JP2014095027A - Amine composition for epoxy curing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amine composition for an epoxy curing agent capable of providing a cured article excellent in a reaction retardation property and flexibility.SOLUTION: An epoxy resin is cured by using an amine composition for an epoxy curing agent containing one or more kinds of polyalkylene polyamine represented by the general formula (1) and having [the total molar number of an alkyl group in the polyalkylene polyamine represented by the general formula (1)]/[the total molar number of the polyalkylene polyamine represented by the general formula (1)] (molar ratio) in a range of 0.8 to 2.5. In the formula (1), Rto Rrepresent each independently a hydrogen atom, a methyl group or an ethyl group and n represents an integer of 1 to 6.

Description

  The present invention relates to an amine composition for an epoxy curing agent.

  The amine composition for epoxy curing agents of the present invention is used as a curing agent for epoxy resins used in paints, adhesives, flooring applications and the like.

  The epoxy resin composition includes an epoxy resin, an epoxy curing agent, various additives, and the like, and is used in various applications such as civil engineering, building materials, and daily necessities. As the epoxy curing agent, a polyfunctional amine is generally used, and examples thereof include aliphatic amines, aromatic amines, polyether amines, amide amines, amine adducts, and Mannich-modified amines.

  Among these amines, for example, polyethylene amines such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA) are used as the aliphatic amine. However, since these polyethyleneamines are highly reactive with epoxy resins, they harden very quickly when cured at room temperature, and there are problems such as insufficient work time and poor stretch properties (flexibility). is there.

  Accordingly, polyether amines known as Jeffamine D230 (manufactured by Huntsman) and alkylated polyalkylene polyamines obtained using a high molecular weight alkylating agent have been proposed as amines having low reactivity with epoxy resins. (For example, refer to Patent Document 1). However, although these amines are excellent in flexibility, there is a problem that the reaction becomes too slow.

  It is known that methylated polyamines obtained by alkylating polyamines with formalin, which is a low molecular weight alkylating agent, instead of high molecular weight alkylating agents are more reactive than unmodified polyethyleneamine. However, with such a method, an amine for an epoxy curing agent having a reasonably low reactivity and good flexibility has not been obtained yet.

European Patent Publication No. 2157112 JP-A-8-325360

  This invention is made | formed in view of said background art, The objective is to provide the amine composition for epoxy hardeners which give the hardened | cured material which is reaction retarding property and excellent in a softness | flexibility.

  As a result of intensive studies on an amine composition for an epoxy curing agent, the present inventors have found a novel amine composition for an epoxy curing agent that can solve the above problems, and have completed the present invention.

  That is, this invention relates to the amine composition for epoxy hardeners as shown below, and an epoxy resin hardened | cured material obtained using it.

  [1] One or more polyalkylene polyamines represented by the following general formula (1) are included, and [the total number of moles of alkyl groups in the polyalkylene polyamine represented by the following general formula (1)] / [below An amine composition for an epoxy curing agent having a total number of moles of polyalkylene polyamine represented by the general formula (1) (molar ratio) in the range of 0.8 to 2.5.

［上記一般式（１）中、Ｒ_１〜Ｒ_５は、それぞれ独立して水素原子、メチル基、又はエチル基を表し、ｎは１〜６の整数を表す。］
［２］上記一般式（１）中のＲ_１〜Ｒ_５が全て水素原子であるポリアルキレンポリアミンの含有量が、当該組成物のガスクロマトグラフィー分析によって算出される面積比で表した場合に、３０％以下であることを特徴とする上記［１］に記載のエポキシ硬化剤用アミン組成物。

[In the general formula _(1), R 1 ~R ₅ are each independently a hydrogen atom, a methyl group, or ethyl group, n is an integer of 1-6. ]
[2] When the content of the polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms is represented by an area ratio calculated by gas chromatography analysis of the composition, The amine composition for epoxy curing agents according to the above [1], which is 30% or less.

[3] The polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a mixture thereof. The amine composition for epoxy curing agents according to the above [1] or [2], wherein

  [4] Polyamideamine-modified product, amidoamine-modified product, Mannich-modified product, amine-epoxy adduct-modified product, or Michael addition-modified product of the amine composition for epoxy curing agent according to any one of [1] to [3] An epoxy curing agent comprising:

  [5] An epoxy resin composition comprising the amine composition for an epoxy curing agent according to any one of [1] to [3] or the epoxy curing agent according to [4], and an epoxy resin.

  [6] [Total number of moles of amine hydrogen atoms in the amine composition for an epoxy curing agent according to any one of [1] to [3] or the epoxy curing agent according to [4]] / [Epoxy resin The epoxy resin composition as described in [5] above, wherein the total number of moles of epoxy groups] (molar ratio) is in the range of 1.5 / 1 to 1 / 1.5.

  [7] A cured epoxy resin obtained by curing the epoxy composition according to the above [5] or [6].

  [8] A method for producing a cured epoxy resin, comprising curing the epoxy composition according to the above [5] or [6].

  The amine composition for epoxy curing agents of the present invention is (1) more excellent in reaction delay with epoxy than polyethyleneamines such as conventional diethylenetriamine, and (2) exhibits a flexibility equal to or higher than that of conventional polyether polyamines. Therefore, it is very useful industrially.

  Hereinafter, the present invention will be described in detail.

  The amine composition for epoxy curing agents of the present invention contains one or more polyalkylene polyamines represented by the above general formula (1), and [in the polyalkylene polyamine represented by the above general formula (1). The total number of moles of alkyl groups] / [total number of moles of polyalkylene polyamine represented by the above general formula (1)] (molar ratio) is in the range of 0.8 to 2.5. .

  The amine composition for epoxy curing agents of the present invention comprises: [total number of moles of alkyl groups in the polyalkylene polyamine represented by the general formula (1)] / [total number of polyalkylene polyamines represented by the general formula (1). By setting the number of moles (molar ratio) to 0.8 or more, the reactivity between the amine composition for an epoxy curing agent of the present invention and the epoxy resin is lowered. On the other hand, when the molar ratio is 2.5 or less, a reaction rate that can be practically used can be maintained.

  In the amine composition for an epoxy curing agent of the present invention, [total number of moles of alkyl groups in the polyalkylene polyamine represented by the above general formula (1)] / [total number of polyalkylene polyamines represented by the above general formula (1) The number of moles] (molar ratio) is in the range of 0.8 to 2.5 as described above, but preferably in the range of 1.5 to 2.3, more preferably 1.9, from the viewpoint of elongation physical properties. It is in the range of -2.3.

The amine composition for an epoxy curing agent of the present invention includes, for example, a polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms (that is, not alkylated), an alkylating agent, and the like. Can be easily obtained by reacting.

This reaction is preferably carried out in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include commonly used hydrogenation catalysts such as nickel, Raney nickel, Raney cobalt platinum black, platinum oxide, palladium, palladium / activated carbon (Pd / C), and the like. The amount of the catalyst used is preferably in the range of 0.1 to 10% by weight relative to the polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms.

Moreover, it is preferable to implement this reaction on 90-150 degreeC temperature conditions. When reacted at a low temperature below 90 ° C, unreacted polyalkylene polyamine may remain, or some polyalkylene polyamine may form a piperazine ring by a cyclization reaction to generate a by-product. Examples of polyalkylene polyamines in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms used as raw materials in this reaction include, for example, diethylenetriamine (DETA), triethylenetetramine (TETA), tetra Examples include polyethyleneamine having a higher molecular weight such as ethylenepentamine (TEPA). Examples of the alkylating agent include low molecular weight alkylating agents such as formaldehyde and acetone.

  In addition, about the amine composition for epoxy hardeners obtained by this reaction, from the molar ratio of polyalkylene polyamine used as a raw material and the alkylating agent and the conversion rate, [polyalkylene polyamine represented by the above general formula (1) The total number of moles of the alkyl group therein] / [the total number of moles of the polyalkylene polyamine represented by the general formula (1)] (molar ratio) can be determined.

In the amine composition for an epoxy curing agent of the present invention, the content of the polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms is calculated by gas chromatography analysis of the composition. When expressed in terms of area ratio, it is preferably 30% or less. In the above general formula (1), when the content of polyalkylene polyamine in which R _{1 to} R ₅ are all hydrogen atoms is 30% or less, the reactivity with epoxy is lowered, and the resulting cured epoxy resin is obtained. The flexibility becomes better.

  Examples of the amine composition for an epoxy curing agent of the present invention include, for example, (non-alkylated) polyalkylene polyamine, monoalkylated polyalkylene polyamine, dialkylated polyalkylene polyamine, trialkylated polyalkylene polyamine, and tetraalkyl. Polyalkylene polyamines, and mixtures thereof. Among these, 20-40% is a monoalkylated polyalkylene polyamine when expressed by an area ratio calculated by gas chromatography analysis from the viewpoint of achieving both moderate delayed curing properties and elongation physical properties, and 20-20 A mixture in which 35% is a trialkylated polyalkylene polyamine is preferred.

  Preferable examples of the monoalkylated polyalkylene polyamine include N-methylated diethylenetriamine, N-methylated triethyltetramine, N-ethylated diethylenetriamine, N-ethylated triethyltetramine, or a mixture thereof.

  Preferable examples of the dialkylated polyalkylene polyamine include N, N′-dimethylated diethylenetriamine, N, N′-dimethylated triethylenetetramine, N, N′-diethylated diethylenetriamine, and N, N′-diethylated triethylene. Examples thereof include tetramine or a mixture thereof.

  Preferable examples of the trialkylated polyalkylene polyamine include N, N ′, N ″ -trimethylated diethylenetriamine, N, N ′, N ″ -trimethylated triethylenetetramine, N, N ′, N ″ -triethylated diethylenetriamine N, N ′, N ″ -triethylated triethylenetetramine, or a mixture thereof.

  Preferable examples of the tetraalkylated polyalkylenepolyamine include N, N, N ′, N ″ -tetramethylated diethylenetriamine, N, N, N ′, N ″ -tetramethylated triethylenetetramine, N, N, N Examples include ', N ″ -tetraethylated diethylenetriamine, N, N, N ′, N ″ -tetraethylated triethylenetetramine, or a mixture thereof.

  Further, the amine composition for epoxy curing agents of the present invention may further contain other polyfunctional amines. Examples of such polyfunctional amines include, but are not limited to, piperazine, 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, 1,4-diaminocyclohexane, Polyoxyalkylene polyamines (for example, Jeffamine D-230) Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-403, etc.) and the like.

  Moreover, the polyamidoamine modified product, the amidoamine modified product, the Mannich modified product, the amine-epoxy adduct modified product, and the Michael addition modified product of the amine composition for an epoxy curing agent of the present invention can also be suitably used as an epoxy curing agent. . These modified products can be prepared by a conventionally known method.

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

  The epoxy resin composition of the present invention contains the above-described amine composition for epoxy curing agent or epoxy curing agent of the present invention and an epoxy resin.

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

  The amine composition for epoxy curing agent or the epoxy curing agent of the present invention contained in the epoxy resin composition of the present invention and the epoxy resin are [the amine composition for the epoxy curing agent of the present invention or the amine in the epoxy curing agent. The total number of moles of hydrogen atoms] / [total number of moles of epoxy groups in the epoxy resin] (molar ratio) is usually in the range of 1.5 / 1 to 1 / 1.5 (molar ratio), preferably 1.2. It is preferable that it is in the range of 1/1 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, “amine hydrogen atom” refers to a hydrogen atom bonded to a nitrogen atom in an amino group.

  In addition to the amine composition for epoxy curing agent or the epoxy curing agent of the present invention, a conventionally known curing accelerator can be used in combination with the epoxy 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, for example, phenol, nonylphenol, cresol, bisphenol A, salicylic acid, dimethylaminomethylphenol, bis (dimethylaminomethyl) phenol, tris (dimethylaminomethyl) phenol, and the like. It is done.

  Moreover, a conventionally well-known plasticizer can be used for the epoxy resin composition of this invention. Such a plasticizer is not particularly limited, and examples thereof include benzyl alcohol, nonylphenol, various phthalates, and the like.

  Furthermore, you may use a solvent, a filler, a pigment, a pigment dispersant, a rheology modifier, a thixotropic agent, a fluidization and smoothing adjuvant, an antifoaming agent, etc. for the epoxy resin composition of this invention. Suitable solvents include, for example, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, ethers, alcohols and the like.

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

  The cured epoxy resin of the present invention is obtained by reacting the amine composition for an epoxy curing agent of the present invention or an epoxy curing agent with an epoxy resin in the epoxy resin composition of the present invention. Although it does not specifically limit about the reaction of the amine composition for epoxy hardeners of this invention or an epoxy hardener, and an epoxy resin, For example, hardened | cured material is formed by making these mix and contact. If necessary, heat treatment can be performed to forcibly cure.

  The present invention will be described in more detail with reference to the following reference examples and examples, but the present invention should not be construed as being limited thereto.

  The reaction product was analyzed by the following method.

<Analysis of reaction products>
(1) Gas chromatography analysis.
Analysis column: DB-5 (manufactured by Agilent Technologies, length 30 m, film thickness 2.5 μm, inner diameter 0.32 mm),
Column temperature: 60 ° C. + 10 ° C./minute temperature increase + 280 ° C./15 minutes.

<Evaluation of reaction delay>
An epoxy resin composition obtained by mixing an epoxy resin and an amine composition for an epoxy curing agent is cured under a constant condition of 25 ° C., and a vibration viscometer (trade name: VM-1G-MJ, manufactured by Yamaichi Electronics Co., Ltd.) ), A data collection system (trade name: NR-1000, manufactured by Keyence Co.) was used to measure the change in viscosity over time. After mixing, the reactivity was evaluated by the time until the viscosity value reached 4000 cP. It shows that reaction delay property is excellent, so that 4000 cP arrival time is long.

<Evaluation of tensile strength and flexibility of coating film>
An epoxy resin composition obtained by mixing an epoxy resin and an amine composition for an epoxy curing agent is uniformly applied onto a polypropylene film (20 cm × 40 cm × 0.2 mm) using a doctor blade adjusted to a gap of 200 micrometers. Using a constant temperature and humidity machine (trade name: PL-3K, manufactured by Espec Corp.), after drying for 24 hours under a constant condition of 25 ° C. and a relative humidity of 50%, further 4 under a constant condition of 80 ° C. and a relative temperature of 50%. Cured for hours.

  Then, the test piece was created using the dumbbell type punch for tensile tests (JIS K 6259 No. 2 type dumbbell shape). The test piece was attached to a Tensilon universal testing machine (trade 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 (MPa) of the sample piece was measured. 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.

Production Example 1 Preparation of amine composition (A) for epoxy curing agent.
In a 1000 ml autoclave with a stirrer, 200 g of diethylenetriamine (manufactured by Tosoh Corporation, trade name: DETA) and 2.0 g of catalyst Pd-C (5% supported) were charged. After sealing the autoclave, the temperature was raised to 130 ° C., and a reaction was carried out by continuously adding 126 g of a 37% formalin aqueous solution, followed by cooling to take out the reaction solution. From the molar ratio of diethylenetriamine and formalin and the conversion, (alkyl group) / (polyalkylene polyamine + polyalkylene polyamine) was 0.8.

  After distilling off low boiling components such as water from the reaction solution using a distillation apparatus, 221 g of product was obtained under reduced pressure. As a result of gas chromatography analysis of this product, the composition of the obtained methylated diethylenetriamine compound was DETA / monomethyl body / dimethyl body / trimethyl body / tetramethyl body / pentamethyl body = 29/56/12/3/0 / 0 (area ratio calculated by gas chromatography analysis).

Production Examples 2 to 12 Preparation of amine compositions (B) to (L) for epoxy curing agents.
An amine composition for an epoxy curing agent was prepared in the same manner as in Production Example 1 except that the types and amounts of raw materials shown in Table 1 were used. The results are also shown in Table 1.

Production Example 13 Preparation of amine composition (M) for epoxy curing agent.
An amine composition for an epoxy curing agent was prepared in the same manner as in Production Example 1 except that acetone was added all at once using the amounts and raw materials shown in Table 1. The results are also shown in Table 1.

実施例１．
エポキシ当量４７４のエポキシ樹脂（エピコート１００１、油化シェルエポキシ社製）をトルエンで７０重量％に希釈したエポキシ樹脂溶液１００重量部に対し、製造例１で得たメチル化ジエチレントリアミン組成物を４．１重量部の割合で添加し、スパチュラを用いて室温下５分間攪拌して得られるエポキシ樹脂組成物を、上記評価方法に従って硬化し、塗膜の硬化速度と物性測定を行った結果を表２に示す。

Example 1.
The methylated diethylenetriamine composition obtained in Production Example 1 was applied to 100 parts by weight of an epoxy resin solution obtained by diluting an epoxy resin having an epoxy equivalent of 474 (Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) to 70% by weight with toluene. Table 2 shows the results of curing the epoxy resin composition obtained by adding at a ratio of parts by weight and stirring for 5 minutes at room temperature using a spatula according to the above evaluation method, and measuring the curing speed and physical properties of the coating film. Show.

  Here, [total number of moles of amine hydrogen atoms in amine composition for epoxy curing agent] / [total number of moles of epoxy groups in epoxy resin] (molar ratio) was 1/1.

実施例２〜実施例１０及び比較例１〜比較例５．
表２に示す種類と量の原料を用いた以外は、実施例１と同様に塗膜の硬化速度と物性測定を行った。その結果を表２に併せて示す。

Examples 2 to 10 and Comparative Examples 1 to 5
The coating rate and physical properties were measured in the same manner as in Example 1 except that the types and amounts of raw materials shown in Table 2 were used. The results are also shown in Table 2.

  As is clear from Examples 1 to 4, the coating film prepared using the amine composition for an epoxy curing agent of the present invention is superior in flexibility as compared with the coating films obtained in Comparative Examples 1 to 5, And it showed moderate reaction delay.

  The amine composition for epoxy curing agents of the present invention is an amine composition for epoxy curing agents that gives a cured product with excellent reaction retardancy and flexibility, and has the potential to be widely used in the field of production of epoxy curing agents. Have.

Claims (8)

One or more polyalkylene polyamines represented by the following general formula (1) are included, and [the total number of moles of alkyl groups in the polyalkylene polyamine represented by the following general formula (1)] / [the following general formula ( An amine composition for an epoxy curing agent having a total number of moles of polyalkylene polyamine represented by 1) (molar ratio) in the range of 0.8 to 2.5.

[In the general formula _(1), R 1 ~R ₅ are each independently a hydrogen atom, a methyl group, or ethyl group, n is an integer of 1-6. ] When the content of the polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms is represented by an area ratio calculated by gas chromatography analysis of the composition, it is 30% or less. The amine composition for epoxy curing agents according to claim 1, wherein the amine composition is for epoxy curing agents. The polyalkylene polyamine in which R _{1 to} R ₅ in the general formula (1) are all hydrogen atoms is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a mixture thereof. The amine composition for epoxy curing agents according to claim 1 or 2, wherein Epoxy curing comprising a polyamidoamine modified product, an amidoamine modified product, a Mannich modified product, an amine-epoxy adduct modified product, or a Michael addition modified product of the amine composition for an epoxy curing agent according to any one of claims 1 to 3. Agent. The epoxy resin composition containing the amine composition for epoxy curing agents in any one of Claims 1 thru | or 3, or the epoxy curing agent of Claim 4, and an epoxy resin. [Amine composition for epoxy curing agent according to any one of claims 1 to 3 or the total number of moles of amine hydrogen atoms in the epoxy curing agent according to claim 4] / [Epoxy group in epoxy resin] The total number of moles] (molar ratio) is in a range of 1.5 / 1 to 1 / 1.5. The epoxy resin hardened | cured material obtained by hardening | curing the epoxy composition of Claim 5 or Claim 6. The manufacturing method of the epoxy resin hardened | cured material characterized by hardening the epoxy composition of Claim 5 or Claim 6.