JP2008179688A - Ketimine composition and epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ketimine composition without aggregating a carbonic acid salt produced from an amine etc., even under a weak solvent atmosphere. <P>SOLUTION: This ketimine composition is obtained by reacting a reaction product obtained by reacting a polyamine compound A with a ketone compound B and having ≥80% ketiminization rate of the amine compound A, with a urethane polymer G obtained by reacting a polyol compound E with a polyisocyanate compound F and having an isocyanate group at its molecular chain terminal. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a ketimine composition particularly useful for the preparation of a weak solvent type curable resin composition, and an epoxy resin composition containing the ketimine composition. This epoxy resin composition is useful as various moisture-curing treatment agents (adhesives, coating agents, etc.).

  Conventionally, strong solvents such as toluene have been used in solvent-based paints, but in recent years weak solvents have been used from the viewpoints of reducing environmental impact, safety during painting, and improving work hygiene. It has become like this.

  On the other hand, in an epoxy-based paint or the like, ketimine is used as a curing agent for the purpose of liquefaction and extension of pot life (see Patent Document 1, etc.). Ketimines can usually be obtained by dehydration condensation of amines and ketones, but it is known that amines and ketimines as raw materials react with carbon dioxide in the air to form carbonates (carbamates). . Such carbonates tend to aggregate and localize due to their high polarity in epoxy resins, particularly in weak solvent systems, and are known to adversely affect physical properties of the coating film. Such carbonates may be present in the raw material or may be produced during the synthesis of ketimine, but are very difficult to remove and no method for simple removal is known.

JP 2000-265121 A

  Accordingly, an object of the present invention is to provide a ketimine composition in which carbonates produced from amines and the like do not aggregate even in a weak solvent atmosphere, and an epoxy resin composition containing the ketimine composition.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are reaction products obtained by reacting an amine with a ketone and having a ketimination rate of the amine of a certain value or more, and having an amino group. When a urethane prepolymer having a terminal isocyanate group of a specific structure is reacted with a reaction product containing a ketimine that does not, an ketimine compound having an amino group and / or an unreacted amine, it is generated from an amine or the like even in a weak solvent. The inventors have found that a ketimine composition in which carbonates do not aggregate is obtained, and the present invention has been completed.

（式中、Ｒ¹は有機基、ｎは２以上の整数を示す）
で表されるアミン化合物Ａと、下記式（２）

（式中、Ｒ²、Ｒ³は、それぞれ有機基を示す。Ｒ²及びＲ³は互いに結合して、隣接する炭素原子とともに環を形成していてもよい）
で表されるケトン化合物Ｂとを反応させて得られる、前記アミン化合物Ａのケチミン化率が８０％以上である反応生成物であって、下記式（３）

（式中、Ｒ¹、Ｒ²、Ｒ³、ｎは前記に同じ。Ｒ²及びＲ³は互いに結合して、隣接する炭素原子とともに環を形成していてもよい）
で表されるケチミン化合物Ｃ、及び下記式（４）

（式中、ｋ及びｍはそれぞれ１以上の整数を示し、ｋ＋ｍ＝ｎである。Ｒ¹、Ｒ²、Ｒ³、ｎは前記に同じ。Ｒ²及びＲ³は互いに結合して、隣接する炭素原子とともに環を形成していてもよい）
で表されるアミノ基を有するケチミン化合物Ｄと未反応の前記アミン化合物Ａの少なくとも何れかを含む反応生成物に対して、下記式（５）

（式中、Ｒ⁴は多価の炭化水素基、ｐは２以上の整数を示す）
で表されるポリオール化合物Ｅと下記式（６）

（式中、Ｒ⁵は有機基、ｑは２以上の整数を示す）
で表されるポリイソシアネート化合物Ｆとの反応により得られる分子鎖末端にイソシアネート基を有するウレタンプレポリマーＧを反応して得られるケチミン組成物を提供する。 That is, the present invention provides the following formula (1):

(In the formula, R ¹ represents an organic group, and n represents an integer of 2 or more)
An amine compound A represented by the following formula (2)

(In the formula, R ² and R ³ each represent an organic group. R ² and R ³ may be bonded to each other to form a ring together with adjacent carbon atoms).
A reaction product obtained by reacting with a ketone compound B represented by the formula (3), wherein the amine compound A has a ketimination rate of 80% or more,

(In the formula, R ¹ , R ² , R ³ and n are the same as above. R ² and R ³ may be bonded to each other to form a ring together with adjacent carbon atoms)
A ketimine compound C represented by formula (4):

(In the formula, k and m each represent an integer of 1 or more, and k + m = n. R ¹ , R ² , R ³ and n are the same as above. R ² and R ³ are adjacent to each other. (It may form a ring with carbon atoms)
For a reaction product containing at least one of the ketimine compound D having an amino group represented by formula (1) and the unreacted amine compound A, the following formula (5):

(Wherein R ⁴ is a polyvalent hydrocarbon group, and p is an integer of 2 or more)
And a polyol compound E represented by the following formula (6)

(Wherein R ⁵ represents an organic group, and q represents an integer of 2 or more)
The ketimine composition obtained by reacting the urethane prepolymer G having an isocyanate group at the molecular chain terminal obtained by the reaction with the polyisocyanate compound F represented by

In the polyol compound E, R ⁴ in the formula (5) is preferably a polyvalent hydrocarbon group having no unsaturated group. The polyol compound E preferably has a weight average molecular weight of 2000 or more.

  As the polyisocyanate compound F, for example, non-aromatic polyisocyanate compounds such as isophorone diisocyanate are preferable.

  The ketiminization rate of the amine compound A is preferably in the range of 90 to 99.5%.

In the ketone compound B, R ² and R ³ in the formula (2) are preferably both hydrocarbon groups having 2 or more carbon atoms, and it is particularly preferable that both R ² and R ³ are ethyl groups.

  The present invention also provides an epoxy resin composition composed of the above ketimine composition and an epoxy resin. The epoxy resin composition may further contain a petroleum solvent or a dehydrating agent.

  In the ketimine composition of the present invention, there is a compound in which a low-polar part (hydrocarbon part derived from a polyol compound) having high solubility in a weak solvent is partially introduced in the molecule. While this low polarity part has an affinity for weak solvents, high polarity parts such as ketimine parts have affinity with carbonates generated from amines, etc. Even in a solvent, aggregation and localization of carbonates formed from amines and the like are prevented. Therefore, the physical property fall of the epoxy resin coating film resulting from the carbonate produced | generated from an amine etc. can be prevented.

[Ketimine composition]
The ketimine composition of the present invention has a ketimination rate of the amine compound A obtained by reacting the amine compound A represented by the formula (1) and the ketone compound B represented by the formula (2). 80% or more of the reaction product, at least of the ketimine compound C represented by the formula (3) and the ketimine compound D having an amino group represented by the formula (4) and the unreacted amine compound A Urethane having an isocyanate group at the end of the molecular chain obtained by the reaction of the polyol compound E represented by the formula (5) and the polyisocyanate compound F represented by the formula (6) with respect to any reaction product It is a composition obtained by reacting prepolymer G.

[Amine compound A]
In the amine compound A represented by the formula (1), R ¹ in the formula (1) represents an organic group. The organic group includes a polyvalent hydrocarbon group, a polyvalent heterocyclic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula, and a group in which two or more of these are bonded.

  The polyvalent hydrocarbon group includes a polyvalent aliphatic hydrocarbon group, a polyvalent alicyclic hydrocarbon group, a polyvalent aromatic hydrocarbon group, and these polyvalent hydrocarbon groups. And polyvalent groups (sometimes referred to as “multivalent complex hydrocarbon groups”). As the polyvalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group such as an alkylene group can be used. Examples of the alkylene group include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, as well as an alkylene group having a branched chain or a substituent (for example, Propylene group, etc.).

The polyvalent alicyclic hydrocarbon group may be a polyvalent alicyclic hydrocarbon group having a monocyclic hydrocarbon ring, or a polyvalent alicyclic carbon group having a polycyclic hydrocarbon ring. It may be a hydrogen group. As the polyvalent alicyclic hydrocarbon group, a divalent alicyclic hydrocarbon group can be suitably used. Examples of the monocyclic hydrocarbon ring include a cycloalkane ring having about 5 to 10 carbon atoms constituting a ring such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. Moreover, as a polycyclic hydrocarbon ring, a bridged ring etc. are mentioned, for example. Examples of the bridge ring include a bicyclic hydrocarbon ring (for example, carbonization in pinane, pinene, bornane, norbornane, norbornene, bicyclo [3.2.1] octane, bicyclo [4.3.2] undecane, etc. Hydrogen rings, etc.), tricyclic hydrocarbon rings (eg adamantane, exotricyclo [5.2.1.0 ^2,6 ] decane, endotricyclo [5.2.1.0 ^2,6 ] decane, etc.) such as a hydrocarbon ring), tetracyclic hydrocarbon rings (e.g., such as a hydrocarbon ring in such tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane), and others in. Such bridged rings include bicyclic to tetracyclic hydrocarbon rings (for example, pinane, bornane, norbornane, norbornene) having about 6 to 16 carbon atoms (particularly about 6 to 14 carbon atoms) constituting the ring. , Hydrocarbon rings in adamantane, etc.) can be suitably used.

  Specifically, examples of the divalent alicyclic hydrocarbon group having a cyclohexane ring include cycloalkylene such as 1,2-cyclohexylene group, 1,3-cyclohexylene group, and 1,4-cyclohexylene group. Groups. Examples of the divalent alicyclic hydrocarbon group having a norbornane ring include norbornane-diyl groups such as norbornane-2,3-diyl, norbornane-2,5-diyl and norbornane-2,6-diyl. Is mentioned.

  As the polyvalent aromatic hydrocarbon group, a divalent aromatic hydrocarbon group such as an arylene group can be used. As the arylene group, for example, a divalent aromatic hydrocarbon group having a benzene ring such as a phenylene group (for example, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, etc.) And divalent aromatic hydrocarbon groups having a naphthalene ring such as a naphthylene group. In addition, as an aromatic ring in a polyvalent aromatic hydrocarbon group, in addition to a benzene ring and a naphthalene ring, 2 to 10 4 to 7-membered carbon rings such as azulene, indacene, anthracene, phenanthrene, triphenylene, and pyrene And a condensed carbocycle in which is condensed.

  Furthermore, examples of the polyvalent group (multivalent complex hydrocarbon group) in which these polyvalent hydrocarbon groups are combined include, for example, a divalent aliphatic hydrocarbon group (such as an alkylene group), a monocyclic group, and the like. A divalent alicyclic hydrocarbon group having a hydrocarbon ring or a polycyclic hydrocarbon ring (such as a cycloalkylene group or a norbornane-diyl group), a benzene ring or a divalent aromatic hydrocarbon group having a condensed carbocycle ( A divalent group (a divalent complex hydrocarbon group) in which a phenylene group, a naphthylene group, or the like) is appropriately combined can be suitably used. Examples of the divalent composite hydrocarbon group include a divalent composite hydrocarbon group in which an aliphatic hydrocarbon group such as an alkylene-phenylene group or an alkylene-phenylene-alkylene group and an aromatic hydrocarbon group are combined; alkylene -A divalent combination of an aliphatic hydrocarbon group such as a cycloalkylene group, an alkylene-cycloalkylene-alkylene group, an alkylene-norbornane-diyl group, an alkylene-norbornane-diyl-alkylene group, and an alicyclic hydrocarbon group. Examples include complex hydrocarbon groups. In the group in which these polyvalent complex hydrocarbon groups are combined, the alkylene moiety, phenylene moiety, cycloalkylene moiety, and norbornane-diyl moiety include the above-exemplified alkylene group, phenylene group, cycloalkylene group, norbornane-diyl group. Etc. can be used.

  Specifically, examples of the multivalent complex hydrocarbon group include a methylene-1,3-phenylene-methylene (m-xylylene) group, a methylene-1,3-cyclohexylene-methylene group, and a methylene-norbornane-2. , 5-diyl-methylene group, methylene-norbornane-2,6-diyl-methylene group, and in these groups, the methylene moiety is another alkylene moiety (eg, ethylene moiety, trimethylene moiety, propylene moiety, etc.). Groups and the like.

  The polyvalent heterocyclic group includes a monocyclic or polycyclic aromatic or non-aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. And a polyvalent heterocyclic group having a carbon atom at the binding site with the nitrogen atom shown in the formula.

  The above polyvalent hydrocarbon group or heterocyclic group may have a substituent (for example, a hydrocarbon group), and the substituent is reactive with an amine-reactive compound such as an epoxy resin. It is important that the hydrolyzability of the ketimine compound and the reactivity between the amine compound produced by hydrolysis of the ketimine compound and the amine-reactive compound such as epoxy resin are not impaired. is there.

As the organic group for R ¹ , a polyvalent hydrocarbon group is preferable, and in particular, a polyvalent aliphatic hydrocarbon group, a polyvalent alicyclic hydrocarbon group, or a polyvalent group in which these are combined. preferable.

  Moreover, n in the said Formula (1) shows an integer greater than or equal to 2. That is, the amine compound A is a polyvalent amine (polyamine). Although it will not restrict | limit especially if n is an integer greater than or equal to 2, For example, it can select from the integer of 2-10 (preferably 2-4, more preferably 2-3, especially preferably 2).

  The amine compound A includes aliphatic polyamines, alicyclic polyamines, aromatic polyamines, araliphatic polyamines, heterocyclic polyamines, and the like. Examples of the aliphatic polyamine include ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,3-pentamethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine, 2,3-butylenediamine, 1,3-butylenediamine, 2-methyl-1,5-pentamethylenediamine, 3-methyl-1,5-pentamethylene In addition to aliphatic diamines such as diamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepenta Min, pentaethylenehexamine and the like. Further, as the aliphatic polyamine, a polyamine having a polyoxyalkylene skeleton such as a diamine having a polyoxyalkylene skeleton can also be used.

  Examples of the alicyclic polyamine include 1,3-cyclopentanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, -Amino-1-methyl-4-aminomethylcyclohexane, 1-amino-1-methyl-3-aminomethylcyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (3-methyl-cyclohexyl) Amine), methyl-2,3-cyclohexanediamine, methyl-2,4-cyclohexanediamine, methyl-2,6-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) Cyclohexane, isophorone diamine, norbornane diamine { For example, alicyclic diamines such as 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, etc.} It is done.

  Aromatic polyamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, naphthylene-1,4-diamine, naphthylene-1,5-diamine, 4, 4'-diphenyldiamine, 4,4'-diphenylmethanediamine, 2,4'-diphenylmethanediamine, 4,4'-diphenyletherdiamine, 2-nitrodiphenyl-4,4'-diamine, 2,2'-diphenyl Fragrances such as propane-4,4'-diamine, 3,3'-dimethyldiphenylmethane-4,4'-diamine, 4,4'-diphenylpropanediamine, 3,3'-dimethoxydiphenyl-4,4'-diamine Group diamine and the like.

  Examples of the araliphatic polyamine include 1,3-xylylenediamine, 1,4-xylylenediamine, α, α, α ′, α′-tetramethyl-1,3-xylylenediamine, α, α, α ′, α′-tetramethyl-1,4-xylylenediamine, ω, ω′-diamino-1,4-diethylbenzene, 1,3-bis (1-amino-1-methylethyl) benzene, 1,4 And aromatic aliphatic diamines such as -bis (1-amino-1-methylethyl) benzene and 1,3-bis (α, α-dimethylaminomethyl) benzene.

  As the amine compound A, aliphatic polyamines, alicyclic polyamines, and araliphatic polyamines are preferable, and alicyclic polyamines are particularly preferable. Amine compound A can be used alone or in combination of two or more.

[Ketone Compound B]
R ² and R ³ in the formula (2) each represents an organic group. The organic group includes a hydrocarbon group, a heterocyclic group having a carbon atom at the bonding site with the carbonyl group shown in the formula, a group in which two or more of these are bonded, and the like.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, s-butyl group, n-pentyl group, 2-methylbutyl group, 3- Methylbutyl group, 2,2-dimethylpropyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, Examples thereof include alkyl groups having about 1 to 20 carbon atoms such as 3-dimethylbutyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, and octadecyl group. The alkyl group is preferably an alkyl group having 2 or more (for example, 2 to 6) carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms. In the present invention, as the alkyl group for R ² and R ³ , an alkyl group having 2 or 3 carbon atoms is particularly preferable, and an ethyl group is particularly preferable.

  Examples of the alicyclic hydrocarbon group include a cycloalkyl group having about 5 to 10 carbon atoms constituting a ring such as a cyclohexyl group, and a polycyclic hydrocarbon ring (for example, a hydrocarbon ring in norbornane). Group having a bridged ring, etc.).

  As an aromatic hydrocarbon group, aryl groups, such as a phenyl group and a naphthyl group, etc. are mentioned, for example. Examples of the aromatic ring in the aromatic hydrocarbon group include a benzene ring and a condensed carbocyclic ring (for example, a condensed carbocyclic ring in which 2 to 10 4 to 7-membered carbocyclic rings such as a naphthalene ring are condensed). .

  The heterocyclic group has a monocyclic or polycyclic aromatic or non-aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. And a heterocyclic group having a carbon atom at the binding site to the nitrogen atom shown in the formula.

  The hydrocarbon group or heterocyclic group may have a substituent (for example, a hydrocarbon group), and the substituent has reactivity with an amine-reactive compound such as an epoxy resin. In addition, it is important that the hydrolyzability of the ketimine compound and the reactivity between the amine compound produced by hydrolysis of the ketimine compound and the amine-reactive compound such as an epoxy resin are not impaired.

R ² and R ³ may be bonded to each other to form a ring with adjacent carbon atoms. Examples of such a ring include a cycloalkane ring having about 3 to 15 members such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclodecane ring, and a cyclododecane ring. Among these, a cyclopentane ring and a cyclohexane ring are preferable.

At least one of R ² and R ³ is preferably a hydrocarbon group having 2 or more carbon atoms (for example, 2 to 6) (for example, an aliphatic hydrocarbon group, especially an alkyl group), and in this case, the other is carbon A hydrocarbon group having a number of 1 to 6 (for example, an aliphatic hydrocarbon group, particularly an alkyl group) is desirable. In particular, when both R ² and R ³ are hydrocarbon groups having 2 or more carbon atoms (for example, 2 to 6) (especially aliphatic hydrocarbon groups, especially alkyl groups), preparation of epoxy resin compositions and the like When used, the hydrolysis rate of the ketimine compound, that is, the generation rate of the amine compound is fast, the formation rate of the crosslinked structure by the reaction with an amine reactive compound such as an epoxy resin is also fast, and excellent fast curability and initial adhesion are obtained. Since it is demonstrated, it is preferable. In the present invention, it is most preferable that R ² and R ³ are both ethyl groups.

Representative examples of the ketone compound B include, for example, dimethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, methyl s-butyl ketone, diethyl ketone, ethyl propyl ketone, Ethyl isopropyl ketone, ethyl butyl ketone, ethyl isobutyl ketone, ethyl t-butyl ketone, ethyl s-butyl ketone, ethyl pentyl ketone, ethyl hexyl ketone, ethyl heptyl ketone, ethyl octyl ketone, ethyl 2-ethylhexyl ketone, dipropyl ketone, propyl isopropyl ketone , Propyl butyl ketone, propyl isobutyl ketone, propyl t-butyl ketone, propyl s-butyl ketone, propyl pentyl ketone, Aliphatic ketones such as pyrhexyl ketone, propyl heptyl ketone, propyl octyl ketone, propyl 2-ethylhexyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, di-t-butyl ketone, di-s-butyl ketone, dipentyl ketone, dihexyl ketone (for example, C _1-20 alkyl-C _1-20 alkyl ketone); and cyclic ketones such as cyclopentanone and cyclohexanone.

  The ketone compound B can be used alone or in combination of two or more.

[Reaction product of amine compound A and ketone compound B]
In the reaction product of amine compound A and ketone compound B in the present invention (hereinafter sometimes referred to as “reaction product H”), the ketimineization rate of amine compound A is 80% or more. Although the ketiminization rate may be 80% or more by the reaction, the ketiminization rate may be adjusted to 80% or more by purification after the reaction. The ketiminization rate is preferably 90 to 99.5%. If the ketiminization rate is less than 80%, gelation or increase in viscosity is undesirable. The ketiminization rate can be determined by the method described later.

  The reaction between the amine compound A and the ketone compound B is not particularly limited, and a known method can be employed. For example, the amine compound A and the ketone compound B are mixed in the absence of a solvent or in the presence of a nonpolar solvent (for example, hexane, cyclohexane, toluene, benzene, etc.), then heated to reflux and produced as necessary. This can be done by removing water azeotropically. In order to increase the reaction rate, a catalyst such as an acid catalyst may be used as necessary, and a dehydrating agent may be present in the system. The dehydrating agent is preferably added to the system when the reaction proceeds to some extent and the reaction rate becomes slow, from the viewpoint of economy and the like.

  The dehydrating agent is not particularly limited as long as it does not inhibit the reaction. For example, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; vinyl group-containing alkoxysilane compounds such as vinyltrimethoxysilane; tetramethoxy Examples thereof include silicone oligomers such as silane oligomers; silazane compounds such as hexamethyldisilazane; alkoxytitanium compounds such as tetramethoxytitanium. The dehydrating agent is preferably a liquid that does not have reactivity with amines.

  In this reaction, either one of the amine compound A and the ketone compound B (particularly, the ketone compound B) may be used excessively. The reaction temperature varies depending on the types of amine compound A and ketone compound B used, but is usually 50 to 200 ° C, preferably 100 to 160 ° C. After completion of the reaction, the remaining ketone compound B, the solvent used, and the amine compound A can be removed by distillation or the like.

  The ketimineization rate of the amine compound A can be controlled by the charged molar ratio of the amine compound A and the ketone compound B, the reaction temperature, the reaction time, the type and amount of the catalyst and dehydrating agent, and the like. In addition, the ketiminization rate may be adjusted by purification after the reaction. A conventionally known method can be adopted as a purification method.

  The reaction product thus obtained is the main product ketimine compound C having an amino group represented by formula (4), as well as the ketimine compound C having no amino group represented by formula (3) and an unreacted product. At least one of the amine compounds A is contained.

[Urethane prepolymer G]
The urethane prepolymer G in the present invention is a compound having an isocyanate group at the molecular chain terminal obtained by the reaction between the polyol compound E represented by the formula (5) and the polyisocyanate compound F represented by the formula (6). .

In the polyol compound E represented by the formula (5), R ⁴ represents a polyvalent hydrocarbon group, and p represents an integer of 2 or more. Examples of the polyvalent hydrocarbon group include saturated or unsaturated linear or branched polyvalent aliphatic hydrocarbon groups (alkylene group, alkenylene group, alkanetriyl group, alkenetriyl group, etc.), many Valent alicyclic hydrocarbon group (1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group A cycloalkylidene group such as a cyclohexylidene group; a polyvalent bridged ring such as a norbornane-2,3-diyl group, a norbornane-2,5-diyl group, a norbornane-2,6-diyl group Formula hydrocarbon groups), polyvalent aromatic hydrocarbon groups (arylene groups such as phenylene groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, etc.), Polyvalent hydrocarbon groups bonded to the like. Preferred R ⁴ includes a saturated or unsaturated linear or branched polyvalent aliphatic hydrocarbon group. R ⁴ is particularly preferably a polyvalent hydrocarbon group having no unsaturated group, and particularly a saturated linear or branched (particularly branched) polyvalent aliphatic hydrocarbon group is preferred. .

The carbon number of the polyvalent hydrocarbon group in R ⁴ is, for example, 50 or more (for example, about 50 to 1000), preferably 80 or more (for example, about 80 to 700), and more preferably 140 or more (for example, about 140 to 500). is there. When the number of carbon atoms is less than 50, the aggregation preventing property of carbonates produced from amines or the like tends to decrease. In addition, when there are too many carbon numbers, it will become high viscosity and gelatinization easily.

  As a preferable polyol compound E, a polydiene polyol having hydroxyl groups at both ends of the molecular chain and a polyolefin polyol having hydroxyl groups at both ends of the molecular chain are preferable. As polydiene polyols having hydroxyl groups at both ends of the molecular chain, polybutadienes having hydroxyl groups at both ends of the molecular chain (1,2-addition type polybutadiene, 1,4-addition type polybutadiene, 1,2- and 1,4- Mixed addition type polybutadiene) and polyisoprene. Examples of polyolefin-based polyols having hydroxyl groups at both ends of the molecular chain include polyethylene and polypropylene having hydroxyl groups at both ends of the molecular chain. The above-mentioned polydiene-based polyols having hydroxyl groups at both ends of the molecular chain are hydrogenated. For example, a product obtained by hydrogenating polybutadiene or polyisoprene having hydroxyl groups at both ends of the molecular chain is preferable. Particularly preferred polyol compound E is a hydrogenated product of 1,2-addition type polybutadiene from the viewpoint of preventing aggregation of carbonate produced from an amine or the like in a weak solvent. When a hydrogenated 1,2-added polybutadiene is used as the polyol compound E, a carbonic acid produced from an amine or the like even if only an aliphatic hydrocarbon having a very low polarity (for example, n-hexane) is used as a weak solvent. No salt aggregation or localization.

  The weight average molecular weight of the polyol compound E is, for example, 700 or more (for example, about 700 to 14000), preferably 1200 or more (for example, about 1200 to 10000), and more preferably 2000 or more (for example, about 2000 to 7000). When the weight average molecular weight is less than 700, the aggregation preventing property of carbonate produced from amine or the like tends to be lowered. When the polyol compound E has a weight average molecular weight of 700 or more, when a mineral spirit containing, for example, an aliphatic hydrocarbon and an aromatic hydrocarbon is used as a weak solvent, aggregation of a carbonate generated from an amine or the like is suppressed. it can. In addition, when the weight average molecular weight is 2000 or more, it is possible to prevent aggregation of carbonates generated from amines or the like even when only extremely low-polarity aliphatic hydrocarbons (for example, n-hexane) are used as weak solvents. Can do. In addition, when the molecular weight of the polyol compound E is too large, it becomes easy to increase viscosity and gel.

  The p is not particularly limited as long as it is an integer of 2 or more, but is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2.

  The polyol compound E can be used alone or in combination of two or more.

In the polyisocyanate compound F represented by the formula (6), R ⁵ represents an organic group, and q represents an integer of 2 or more. Examples of the organic group include the same organic groups as those described above for R ¹ . That is, the organic group includes a polyvalent hydrocarbon group, a polyvalent heterocyclic group having a carbon atom at the binding site with the nitrogen atom shown in the formula, a group in which two or more of these are bonded, and the like.

As the organic group for R ⁵ , a polyvalent hydrocarbon group is preferable, and in particular, a polyvalent aliphatic hydrocarbon group, a polyvalent alicyclic hydrocarbon group, or a polyvalent group in which these are combined is preferable. .

  Moreover, q in the said Formula (6) shows an integer greater than or equal to 2. That is, the polyisocyanate compound F is a polyvalent isocyanate compound. Although it will not restrict | limit especially if q is an integer greater than or equal to 2, Preferably it is 2-6, More preferably, it is 2-4, Most preferably, it is 2.

  Examples of the polyisocyanate compound F include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Polyisocyanate compound F can be used alone or in combination of two or more.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexa Methylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl -1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate Lysine diiso Ane - and aliphatic diisocyanates such as bets and the like.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4. '-Methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate And alicyclic diisocyanates such as norbornane diisocyanate.

  Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthylene. 1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane Isocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3, 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4, And aromatic diisocyanates such as 4'-diisocyanate.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis. Aroaliphatic diisocyanates such as (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene Etc.

  As polyisocyanate compound F, 1,6-hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) Cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-Xylylene diisocyanate, norbornane diisocyanate, and 1,3-bis (α, α-dimethylisocyanatomethyl) benzene can be suitably used. In particular, when a non-aromatic polyisocyanate (aliphatic polyisocyanate or alicyclic polyisocyanate) is used as the polyisocyanate compound F, a resin with little discoloration can be obtained. As the polyisocyanate compound F, an alicyclic polyisocyanate is preferable, and isophorone diisocyanate is particularly preferable.

  In the present invention, as the polyisocyanate compound F, the exemplified aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, dimer or trimer by araliphatic polyisocyanate, Reaction product or polymer (eg diphenylmethane diisocyanate dimer or trimer, reaction product of trimethylolpropane and tolylene diisocyanate, reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl Isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) can also be used.

  The reaction method of the polyol compound E and the polyisocyanate compound F is not specifically limited, A well-known method is employable. For example, the urethane prepolymer G having an isocyanate group at the molecular chain terminal can be obtained by mixing the polyol compound E and the polyisocyanate compound F in a solvent or without a solvent.

  In the reaction, a polymerization catalyst can be used. As a polymerization catalyst, a well-known thru | or usual polymerization catalyst (curing catalyst) used when making a polyol compound and a polyisocyanate compound react can be used. More specifically, examples of the polymerization catalyst include organic tin compounds, metal complexes, basic compounds such as amine compounds, and organic phosphoric acid compounds.

  The molar ratio of both components when the polyisocyanate compound F and the polyol compound E are reacted is, for example, 1.2 to 3, preferably 1.4 to 2.8, more preferably as NCO / OH (molar ratio). Is about 1.5 to 2.5. When NCO / OH (molar ratio) is less than 1.2, the molecular weight of the urethane prepolymer G is increased, so that gelation and high viscosity are easily achieved. On the other hand, when NCO / OH (molar ratio) exceeds 3, the remaining polyisocyanate compound is increased, so that a compound insoluble in a weak solvent is easily generated. The reaction temperature is, for example, 60 to 100 ° C, preferably 70 to 85 ° C.

  The isocyanate group (NCO) content in the urethane prepolymer G is, for example, about 0.3 to 10% by mass, preferably about 1 to 8% by mass, and more preferably about 1.5 to 5% by mass.

  The ketimine composition of the present invention can be obtained by reacting the reaction product H with the urethane prepolymer G having an isocyanate group at the molecular chain terminal.

  The reaction method of reaction product H and urethane prepolymer G is not particularly limited, and is a known method used when reacting an isocyanate-reactive compound (for example, polyol or polyamine) with a terminal isocyanate group-containing urethane prepolymer. Can be adopted. For example, the ketimine composition of the present invention can be obtained by mixing the reaction product H and the urethane prepolymer G in a solvent or without a solvent.

The molar ratio of both components when the urethane prepolymer G having an isocyanate group at the molecular chain terminal is reacted with the reaction product H is, for example, (NCO in the urethane prepolymer G) / (NH in the reaction product H). ₂ ) (Molar ratio) is 0.0001 to 5, preferably 0.005 to 4, more preferably about 0.01 to 3. Moreover, as the usage-amount of the urethane prepolymer G which has an isocyanate group at the molecular chain terminal, with respect to 100 mass parts of total amounts of the ketimine compound C in the reaction product H, the ketimine compound D which has an amino group, and the amine compound A, It is 0.1-300 mass parts, Preferably it is 0.5-200 mass parts, More preferably, it is 1-100 mass parts. If the amount of the urethane prepolymer G is too small, the anti-coagulation property of carbonate in a weak solvent tends to be lowered. Conversely, if the amount of the urethane prepolymer G is too large, the content of urethane showing flexibility is increased. It becomes higher and the physical properties tend to be lowered. The reaction temperature is, for example, 0 to 100 ° C, preferably 30 to 70 ° C.

  In the ketimine composition of the present invention, as described above, there is a compound in which a low polarity site (hydrocarbon site derived from a polyol compound) having high solubility in a weak solvent is partially introduced in the molecule. Yes. While this low polarity part has an affinity for weak solvents, high polarity parts such as ketimine parts have affinity with carbonates generated from amines, etc. Even in a solvent, aggregation and localization of carbonates formed from amines and the like are prevented. On the other hand, ketimine is hydrolyzed by moisture in the air to produce an amine, so that it can be used as a latent curing agent for amine-reactive compounds such as epoxy resins. Moreover, since the ketimine composition of the present invention is modified with urethane, the physical properties of the cured product can be improved. For example, toughness can be imparted to the cured product. Therefore, the ketimine composition of the present invention can be suitably used as a raw material for a curable resin composition such as a weak solvent type epoxy resin composition.

[Epoxy resin composition]
The epoxy resin composition of this invention is comprised with said ketimine composition and an epoxy resin.

  Examples of epoxy resins include biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, bisphenol S type epoxy resins and derivatives thereof (for example, hydrogenated products and brominated products), novolaks, etc. Type epoxy resin (for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin), glycidyl ester type epoxy resin, urethane modified epoxy resin having urethane bond, nitrogen-containing epoxy resin (for example, metaxylenediamine, hydantoin, etc.) Epoxidized amines, glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane and triglycidylparaaminophenol), rubber-modified epoxy resins (eg rubber As such an epoxy resin containing a synthetic rubber or natural rubber such as polybutadiene), cyclic aliphatic epoxy resins, and long-chain aliphatic epoxy resins.

  The epoxy resin composition of the present invention may contain a dehydrating agent and a curing catalyst in addition to the ketimine composition and the epoxy resin.

  The dehydrating agent is not particularly limited as long as it has a dehydrating action and does not impair the curability during use, and examples thereof include silane compounds that are reactive with water. Examples of the silane compound include tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, diethoxydimethylsilane, and ethoxytrimethylsilane; Vinyl group-containing alkoxysilane compounds such as methoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, vinyltriethoxysilane, vinyldiethoxymethylsilane, vinylethoxydimethylsilane; β-glycidoxyethyltrimethoxysilane, β-glycine Sidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrip Glycidoxyalkyltrialkoxysilanes such as lopoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl In addition to glycidoxyalkylalkyldialkoxysilanes such as diethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane and the like, glycidoxyalkyldialkylalkoxysilanes corresponding to these Silane compounds having an epoxy group; polytetraalkoxysilanes such as polytetramethoxysilane, polytetraethoxysilane, polytetrapropoxysilane, polytetraisopropoxysilane, and polytetrabutoxysilane; Poly (alkoxysilane) such as poly (alkoxyalkoxysilane) such as (methoxyethoxysilane), poly (methoxysilane), poly (ethoxysilane), poly (propoxysilane), poly (isopropoxysilane), poly (butoxysilane) ), Poly (methoxymethylsilane), poly (methoxyethylsilane), poly (alkoxyalkylsilane) and other polymer type silane compounds; isocyanate group-containing silane compounds, containing amino groups And silane compounds.

  As silane compounds, in particular, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; silanes having an epoxy group such as glycidoxyalkyltrialkoxysilane, glycidoxyalkylalkyldialkoxysilane and glycidoxyalkyldialkylalkoxysilane Compounds and the like are preferred. The silane compound also has a function as a stabilizer for the ketimine compound and a function as a reactive diluent.

  In addition, the amine compound produced | generated by the hydrolysis of a ketimine in the reaction by an epoxy resin is a reaction component in reaction of this amine compound and an epoxy resin, and also has a function as a catalyst.

  As the curing catalyst, for example, a known curing catalyst can be used as a curing catalyst for polyorganosiloxane. Specifically, examples of the curing catalyst include a tin-based curing catalyst [an alkyltin-based compound such as dibutyltin diacetate and dibutyltin bis (acetylacetonate)], a titanium-based curing catalyst, an iron-based curing catalyst, and a zirconium-based curing catalyst. Bismuth-based curing catalyst, boron-based curing catalyst, and the like. As the curing catalyst, a tin-based curing catalyst and a titanium-based curing catalyst are preferable, and a tin-based curing catalyst is particularly preferable. A curing catalyst can be used individually or in combination of 2 or more types. In addition to the curing catalyst, an acid catalyst (for example, organic acids such as formic acid, acetic acid, monochloroacetic acid, propionic acid, butyric acid, maleic acid, oxalic acid and citric acid; inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid) ) And nitrogen atom-containing catalysts [for example, organic amines such as triethanolamine; aminoalkylsilanes such as N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; fourth compounds such as organosilicon quaternary ammonium salts; Various catalysts such as ammonium salts], promoters, and the like may be used. Such a catalyst such as a curing catalyst and a co-catalyst may be used by adding them to the system when preparing the epoxy resin composition, and before the preparation of the epoxy resin composition, It may be used by adding it to the system in advance when preparing the product.

  The epoxy resin composition of the present invention can be prepared, for example, by mixing the ketimine composition and the epoxy resin, and if necessary, a dehydrating agent, a curing catalyst, other additives, and the like. The mixing of each component is preferably performed under an inert gas atmosphere (for example, under a nitrogen atmosphere) and / or under reduced pressure. Moreover, in order to remove the water | moisture content contained in an additive etc., you may mix, dehydrating by heating, pressure reduction, etc.

  The ketimine composition and the epoxy resin may be used in a premixed state, or may be used by mixing the ketimine composition and the epoxy resin at the time of use. That is, the epoxy resin composition of the present invention may be a one-pack type or a two-pack type. In addition, since the epoxy resin composition of this invention is excellent in storage stability, it can be used conveniently as a 1 liquid type.

  The one-pack type epoxy resin composition is an epoxy resin (polymer curing component; main agent) and a ketimine compound (curing agent) placed in a single container (mixed state), and can be substantially sold. This means that even when stored (or stored) at room temperature for a long period of time, little or no gelation or curing occurs, and the initial state (initial dispersion state) can be maintained for a long period of time. ing. Therefore, the one-pack type epoxy resin composition can be used by being applied to a predetermined site as it is. The long-term storage period can be appropriately selected, for example, 6 months or longer, 1 year or longer, 1 year 6 months or longer, but is preferably at least 6 months or longer.

  On the other hand, a two-pack type epoxy resin composition is sold in a state where an epoxy resin (polymer curing component; main agent) and other components such as a ketimine compound (curing agent) or an auxiliary agent are put in different containers. In use, it means that these are mixed and the mixture is applied to a predetermined site to be used. Therefore, the two-pack type epoxy resin composition is basically mixed into two liquids at the time of use to make one liquid. No one-pack type is practically impossible to sell. In addition, the epoxy resin composition that can be used as a one-pack type, as a two-pack type epoxy resin composition, an epoxy resin (polymer curing component; main agent) and other components such as a ketimine compound (curing agent) or an auxiliary agent Can also be sold in different containers.

  In the epoxy resin composition of the present invention, the amount of the epoxy resin used can be appropriately set according to the type of epoxy resin, the type of ketimine compound, and the like. The amino group of the amine compound produced by hydrolysis of the ketimine compound can react at a ratio of 0.5 mol with respect to 1 mol of the epoxy group of the epoxy resin. Therefore, in this case, the blending ratio of the epoxy resin and the ketimine compound is, for example, (number of moles of amino group of amine compound generated by hydrolysis of ketimine compound) / (number of moles of epoxy group in epoxy resin) is 0. It is preferable to select from a range of ratios such that .25 to 1.0 (preferably 0.4 to 0.6).

  In addition, when a dehydrating agent (such as a silane compound) is included in the epoxy resin composition, the ratio of the dehydrating agent is not particularly limited, depending on the type of dehydrating agent, the type of ketimine compound, epoxy resin, or the like. Can be selected as appropriate. The proportion of the dehydrating agent (such as a silane compound) is, for example, 50 parts by mass or less (for example, 1 to 50 parts by mass, preferably 5 to 45 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin. ) Can be selected from a range of degrees.

  In addition, when using a curing catalyst, as the usage-amount of a curing catalyst, although it does not restrict | limit, For example, 0.001-10 mass parts (preferably 0.01-5 mass parts with respect to 100 mass parts of epoxy resins, Furthermore, Preferably, it can select from the range of 0.1-2 mass parts).

  In the present invention, the epoxy resin composition contains additives [for example, fillers (calcium carbonate, kaolin, clay, talc, silica, silica sand, etc.), plasticizers, pigments (titanium oxide, carbon black, etc.), dyes, aging. Inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, adhesion promoters, dispersants, thixotropic agents (eg fumed silica, amide wax, vegetable oil derivatives, fibrillated fibers) Etc.), reactive diluents, extenders, modifiers, polymer powders (for example, acrylic polymer powders, etc.)] and other latent curing agents (for example, other ketimine compounds, aldimine compounds, Oxazolidine compounds, etc.) and viscosity modifiers (for example, solvents such as ketones, aromatic hydrocarbons, aliphatic hydrocarbons, etc.) may be included. In addition, the epoxy resin composition includes, for example, a modified silicone, a silyl group-terminated urethane polymer, a polymer having a silyl group and a main chain having a polyoxyalkylene skeleton, as long as adhesion and adhesion are not impaired. In addition, a carboxylic acid vinyl ester compound may be added. Moreover, these compounding ratios can be appropriately selected from known or commonly used ratios.

  Since the epoxy resin composition of the present invention uses a ketimine composition that does not cause aggregation or localization of carbonate even in an atmosphere of a petroleum solvent or a weak solvent, it is soluble in a petroleum solvent or a weak solvent as an epoxy resin. And a weak solvent-type epoxy resin composition using a petroleum solvent or a weak solvent as a solvent (viscosity modifier). The solid content concentration in the epoxy resin composition (including the weak solvent type epoxy resin composition) is, for example, about 10 to 75% by mass, and preferably about 30 to 70% by mass.

  The petroleum solvent is a paraffinic solvent, a naphthenic solvent or an aromatic solvent, and may be a single component solvent or a mixed solvent. As the petroleum solvent, those having a paraffinic solvent and naphthenic solvent content of more than 50% by mass, or those having an aromatic solvent content of 50% by mass or less are preferable. Among petroleum-based solvents, examples of the mixed solvent include mineral spirit, white spirit, mineral terpene, isoparaffin, solvent kerosene, aromatic naphtha, VM & P naphtha, and solvent naphtha. As commercial products of mineral spirits, Pegasol 3040 (manufactured by ExxonMobil), Swaclean 150 (manufactured by Maruzen Petrochemical), Solvesso 100 (manufactured by Asahi Kasei), Solvent (LAWS) (manufactured by Showa Shell Sekiyu), Isopar H ( Exxon Mobil Corporation). Other commercially available petroleum-based solvents include Isopar E, Isopar G, A Solvent (above, Shin Nippon Oil Co., Ltd.) Pegasol AN45, Exxon Naphtha No. 6. Exxon naphtha no. 5. Exxon naphtha no. 3. Exol D40, Exol D80 (exxon mobile), IP solvent 1620, IP solvent 2028 (ex, Idemitsu Petrochemical). Examples of the single-component solvent include paraffinic solvents such as n-butane, n-hexane, n-heptane, n-octane, isononane, n-decane, n-dodecane, cyclobutane, cyclopentane, and cyclohexane, or naphthenic solvents. A solvent is mentioned. The weak solvent is an organic solvent corresponding to the third type organic solvent and the third type organic solvent of the Industrial Safety and Health Law, and most of the petroleum solvents correspond to weak solvents. Petroleum solvents, especially those with a low aromatic solvent content, are suitable for refurbishment because they have the property of not easily attacking the coating film and substrate that have already been formed. Can be useful.

  In addition, since the epoxy resin composition of the present invention uses a ketimine composition modified with urethane, a cured product having improved physical properties such as toughness compared to an epoxy resin composition using a conventional ketimine. Is obtained. Moreover, even if the epoxy resin composition of the present invention is a one-component curable composition, the storage stability is extremely excellent. However, once the one-component curable composition is taken out of the container, the moisture in the air causes hydrolysis of the ketimine compound to produce an amine compound, which reacts with the epoxy resin to form a crosslinked structure. Is formed and curing proceeds, and excellent mechanical strength and adhesiveness are exhibited. In addition, by selecting a ketimine compound, the hydrolysis rate due to moisture in the air can be increased, so the curing rate of the epoxy resin is also increased, the adhesiveness is exhibited very quickly, and excellent mechanical strength Can also be expressed. Thus, the epoxy resin composition of the present invention can be used as a substantially one-component curable composition. When used as an adhesive, a coating agent, etc., excellent initial adhesion ( Initial adhesiveness, initial adhesion, etc.) can be exhibited. Moreover, when the curable composition is a two-component curable composition, excellent initial adhesion (initial adhesiveness, initial adhesiveness, etc.) can be exhibited similarly.

  The epoxy resin composition (curable composition) of the present invention comprises an adhesive [for example, an adhesive for automobile interior, an adhesive for various vehicles (for example, an adhesive used for vehicles such as trains), an adhesive for building interior construction. Agents, adhesives for building materials, adhesives for electrical and electronic parts, furniture adhesives, household adhesives, etc.], coating agents [eg, paints (eg concrete paints, metal paints, wood paints, tiles) Paints, paints for plastics, heavy anti-corrosion paints, top coats, floor polishes, etc.], undercoats (undercoats), and binders (for example, inks, pigment prints, ceramic materials, nonwoven fabrics, fiber sizing agents, rubbers) , Binders in wood flour, etc.), sealing materials, sealing materials (sealers), potting materials, putty materials, primer materials, laminate materials, sizing agents, etc. Can.

  As described above, the epoxy resin composition (one-component or two-component curable composition) of the present invention can be used in a wide range of applications, and has adhesiveness (adhesiveness) to a wide range of substrates. And various physical properties (flexibility, adhesiveness, gloss, etc.) can be improved, and can be used with excellent workability in various applications. In particular, by using a curing catalyst, excellent rapid curability can also be exhibited. For example, when used as an adhesive, it can improve the fit, so it is necessary for curing and temporary pressing during bonding. Short work time, good workability for bonding adherends to each other, and work time can be greatly reduced. On the other hand, when used as a coating agent, it can be used for curing application layers (coating films). The time required is short, and also in this case, the workability of forming the coating layer on the coated body is good, and the working time can be greatly shortened.

  When the epoxy resin composition is used as an adhesive, both adherends may be either porous or nonporous as adherends (applicable base materials), but at least one of them is porous. It is preferable that it is quality. Such adherends may be adherends made of the same material or adherends made of different materials. Moreover, when utilizing a curable composition as a coating agent, the to-be-coated body (application base material) in which a coating layer is formed is not restrict | limited in particular, Either porous or a non-porous may be sufficient.

  More specifically, the epoxy resin composition of the present invention is an epoxy resin composition, but also for inorganic materials (concrete, etc.) and metal materials (aluminum, stainless steel, etc.) as well as various plastic materials. Good adhesion (adhesion, adhesion, etc.) can be exhibited. Therefore, the epoxy resin composition of the present invention can be used in various applications (adhesion, film formation, etc.), for example, inorganic materials (eg, concrete, mortar, tile, stone, etc.), metal materials (eg, aluminum, copper, Iron, stainless steel, etc.), wood materials (eg, wood, chipboard, particle board, hardboard, wood boards such as MDF, plywood, etc.), paper materials (eg, paper such as corrugated paper, paperboard, kraft paper, paper similar Substances, processed paper such as moisture-proof paper), fiber materials (eg, non-woven fabrics, woven fabrics, etc.), leather materials, glass materials, porcelain materials, various plastic materials [eg, polyvinyl chloride, polyamide (nylon), polyester (polyethylene) Terephthalate, polyethylene naphthalate, etc.), styrene resin (polystyrene, acrylonitrile-butane) Ene-styrene copolymer, butadiene-styrene copolymer, etc.), polyurethane, olefin resin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), acrylic resin (polyacrylate ester, polymethacrylate ester, etc.) , Polycarbonate resin, etc.], rubber materials [e.g., natural rubber; olefin rubber (ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, etc.), styrene rubber (styrene-isoprene copolymer rubber). , Styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, etc.), polyisoprene rubber, polybutadiene rubber, synthetic rubber such as silicon rubber, etc.] For various base materials It is possible to apply. The shape of these base materials is not particularly limited, and may be any shape such as a film or sheet shape, a plate shape, a prism shape, or a column shape. Moreover, when a base material is formed with the plastic material, a foam etc. may be sufficient.

  In addition, when applying to these base materials, well-known thru | or usual methods, such as application | coating with a brush, a roller, spraying, immersion, etc., are employable. Moreover, after apply | coating the epoxy resin composition of this invention to a base material (a to-be-adhered body, a to-be-coated body etc.), it can dry on various drying conditions (natural drying, forced drying, etc.).

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In the following, “part” means “part by mass”, “%” means “mass%”, and “ppm” means “mass ppm” unless otherwise specified. Mw represents a weight average molecular weight.

The materials used in the examples and comparative examples are as follows.
[Amine compound A]
(1) Norbornanediamine (trade name “NBDA”, manufactured by Mitsui Chemicals; may be referred to as “amine (A1)”)
(2) Isophoronediamine (trade name “IPDA”, manufactured by PTI Japan Ltd .; sometimes referred to as “amine (A2)”)
(3) 1,3-bis (aminomethyl) cyclohexane (trade name “1,3-BAC”, manufactured by Mitsubishi Gas Chemical Company; may be referred to as “amine (A3)”)
[Ketone Compound B]
(1) Diethyl ketone (sometimes called "ketone (B1)")
(2) Methyl isobutyl ketone (sometimes called "ketone (B2)")

[Ketimine]
(1) Product name “Versamine 15N” [DETA (diethylenetriamine) / MIBK (methyl isobutyl ketone) / styrene oxide; ketimine conversion rate 92%; manufactured by Cognis Japan Co., Ltd.]

[Polyol compound E]
(1) Hydrogenated polybutadiene diol (1,2-addition only) (trade name “GI2000”, manufactured by Nippon Soda Co., Ltd., weight average molecular weight 2352; sometimes referred to as “polyol (E1)”)
(2) Hydrogenated polybutadiene diol (1,2-addition only) (trade name “GI1000”, manufactured by Nippon Soda Co., Ltd., weight average molecular weight 1621; sometimes referred to as “polyol (E2)”)
(3) Hydrogenated polybutadiene diol (1,2-addition only) (trade name “GI3000”, manufactured by Nippon Soda Co., Ltd., weight average molecular weight 3869; sometimes referred to as “polyol (E3)”)
(4) Polybutadiene diol (1,2-addition only) (trade name “G3000”, manufactured by Nippon Soda Co., Ltd., weight average molecular weight 3421; sometimes referred to as “polyol (E4)”)
(5) Polyisoprene diol (trade name “Poly ip”, manufactured by Idemitsu Oil Co., Ltd., weight average molecular weight 2387; sometimes referred to as “polyol (E5)”)
(6) Polybutadiene diol (1,2-addition + 1,4-addition) (trade name “R45-HT”, manufactured by Idemitsu Oil Co., Ltd., weight average molecular weight 2407; sometimes referred to as “polyol (E6)”)
(7) Polypropylene glycol (trade name “Sumiphen 3600K”, manufactured by Sumika Bayer Urethane Co., Ltd .; sometimes referred to as “polyol (E7)”)

[Polyisocyanate compound F]
(1) Isophorone diisocyanate (trade name “Desmodur I”, manufactured by Sumika Bayer Urethane Co., Ltd .; sometimes referred to as “polyisocyanate (F1)”)
(2) 4,4′-diphenylmethane diisocyanate (trade name “G412”, manufactured by Sumika Bayer Urethane Co., Ltd .; sometimes referred to as “polyisocyanate (F2)”)

[Method for measuring ketiminization rate of amine compound]
The reaction mixture containing the ketimine compound is dissolved in toluene, and the mass (M ₁ ) of the ketimine compound not having the primary amino group (ketimine compound C) and the primary amino group are determined by gas chromatography measurement. The mass (M ₂ ) of the compound (the ketimine compound D having a primary amino group + the unreacted amine compound A) is obtained, and the ketimineization rate (mass%) of the amine compound is obtained using the following formula To calculate. The ketimine conversion rate is the ratio of the peak area of the gas chromatogram [the peak area of the ketimine compound having no primary amino group (ketimine compound C) / {the ketimine compound having no primary amino group (ketimine compound). The peak area of C) + a compound having a primary amino group (a peak area of a ketimine compound D having a primary amino group + an unreacted amine compound A) × 100].
Ketiminization rate (%) = [M ₁ / (M ₁ + M ₂ )] × 100

The measurement conditions in gas chromatography measurement are as follows.
(Measurement conditions for gas chromatography)
Measurement method: FID method Column temperature: After 1 minute at 80 ° C., the temperature is increased to 280 ° C. at a temperature increase rate of 10 ° C./min, and the condition is 280 ° C. for 1 minute. Temperature: 280 ° C. (Injection) 280 ° C (Detector)
Carrier gas: helium (He) (flow rate: 30 ml / min), hydrogen (H ₂ ) (flow rate: 30 ml / min), air (flow rate: 400 ml / min)

Preparation Example 1 (Preparation of urethane prepolymer)
A dehydration treatment was performed by stirring 300 g of polyol (E1) [hydrogenated polybutadiene diol (1,2-addition only)] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 56.63 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G1) (Mw: 2796, NCO: 3.00%).

Preparation Example 2 (Preparation of urethane prepolymer)
A dehydration treatment was performed by stirring 300 g of polyol (E2) [hydrogenated polybutadiene diol (1,2-addition only)] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 82.17 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G2) (Mw: 2065, NCO: 4.07%).

Preparation Example 3 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E3) [hydrogenated polybutadiene diol (1,2-addition only)] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture is cooled to 80 ° C., 34.43 g of polyisocyanate (F1) (isophorone diisocyanate) is added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) is added. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G3) (Mw: 4313, NCO: 1.95%).

Preparation Example 4 (Preparation of urethane prepolymer)
210 g of polyol (E1) [hydrogenated polybutadiene diol (1,2-addition only)] was stirred at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour for dehydration treatment. Thereafter, the mixture was cooled to 80 ° C., 44.64 g of polyisocyanate (F2) (4,4′-diphenylmethane diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst ( 100 ppm of a trade name “Stan BL” (manufactured by Sankyo Co., Ltd.) was added and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G4) (Mw: 2852, NCO: 2.95%).

Preparation Example 5 (Preparation of urethane prepolymer)
A dehydration treatment was performed by stirring 300 g of polyol (E1) [hydrogenated polybutadiene diol (1,2-addition only)] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 48.14 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 1.70], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G5) (Mw: 2796, NCO: 3.00%).

Preparation Example 6 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E4) [polybutadienediol (1,2-addition only)] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 38.94 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G6) (Mw: 3865, NCO: 2.17%).

Preparation Example 7 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E5) (polyisoprene diol) at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 55.82 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sankyo Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G7) (Mw: 2831, NCO: 2.97%).

Preparation Example 8 (Preparation of urethane prepolymer)
300 g of polyol (E6) [polybutadienediol (1,2-addition + 1,4-addition)] was stirred at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour for dehydration treatment. Thereafter, the mixture was cooled to 80 ° C., 55.34 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G8) (Mw: 2851, NCO: 2.95%).

Preparation Example 9 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E7) (polypropylene glycol) at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 56.63 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added. 100 ppm, manufactured by Sankyo Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G9) (Mw: 2444, NCO: 3.44%).

Example 1
154 parts of amine (A1) (norbornanediamine) and 344 parts of ketone (B1) (diethylketone) are placed in a flask, and the temperature at which the ketone (B1) is refluxed while removing the water formed by azeotropic distillation (120 to 150 ° C. ) For 12 hours under reflux, the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and a reaction product containing a ketimine compound (sometimes referred to as "reaction product (H1)") ) The ketiminization rate was 95.8%.
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 2
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
The reaction product (H1) 100 parts and the urethane prepolymer (G2) 100 parts obtained in Preparation Example 2 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 3
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G3) obtained in Preparation Example 3 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 4
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G4) obtained in Preparation Example 4 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 5
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G5) obtained in Preparation Example 5 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 6
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G6) obtained in Preparation Example 6 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 7
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 5 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 8
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 1 part of the urethane prepolymer (G1) obtained in Preparation Example 1 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 9
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 39 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 10
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G7) obtained in Preparation Example 7 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 11
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G8) obtained in Preparation Example 8 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 12
Ketimine prepared from diethylenetriamine and methyl isobutyl ketone (secondary amino group is blocked by styrene oxide) (trade name “Versamine 15N”; ketimination rate 92%; manufactured by Cognis Japan) and Preparation Example 1 100 parts of the urethane prepolymer (G1) obtained in the above was stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition.

Example 13
170 parts of amine (A2) (isophoronediamine) and 344 parts of ketone (B1) (diethylketone) are placed in a flask, and the temperature at which the ketone (B1) is refluxed while removing the produced water by azeotropic distillation (120 to 150 ° C. ) For 24 hours under reflux, the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and a reaction product containing a ketimine compound (sometimes referred to as "reaction product (H2)") ) The ketiminization rate was 91.8%.
100 parts of the reaction product (H2) and 100 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Example 14
142 parts of amine (A3) [1,3-bis (aminomethyl) cyclohexane] and 400 parts of ketone (B2) (methyl isobutyl ketone) are placed in a flask, and water formed is removed azeotropically, while ketone (B2) Is reacted at reflux temperature (120 to 150 ° C.) for 24 hours, and then the ketone (B2) is removed by distillation under reduced pressure using an evaporator to obtain a reaction product containing a ketimine compound (“reaction product” (H3) ”). The ketiminization rate was 94.2%.
100 parts of the reaction product (H3) and 100 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Comparative Example 1
A reaction product (“reaction product (H1)”) containing a ketimine compound obtained in the same manner as in Example 1 was used as the ketimine composition.

Comparative Example 2
In the same manner as in Example 1, a reaction product containing a ketimine compound (“reaction product (H1)”) was obtained (ketimination rate 95.8%).
100 parts of the reaction product (H1) and 100 parts of the urethane prepolymer (G9) obtained in Preparation Example 9 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a ketimine composition. .

Evaluation test About the ketimine composition obtained in Examples 1-14 and Comparative Examples 1-2, the solubility test was done as follows.
30 g of mineral spirit (trade name “Pegasol 3040”, manufactured by ExxonMobil Co., Ltd.) was placed in a glass bottle, and 6 g of each ketimine composition was placed therein and left at 5 ° C. for 3 days. The case where no cloudiness or precipitation was generated was evaluated as “◯”, and the case where cloudiness or precipitation was confirmed was evaluated as “x”. As a result, all the ketimine compositions obtained in Examples 1 to 14 were evaluated as “◯”. On the other hand, all the ketimine compositions obtained in Comparative Examples 1 and 2 were evaluated as “x”. The above results are summarized in Tables 1 and 2. In the table, the numbers in the columns of polyol compound E and polyisocyanate compound F indicate the number of grams. “◯” in the column of ketimine reaction product H means that the component was used.
In addition, about the ketimine composition obtained in Example 1, 3, 4, 5, 9, 13, and 14, the solubility test similar to the above was performed except having used 30 g of hexane instead of said mineral spirit. In this case, however, no cloudiness or precipitation was observed.
Moreover, about the ketimine composition obtained in Example 1, instead of said mineral spirit, Pegasol 3040 (made by ExxonMobil Co., Ltd.), Swaclean 150 (made by Maruzen Petrochemical Co., Ltd.), Solvesso 100 (made by Asahi Kasei Co., Ltd.), A solubility test similar to the above was performed except that 30 g of Solvent (LAWS) (manufactured by Showa Shell Sekiyu KK) or Isopar H (manufactured by ExxonMobil Corp.) was used. Production was not observed.

Claims (11)

Following formula (1)

(In the formula, R ¹ represents an organic group, and n represents an integer of 2 or more)
An amine compound A represented by the following formula (2)

(In the formula, R ² and R ³ each represent an organic group. R ² and R ³ may be bonded to each other to form a ring together with adjacent carbon atoms).
A reaction product obtained by reacting with a ketone compound B represented by the formula (3), wherein the amine compound A has a ketimination rate of 80% or more,

(In the formula, R ¹ , R ² , R ³ and n are the same as above. R ² and R ³ may be bonded to each other to form a ring together with adjacent carbon atoms)
A ketimine compound C represented by formula (4):

(In the formula, k and m each represent an integer of 1 or more, and k + m = n. R ¹ , R ² , R ³ and n are the same as above. R ² and R ³ are adjacent to each other. (It may form a ring with carbon atoms)
For a reaction product containing at least one of the ketimine compound D having an amino group represented by formula (1) and the unreacted amine compound A, the following formula (5):

(Wherein R ⁴ is a polyvalent hydrocarbon group, and p is an integer of 2 or more)
And a polyol compound E represented by the following formula (6)

(Wherein R ⁵ represents an organic group, and q represents an integer of 2 or more)
A ketimine composition obtained by reacting a urethane prepolymer G having an isocyanate group at the molecular chain terminal obtained by reaction with a polyisocyanate compound F represented by the formula: The ketimine composition according to claim 1, wherein in the polyol compound E, R ⁴ in the formula (5) is a polyvalent hydrocarbon group having no unsaturated group.   The ketimine composition according to claim 1 or 2, wherein the polyol compound E has a weight average molecular weight of 2000 or more.   The ketimine composition according to any one of claims 1 to 3, wherein the polyisocyanate compound F is a non-aromatic polyisocyanate compound.   The ketimine composition according to any one of claims 1 to 4, wherein the polyisocyanate compound F is isophorone diisocyanate.   The ketimine composition according to any one of claims 1 to 5, wherein the ketimine conversion rate of the amine compound A is 90 to 99.5%. In the ketone compound B, the formula ⁽²⁾ R 2, R ³ are ketimine composition according to any one of claims 1 to 6 are both number 2 or more hydrocarbon group having a carbon in. In the ketone compound B, the formula (2) ketimines composition according to any one of claims 1 to 7 R ^2, R ³ are both ethyl groups in the.   The epoxy resin composition comprised by the ketimine composition and epoxy resin as described in any one of Claims 1-8.   The epoxy resin composition according to claim 9, further comprising a petroleum solvent.   The epoxy resin composition according to claim 9 or 10, further comprising a dehydrating agent.