WO2021049503A1 - Diamine compound and method for producing same - Google Patents

Abstract

Disclosed are a diamine compound and a method for producing the same. This diamine compound is a compound represented by formula (I): H2N-R1-NH2 (in formula (I), R1 is an alkylene group or an alkenylene group having a total carbon number of C14-C28, the alkylene group or alkenylene group either being linear or having a branched chain of one or a more C1-C4 alkyl groups and/or alkenyl groups). This diamine compound can impart appropriate flexibility to a resin such as an epoxy resin.

Description

Diamine compound and its manufacturing method

The present invention relates to a diamine compound and a method for producing the same. More specifically, the present invention is used in coexistence with a monomer or a curing agent capable of constituting a polymer material such as a thermosetting resin or a thermoplastic resin, or the polymer material. The present invention relates to a diamine compound useful as an additive and a method for producing the same.

Resin materials composed of polymers are used in a wide range of applications such as paints, building materials, flooring materials, earth and wood, and electronic materials. Since the required properties differ depending on these uses, there are a wide variety of resin materials that satisfy the properties.

In particular, resin materials such as epoxy resin, polyimide, and polyamide-imide, which are polymers whose main chain is composed of aromatic rings, have excellent mechanical and electrical properties, but are hard and brittle, and are generally resistant. It has been pointed out that it lacks impact resistance and toughness. Therefore, it is necessary to alleviate the brittleness depending on the application, and various means have been proposed so far.

As one of such means, a method of modifying the polymer by introducing a flexible chain into the main chain of the polymer to impart flexibility is known. As a method for introducing such a flexible chain, for example, in the case of producing a thermosetting resin, a compound having a flexible chain (for example, a polar group such as an ether group, an ester group, an amide group, or a urethane group) is used as a main agent or cured. It is known to be used as an agent. Alternatively, when producing a thermoplastic resin, it is known to use a compound having such a flexible chain as a raw material monomer.

However, these methods change or reduce other undesired properties such as reduced compatibility and viscosity, reduced curability, and changes in properties other than flexibility with respect to the resulting cured product. I have something to do. It is considered that these are caused by interposing the polar group introduced as a flexible chain.

An object of the present invention is to solve the above problems, and an object of the present invention is to be flexible with respect to the resin without introducing a polar group into the constituent molecules of the resin such as an epoxy resin. It is an object of the present invention to provide a diamine compound which can be used as a resin additive and a method for producing the same, which can impart the above-mentioned substances and have little influence on other properties.

The present invention has the following formula (I):

In formula (I),
R ¹ is an alkylene or alkenylene group having a total carbon number of C ₁₄ to C _28, which is linear or has one or more C ₁ to C ₄ alkyl and / or alkenyl groups. An alkylene group or an alkenylene group having a branched chain of
It is a diamine compound represented by.

In one embodiment, in formula (I), the main chain portion of the alkylene group or alkenylene group constituting ^{R 1} _{has C 2n} carbon atoms (where n is 7 to 14).

In one embodiment, in formula (I), the linear alkylene group or linear alkenylene group of _{C 14} to C ₂₈ ^{constituting R 1} has a branched chain composed of an ethyl group.

In one embodiment, the diamine compound of the present invention is 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene.

The present invention is also a method for producing a diamine compound represented by the above formula (I).
The following formula (II):

A step of reacting a dibasic acid ester represented by (1) with hydrazine to obtain a dihydrazide compound.
A step of reacting the dihydrazide compound with a nitrite compound to obtain an azide, and a step of heating and hydrolyzing the azide.
Including,
In formula (II),
R ¹ is an alkylene or alkenylene group having a total carbon number of C ₁₄ to C _28, which is linear or has one or more C ₁ to C ₄ alkyl and / or alkenyl groups. An alkylene group or an alkenylene group having a branched chain of
R ² is a linear alkyl group of _{C 1} to C _4,
The method.

In one embodiment, in formula (II), the main chain portion of the alkylene group or alkenylene group constituting ^{R 1} _{has C 2n} carbon atoms (where n is 7 to 14).

The present invention is also a method for producing a diamine compound represented by the above formula (I).
The following formula (III):

A step of reacting a dibasic acid represented by (1) with ammonia to obtain a diamide compound, and a step of nitriding and hydrogen reducing the diamide compound.
Including,
In formula (III),
R ¹ is an alkylene or alkenylene group having a total carbon number of C ₁₄ to C _28, which is linear or has one or more C ₁ to C ₄ alkyl and / or alkenyl groups. An alkylene group or an alkenylene group having a branched chain of
The method.

In one embodiment, in formula (III), the main chain portion of the alkylene group or alkenylene group constituting ^{R 1} _{has C 2n} carbon atoms (where n is 7 to 14).

The present invention is also a resin additive containing the above diamine compound.

The present invention is also a resin composition containing a resin and the above resin additive.

The present invention is also a resin composition containing one or more monomer compounds and a resin composed of the above resin additives.

The present invention is also a lubricating rust preventive for metal products containing the above diamine compound.

According to the present invention, it is possible to provide flexibility to a resin such as an epoxy resin. On the other hand, it is avoided that the other properties of the resin are significantly changed. In addition to such resin additives, the diamine compound of the present invention can also be applied as an active ingredient such as a softener as a cationic surfactant and a rust preventive.

Hereinafter, the present invention will be described in detail.

(Diamine compound)
The diamine compound of the present invention has the following formula (I):

It is a compound represented by. Here, in the formula (I), R ¹ is an alkylene group or an alkylene group having a total carbon number of C ₁₄ to C ₂₈ , preferably C ₁₆ to C ₂₄ , and more preferably C ₁₈ to C _22. An alkylene or alkenylene group that is linear or has one or more _{branched chains of C 1} to C _{4 alkyl and / or alkenyl groups.}

As used herein, the term " _{alkylene group or alkenylene group having a total carbon number of C 14} to C ₂₈ " is a linear or branched alkylene group having 14 to 28 carbon atoms and 14 carbon atoms. It includes a linear or branched alkenylene group having ~ 28.

Examples of an alkylene group or an alkenylene group having 14 to 28 carbon atoms are an alkylene group having a total carbon number of C ₁₄ to C ₂₈ and a linear structure; a total carbon number of C ₁₄ to C ₂₈ and 1 An alkylene group having a branched chain of one or more C ₁ to C _{4 alkyl groups and / or alkenyl groups; an alkenylene group having a total carbon number of C 14} to C ₂₈ and being linear; a total carbon number of Alkenylene groups; which are C ₁₄ to C ₂₈ and have one or more branched chains of alkyl and / or alkenyl groups of _{C 1} to C _4;

Examples of the alkylene group having a total carbon number of C ₁₄ to C ₂₈ and being linear include an n-tetradecanylene group, an n-pentadecanylene group, an n-hexadecanylene group, an n-heptadecanelen group, and an n-octadecanylene group. , N-nonadecanylene group, n-icosanilen group, n-henicosanilen group, n-docosanilen group, n-tricosanilen group, n-tetracosanilen group, n-pentacosanilen group, n-hexacosanilen group, n-heptacosanilen group, and n-octacosanilen group. The group is mentioned. Examples of the alkenylene group having a total carbon number of C ₁₄ to C ₂₈ and being linear include a tetradecenelene group, a pentadeceneylene group, a hexadecenelene group, a heptadecenelene group, an octadecenelene group, a nonadekenylene group, an icosenylene group, a henicosenylene group, and a docosenylene group. , Tricosenylene group, tetracosenylene group, pentacosenylene group, hexacosenylene group, heptacosenylene group, and octacosenylene group.

"Total carbon atoms having a branched-chain alkyl groups and / or alkenyl group _C 14 is _{~ C 28} and one or more of _C 1 ~ _{C 4,} alkylene _group", C 1 ~ _{C 4} alkyl group and Refers to an alkylene group _{having a total carbon number of C 14} to C ₂₈ , which comprises at least one group selected from the group consisting of C ₁ to C _{4 alkenyl groups as a branched chain.} "Total carbon atoms having a branched-chain alkyl groups and / or alkenyl group _C 14 is _{~ C 28} and one or more of _C 1 ~ _{C 4,} alkenylene _group", C 1 ~ _{C 4} alkyl group and Refers to an alkylene group _{having a total carbon number of C 14} to C ₂₈ , which comprises at least one group selected from the group consisting of C ₁ to C _{4 alkenyl groups as a branched chain.} Examples of alkyl groups C ₁ to C ₄ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of alkenyl groups of C ₁ ~ _{C 4,} a vinyl group, 1-propenyl group, an allyl group, a 1-butenyl group, 2-butenyl group, and 3-butenyl groups.

When the diamine compound of the present invention is used, for example, as a constituent component of a resin additive described later, R ^{1 of the formula (I) can be imparted with appropriate flexibility to the obtained resin composition.} Is an alkylene group having a total carbon number of C ₁₄ to C _28, which is linear or has a branched chain of _{one or more C 1} to C _{4 alkyl groups.} Is more preferable, and an alkylene group having a total carbon number of C ₁₄ to C _{28 and having a branched chain of one alkyl group of C 1} to C ₄ is more preferable, and a total carbon number of C _{14 is preferable.} It is even more preferable that the alkylene group having ~ C ₂₈ is an alkylene group having a branched chain of one ethyl group.

Alternatively, the diamine compound of the present invention can be easily produced using a commercially available dibasic acid or a derivative thereof as described later, and therefore, in the above formula (I), the alkylene group constituting ^{R 1 or} It is preferable that the main chain portion of the alkenylene group (that is, the chain hydrocarbon portion excluding the branched chain) has C _2n carbon atoms (where n is 7 to 14).

As a more specific example of such a diamine compound,
Linear saturated diamines such as tetradecane diamine, hexadecane diamine, octadecane diamine, eikosa diamine, docosa diamine, tetracosa diamine, octacosa diamine;
Tetradecanediamine-7-ene, hexadecanediamine-6-ene, hexadecanediamine-8-ene, octadecanediamine-8-ene, octadecanediamine-10-ene, eikosadiamine-6-ene, eikosadiamine-8-ene , Eikosadiamine-12-ene, Eikosadiamine-8,12-diamine, Eikosadiamine-10,14-diamine, docosadiamine-7,11,15-triene, docosadiamine-8,12,16-triene, 1 , 24-Tetracosadiamine-8,12,16-Triene, Tetracosadiamine-10,14,18-Triene and other linear unsaturated diamines;
6,8-Dimethyltetradecanediamine, 7-ethyltetradecanediamine, 7-propyltetradecanediamine, 7-ethylhexadecanediamine, 7-butylhexadecandiamine, 7-isopropyl-10-methylhexadecanediamine, 8-ethyloctadecandiamine, 8- Branch saturated diamines such as isopropyl-11-methyloctadecanediamine, 8,13-diethyloctadecanediamine, 8,13-dimethyleicosadiamine, 9,12-dimethyleicosadiamine, 9,12-diethyleicosadiamine;
7-Vinyltetradecanediamine, 7-vinylhexadecanediamine-8-ene, 7-isopropenyl-10-methylhexadecanediamine-9-ene, 8-vinyl-octadecandiamine-9-ene, 7,12-dimethyloctadecanediamine -7,11-diamine, 7,12-diethyloctadecanediamine-7,11-diamine, 8-isopropenyl-11-methyloctadecandiamine-10-ene, 8-ethyl-11-isopropenyloctadecandiamine-10 Branched unsaturated diamines such as -ene, 8,13-dimethyleicosadiamine-8,12-diamine, 9,12-dimethyleicosadiamine-8,12-diamine;
And so on.

(Manufacturing method of diamine compound)
The diamine compound represented by the above formula (I) can be produced, for example, by the following first method or second method.

The first method for producing the diamine compound represented by the formula (I) will be described.

In the first method of the present invention, first, the following formula (II):

A dihydrazide compound is synthesized by reacting the dibasic acid esters represented by (1) with hydrazine.

In formula (II), R ¹ is an alkylene group or an alkylene group having a total carbon number of C ₁₄ to C ₂₈ , preferably C ₁₆ to C ₂₄ , more preferably C ₁₈ to C _{22, and is linear.} Or an alkylene or alkenylene group having a branched chain of one or more C ₁ to C ₄ ^{alkyl groups and / or alkenyl groups, where R 2} is a C ₁ to C ₄ linear alkyl. It is a group.

In formula (II), R ¹ is similar to that defined in formula (I) above.

In formula (II), when the diamine compound is used, for example, as a constituent component of a resin additive described later, R ^{1 can impart appropriate flexibility to the obtained resin composition.} , An alkylene group having a total carbon number of C ₁₄ to C _28, which is linear or has a branched chain of _{one or more C 1} to C _{4 alkyl groups.} preferably, the total number of carbon atoms is an alkylene group which is _C 14 _{~ C 28,} more preferably an alkylene group having one branched alkyl group of _C 1 ~ _{C 4,} the total number of carbon atoms is _{C 14} ~ It is even more preferable that the alkylene group is C _{28 and has a branched chain of one ethyl group.} Alternatively, compounds of the formula (II) are, for reasons of easy availability commercially as will be described later, in the above formula (II), the main chain portion of the alkylene group or alkenylene group constituting R ¹ It is preferable that (that is, the chain hydrocarbon moiety excluding the branched chain) has C _2n carbon atoms (where n is 7 to 14).

On the other hand, in the formula (II), _{examples of the linear alkyl groups C 1} to C ₄ that can constitute ^{R 2} include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.

The dibasic acid esters represented by the above formula (II) are known and are commercially available, for example, by Okamura Oil Refinery Co., Ltd.

The reaction between the dibasic acid esters represented by the formula (II) and hydrazine is carried out, for example, by heating under reflux in an appropriate organic solvent. Examples of usable organic solvents include alcohols such as methanol, ethanol, 1-propanol and 2-propanol. The time required for heating and reflux can be appropriately selected by those skilled in the art depending on the dibasic acid esters used and the amount.

In this way, the dibasic acid esters of the formula (II) are hydrazideized, and a dihydrazide compound (carboxylic acid hydrazide) can be obtained.

Next, this dihydrazide compound reacts with a nitrite compound to produce an azide.

In the present invention, the nitrite compound is a compound capable of producing an azide (carboxylic acid azide) from the above dihydrazide compound (carboxylic acid hydrazide). Examples of nitrite compounds include nitrites and nitrite esters.

In the production of this azide, reaction conditions can be appropriately selected by those skilled in the art.

After that, the azide is heat-dislocated and hydrolyzed.

Specifically, the azide is converted to isocyanate through the Curtius rearrangement by heating, and the subsequent hydrolysis produces the diamine compound represented by the above formula (I). The conditions for the Curtius rearrangement and hydrolysis can also be appropriately selected by those skilled in the art.

Next, a second method for producing the diamine compound represented by the formula (I) will be described.

In the second method of the present invention, first, the following formula (III):

A diamide compound is produced by reacting the dibasic acid represented by (1) with ammonia.

In formula (III), R ¹ is an alkylene group or an alkenylene group having a total carbon number of C ₁₄ to C ₂₈ , preferably C ₁₆ to C ₂₄ , more preferably C ₁₈ to C _{22, and is linear.} Or an alkylene or alkenylene group having a branched chain of one or more C ₁ to C _{4 alkyl and / or alkenyl groups.}

In formula (III), R ¹ is similar to that defined in formula (I) above.

In formula (III), when the obtained diamine compound is used, for example, as a constituent component of a resin additive described later, R can be imparted to the obtained resin composition with appropriate flexibility. ^{Reference numeral 1} denotes an alkylene group having a total carbon number of C ₁₄ to C _28, which is linear or has a branched chain of _{one or more C 1} to C _{4 alkyl groups.} It is more preferable that the alkylene group has a total carbon number of C ₁₄ to C ₂₈ , and the alkylene group has _{a branched chain of one C 1} to C ₄ alkyl group, and the total carbon number is C. _{It is even more preferable that the alkylene group is 14} to C ₂₈ , and the alkylene group has a branched chain of one ethyl group. Alternatively, the compound represented by the formula (III) has a main chain portion of an alkylene group or an alkenylene group constituting ^{R 1} in the above formula (III) because it is easily available on the market as described later. It is preferable that (that is, the chain hydrocarbon moiety excluding the branched chain) has C _2n carbon atoms (where n is 7 to 14).

The dibasic acid represented by the above formula (III) is known and is commercially available, for example, by Okamura Oil Refinery Co., Ltd.

The reaction between the dibasic acid represented by the formula (III) and ammonia is preferably carried out under pressure and heating. The conditions of pressurization and heating and the time required for them can be appropriately selected by those skilled in the art depending on the dibasic acid and the amount used.

In this way, the diamide compound can be obtained from the dibasic acid of the formula (III).

Next, this diamide compound is nitridated and hydrogenated.

The conditions for nitridation and hydrogen reduction are not particularly limited, and appropriate conditions can be appropriately selected by those skilled in the art.

In this way, the diamine compound represented by the above formula (I) of the present invention is produced.

(Resin additive and resin composition)
The resin additive of the present invention contains a diamine compound represented by the above formula (I).

Here, the term "resin additive" used in the present specification is used in a broad sense, and for example, (1) when constituting a resin composition, it is added independently of the resin which is a constituent component. Thereby, those caused by the improvement of the stability and / or the impartation of functionality of the obtained resin composition (for example, those capable of improving the stability of stabilizers, antioxidants, ultraviolet absorbers, etc.). , And / or those that can impart predetermined functions such as plasticizers, flame retardants, nucleating agents, clearing agents, antistatic agents, lubricants, etc.); It includes those that are physically or chemically linked or reacted with each other (for example, a cross-linking agent and a curing agent); and (3) those that can form the resin itself through the reaction (for example, a raw material monomer).

The resin additive of the present invention may contain other components that can be added in a normal resin composition, in addition to the diamine compound represented by the above formula (I). Such other components are not particularly limited, but are, for example, antioxidants such as phenol-based antioxidants, sulfur-based antioxidants, and / or phosphorus-based antioxidants; anionic activators, cationic activities. Antistatic agents such as agents, nonionic activators, amphoteric activators; lubricants such as hydrocarbon-based lubricants, fatty acid-based lubricants, higher alcohol-based lubricants, fatty acid amide-based lubricants, metallic soap-based lubricants, ester-based lubricants; organic Flame retardants such as flame retardants and inorganic flame retardants; and combinations thereof; The content of the above other components that can be contained in the resin additive of the present invention is not particularly limited, and any amount can be selected by those skilled in the art.

In one embodiment, the resin composition of the present invention contains the above resin additive and resin (hereinafter, such a resin composition is referred to as "first resin composition").

The resin that can constitute the first resin composition of the present invention is a thermosetting resin or a thermoplastic resin, and examples thereof include various resins obtained by reacting with an amino group. Examples of such examples include epoxy resins, polyurethanes, polyimides, polyamideimides, maleimide resins, and polyamides. The resin additive (that is, the diamine compound represented by the formula (I)) is preferably a curing agent or resin constituent material of the resin, more preferably, because it can impart appropriate flexibility. Can be used as a curing agent for epoxy resins.

In the first resin composition of the present invention, the contents of the resin and the resin additive are not particularly limited, and an appropriate content can be selected by those skilled in the art.

In one embodiment, the resin composition of the present invention contains one or more monomer compounds and a resin composed of the above resin additives (hereinafter, such a resin composition is referred to as "second resin". Composition ").

The monomer compound that can constitute the second resin composition of the present invention is one or more compounds that can constitute a thermoplastic resin or a thermosetting resin, and is, for example, ε-caprolactam; undecanelamtam; Lauryl lactam; combination of hexamethylenediamine and adipic acid; combination of hexamethylenediamine and sebacic acid; combination of hexamethylenediamine and terephthalic acid; combination of hexamethylenediamine and isophthalic acid; combination of nonanediamine and terephthalic acid Combination of methylpentanediamine and terephthalic acid; combination of ε-caprolactam and lauryllactam; combination of p-phenylenediamine and terephthalic acid; combination of m-phenylenediamine and isophthalic acid; pyromellitic acid anhydride; anhydrous Examples include a combination of trimellitic acid and diisocyanates; and a combination of trimellitic anhydride chloride and diamines.

In the second resin composition of the present invention, the resin additive (or the diamine compound represented by the above formula (I)) constitutes a resin with respect to one or more of the above monomer compounds. Can function as a monomer component. The above-mentioned monomer compound and the above-mentioned resin additive (or the above-mentioned diamine compound represented by the formula (I)) can be polymerized by using, for example, a coupling reaction known to those skilled in the art. The mixing ratio of the monomer compound and the resin additive (or the diamine compound represented by the above formula (I)) is not particularly limited, and combinations of various contents can be appropriately selected by those skilled in the art. As a result, a resin composed of one or more monomer compounds and the above resin additive is produced.

The first resin composition and the second resin composition of the present invention may also contain other resin additives. Examples of such other resin additives are not particularly limited, but include those included in other components that may be contained in the resin additive of the present invention. The blending amount of the other resin additive that can be contained in the resin additive of the present invention is not particularly limited, and any amount can be selected by those skilled in the art.

Both the first resin composition and the second resin composition of the present invention are suitable for the constituent resin by, for example, the contained resin additive (that is, the diamine compound represented by the formula (I)). Flexibility can be imparted. At that time, the first resin composition and the second resin composition of the present invention are preferably other than flexible as compared with the case where a flexible chain of a polar group is introduced into the constituent molecules of the resin as described above. There is no significant variation in other properties. Further, the flexibility imparted by such a resin additive can be easily adjusted by, for example, the blending amount of the resin additive. When the resin contained in the second resin composition of the present invention is a resin such as an epoxy resin, a polyimide, or a polyamide-imide, which is a polymer whose main chain is composed of an aromatic ring, such a resin is used. For example, it may have excellent physical properties in terms of low dielectric constant, low dielectric loss tangent, low transmission loss, and the like. Therefore, the second resin composition of the present invention is expected to be useful in the field of electronic materials, for example.

(Other uses)
The diamine compound represented by the formula (I) can be applied to other uses other than the resin additives as described above. Examples of such other applications are fabric softeners, antistatic agents, and surfactants such as lubricants and rust inhibitors that can prevent corrosion of metal products (eg steel, stainless steel, aluminum products). For example, a cationic surfactant).

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

(Example 1: _{Synthesis of C18} saturated branched diamine compound)
In a 5 L four-necked flask equipped with a thermometer and a stirrer, 1500 g of long-chain dibasic acid diester (SB-20MM manufactured by Okamura Oil Co., Ltd./main component: dimethyl isoeicosate, molecular weight 370) and hydrazine monohydrate 804 g (16.1 mol) and 1500 mL of 2-propanol as a solvent were charged and refluxed for 5 hours. After completion of the reaction, infrared spectroscopy: by (FT-IR JASCO Corp.), Isoeikosa disappearance and peaks corresponding to the hydrazide bond acid dimethyl peaks corresponding to the ester bond (1731cm ^-1) (1627cm ^-1 And the formation of 1533 cm ^-1 ) was confirmed. At the same time, by high performance liquid chromatograph mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), the peak of dimethyl isoeicosate (molecular weight 370), which is a raw material, disappeared and dihydrazide isoeicosadioate (molecular weight 370) was obtained. The appearance of the corresponding new peak was confirmed. In this way, dihydrazide 1a corresponding to isoeicosadioic acid dihydrazide was obtained.

To a 5 L four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, add dihydrazide 1a (450 g), 2100 mL of water and 759 g of 35% hydrochloric acid obtained above, and bring the temperature to 10 ° C. or lower while stirring. Cooled. Then, a 170 g (2.5 mol) aqueous solution of sodium nitrite dissolved in 300 mL of water was added dropwise while maintaining 10 ° C. or lower to generate an azide in this solution. Then, the obtained solution was heated under reflux to perform Curtius rearrangement of the produced azide, and the generation of nitrogen and carbon dioxide was visually confirmed. Further, after refluxing for 3 hours, 714 g (8.7 mol) of a 49% aqueous sodium hydroxide solution was added for hydrolysis, diamine was extracted with toluene, and the mixture was washed with water. Further, toluene was distilled off under reduced pressure, and the amine value was measured according to JIS K 7237. As a result, 221.3 g of _C18 saturated branched diamine 1b having an amine value of 321 was obtained.

Infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) confirmed the disappearance of ^{the peaks (1627 cm -1} and 1533 cm ^{-1) corresponding to the hydrazide bond observed in the dihydrazide 1a.} However, new appearances of ^{peaks (1722 cm -1} and 1571 cm ^-1 ) corresponding to the amino group were confirmed. In addition, high performance liquid chromatograph mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation) confirmed the disappearance of the peak confirmed by dihydrazide 1a (molecular weight 370). Further, gas chromatography-mass spectrometry: by (GC-MSQP-2010 manufactured by Shimadzu Corporation), during diamine 1b, as _{C 18} saturated branched diamine as the main component, 7-ethyl-hexadecane-diamine, and _{C 16} saturated branched diamine It was confirmed that 7-ethyltetradecanediamine (molecular weight 256) was contained. Their characteristic fragments were as follows.

(7-Ethyl hexadecane diamine)
m / z 284 (molecular ion peak), m / z 100 (reference peak)
(7-Ethyltetradecanediamine)
m / z 256 (molecular ion peak), m / z 100 (reference peak)

Next, the diamine 1b obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3/1 (volume ratio)), and the main components were 7-ethylhexadecanediamine (91%) and 7-. Ethyltetradecanediamine (3%) was isolated respectively. ^{1 1} H NMR analysis (Mercury-300: manufactured by Varian) was performed on each of the isolated diamines. The δ values are shown in Table 1 (CDCl ₃ ).

_(Synthesis to _{C 20} unsaturated branched diamine compound Example 2)
1000 g of long-chain dibasic acid diester (IPU-22MM manufactured by Okamura Oil Co., Ltd./main component: dimethyl isodocosadiene diate, molecular weight 394), 527 g (10.5 mol) of hydrazine monohydrate, and 1000 mL of 2-propanol as a solvent are used. 999 g of dihydrazide 2a (isodocosadiene dianodic acid dihydrazide) was obtained in the same manner as in Example 1.

The obtained dihydrazide 2a was subjected to infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to ^{eliminate the peak (1731 cm -1} ) corresponding to the ester bond of dimethyl isodocosaziendiate and the peak corresponding to the hydrazide bond (1731 cm -1). The formation of 1627 cm ^-1 and 1533 cm ^-1 ) was confirmed. At the same time, by high performance liquid chromatograph mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation), the peak of dimethyl isoeicosate (molecular weight 394), which is a raw material, disappeared, and dihydrazide isodocosadiene diacid (molecular weight 394) was obtained. The appearance of the corresponding new peak was confirmed.

Instead of dihydrazide 1a, 400 g (1.0 mol) of the dihydrazide 2a obtained above was used, and instead of hydrochloric acid, 582 g (6.1 mol) of methanesulfonic acid was used, and the amount of sodium nitrite was 167 g (2.4 mol). it was changed to), the same procedure as in example 1 to obtain 100.7g of _{C 20} unsaturated branched diamines 2b amine value 339.

Infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) confirmed the disappearance of ^{the peaks (1627 cm -1} and 1533 cm ^{-1) corresponding to the hydrazide bond observed in the dihydrazide 2a.} However, new appearances of ^{peaks (1722 cm -1} and 1572 cm ^-1 ) corresponding to the amino group were confirmed. In addition, high performance liquid chromatograph mass spectrometry (LC-MS-20: manufactured by Shimadzu Corporation) confirmed the disappearance of the peak confirmed by dihydrazide 2a (molecular weight 394). Furthermore, according to gas chromatograph mass spectrometry (GC-MSQP-2010: manufactured by Shimadzu Corporation), 7,12 dimethyl octadecane diamine-7,11- as the _{main component C 20 unsaturated branched diamine in diamine 2b.} It was confirmed that diene and 7-isopropenyl-10-methylhexadecanediamine-9-ene (molecular weight 308) were contained. Their characteristic fragments were as follows.

(7,12-Dimethyloctadecanediamine-7,11-diene)
m / z 308 (molecular ion peak), m / z 181 (reference peak)
(7-Isopropanol-10-Methylhexadecanediamine-9-ene)
m / z 308 (molecular ion peak), m / z 100 (reference peak)

Next, the diamine 2b obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3/1 (volume ratio)), and the main component was 7,12 dimethyl-7,11-eikosadiamine. -7,11-diene (49%) and 7-isobutenyl-10-methylhexadecanediamine-9-ene (30%) were isolated, respectively. ^{1 1} H NMR analysis (Mercury-300: manufactured by Varian) was performed on each of the isolated diamines. The δ values are shown in Table 2 (CDCl ₃ ).

(Example 3: _{Synthesis of C 22} unsaturated diamine compound)
1661 g of long-chain dibasic acid (IPU-22 manufactured by Okamura Oil Co., Ltd./main component: isodocosadiene diacid, molecular weight 366) and 50 g of silica gel were charged into a 5 L autoclave equipped with a thermometer and a stirrer, and under pressurized conditions. The reaction was carried out at 300 ° C. for 2 hours with 300 g (17.6 mol) of ammonia gas. Next, 650 mL of methanol and 70 g of nickel supported on activated carbon were added, and the mixture was further reacted with 130 g (7.6 mol) of ammonia gas and 420 g (210 mol) of hydrogen gas at 180 ° C. for 2 hours under pressurized conditions. After cooling, the obtained reaction solution was filtered, and dilute sulfuric acid was added to remove the lower layer. The organic layer was washed with water and the water content was removed under reduced pressure to obtain 1495 g of diamine 3 having an amine value of 290.

The obtained diamine 3 was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) to confirm the disappearance of ^{the peak (1711 cm -1) corresponding to the carboxyl group derived from the raw material isodocosadiene diacid.} New appearances of ^{peaks (1722 cm -1} and 1572 cm ^-1 ) corresponding to the amino group were confirmed. Furthermore, gas chromatograph mass spectrometry (GC-MSQP-2010: manufactured by Shimadzu Corporation) confirmed the disappearance of the peak corresponding to the raw material isodocosadiene diacid (molecular weight 366). In addition, during diamine 2b, as _{C 20} unsaturated branched diamine as the main component, 8,13- dimethyl -8,12- docosanol diene diamine and 8 isopropenyl-11-methyl-10-octadecadienoic engine It was confirmed that amine (molecular weight 336) was contained. Their characteristic fragments were as follows.

(8,13-Dimethyleicosadiamine-8,12-diene)
m / z 336 (molecular ion peak), m / z 195 (reference peak)
(8-Isopropanol-11-methyloctadecanediamine-10-ene)
m / z 336 (molecular ion peak), m / z 114 (reference peak)

Next, the diamine 3 obtained above was purified by silica gel column chromatography (ethyl acetate / n-hexane = 3/1 (volume ratio)), and the main component was 8,13-dimethyleicosadiamine-8,12. -Diene (50%) and 8-isopropenyl-11-methyloctadecanediamine-10-ene (28%) were isolated, respectively. ^{1 1} H NMR analysis (Mercury-300: manufactured by Varian) was performed on each of the isolated diamines. The δ values are shown in Table 3 (CDCl ₃ ).

(Example 4: Preparation of cured epoxy resin (E1))
10.0 g of bisphenol A type epoxy resin (EPOMIC manufactured by Mitsui Chemicals, Inc., epoxy equivalent (hereinafter, WPE) 188) and 4.4 g of diamine 1b (0.95 equivalent with respect to WPE) obtained in Example 1 as a curing agent. And 0.1 g (1 phr) of N, N-dimethylbenzylamine as a curing accelerator was mixed to prepare an epoxy resin composition. Next, 10 g of this resin composition was weighed in a heat-resistant container, heated at 70 ° C. for 15 hours, and further heat-cured at 120 ° C. for 1 hour to obtain an epoxy resin cured product (E1). For the obtained cured epoxy resin (E1), a sample was held at −50 ° C. for 10 minutes using a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation), and then at 10 ° C. per minute. By heating to 200 ° C. at a heating rate, the glass transition point (Tg) was measured from the change in calorific value with respect to the temperature rise. Further, in order to measure the gelation rate of the cured epoxy resin (E1), a 5 g sample was extracted with acetone for 5 hours by Soxhlet extraction. The gelation rate of the resin was measured by the ratio of the mass of the raw material before extraction to the mass of the extract. The results obtained are shown in Table 4.

(Example 5: Preparation of cured epoxy resin (E2))
An epoxy resin cured product (E2) was prepared in the same manner as in Example 1 except that the diamine 2b (4.2 g) prepared in Example 2 was used instead of the diamine 1b as the curing agent. With respect to the obtained epoxy resin cured product (E2), DSC analysis and gelation rate measurement of the cured product were performed in the same manner as in Example 1. The results obtained are shown in Table 4.

(Example 6: Preparation of cured epoxy resin (E3))
An epoxy resin cured product (E3) was prepared in the same manner as in Example 1 except that diamine 3 (4.9 g) prepared in Example 3 was used instead of diamine 1b as a curing agent. With respect to the obtained epoxy resin cured product (E3), DSC analysis and gelation rate measurement of the cured product were performed in the same manner as in Example 1. The results obtained are shown in Table 4.

(Comparative Example 1: Preparation of Epoxy Resin Cured Product (CE1))
An epoxy resin cured product (CE1) was prepared in the same manner as in Example 1 except that tetraethylenepentamine (1.4 g) was used as the curing agent instead of diamine 1b. The obtained epoxy resin cured product (CE1) was subjected to DSC analysis and gelation rate measurement of the cured product in the same manner as in Example 1. The results obtained are shown in Table 4.

(Comparative Example 2: Preparation of Epoxy Resin Cured Product (CE2))
An epoxy resin cured product (CE2) was prepared in the same manner as in Example 1 except that triethylenetetramine (1.2 g) was used as the curing agent instead of diamine 1b. The obtained epoxy resin cured product (CE2) was subjected to DSC analysis and gelation rate measurement of the cured product in the same manner as in Example 1. The results obtained are shown in Table 4.

(Comparative Example 3: Preparation of Epoxy Resin Cured Product (CE3))
An epoxy resin cured product (CE3) was prepared in the same manner as in Example 1 except that hexamethylenediamine (1.5 g) was used as the curing agent instead of diamine 1b. The obtained epoxy resin cured product (CE3) was subjected to DSC analysis and gelation rate measurement of the cured product in the same manner as in Example 1. The results obtained are shown in Table 4.

(Comparative Example 4: Preparation of Epoxy Resin Cured Product (CE4))
An epoxy resin cured product (CE4) was prepared in the same manner as in Example 1 except that 1,10-decanediamine (2.1 g) was used instead of diamine 1b as the curing agent. With respect to the obtained epoxy resin cured product (CE4), DSC analysis and gelation rate measurement of the cured product were performed in the same manner as in Example 1. The results obtained are shown in Table 4.

(Comparative Example 5: Preparation of Epoxy Resin Cured Product (CE5))
Epoxy resin cured product (CE5) in the same manner as in Example 1 except that a polyether diamine (Baxxodure EC302 manufactured by Mitsui Kagaku Ifine Co., Ltd .; average molecular weight 400) (5.6 g) was used as the curing agent. ) Was prepared. The obtained epoxy resin cured product (CE5) was subjected to DSC analysis and gelation rate measurement of the cured product in the same manner as in Example 1. The results obtained are shown in Table 4.

As shown in Table 4, the epoxy resin cured products (E1) to (E3) produced in Examples 4 to 6 are epoxy resin cured products (CE1) using the general-purpose amine-based curing agents of Comparative Examples 1 and 2. And (CE2) have a lower Tg, and moreover, Tg is higher than the epoxy resin cured product (CE3) using _{C 6} diamine of Comparative Example 3 and the epoxy resin cured product (CE 4) using _{C 10 diamine of Comparative Example 4.} It was low and had an excellent flexibility-imparting effect. That is, the longer the carbon chain arranged between the two amino groups in one molecule, the higher the flexibility can be imparted to the epoxy resin, and the longer the carbon chain is, the more flexible the epoxy resin is, and the more the carbon chain is composed of only the amino group and the carbon chain. The epoxy resin cured products (E1) to (E3) of Examples 1 to 3 using diamines 1b, 2b or 3 are the epoxy resin cured products (CE5) of Comparative Example 5 using a curing agent containing a polyether chain. It can be seen that they had substantially the same Tg and gelation rate.

(Example 7: Evaluation of curability of epoxy resin composition (EC1))
Using the diamine 1b obtained in Example 1 as a curing agent, 50 g of an epoxy resin composition (EC1) was prepared in the same manner as in Example 4, and this was charged into a glass sample tube. This was immersed in an oil bath at 70 ° C., and the temperature of the resin was plotted every hour (every 20 seconds) as a state of heat-generating curing. From the obtained heat-generating curve, the gelation point, gelation time, maximum heat-generating point, minimum curing time, and pot life were determined. The pot life was calculated to be 0.8 times (× 0.8) the gelation time. The results obtained are shown in Table 5.

(Example 8: Evaluation of curability of epoxy resin composition (EC2))
An epoxy resin composition (EC2) was prepared in the same manner as in Example 4 except that the diamine 2b (21.0 g) prepared in Example 2 was used instead of the diamine 1b as a curing agent. In the same manner as in No. 4, the gel point, gelation time, maximum heat generation point, minimum curing time, and pot life were determined from the heat curing curve of the resin composition. The results obtained are shown in Table 5.

(Example 9: Evaluation of curability of epoxy resin composition (EC3))
An epoxy resin composition (EC3) was prepared in the same manner as in Example 4 except that diamine 3 (24.5 g) prepared in Example 3 was used instead of diamine 1b as a curing agent. In the same manner as in No. 4, the gel point, gelation time, maximum heat generation point, minimum curing time, and pot life were determined from the heat curing curve of the resin composition. The results obtained are shown in Table 5.

(Comparative Example 6: Evaluation of Curability of Epoxy Resin Composition (CC1))
An epoxy resin composition (CC1) was prepared in the same manner as in Example 4 except that tetraethylenepentamine (7.0 g) was used as the curing agent instead of diamine 1b, and in the same manner as in Example 4. From the heat-generating curing curve of the resin composition, the gelation point, gelation time, maximum heat-generating point, minimum curing time, and pot life were determined. The results obtained are shown in Table 5.

(Comparative Example 7: Evaluation of Curability of Epoxy Resin Composition (CC2))
An epoxy resin composition (CC2) was prepared in the same manner as in Example 4 except that triethylenetetramine (6.0 g) was used as the curing agent instead of diamine 1b, and the same was applied in the same manner as in Example 4. From the heat-curing curve of the resin composition, the gelation point, gelation time, maximum heat-generating point, minimum curing time, and pot life were determined. The results obtained are shown in Table 5.

(Comparative Example 8: Evaluation of Curability of Epoxy Resin Composition (CC3))
An epoxy resin composition (CC3) was prepared in the same manner as in Example 4 except that hexamethylylenediamine (7.5 g) was used as the curing agent instead of diamine 1b, and in the same manner as in Example 4. From the heat-generating curing curve of the resin composition, the gelation point, gelation time, maximum heat-generating point, minimum curing time, and pot life were determined. The results obtained are shown in Table 5.

(Comparative Example 9: Evaluation of Curability of Epoxy Resin Composition (CC4))
An epoxy resin composition (CC4) was prepared in the same manner as in Example 4 except that 1,10-decanediamine (10.5 g) was used as the curing agent instead of diamine 1b, and the same as in Example 4. From the heat-generating curing curve of the resin composition, the gelation point, gelation time, maximum heat-generating point, minimum curing time, and pot life were determined. The results obtained are shown in Table 5.

(Comparative Example 10: Evaluation of Curability of Epoxy Resin Composition (CC5) 1)
An epoxy resin composition (CC5) was prepared in the same manner as in Example 4 except that a polyether diamine (28.0 g) was used instead of the diamine 1b as a curing agent. An attempt was made to prepare a heat-generating curve of the resin composition. However, it was found that the composition (CC5) had extremely low curability without heat generation even 30 minutes after the resin temperature reached 70 ° C., which is the same temperature as the oil bath temperature.

(Comparative Example 11: Evaluation of curability of epoxy resin composition (CC5) 2)
An epoxy resin composition (CC5) was prepared in the same manner as in Example 4 except that polyether diamine (28.0 g) was used instead of diamine 1b as a curing agent, and the oil bath temperature was set to 120 ° C. The gelation point, gelation time, maximum heat generation point, minimum curing time, and pot life were obtained from the heat-generating curing curve of the resin composition in the same manner as in Example 4 except for the above. The results obtained are shown in Table 5.

As shown in Table 5, the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 have a long gelation time and minimum curing time, and therefore the epoxy resin compositions of Comparative Examples 6 to 11 It had the characteristic of curing more slowly than those of (CC1) to (CC6). Regarding the pot life at the time of curing, the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 were compared with the epoxy resin compositions (CC1) to (CC6) of Comparative Examples 6 to 11. It is about 2 to 3 times longer. Focusing on the gelation temperature and the maximum heat generation point, the heat generation of the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 is the heat generation of the epoxy resin compositions (CC1) of Comparative Examples 6 to 11. It is considered from the results of Comparative Examples 10 and 11 that the polyether diamine, which is a flexibility-imparting agent which is similar to that of (CC6) and shows high reactivity, has low reactivity, and therefore at a low temperature. Was inferior in curability. That is, the diamines 1b, 2b and 3 used in the epoxy resin compositions (EC1) to (EC3) produced in Examples 7 to 9 are Comparative Examples 6 to 11 which are also known as commercially available amine-based curing agents. It can be seen that the pot life is longer than that of the curing agents of the epoxy resin compositions (CC1) to (CC6) of No. 1 and the temperature curability is superior to that of other flexibility-imparting agents.

(Example 10: Water resistance of the cured epoxy resin (E1))
The epoxy resin cured product (E1) (containing diamine 1b as a curing agent) prepared in Example 4 was put into boiling water and boiled for 1 hour. The mass of the resin before charging and the resin after boiling for 1 hour (the water adhering to the surface was removed) was measured, and the following formula:
Water absorption rate (%) = (mass of resin after boiling-mass of resin before charging) / (mass of resin before charging) x 100
The water absorption rate (%) of the cured epoxy resin (E1) was calculated from the above, and this was evaluated as the water resistance of the cured epoxy resin (E1). The results obtained are shown in Table 6.

(Example 11: Water resistance of the cured epoxy resin (E2))
Boil the cured product in the same manner as in Example 10 except that the epoxy resin cured product (E2) (containing diamine 2b as a curing agent) prepared in Example 5 was used instead of the epoxy resin cured product (E1). The water absorption rate (%) of the cured epoxy resin (E2) was calculated. The results obtained are shown in Table 6.

(Example 12: Water resistance of the cured epoxy resin (E3))
Boil the cured product in the same manner as in Example 10 except that the epoxy resin cured product (E3) (containing diamine 3 as a curing agent) prepared in Example 6 was used instead of the epoxy resin cured product (E1). The water absorption rate (%) of the cured epoxy resin (E3) was calculated. The results obtained are shown in Table 6.

(Comparative Example 12: Water resistance of cured epoxy resin (CE1))
Boil the cured product in the same manner as in Example 10 except that the epoxy resin cured product (CE1) (tetraethylenepentamine as a curing agent) prepared in Comparative Example 1 was used instead of the epoxy resin cured product (E1). The water absorption rate (%) of the cured epoxy resin (CE1) was calculated. The results obtained are shown in Table 6.

(Comparative Example 13: Water resistance of hardened epoxy resin (CE5))
The cured product was boiled in the same manner as in Example 10 except that the epoxy resin cured product (CE5) (polyetherdiamine as a curing agent) prepared in Comparative Example 5 was used instead of the epoxy resin cured product (E1). Then, the water absorption rate (%) of the cured epoxy resin (CE5) was calculated. The results obtained are shown in Table 6.

As shown in Table 6, the epoxy resin cured products (E1) to (E3) evaluated in Examples 10 to 12 (containing diamines 1b, 2b or 3 as a curing agent) and the general-purpose products evaluated in Comparative Example 12 In the corresponding epoxy resin cured product (CE1) (containing tetraethylenepentamine as a curing agent), the water absorption rate of the cured product was 0%, and the cured product had sufficient water resistance. On the other hand, the epoxy resin cured product (CE5) evaluated in Comparative Example 13 containing a polyether diamine (molecular weight 400), which is also known as a flexibility-imparting agent, as a curing agent has a water absorption rate of about 1%. Was shown. That is, the polyether diamine is accompanied by a decrease in water resistance in exchange for imparting flexibility, whereas a cured epoxy resin (E1) using diamines 1b, 2b or 3 (produced in Examples 4 to 6) is used. It can be seen that in (E3), flexibility was imparted without impairing water resistance.

(Example 13: Preparation of bismaleimide prepolymer (EM1))
In a 500 mL four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, 21.5 g (60.1 mmol) of 4,4'-bismaleimidediphenylmethane and 200 mL of THF were charged and obtained as a modifier in Example 1. Diamine 1b (5.2 g) (30.0 mmol equivalent as an amino group) was added dropwise. The temperature was raised to 50 ° C. with stirring, and the mixture was further stirred for 1.5 hours. Then, 3.1 g (30.1 mmol) of acetic anhydride was added, and the mixture was further stirred for 1 hour, and THF was removed under reduced pressure to obtain 27.6 g of bismaleimide prepolymer (EM1).

The obtained bismaleimide prepolymer (EM1) was subjected to infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation) with a decrease ^{in peaks (1606 cm -1) corresponding to α, β-unsaturated bonds and an imide.} The peaks corresponding to the bonds (1705 cm ^-1 and 1510 cm ^-1 ) and the peaks corresponding to the amide bonds (1636 cm ^-1 ) were confirmed.

Further, 10 g of this bismaleimide prepolymer (EM1) was weighed in a heat-resistant container and heated at 170 ° C. for 2 hours to cure. For the obtained cured product, a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation) was used to hold the sample at 0 ° C. for 10 minutes, and then the temperature was raised to 400 ° C. at 10 ° C. per minute. The glass transition point (Tg) was measured from the change in calorific value with respect to the temperature rise. The results obtained are shown in Table 7.

(Example 14: Preparation of bismaleimide prepolymer (EM2))
27.8 g of bismaleimide prepolymer (EM2) was obtained in the same manner as in Example 13 except that diamine 2b (5.0 g) prepared in Example 2 was used instead of diamine 1b as a modifier. This bismaleimide prepolymer (EM2) was subjected to DSC analysis of the cured product in the same manner as in Example 13. The results obtained are shown in Table 7.

(Example 15: Preparation of bismaleimide prepolymer (EM3))
58.0 g of bismaleimide prepolymer (EM3) was obtained in the same manner as in Example 13 except that diamine 3 (5.8 g) prepared in Example 3 was used instead of diamine 1b as a modifier. This bismaleimide prepolymer (EM3) was subjected to DSC analysis of the cured product in the same manner as in Example 13. The results obtained are shown in Table 7.

(Comparative Example 14: Preparation of Bismaleimide Prepolymer (CM1))
22.5 g of bismaleimide prepolymer (CM1) was obtained in the same manner as in Example 13 except that hexamethylenediamine (1.8 g) was used instead of diamine 1b as a modifier. This bismaleimide prepolymer (CM1) was subjected to DSC analysis of the cured product in the same manner as in Example 13. The results obtained are shown in Table 7.

(Comparative Example 15: DSC analysis of 4,4'-bismaleimidediphenylmethane)
For comparison, 10 g of 4,4′-bismaleimidediphenylmethane was cured alone without adding diamine 1b, and DSC analysis was performed in the same manner as in Example 13. The results obtained are shown in Table 7.

As shown in Table 7, the cured products of the bismaleimide prepolymers (EM1) to (EM3) prepared in Examples 13 to 15 are all compared with the bismaleimide prepolymer (CM1) prepared in Comparative Example 14. Compared with the cured product of 4,4'-bismaleimide diphenylmethane (without modifier) of Example 15, the Tg was significantly lower, and the two amino groups constituting diamines 1b, 2b and 3 used as the modifier were used. It can be seen that the longer the carbon chain arranged between them, the higher the flexibility can be imparted to the obtained cured product.

(Example 16: Preparation of polyamides 18 and 6)
In a 200 ml beaker, 1b (3.8 g) of diamine obtained in Example 1 (21.8 mmol equivalent as an amino group), triethylamine (2.2 g) (21.8 mmol) and 50 mL of hexane were charged and dissolved in 50 mL of hexane. Adipoyl chloride (2.0 g) (10.9 mmol) was added with stirring, and solution polymerization was carried out. After stirring for 30 minutes, the mixture was filtered, the filtrate was washed with water and acetone, and dried to obtain 2.3 g of polyamides 18 and 6.

^{For the obtained polyamides 18 and 6, peaks (1635 cm -1} , 1542 cm ^-1 ) corresponding to the amide bond were confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation).

Further, for the polyamides 18 and 6, a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation) was used to hold the sample at 0 ° C. for 10 minutes, and then the temperature was raised at 5 ° C. per minute. By heating to 100 ° C., the glass transition point (Tg) was measured from the change in calorific value with respect to the temperature rise. The results obtained are shown in Table 8.

(Example 17: Preparation of polyamides 20 and 6)
2.5 g of polyamide 6.6 was obtained in the same manner as in Example 16 except that the diamine 2b (3.6 g) prepared in Example 2 was used instead of the diamine 1b. The polyamide 20.6 was subjected to DSC analysis of the cured product in the same manner as in Example 16. The results obtained are shown in Table 8.

(Example 18: Preparation of polyamides 2 and 6)
2.3 g of polyamide 6.6 was obtained in the same manner as in Example 16 except that diamine 3 (3.8 g) prepared in Example 3 was used instead of diamine 1b. The polyamide 22.6 was subjected to DSC analysis of the cured product in the same manner as in Example 16. The results obtained are shown in Table 8.

(Comparative Example 16: Fabrication of Polyamides 2 and 6)
Ethylenediamine (0.7 g) (10.9 mmol), 49% sodium hydroxide (0.9 g) (10.9 mmol) and 50 mL of water were placed in a 200 ml beaker, and adipoyl chloride (2.0 g) dissolved in 50 mL of hexane was added. ) (10.9 mmol) was added with stirring and interfacial polymerization was carried out. After stirring for 30 minutes, the mixture was filtered, the filtrate was washed with water and acetone, and dried to obtain 0.9 g of polyamides 2 and 6. The polyamide 2.6 was subjected to DSC analysis of the cured product in the same manner as in Example 16. The results obtained are shown in Table 8.

(Comparative Example 17: Fabrication of Polyamides 6 and 6)
0.7 g of polyamide 6.6 was obtained in the same manner as in Comparative Example 16 except that hexamethylenediamine (1.3 g) was used instead of ethylenediamine. The polyamide 6.6 was subjected to DSC analysis of the cured product in the same manner as in Example 16. The results obtained are shown in Table 8.

As shown in Table 8, the polyamides (polyamide 18.6, polyamide 20.6, polyamide 22.6) prepared in Examples 16 to 18 are all compared with the polyamide 2.6 prepared in Comparative Example 16. Tg is significantly lower than that of Polyamide 6.6 in Example 17. As in the other examples, the longer the carbon chain arranged between the two amino groups constituting the diamines 1b, 2b and 3 used in the polyamide, the higher the flexibility of the obtained cured product. You can see that it was possible.

(Example 19: Fabrication of polyimide (ED1))
A reactor equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube was charged with pyromellitic anhydride (50.0 g) and cyclohexanone (200 ml) and heated to 60 ° C. Next, 40.0 g of the diamine 1b obtained in Example 1 dissolved in toluene (100 ml) was added, imidized at 140 ° C. for 3 hours, the solvent was removed under reduced pressure, and 80.1 g of polyimide (ED1) was obtained. It was.

With respect to the obtained polyimide (ED1), a peak (1769 cm- ¹ ) corresponding to an imide bond was confirmed by infrared spectroscopic analysis (FT-IR: manufactured by JASCO Corporation).

Further, for this polyimide (ED1), a differential scanning calorimeter (DSC) (DSC-60 manufactured by Shimadzu Corporation) was used to hold the sample at 0 ° C. for 10 minutes, and then the temperature was raised at 10 ° C. per minute. By heating to 400 ° C., the glass transition point (Tg) was measured from the change in calorific value with respect to the temperature rise. The results obtained are shown in Table 9.

(Example 20: Fabrication of polyimide (ED2))
78.9 g of polyimide (ED2) was obtained in the same manner as in Example 19 except that the diamine 2b (37.9 g) prepared in Example 2 was used instead of the diamine 1b. The polyimide (ED2) was subjected to DSC analysis of the resin in the same manner as in Example 19. The results obtained are shown in Table 9.

(Example 21: Fabrication of polyimide (ED3))
81.3 g of polyimide (ED3) was obtained in the same manner as in Example 19 except that the diamine 3 (44.3 g) prepared in Example 3 was used instead of the diamine 1b. For this polyimide (ED3), DSC analysis of the resin was carried out in the same manner as in Example 19. The results obtained are shown in Table 9.

(Comparative Example 18: Fabrication of Polyimide (CD1))
69.7 g of polyimide (CD1) was obtained in the same manner as in Example 19 except that p-phenylenediamine (24.8 g) was used instead of diamine 1b. For this polyimide (CD1), DSC analysis of the resin was carried out in the same manner as in Example 19. The results obtained are shown in Table 9.

(Comparative Example 19: Fabrication of Polyimide (CD2))
70.9 g of polyimide (CD2) was obtained in the same manner as in Example 19 except that hexamethylenediamine (26.6 g) was used instead of diamine 1b. For this polyimide (CD2), DSC analysis of the resin was carried out in the same manner as in Example 19. The results obtained are shown in Table 9.

As shown in Table 9, in Comparative Examples 18 and 19, Tg was lower in Comparative Example 19 using an aliphatic diamine even though it was a diamine having the same carbon number of 6. On the other hand, the diamines used in Examples 19 to 20 were aliphatic diamines having a higher carbon number, and their Tg was lower than that of Comparative Example 19. Therefore, as in the other examples, the longer the carbon chain arranged between the two amino groups constituting the diamines 1b, 2b and 3 used in the polyimide, the higher the flexibility is imparted to the obtained polymer. You can see that it was possible.

(Brief Summary)
Summarizing the above examples, when the diamine compound of the present invention (diamine 1b, 2b and 3) having a long carbon chain between two amino groups is used as a resin additive, flexibility is imparted to the resin. (See, for example, Table 4, Table 7, Table 8, and Table 9). Further, from Table 2, these diamine compounds have slower reactivity than commercially available amine curing agents as epoxy resin curing agents as used in Comparative Examples 6 to 11, but gels from Table 1 show. The conversion rate is high, and it can be seen that the curing reaction is sufficiently progressing. Therefore, it is the most suitable material for adjusting the pot life. On the other hand, the polyether diamine (molecular weight 400), which had a flexibility-imparting effect, had a flexibility-imparting effect corresponding to the molecular weight (Table 1), but the reactivity was remarkably low (70 ° C.). At worst, the curing reaction proceeds at 120 ° C. (Table 2). Further, from Table 3, the cured product using a polyether diamine is inferior in water resistance, while the cured product using a long-chain diamine has the same water resistance as a general-purpose amine curing agent without impairing the water resistance. Be done. For this reason, the diamine compound of the present invention is more useful than the current flexibility-imparting agent, polyether diamine.

(Example 22: Corrosion prevention effect on metal products)
A glass sample tube was charged with 50 mL of an aqueous solution containing the diamine 1b obtained in Example 1 as a corrosion inhibitor in a proportion of 0.05% by mass in 10% hydrochloric acid. A standard test plate (JIS G 3141; manufactured by Nippon Test Panel Co., Ltd.), which was subjected to polishing and toluene cleaning treatment three times, was immersed in this aqueous solution and heated at 60 ° C. for 1 hour to corrode the test plate. The test plate after corrosion was washed with water and dried, and the corrosion rate (%) was calculated according to the following formula from the mass difference before and after immersion.
Corrosion rate (%) = (mass of test plate before immersion-mass of test plate after immersion) / (mass of test plate before immersion) x 100

The results obtained are shown in Table 10.

(Comparative Example 20: Corrosion prevention effect on metal products)
The corrosion rate of the standard test plate was measured in the same manner as in Example 22 except that the corrosion inhibitor (diamine 1b of Example 1) was not added. The results obtained are shown in Table 10.

(Comparative Example 21: Corrosion prevention effect on metal products)
The corrosion rate of the standard test plate was measured in the same manner as in Example 22 except that 0.05% by mass of dodecylamine was used instead of diamine 1b as the corrosion inhibitor. The results obtained are shown in Table 10.

(Comparative Example 22: Corrosion prevention effect on metal products)
The corrosion rate of the standard test plate was measured in the same manner as in Example 22 except that 0.05% by mass of hexamethylenediamine was used as the corrosion inhibitor instead of diamine 1b. The results obtained are shown in Table 10.

As shown in Table 10, it can be seen that the diamine 1b (isooctadecanediamine) used in Example 22 has the lowest corrosion rate of the steel sheet and has a high anticorrosive effect against an acidic aqueous solution. Such corrosion inhibitors are useful during cleaning treatments such as pickling, acid immersion, and etching of metals.

According to the diamine compound of the present invention, it is possible to provide a resin composition having excellent flexibility by using various resins. The resin composition is used as a material composed of resins such as epoxy, polyurethane, polyimide, polyamideimide, maleimide, and polyamide, for example, in earth and wood, building materials, repair materials for flooring materials, various paints, various adhesives, and electronic materials. Useful in various technical fields such as sealants (underfills), insulating members, mold resins, resist materials, resin-reinforced solder solder paste materials, flexible printed substrate materials, various films, plastic molded products in thermoplastic resins, nylon fibers, etc. Is. Furthermore, when the diamine compound of the present invention is used as a cationic surfactant in a lubricating rust preventive, it can exert a high corrosion prevention effect on metal products. Therefore, it is also useful in the fields of metal processing, machinery, and the like.

Claims (12)

1. The following formula (I):
   

   

   In formula (I),
   R ¹ is an alkylene or alkenylene group having a total carbon number of C ₁₄ to C _28, which is linear or has one or more C ₁ to C ₄ alkyl and / or alkenyl groups. An alkylene group or an alkenylene group having a branched chain of
   A diamine compound represented by.
2. In formula (I), the main chain portion of the alkylene group or alkenylene group constituting R ¹ has a carbon atom of the C _2n pieces (where n is 7-14), the diamine compound of Claim 1.
3. The diamine compound according to claim 1 or 2, wherein in the formula (I), _{the linear alkylene group or the linear alkenylene group of C 14} to C ₂₈ ^{constituting R 1} has a branched chain composed of an ethyl group. ..
4. The diamine compound according to claim 1, which is 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene.
5. The method for producing a diamine compound according to claim 1.
   The following formula (II):
   

   

   A step of reacting a dibasic acid ester represented by (1) with hydrazine to obtain a dihydrazide compound.
   A step of reacting the dihydrazide compound with a nitrite compound to obtain an azide, and a step of heating and hydrolyzing the azide.
   Including,
   In formula (II),
   R ¹ is an alkylene or alkenylene group having a total carbon number of C ₁₄ to C _28, which is linear or has one or more C ₁ to C ₄ alkyl and / or alkenyl groups. An alkylene group or an alkenylene group having a branched chain of
   R ² is a linear alkyl group of _{C 1} to C _4,
   Method.
6. In Formula (II), the main chain portion of the alkylene group or alkenylene group constituting R ¹ has a carbon atom of the C _2n pieces (where n is 7-14) The method of claim 5.
7. The method for producing a diamine compound according to claim 1.
   The following formula (III):
   

   

   A step of reacting a dibasic acid represented by (1) with ammonia to obtain a diamide compound, and a step of nitriding and hydrogen reducing the diamide compound.
   Including,
   In formula (III),
   R ¹ is an alkylene or alkenylene group having a total carbon number of C ₁₄ to C _28, which is linear or has one or more C ₁ to C ₄ alkyl and / or alkenyl groups. An alkylene group or an alkenylene group having a branched chain of
   Method.
8. In the formula (III), the main chain portion of the alkylene group or alkenylene group constituting R ¹ has a carbon atom of the C _2n pieces (where n is 7-14) The method of claim 7.
9. A resin additive containing the diamine compound according to any one of claims 1 to 4.
10. A resin composition containing a resin and the resin additive according to claim 9.
11. A resin composition containing one or more monomer compounds and a resin composed of the resin additive according to claim 9.
12. A lubricating rust preventive for metal products containing the diamine compound according to any one of claims 1 to 4.