperature of 25 ° C. and a relative humidity of 50% using a low temperature and humidity chamber (product name: PL-3K, manufactured by Espec), using an RC type drying time recorder (manufactured by Coating Tester) It was measured. The curability was evaluated by the secondary linear mark disappearance time (Hr.) Indicated by this measurement.

<Evaluation of tensile strength and flexibility of coating film>
The epoxy resin composition is uniformly applied onto a polypropylene film (20 cm × 40 cm × 0.2 mm) using a doctor blade whose gap is adjusted to 200 micrometers, and a low temperature and temperature and humidity chamber (manufactured by Espec Corp., product name: PL) -3K) was dried and cured for 48 hours under constant conditions of 25 ° C. and 50% relative humidity.

Then, the test piece was created using the dumbbell type punch for tensile tests (JIS K 6259 No. 2 type dumbbell shape). A test piece is attached to a Tensilon universal testing machine (product name: RTM500, manufactured by Orientec Co., Ltd.) using a parallel fastening lock, pulled at a speed of 30 mm / min, and the maximum tensile strength (kgf / mm ² ) of the sample piece is measured. did. At the same time, the distance between the marked lines when the test piece was broken (initially 40 mm) was measured with a ruler, and the tensile elongation (%) at break was measured. It is judged that the greater the tensile elongation (%), the higher the flexibility of the coating film.

Synthesis Example 1 Synthesis of 1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol.
In a 1 L autoclave, 100 g (0.97 mol) of diethyltriamine (DETA) was added, and the inside of the autoclave was purged with nitrogen, and then the internal pressure was set to 1 kg / cm 2 f and the internal temperature was set to 120 ° C. While maintaining the internal temperature at 120 ° C., 56 g (0.97 mol) of propylene oxide (PO) was added to the autoclave over 4 hours with stirring, and further aged at 120 ° C. for 2 hours. Thereafter, the mixture was cooled to 80 ° C., and unreacted propylene oxide was recovered to obtain 1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol (1TA adduct of DETA).

Synthesis Example 2 Synthesis of 1,1 ′-[iminobis (2,1-ethanediylimino)] bis (2-propanol).
1,1 ′-[iminobis (2,1-ethanediylimino)] bis (2-propanol) was obtained in the same manner as in Synthesis Example 1 except that 112 g (1.94 mol) of propylene oxide was used ( 2TA adduct of DETA).

Synthesis Example 3 Synthesis of 1-[(2-aminoethyl) amino] -2-propanol.
1-[(2-Aminoethyl) amino]-was prepared in the same manner as in Synthesis Example 1 except that diethylenetriamine was changed to 100 g (1.66 mol) of ethylenediamine (EDA) and 97 (1.66 mol) g of propylene oxide. 2-Propanol was obtained (1PO adduct of EDA).

Synthesis Example 4 Synthesis of 1,1 ′-[(1,2-ethanediyl) bisimino] bis (2-propanol).
Except for 193 g (3.33 mol) of propylene oxide, 1,1 ′-[(1,2-ethanediyl) bisimino] bis (2-propanol) was obtained in the same manner as in Synthesis Example 3 (EDA 2PO adduct).

Synthesis Example 5 Synthesis of 2PO adduct of bis (3-aminopropyl) ether.
Bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 g (0.75 mol) and propylene oxide 87.7 g (1.50 mol) in the same manner as in Synthesis Example 1, except that diethylenetriamine was changed to 100 g (0.75 mol). A 2PO adduct of (3-aminopropyl) ether was obtained.

Synthesis Example 6 Synthesis of partially N-methylated diethylenetriamine.
In a 1000 ml autoclave with a stirrer, 200 g of diethylenetriamine (manufactured by Tosoh Corporation, product name: DETA), 100 g of water and 2.0 g of catalyst Pd-C (5% supported) were charged. The autoclave was sealed and replaced with hydrogen, and then heated to 130 ° C. with stirring. Subsequently, while introducing hydrogen at a pressure of 3 MPa into the autoclave, 314 g of 37% formalin aqueous solution was supplied by a pump over 7 hours. After aging reaction for 1 hour, the reaction solution was taken out by cooling.

  After distilling off water from the reaction solution using a distillation apparatus, 236 g of product was obtained under reduced pressure. 40% of the hydrogen groups bonded to the nitrogen atom of diethylenetriamine were converted to methyl groups. Hereinafter, the composition obtained by partially N-methylating the diethylenetriamine obtained in this production example is referred to as “DETA-2M”.

Example 1.
Into a 1000 ml glass container was added 100 g of a composition of amani fatty acid dimer containing 7% by weight of monomeric acid and 14% by weight of trimer acid [manufactured by Chikuno Food Industry Co., Ltd., product name: Tsunodim 216, acid value 193.6 mgKOH / g]. Further, 43.1 g of 1.1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol (Synthesis Example 1) was slowly added with stirring.

  It heated at 120 degreeC and stirred until it became completely uniform. The stirring speed was increased to 150 rpm, heating was performed at 200 ° C. for 4 hours under a nitrogen atmosphere, and 6.2 g of water was removed by distillation. Furthermore, reaction was performed at 200 degreeC and 10 mmHg for 1 hour. Next, the reaction vessel was cooled to 100 ° C., toluene was added to a solid concentration of 70% by weight and stirred to obtain a uniform toluene solution, and then cooled to room temperature.

  Dimer acid polyamidoamine obtained as a polyamide resin composition with respect to 36 parts by weight of an epoxy resin solution in which an epoxy resin having an epoxy equivalent of 474 (product name: Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) was diluted to 70% with toluene A toluene solution of the condensate was added at a ratio of 64 parts by weight, and the mixture was sheared and stirred for 5 minutes at room temperature using a spatula. Here, [amine hydrogen atom in polyamide resin composition of the present invention] / [epoxy group in epoxy resin] was 1/1 (molar ratio). Table 1 shows the results of measuring the curing rate and physical properties of the coating film according to the evaluation method described above.

Examples 2-8 and Comparative Examples 1-4.
The same procedure as in Example 1 was performed except that the types and amounts of raw materials shown in Table 1 were used. The results are also shown in Table 1.

  According to the polyamide curing agent of the present invention, it is possible to provide a polyamide resin composition exhibiting flexibility superior to that of a commonly used triethylenetetramine-derived polyamide curing agent. It can be suitably used in the field. Moreover, the epoxy resin composition of this invention is used suitably for a wide range of uses, such as a coating material, an adhesive agent, civil engineering, and a building material, for example.

Claims (8)

Mixing an amine component (A) containing a polyamine having one or more hydroxyl groups and two or more active hydrogens in the molecule and a dimer acid component (B) composed of dimer acid, dimer acid ester, or both And a polyamide resin composition obtained by a condensation reaction, wherein [amine component (A)] / [dimer acid component (B)] is in the range of 2/1 to 4/3 (molar ratio). A characteristic polyamide resin composition. The polyamide resin composition according to claim 1, wherein the polyamine having one or more hydroxyl groups and at least two or more active hydrogens in the molecule is a polyamine represented by the following formula (1).

[In the formula (1), R _{1 to} R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, It represents a substituent represented by a C2-C6 aminoalkyl group, C2-C6 monomethylaminoalkyl group, C2-C6 dimethylaminoalkyl group, and n and m are each independently 1-11. And a and b each independently represent an integer of 0 to 10. However, R ₇ and R ₁ or R ₂ may be bonded to form a cyclic compound. ] Polyamines having one or more hydroxyl groups and at least two or more active hydrogens in the molecule are 2- (2-aminoethylamino) ethanol, 1-[(2-aminoethyl) amino] -2-propanol, 1 , 1 ′ [(1,2-ethanediyl) bisimino] bis (2-propanol), 1- [2-[(2-aminoethyl) amino] ethyl] amino-2-propanol, 1,1 ′-[iminobis ( The polyamide resin composition according to claim 1, which is 2,1-ethanediylimino)] bis (2-propanol) or a mixture thereof. The dimer acid component (B) contains 70 to 95% by weight of dimer acid with respect to the whole component (B), contains trimer acid and an acid having a higher degree of polymerization in the range of 0 to 30% by weight, and the balance The polyamide resin composition according to any one of claims 1 to 3, wherein is a monomeric fatty acid. The hardening | curing agent composition for epoxy resins which consists of a polyamide resin composition in any one of Claim 1 thru | or 4. A cured epoxy resin obtained by bringing the polyamide resin composition according to any one of claims 1 to 5 and an epoxy resin into contact with each other. The cured epoxy resin product according to claim 6, wherein the stoichiometric ratio of the polyamide resin composition amine hydrogen to the amine hydrogen in the epoxy resin is in the range of 1.5: 1 to 1: 1.5. 8. The epoxy resin according to claim 6 or 7, wherein the epoxy resin is glycidyl ether of bisphenol A, improved glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, epoxy novolac resin, or a mixture thereof. Epoxy resin cured product.