JP2008285520A - Ketimine composition and epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ketimine composition which is prepared by a method for modifying various kinds of ketimines with a urethane and further a curable resin composition having improved internal curability. <P>SOLUTION: The ketimine composition comprises a ketimine compound and a urethane modified ketimine compound prepared by reacting a reaction product that is prepared by reacting a primary amine compound represented by formula (1) with a ketone compound represented by formula (2), in which the ketimination rate of the primary amine is ≥80%, with a urethane prepolymer containing an isocyanate group at the molecular chain terminal obtained by reacting a polyol compound with a polyisocyanate compound. The curable resin composition comprises the ketimine composition and an epoxy resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a urethane-modified ketimine composition and an epoxy resin composition containing the ketimine composition. The present invention also relates to a room temperature curing type hard one-part epoxy resin composition having excellent internal curability (deep part curability). This epoxy resin composition is useful as various moisture-curing treatment agents (adhesives, coating agents, etc.). Here, the “ketimine composition” in the present invention refers to a ketimine compound in which all the primary amino groups contained in the primary amine compound are ketiminated, and a part of the primary amino groups remaining without being ketiminized. Is composed of a urethane-modified ketimine compound modified with urethane and has a function as a latent curing agent.

  Conventionally, the urethane modification of ketimine compounds is limited to those having a hydroxyl group or a secondary amino group at the end, and there is a limit to the structures of ketimines that can be used (see Patent Documents 1 and 2). In addition, with respect to urethane modification of ketimine compounds having primary amino groups, when ketimine with a ketiminization rate of 80% or less is added to the urethane prepolymer, gelation proceeds and it is very difficult to maintain in liquid form. Therefore, there is known a method of mixing two separately prepared ketimines having primary amino groups and an isocyanate group-terminated urethane prepolymer at the time of use, and curing them as they are (see Patent Document 3). ) No one-component type is known.

  On the other hand, the conventional moisture curable resin composition has a problem that the inside of the resin is difficult to be cured because the curing starts with moisture in the air. Therefore, a method of adding water has been taken to improve internal curability. However, this method has a problem that water is difficult to disperse in the resin and uniform curing is difficult to proceed, and when water remains in the resin, the physical properties are remarkably deteriorated.

Japanese Patent Publication No. 7-107039 JP 2001-302769 A JP 2003-113217 A

  Accordingly, an object of the present invention is to provide a ketimine composition having a wide variety of structures and an epoxy resin composition containing the ketimine composition. Another object of the present invention is to provide a room temperature curable epoxy resin composition having excellent internal curability.

  As a result of intensive studies to solve the above problems, the present inventors are reaction products in which the ketimine compound obtained by reacting a primary amine and a ketone has a ketimination rate of a certain value or more. When a urethane prepolymer having a terminal isocyanate group having a specific structure is reacted with a reaction product containing a ketimine having no primary amino group, a ketimine compound having a primary amino group and / or an unreacted primary amine Although it is a ketimine having a primary amino group, it reacts mildly with the isocyanate group of the urethane prepolymer and does not cause gelation, so that urethane-modified ketimine compounds having various structures can be obtained easily and efficiently. The present invention has been completed. Furthermore, an epoxy resin composition containing a ketimine composition obtained by reacting a urethane prepolymer having a terminal isocyanate group synthesized from a specific polyol compound and an isocyanate compound has an internal curability (deep curability without adding water). 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１級アミン化合物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１級アミン化合物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もよい）
で表される１級アミノ基を有するケチミン化合物Ｄと未反応の前記１級アミン化合物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は少なくともヘテロ原子を含む多価の有機基、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、ケチミン化合物Ｃとウレタン変性されたケチミン化合物を含有するケチミン組成物を提供する。 That is, the present invention provides the following formula (1):
Following formula (1)

(In the formula, R ¹ represents an organic group, and n represents an integer of 2 or more)
A primary amine compound A represented by 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 primary amine compound A has a ketimination rate of 80% or more,

(Wherein 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 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. A ring may be formed with a carbon atom)
For the reaction product containing at least one of the ketimine compound D having a primary amino group represented by the above and the unreacted primary amine compound A, the following formula (5):

(Wherein R ⁴ is a polyvalent organic group containing at least a hetero atom, 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 containing a ketimine compound C and a urethane-modified ketimine compound obtained by reacting a urethane prepolymer G having an isocyanate group at the molecular chain end obtained by the reaction with the polyisocyanate compound F represented by provide.

  The urethane prepolymer G is reacted at a ratio of 1 to 5 moles of isocyanate groups with respect to 1 mole of the total amount of primary amino groups of the ketimine compound D having primary amino groups and the unreacted primary amine compound A. It is preferable to do so.

  As the polyisocyanate compound F, a non-aromatic polyisocyanate compound is preferable, and isophorone diisocyanate is particularly preferable.

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

R ² and R ³ in the ketone compound B 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 polyol compound E is preferably at least one polyol compound selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols. Further, the polyol compound E is preferably a polyether polyol containing 5 to 40% by mass of oxyethylene units, the polyol compound E is preferably a copolymer of polyethylene glycol and polypropylene glycol, and the polyol compound E is further polyethylene glycol / polypropylene glycol / Polyethylene glycol block copolymers are preferred.

  The ketimine composition of the present invention includes an acrylic copolymer-containing ketimine composition obtained by polymerizing an acrylic monomer in the ketimine composition. As the acrylic monomer, it is particularly preferable to use an acrylic monomer containing a reactive silyl group.

  The present invention also provides an epoxy resin composition comprising the ketimine composition and an epoxy resin. This epoxy resin composition may further contain a dehydrating agent. A silane compound is preferable as the dehydrating agent.

  The ketimine composition of the present invention comprises a ketimine compound having a primary amino group and / or unreacted by using a ketimine compound in which a polyfunctional amine is ketiminized at a high ketiminization rate and all functional groups are ketiminized. A urethane-modified ketimine compound can be obtained without gelation by allowing the reaction between the primary amino group and the isocyanate group contained in the primary amine to proceed mildly. Therefore, a wide variety of ketimine compositions can be provided. Moreover, since the urethane prepolymer containing an organic group containing a hetero atom as a structural unit is reacted, the ketimine composition comes to have hydrophilicity, and when the epoxy resin composition containing such a ketimine composition is cured. In this case, moisture easily passes from the surface of the coating to the inside, and the internal curability can be improved without adding water. Moreover, according to the epoxy resin composition of this invention, resin (hardened | cured material) excellent in toughness can be obtained. Furthermore, by curing the acrylic polymer-containing urethanized ketimine composition, a resin (cured product) excellent in flexibility and weather resistance can be obtained.

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

[Primary amine compound A]
In the primary 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 primary 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 primary 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 primary amine compound A, aliphatic polyamines, alicyclic polyamines, and araliphatic polyamines are preferable, and alicyclic polyamines are particularly preferable. The primary 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 primary amine compound A and ketone compound B]
In the reaction product of the primary amine compound A and the ketone compound B in the present invention (hereinafter sometimes referred to as “reaction product H”), the ketimineization rate of the primary 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 95%. A ketiminization rate of less than 80% is not preferred because it tends to gel or increase viscosity. The ketiminization rate can be determined by the method described later.

  The reaction between the primary amine compound A and the ketone compound B is not particularly limited, and a known method can be employed. For example, the primary 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.), and then heated to reflux, as necessary. This can be done by removing the water produced by azeotropic distillation. 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 tetrabutoxytitanium. The dehydrating agent is preferably a liquid that has no reactivity with amines.

  In this reaction, either one of the primary amine compound A and the ketone compound B (particularly the ketone compound B) may be used in excess. The reaction temperature varies depending on the types of primary 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 primary amine compound A can be removed by distillation or the like.

  The ketiminization rate of the primary amine compound A can be controlled by the charged molar ratio of the primary 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 includes the ketimine compound C having a primary amino group represented by the formula (4) and the ketimine compound C having no amino group represented by the formula (3), which is the main product. It contains at least one of the primary amine compounds A of the reaction.

[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 organic group containing at least a hetero atom, and p represents an integer of 2 or more. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the polyvalent organic group containing at least a hetero atom include a polyvalent hydrocarbon group, an ether group (—O—), a thioether group (—S—), an amino group (—NR′—), and a carbonyl group. A polyvalent organic group composed of a combination with a heteroatom-containing group such as (—CO—) can be mentioned. R ′ represents a hydrogen atom, an alkyl group, or an amino-protecting group. As the polyvalent hydrocarbon group, a saturated or unsaturated linear or branched polyvalent aliphatic hydrocarbon group (an alkylene group, an alkenylene group, an alkanetriyl group, an alkenetriyl group, etc.), Multivalent alicyclic hydrocarbon group (1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene A cycloalkylene group such as a cyclohexylidene group; a cycloalkylidene group such as a cyclohexylidene group; a multivalent bridge such as a norbornane-2,3-diyl group, norbornane-2,5-diyl group, norbornane-2,6-diyl group Cyclic 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.), It includes polyvalent hydrocarbon groups bonded above.

  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 preferred polyol compound E is preferably at least one polyol compound selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols. More preferably, the polyol compound E is a polyether polyol containing 5 to 40% by weight of oxyethylene units, more preferably the polyol compound E is a copolymer of polyethylene glycol and polypropylene glycol, more preferably the polyol compound E is polyethylene glycol / polypropylene. It is a block copolymer of glycol / polyethylene glycol.

  When the polyol compound E is a copolymer of polyethylene glycol and polypropylene glycol, the composition has a polyethylene glycol / polypropylene glycol mass% ratio of, for example, 0/100 to 100/0, preferably 5/95 to 80/20, More preferably, it is 40/60. The composition of the polyol compound E is preferably a block copolymer of polyethylene glycol / polypropylene glycol / polyethylene glycol as compared to a random copolymer of polyethylene glycol / polypropylene glycol.

  The weight average molecular weight of the polyol compound E is 500-10000, for example, Preferably, it is 1000-5000. If this average molecular weight is less than 500, the effect of imparting flexibility tends to be low, and the viscosity tends to increase. On the other hand, if it exceeds 10,000, it is necessary to add a large amount of catalyst to the prepolymer synthesis, and the physical properties tend to be lowered.

  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. Further, if the NCO / OH (molar ratio) exceeds 3, the remaining polyisocyanate compound increases, so that the reaction between the primary amino group and the polyisocyanate proceeds rapidly, and gelation easily occurs, or high viscosity There is a possibility. 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 2 in the reaction product H). ) (Molar ratio) is 0.0001 to 5, preferably 0.005 to 4, more preferably about 0.01 to 3. The amount of the urethane prepolymer G having an isocyanate group at the molecular chain terminal is 100 parts by mass in total of the ketimine compound C, the ketimine compound D having a primary amino group, and the primary amine compound A in the reaction product H. Is 0.1 to 300 parts by mass, preferably 0.5 to 200 parts by mass, and more preferably 1 to 100 parts by mass. When the amount of the urethane prepolymer G is too small, the terminal primary amino group is not blocked with an isocyanate group, and the stability when blended in a resin as a latent curing agent is lowered. On the other hand, when the amount of the urethane prepolymer G is too large, the content of urethane exhibiting flexibility increases, and the physical properties deteriorate. The reaction temperature is, for example, 0 to 100 ° C, preferably 30 to 70 ° C.

[Acrylic polymer-containing ketimine composition]
The ketimine composition of the present invention includes an acrylic polymer-containing ketimine composition obtained by polymerizing an acrylic monomer in the above-mentioned ketimine composition. Since such a composition polymerizes an acrylic monomer in the ketimine composition, the acrylic polymer is compared with a composition obtained by separately preparing an acrylic polymer and mixing with the ketimine. There is an advantage that a step for removing the solvent used in the preparation is not required. Moreover, since the primary amine compound is hardly contained in the ketimine composition (the primary amine is reacted with the isocyanate group of the urethane prepolymer), polymerization inhibition due to the chain transfer action of the primary amine is prevented. It does not occur and polymerization proceeds smoothly. The acrylic polymer in the ketimine composition has an effect of improving the physical properties of a curable composition in which an amine-reactive compound such as an epoxy resin is used as a curing component (resin component).

  As an acryl-type monomer, (meth) acrylic acid ester etc. are mentioned, for example. Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, and (meth) acrylic acid aryl ester. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth (Meth) acrylic acid C1-20 alkyl esters such as hexyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate [preferably ( And (meth) acrylic acid C1-12 alkyl ester, more preferably (meth) acrylic acid C1-8 alkyl ester]. (Meth) acrylic acid cycloalkyl ester includes, for example, (meth) acrylic acid cyclohexyl. Examples of the (meth) acrylic acid aryl ester include (meth) acrylic acid phenyl ester.

  An acrylic monomer having a reactive silyl group can also be used as the acrylic monomer. When an acrylic monomer having a reactive silyl group is used, for example, when an epoxy resin composition is prepared, the compatibility between the resulting acrylic polymer and the epoxy resin is improved. Examples of the acrylic monomer having a reactive silyl group include (meth) acryloyloxymethyl-trimethoxysilane, (meth) acryloyloxymethyl-triethoxysilane, 2- (meth) acryloyloxyethyl-trimethoxysilane, 2 -(Meth) acryloyloxyethyl-triethoxysilane, 2- (meth) acryloyloxyethyl-tripropoxysilane, 2- (meth) acryloyloxyethyl-triisopropoxysilane, 2- (meth) acryloyloxyethyl-tri Butoxysilane, 3- (meth) acryloyloxypropyl-trimethoxysilane, 3- (meth) acryloyloxypropyl-triethoxysilane, 3- (meth) acryloyloxypropyl-tripropoxysilane, 3- (meth) acryloylo (Meth) acryloyloxyalkyl-trialkoxysilane such as cyclopropyl-triisopropoxysilane, 3- (meth) acryloyloxypropyl-tributoxysilane; (meth) acryloyloxymethyl-methyldimethoxysilane, (meth) acryloyloxymethyl- Methyldiethoxysilane, 2- (meth) acryloyloxyethyl-methyldimethoxysilane, 2- (meth) acryloyloxyethyl-methyldiethoxysilane, 2- (meth) acryloyloxyethyl-methyldipropoxysilane, 2- (meth ) Acryloyloxyethyl-methyldiisopropoxysilane, 2- (meth) acryloyloxyethyl-methyldibutoxysilane, 3- (meth) acryloyloxypropyl-methyldimethoxysilane, 3- (meth) ) Acryloyloxypropyl-methyldiethoxysilane, 3- (meth) acryloyloxypropyl-methyldipropoxysilane, 3- (meth) acryloyloxypropyl-methyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-methyldi Butoxysilane, 3- (meth) acryloyloxypropyl-ethyldimethoxysilane, 3- (meth) acryloyloxypropyl-ethyldiethoxysilane, 3- (meth) acryloyloxypropyl-ethyldipropoxysilane, 3- (meth) acryloyl Oxypropyl-ethyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-ethyldibutoxysilane, 3- (meth) acryloyloxypropyl-propyldimethoxysilane, 3- (meth) acryl Royloxypropyl-propyldiethoxysilane, 3- (meth) acryloyloxypropyl-propyldipropoxysilane, 3- (meth) acryloyloxypropyl-propyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-propyldibutoxy Examples include (meth) acryloyloxyalkyl-alkyldialkoxysilanes such as silane, and (meth) acryloyloxyalkyl-dialkyl (mono) alkoxysilanes corresponding to these. Acrylic monomers can be used alone or in combination of two or more. For example, the (meth) acrylic acid alkyl ester and an acrylic monomer having a reactive silyl group can be used as the acrylic monomer.

  In the present invention, a copolymerizable monomer copolymerizable with an acrylic monomer can be used together with the acrylic monomer. As copolymerizable monomers, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxyalkyl (meth) acrylate (carboxyethyl acrylate, etc.) and other carboxyl group-containing monomers Body; acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy (meth) acrylate Hydroxyl group-containing monomers such as hexyl, hydroxyoctyl (meth) acrylate; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Aminoethyl (meth) acrylate, N, N- (meth) acrylate Dimethylaminoethyl, t-butylaminoethyl (meth) acrylate, etc. Amino group-containing monomers; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; styrene monomers such as styrene and α-methylstyrene; olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene Body; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether; (Meth) such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Alkoxyalkyl acrylate monomers; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meta ) (N-substituted) acrylamide monomers such as acrylamide; N-vinyl carboxylic acid amides; N-vinyl lactams such as N-vinyl caprolactam; N-vinyl pyridine, N-vinyl pyrimidine, N-vinyl pyrazine, Heterocycle-containing vinyl systems such as N-vinylpyrrole, N-vinylimidazole, N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinyloxazole, N-vinylmorpholine Monomer; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol and other (meth) acrylic acid alkylene glycol monomers Styling Sulfonic acid group-containing vinyl monomers such as sulfonic acid and allyl sulfonic acid; Phosphoric acid group-containing vinyl monomers such as 2-hydroxyethylacryloyl phosphate; Other halogen atom-containing vinyl monomers such as vinyl chloride And polymerizable unsaturated monomers having a silicon atom-containing group whose specific examples are shown below.

  Examples of the copolymerizable monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol di (meth). Acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyldi ( Various polyfunctional monomers such as (meth) acrylate and hexyl di (meth) acrylate can be appropriately selected and used.

  Examples of the polymerizable unsaturated monomer having a silicon atom-containing group include compounds in which a vinyl group is directly bonded to a silicon atom in a reactive silyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltripropoxy. Vinyltrialkoxysilanes such as silane, vinyltriisopropoxysilane, vinyltributoxysilane; vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, vinylmethyldiisopropoxysilane, vinylmethyldibutoxysilane, vinyl Ethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldipropoxysilane, vinylethyldiisopropoxysilane, vinylethyldibutoxysilane, vinylpropyldimethoxysilane, vinylpropyldiethoxy Silane, vinyl propyl dipropoxy silane, vinyl propyl diisopropoxy silane, and (vinyl) alkyl dialkoxy silane such as vinyl propyl dibutoxy silane, such as those in the corresponding (vinyl) dialkyl (mono) alkoxysilanes.

  Further, as the polymerizable unsaturated monomer having a silicon atom-containing group, a compound in which a vinyl group is bonded to a silicon atom in a reactive silyl group through an alkylene group, such as vinylmethyltrimethoxysilane, vinylmethyl Triethoxysilane, β-vinylethyltrimethoxysilane, β-vinylethyltriethoxysilane, β-vinylethyltripropoxysilane, β-vinylethyltriisopropoxysilane, β-vinylethyltributoxysilane, γ-vinylpropyltri Vinylalkyltrialkoxysilanes such as methoxysilane, γ-vinylpropyltriethoxysilane, γ-vinylpropyltripropoxysilane, γ-vinylpropyltriisopropoxysilane, γ-vinylpropyltributoxysilane; β-vinylethylmethyldimethoxysilane , Β-vinylethylmethyldiethoxysilane, γ-vinylpropylmethyldimethoxysilane, γ-vinylpropylmethyldiethoxysilane, γ-vinylpropylmethyldipropoxysilane, γ-vinylpropylmethyldiisopropoxysilane, γ-vinylpropyl Methyldibutoxysilane, γ-vinylpropylethyldimethoxysilane, γ-vinylpropylethyldiethoxysilane, γ-vinylpropylethyldipropoxysilane, γ-vinylpropylethyldiisopropoxysilane, γ-vinylpropylethyldibutoxysilane, etc. (Vinylalkyl) alkyldialkoxysilanes and the corresponding (vinylalkyl) dialkyl (mono) alkoxysilanes can also be used.

  There is no particular limitation on the method for polymerizing the acrylic monomer in the ketimine composition. For example, the acrylic monomer is dropped into the ketimine composition to which a solvent is added as necessary, and polymerized appropriately. Any of a method of dropping a ketimine composition and an acrylic monomer into a solvent and polymerizing the same may be used.

  The amount of the acrylic monomer used is, for example, 1 to 100 parts by mass, preferably 5 to 100 parts by mass of the reaction product (excluding the solvent and diluent) of the reaction product H and the urethane prepolymer G. About 80 parts by mass.

  For the polymerization, a known or conventional polymerization initiator can be used. Examples of such a polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis (2,4-dimethyl). Initiated polymerization of azo compounds such as valeronitrile), 2,2'-azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile) And peroxide polymerization initiators such as benzoyl peroxide, t-alkyl peroxyester, acetyl peroxide, and diisopropyl peroxycarbonate.

  In the polymerization, additives such as a chain transfer agent and a diluent may be included as long as the stability is not affected. In addition, as said diluent, the ketone compound B etc. which are used at the time of ketimine composition preparation are mentioned. The diluent can be removed during the polymerization or after the polymerization. The polymerization temperature can be appropriately selected according to the type of acrylic monomer and polymerization initiator, and is usually about 20 to 200 ° C, preferably about 50 to 150 ° C.

  In the present invention, since the urethane prepolymer is reacted with the reaction product having a ketiminization rate of 80% or more as described above, the compound in which all functional groups (carbonyl groups) are ketiminated functions as a solvent. Since the reaction between the remaining primary amino group and the isocyanate group proceeds mildly and can be urethaned, urethane-modified ketimine can be obtained without gelation. Further, the obtained ketimine composition is derived from a polyol compound having an organic group containing a hetero atom (for example, at least one polyol compound selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol). Since the compound is contained, when the curable resin composition containing the ketimine composition is cured, moisture easily penetrates into the interior, so that the internal curability can be improved. By this invention, toughness can be provided to hardened | cured material by making the obtained ketimine composition react with each resin. Therefore, the ketimine composition of the present invention can be suitably used as a raw material for a curable resin composition such as an 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 the silane compound, in particular, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane (ethyl silicate); epoxies such as glycidoxyalkyltrialkoxysilane, glycidoxyalkylalkyldialkoxysilane and glycidoxyalkyldialkylalkoxysilane A silane compound having a group is preferred. Among these, tetraethoxysilane (ethyl silicate) is particularly preferable. 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 above-mentioned ketimine composition and 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, and 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 a ketimine compound (curing agent) or other component such as an auxiliary agent are put in different containers. It means that these are mixed at the time of use, and the mixture is applied to a predetermined site for use. Therefore, the two-pack type epoxy resin composition is basically mixed into two liquids at the time of use to make one liquid. In addition, it is practically impossible to sell as a one-pack type. An epoxy resin composition that can be used as a one-pack type is a two-pack type epoxy resin composition that includes an epoxy resin (polymer curing component: main agent) and other components such as a ketimine compound (curing agent) or an auxiliary agent. Can 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 (or thixotropic agents such as fumed silica, amide wax, vegetable oil derivatives, fibrillated fibers, etc. ), Reactive diluents, extenders, modifiers, polymer powders (eg, acrylic polymer powders, etc.)] and other latent curing agents (eg, other ketimine compounds, aldimine compounds, oxazolidine) System compounds) and viscosity modifiers (for example, solvents such as ketones, aromatic hydrocarbons, aliphatic hydrocarbons, etc.). In addition, the epoxy resin composition has, for example, a modified silicone, a urethane prepolymer, a silyl group-terminated urethane polymer, a silyl group, and a main chain having a polyoxyalkylene skeleton as long as the adhesion and adhesion are not impaired. Polymers, carboxylic acid vinyl ester compounds and the like may be added. Moreover, these compounding ratios can be appropriately selected from known or commonly used ratios.

  In addition, since the epoxy resin composition of the present invention uses a ketimine composition modified with urethane, the cured resin has improved physical properties such as toughness as compared with the conventional epoxy resin composition using ketimine. You can get things. In addition, the epoxy resin composition of the present invention is extremely excellent in storage stability as a one-component curable composition. 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 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. Similarly, a two-component curable composition can also exhibit excellent initial adhesion (such as initial adhesion and initial adhesion).

  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. The time is short, the workability for bonding adherends to each other is good, and the work time can be greatly shortened. On the other hand, when used as a coating agent, the time required for curing during the formation of the coating layer (coating film) is short, and in this case, the workability for forming the coating layer on the coated body is good and the working time is greatly increased. Can be shortened.

  When the epoxy resin composition is used as an adhesive, both adherends may be either porous or non-porous as adherends (applicable base materials), at least one of which is It is preferably porous. 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.

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

[Polyol compound E]
(1) Polypropylene glycol (trade name “3600K”, manufactured by Sumika Bayer Urethane Co., Ltd., weight average molecular weight 2000; sometimes referred to as “polyol (E1)”)
(2) Polyethylene glycol (trade name “PEG1000”, manufactured by NOF Corporation, weight average molecular weight 1007; sometimes referred to as “polyol (E2)”)
(3) Polyethylene glycol (trade name “PEG2000”, manufactured by Nippon Oil & Fats Co., Ltd., weight average molecular weight 2000; sometimes referred to as “polyol (E3)”)
(4) Polytetramethylene glycol ether / polyethylene glycol random copolymer; polytetramethylene glycol ether / polyethylene glycol mass ratio 38/62 (trade name “polyserine DC-1800E”, manufactured by NOF Corporation, weight average molecular weight 1715; may be referred to as “polyol (E4)”)
(5) Polyethylene glycol / polypropylene glycol block copolymer; polyethylene glycol / polypropylene glycol mass ratio 40/60 (trade name “Pronon # 104”, manufactured by NOF Corporation, weight average molecular weight 1670; “polyol (E5) ”)
(6) Polyethylene glycol / polypropylene glycol block copolymer; polyethylene glycol / polypropylene glycol mass ratio 40/60 (trade name “Pronon # 204”, manufactured by NOF Corporation, weight average molecular weight 3330; “polyol (E6) ”)
(7) Polyethylene glycol / polypropylene glycol block copolymer; polyethylene glycol / polypropylene glycol mass ratio 25/75 (trade name “PML-5005”, manufactured by Asahi Glass Co., Ltd., weight average molecular weight 3993; “polyol (E7)” There is)
(8) Polyethylene glycol / polypropylene glycol block copolymer; polyethylene glycol / polypropylene glycol mass ratio 8/92 (trade name “PML-5001”, manufactured by Asahi Glass Co., Ltd., weight average molecular weight 3978; “polyol (E8)” There is)
(9) Polyester polyol (trade name “eternacoll 3040”, manufactured by Ube Industries, Ltd., weight average molecular weight 3562; sometimes referred to as “polyol (E9)”)
(10) Polyethylene glycol / polypropylene glycol random copolymer; polyethylene glycol / polypropylene glycol mass ratio 70/30 (trade name “PR-3007”, manufactured by ADEKA, weight average molecular weight 3108; “polyol (E10)” There is)
(11) Polycarbonate polyol (trade name “eternacoll UH-200”, manufactured by Ube Industries, Ltd., weight average molecular weight 2000; sometimes referred to as “polyol (E11)”)
(12) Polytetramethylene ether glycol (trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 2000; sometimes referred to as “polyol (E12)”)

[Polyisocyanate compound F]
(1) Isophorone diisocyanate (IPDI) (trade name “Desmodur I”, manufactured by Sumika Bayer Urethane Co., Ltd .; sometimes referred to as “polyisocyanate (F1)”)
(2) Tolylene diisocyanate (TDI) (trade name “Cosmonate T-80”, manufactured by Mitsui Chemicals Polyurethanes; sometimes referred to as “polyisocyanate (F2)”)
(3) Diphenylmethane diisocyanate (MDI) (trade name “G412”, manufactured by Sumika Bayer Urethane Co., Ltd .; sometimes referred to as “polyisocyanate (F3)”)

[Method for Measuring Ketiminization Rate of Primary Amine Compound]
A reaction mixture containing a ketimine compound is dissolved in toluene, and the peak area of the ketimine compound having no primary amino group (ketimine compound C) and the primary amine compound as a raw material are analyzed by gas chromatography. The peak area A of the compound in which x out of n primary amino groups is ketiminated and the sum of the peak areas are obtained, and the ketimination ratio (% by mass) of the primary amine compound is calculated using the following formula.

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 (flow rate: 30 ml / min), air (flow rate: 400 ml / min)

Preparation Example 1 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E1) [polypropylene glycol] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 74.93 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.25], 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: 2444, NCO: 3.44%).

Preparation Example 2 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E2) [polyethylene glycol] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 148.81 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.25], 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: 1451, NCO: 6.65%).

Preparation Example 3 (Preparation of urethane prepolymer)
270 g of polyol (E3) [polyethylene glycol] 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., 84.50 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.82], 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 (G3) (Mw: 1443.3, NCO: 5.82%).

Preparation Example 4 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E4) [polytetramethylene glycol ether / polyethylene glycol random copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 87.38 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.25], 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 (G4) (Mw: 2159, NCO: 3.80%).

Preparation Example 5 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E5) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 89.73 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.25], 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: 2114, NCO: 3.94%).

Preparation Example 6 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E6) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 45.00 g of polyisocyanate (F1) (isophorone diisocyanate) was added [NCO / OH (molar ratio) = 2.25], 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: 3774, NCO: 2.23%).

Preparation Example 7 (Preparation of urethane prepolymer)
A dehydration treatment was performed by stirring 500 g of polyol (E7) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 55.70 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 (G7) (Mw: 4421.1, NCO: 1.90%).

Preparation Example 8 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 500 g of polyol (E8) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 55.81 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 as a catalyst. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G8) (Mw: 4421.1, NCO: 1.90%).

Preparation Example 9 (Preparation of urethane prepolymer)
A dehydration treatment was performed by stirring 500 g of polyol (E7) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 55.60 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 (G9) (Mw: 4437.0, NCO: 1.89%).

Preparation Example 10 (Preparation of urethane prepolymer)
A dehydration treatment was performed by stirring 500 g of polyol (E6) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 66.67 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 as a catalyst. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G10) (Mw: 3774.0, NCO: 2.23%).

Preparation Example 11 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E9) [polyester polyol] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 37.39 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 (G11) (Mw: 4006, NCO: 2.10%).

Preparation Example 12 (Preparation of urethane prepolymer)
430 g of polyol (E7) [polyethylene glycol / polypropylene glycol block copolymer] 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., 37.48 g of polyisocyanate (F2) (tolylene diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “stan BL "(manufactured by Sankyo Co., Ltd.) was added at 100 ppm, followed by stirring at 80 ° C. for 2 hours to obtain a urethane prepolymer (G12) (Mw: 4341.0, NCO: 1.94%).

Preparation Example 13 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 500 g of polyol (E6) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 52.25 g of polyisocyanate (F2) (tolylene diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “stan BL "(manufactured by Sankyo Co., Ltd.) was added at 100 ppm and stirred at 80 ° C for 2 hours to obtain a urethane prepolymer (G13) (Mw: 3678.0, NCO: 2.28%).

Preparation Example 14 (Preparation of urethane prepolymer)
393 g of polyol (E6) [polyethylene glycol / polypropylene glycol block copolymer] 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., 59.01 g of polyisocyanate (F3) (diphenylmethane diisocyanate) was added [NCO / OH (molar ratio) = 2.00], and a tin-based catalyst (trade name “Stan BL”) was added as a catalyst. “Sanshaiki Co., Ltd.) 100 ppm was added and stirred at 80 ° C. for 2 hours to obtain urethane prepolymer (G14) (Mw: 3830.0, NCO: 2.19%).

Preparation Example 15 (Preparation of urethane prepolymer)
380 g of polyol (E10) [polyethylene glycol / polypropylene glycol random copolymer] 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., 54.35 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 as a catalyst. 100 ppm, manufactured by Sansha Co., Ltd.) and stirred at 80 ° C. for 2 hours to obtain a urethane prepolymer (G15) (Mw: 3544.3, NCO: 2.37%).

Preparation Example 16 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E7) [polyethylene glycol / polypropylene glycol block copolymer] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 33.39 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 (G16) (Mw: 4421.0, NCO: 1.90%).

Preparation Example 17 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E11) [polycarbonate polyol] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 66.8 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 (G17) (Mw: 2399, NCO: 3.5%).

Preparation Example 18 (Preparation of urethane prepolymer)
Dehydration was performed by stirring 300 g of polyol (E12) [polytetramethylene ether glycol] at 100 ° C. under reduced pressure (about 10 mmHg) for 1 hour. Thereafter, the mixture was cooled to 80 ° C., 68.1 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 (G17) (Mw: 2399, NCO: 3.5%).

Example 1
154 parts of amine (A1) (norbornanediamine) and 129 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)") (Ketimine conversion rate 89.40%) was obtained. The reaction product (H1), 82.84 parts, was reacted with 90 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH1)”). 104 parts of the urethanized ketimine composition (UH1), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin 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 89.40%). The reaction product (H1) 83.72 parts was reacted with 54 parts of the urethane prepolymer (G2) obtained in Preparation Example 2 at 70 ° C. for 1 hour in a nitrogen atmosphere to react to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH2)”). 82 parts of the urethanized ketimine composition (UH2), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin 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 84.03%). The reaction product (H1) 90.93 parts, 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 urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH3)”). 105 parts of the urethanized ketimine composition (UH3), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin 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 91.41%). The reaction product (H1), 81.29 parts, was reacted by stirring 70 parts of the urethane prepolymer (G4) obtained in Preparation Example 4 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH4)”). 93 parts of the urethanized ketimine composition (UH4), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin 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 91.41%). The reaction product (H1) 83.02 parts, 70 parts of the urethane prepolymer (G5) obtained in Preparation Example 5 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere, and the urethanized ketimine composition ( Which may be referred to as “urethanized ketimine composition (UH5)”. 92 parts of the urethanized ketimine composition (UH5), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin 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 91.41%). The reaction product (H1) (66.44 parts) was reacted with 100 parts of the urethane prepolymer (G6) obtained in Preparation Example 6 at 70 ° C. for 1 hour in a nitrogen atmosphere to react with the urethanized ketimine composition ( Which may be referred to as “urethanized ketimine composition (UH6)”. 125 parts of the urethanized ketimine composition (UH6), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 7
154 parts of amine (A1) (norbornanediamine) and 107.5 parts of ketone (B1) (diethylketone) were placed in a flask, and the temperature at which the ketone (B1) was refluxed while removing the water formed by azeotropic distillation (120 to The reaction is carried out by refluxing at 150 ° C. for 12 hours, the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and the reaction product containing a ketimine compound (referred to as “reaction product (H2)”) (The ketimine conversion rate was 91.41%). The reaction product (H2) (68.06 parts) was reacted with 100 parts of the urethane prepolymer (G7) obtained in Preparation Example 7 under a nitrogen atmosphere at 70 ° C. for 1 hour to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH7)”). 123 parts of the urethanized ketimine composition (UH7), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin 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 91.41%). The reaction product (H1) (56.71 parts) was reacted with 100 parts of the urethane prepolymer (G8) obtained in Preparation Example 8 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition ( (Sometimes referred to as “urethanized ketimine composition (UH8)”). 138 parts of the urethanized ketimine composition (UH8), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 9
154 parts of amine (A1) (norbornanediamine) and 134.16 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 The reaction is carried out by refluxing at 150 ° C. for 12 hours, the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and the reaction product containing the ketimine compound (referred to as “reaction product (H3)”) (The ketimine conversion rate was 95.29%). The reaction product (H3) (249.85 parts) was reacted with 200 parts of the urethane prepolymer (G9) obtained in Preparation Example 9 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH9)”). 100 parts of the urethanized ketimine composition (UH9), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 10
154 parts of amine (A1) (norbornanediamine) and 157.38 parts of ketone (B1) (diethylketone) were placed in a flask, and the temperature at which the ketone (B1) was refluxed while azeotropically removing the generated water (120 to The reaction is carried out under reflux for 12 hours at 150 ° C., then the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and the reaction product containing the ketimine compound (referred to as “reaction product (H4)”) (The ketimine conversion rate was 95.29%). The reaction product (H4) 250.40 parts was reacted with 200 parts of the urethane prepolymer (G10) obtained in Preparation Example 10 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH10)”). 100 parts of the urethanized ketimine composition (UH10), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 11
154 parts of amine (A1) (norbornanediamine) and 150.50 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 The reaction is carried out by refluxing at 150 ° C. for 12 hours, the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and a reaction product containing a ketimine compound (referred to as “reaction product (H5)”) (The ketimine conversion rate was 95.29%). The reaction product (H5) (246.69 parts) was reacted with 200 parts of the urethane prepolymer (G11) obtained in Preparation Example 11 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH11)”). 91 parts of the urethanized ketimine composition (UH11), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 12
In the same manner as in Example 10, a urethanized ketimine composition (UH10) was obtained (sometimes referred to as “solvent system (T1)”).

  Also, 45 parts of butyl acrylate, 5 parts of γ-methacryloxypropyltrimethoxysilane (trade name “KBM503”, manufactured by Shin-Etsu Silicone), 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator ) 0.75 parts was added to prepare a monomer liquid (sometimes referred to as “droplet system (T1)”).

  Nitrogen was introduced into a reaction vessel equipped with a nitrogen introducer, a thermometer, and a stirrer, and the solvent system (T1) was charged in a nitrogen atmosphere, and the temperature was raised to 85 ° C. while stirring. Then, the said drop system (T1) was dripped uniformly over 1 hour, hold | maintaining the same temperature (85 degreeC) under nitrogen atmosphere, and stirring. After completion of the dropwise addition, the mixture was further stirred for 2 hours while maintaining the same temperature (85 ° C.). Thereafter, 0.05 part of a polymerization initiator (AIBN) was further added, and stirring was performed for 2 hours while maintaining the same temperature (85 ° C.), and this was repeated three times. Thereafter, the mixture was cooled to room temperature to obtain a reaction mixture (sometimes referred to as “urethanized ketimine composition (A-UH1)”). 100 parts of the urethanized ketimine composition (A-UH1), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone) 10 parts of silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) were mixed to obtain an epoxy resin composition.

Example 13
154 parts of amine (A1) (norbornanediamine) and 136.74 parts of ketone (B1) (diethylketone) are placed in a flask, and the temperature at which the ketone (B1) is refluxed while azeotropically removing the water produced. The reaction is carried out by refluxing at 150 ° C. for 12 hours, and the ketone (B1) is removed by distillation under reduced pressure using an evaporator. The reaction product containing the ketimine compound is sometimes referred to as “reaction product (H6)”. (There was a ketimine conversion rate of 95.29%). The reaction product (H6) 250.56 parts and the urethane prepolymer (G12) 200 parts obtained in Preparation Example 12 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. Product was obtained (sometimes referred to as “solvent system (T2)”).

  In the same manner as in Example 12, the solvent system (T2) is reacted with the dropping system (T1) to obtain a reaction mixture (sometimes referred to as “urethanized ketimine composition (A-UH2)”). It was. 80 parts of the urethanized ketimine composition (A-UH2), 100 parts of an epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 14
154 parts of amine (A1) (norbornanediamine) and 161.68 parts of ketone (B1) (diethylketone) were placed in a flask, and the temperature at which the ketone (B1) was refluxed while removing the water formed by azeotropic distillation (120 to The reaction is carried out at 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 (referred to as "reaction product (H7)") (The ketimine conversion rate was 95.29%). The reaction product (H7) 250.11 parts and the urethane prepolymer (G13) 200 parts obtained in Preparation Example 13 were stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. Product was obtained (sometimes referred to as “solvent system (T3)”).

  In the same manner as in Example 12, the solvent system (T3) is reacted with the dropping system (T1) to obtain a reaction mixture (sometimes referred to as “urethanized ketimine composition (A-UH3)”). It was. 80 parts of the urethanized ketimine composition (A-UH3), 100 parts of an epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 15
154 parts of amine (A1) (norbornanediamine) and 215 parts of ketone (B1) (diethylketone) are placed in a flask, and the temperature at which 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 (H8)") (The ketimine conversion rate was 95.29%). The reaction product (H8) 250.00 parts and the urethane prepolymer (G14) 200 parts obtained in Preparation Example 14 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. Product was obtained (sometimes referred to as “solvent system (T4)”).

  In the same manner as in Example 12, the solvent system (T4) was reacted with the dropping system (T1) to obtain a reaction mixture (sometimes referred to as “urethanized ketimine composition (A-UH4)”). . 80 parts of the urethanized ketimine composition (A-UH4), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 16
In the same manner as in Example 12, a urethanized ketimine composition (A-UH1) was obtained. 80 parts of the urethanized ketimine composition (A-UH1), 100 parts of an epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 17
In the same manner as in Example 10, a urethanized ketimine composition (UH10) was obtained (sometimes referred to as “solvent system (T1)”).

  Also, 90 parts of butyl acrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane (trade name “KBM503”, manufactured by Shin-Etsu Silicone), 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator ) 1.50 parts were blended to prepare a monomer liquid (sometimes referred to as “droplet system (T2)”).

  Nitrogen was introduced into a reaction vessel equipped with a nitrogen introducer, a thermometer, and a stirrer, and the solvent system (T1) was charged in a nitrogen atmosphere, and the temperature was raised to 85 ° C. while stirring. Then, the said drop system (T2) was dripped uniformly over 1 hour, hold | maintaining the same temperature (85 degreeC) under nitrogen atmosphere, and stirring. After completion of the dropwise addition, the mixture was further stirred for 2 hours while maintaining the same temperature (85 ° C.). Thereafter, 0.10 parts of a polymerization initiator (AIBN) was further added, and stirring was performed for 2 hours while maintaining the same temperature (85 ° C.), and this was repeated three times. Then, it cooled to room temperature and obtained the reaction mixture ("urethanized ketimine composition (A-UH5)"). 88 parts of the urethanized ketimine composition (A-UH5), 100 parts of an epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 18
In the same manner as in Example 10, a urethanized ketimine composition (UH10) was obtained (sometimes referred to as “solvent system (T1)”).

  Also, 50 parts of butyl acrylate and 40 parts of methyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane (trade name “KBM503”, manufactured by Shin-Etsu Silicone), 2,2′-azo as a polymerization initiator Bisisobutyronitrile (AIBN) 1.50 parts was blended to prepare a monomer liquid (sometimes referred to as “droplet system (T3)”).

  In the same manner as in Example 17, the solvent system (T1) was reacted with the dropping system (T3) to obtain a reaction mixture (“urethanized ketimine composition (A-UH6)”). 88 parts of the urethanized ketimine composition (A-UH6), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 19
In the same manner as in Example 10, a urethanized ketimine composition (UH10) was obtained (sometimes referred to as “solvent system (T1)”).

  Also, 65 parts of butyl acrylate and 25 parts of methyl methacrylate, 10 parts of γ-methacryloxypropyltrimethoxysilane (trade name “KBM503”, manufactured by Shin-Etsu Silicone), 2,2′-azo as a polymerization initiator Bisisobutyronitrile (AIBN) (1.50 parts) was blended to prepare a monomer liquid (sometimes referred to as “droplet system (T4)”).

  In the same manner as in Example 17, the drop system (T4) was reacted with the solvent system (T1) to obtain a reaction mixture (“urethanized ketimine composition (A-UH7)”). 88 parts of the urethanized ketimine composition (A-UH7), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone) 55 Part and silica (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) 10 parts were mixed to obtain an epoxy resin composition.

Example 20
In the same manner as in Example 7, a reaction product (H2) containing a ketimine compound was obtained (ketimination rate 84.03%). The reaction product (H2) 35.62 parts were reacted with 100 parts of the urethane prepolymer (G16) obtained in Preparation Example 16 at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH12)”). 155 parts of the urethanized ketimine composition (UH12), 100 parts of an epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 55 parts of ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone), silica 10 parts (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) were blended to prepare an epoxy resin composition.

Example 21
In the same manner as in Example 7, a reaction product (H2) containing a ketimine compound was obtained (ketimination rate 91.41%). 100 parts of the urethane prepolymer (G15) obtained in Preparation Example 15 was stirred in 70.degree. C. for 1 hour in a nitrogen atmosphere to 84.89 parts of the reaction product (H2), and the urethanized ketimine composition ( In some cases, it was referred to as “urethanized ketimine composition (UH13)”. 109 parts of the urethanized ketimine composition (UH13), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 22
142 parts of amine (A2) (1,3-bis (aminomethyl) cyclohexane) and 157.38 parts of ketone (B1) (diethylketone) were placed in a flask, and water formed was removed by azeotropic distillation. ) Is refluxed for 12 hours at a reflux temperature (120 to 150 ° C.), the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and a reaction product containing a ketimine compound (“reaction product” Product (H9) ”) (ketiminization rate 95.29%). The reaction product (H9) 250.0 parts was reacted with 200 parts of the urethane prepolymer (G10) obtained in Preparation Example 10 in a nitrogen atmosphere at 70 ° C. for 1 hour to obtain a urethanized ketimine composition. (It may be referred to as “urethanized ketimine composition (UH14)”). 72 parts of the urethanized ketimine composition (UH14), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 55 parts of ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone), silica 10 parts (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) were blended to prepare an epoxy resin composition.

Example 23
170 parts of amine (A3) (isophoronediamine) and 157.38 parts of ketone (B1) (diethylketone) were placed in a flask, and the temperature at which ketone (B1) was refluxed while removing the water formed by azeotropic distillation (120 to The reaction is carried out by refluxing at 150 ° C. for 12 hours, the ketone (B1) is removed by distillation under reduced pressure using an evaporator, and a reaction product containing a ketimine compound (referred to as “reaction product (H10)”) (The ketimine conversion rate was 95.29%). The reaction product (H10) 250.0 parts and the urethane prepolymer (G10) 200 parts obtained in Preparation Example 10 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition. (It may be referred to as “urethane-modified ketimine composition (UH15)”). 72 parts of the urethanized ketimine composition (UH15), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 55 parts of ethyl silicate (trade name “TSL8124”, manufactured by GE Toshiba Silicone), silica 10 parts (trade name “RY200S”, manufactured by Nippon Aerosil Co., Ltd.) were blended to prepare an epoxy resin composition.

Example 24
In the same manner as in Example 10, a reaction product containing a ketimine compound (sometimes referred to as “reaction product (H4)”) was obtained (ketimination rate: 95.29%). In 364 parts of the reaction product (H4), 200 parts of the urethane prepolymer (G17) obtained in Preparation Example 17 were reacted by stirring at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition (“ A urethanized ketimine composition (UH16) ”may be obtained. 77 parts of the urethanized ketimine composition (UH16), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Example 25
In the same manner as in Example 10, a reaction product containing a ketimine compound (sometimes referred to as “reaction product (H4)”) was obtained (ketimination rate: 95.29%). To 370 parts of the reaction product (H4), 200 parts of the urethane prepolymer (G18) obtained in Preparation Example 18 was stirred and reacted at 70 ° C. for 1 hour in a nitrogen atmosphere to obtain a urethanized ketimine composition (“ A urethanized ketimine composition (UH17) ”may be obtained). 77 parts of the urethanized ketimine composition (UH17), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin Co., Ltd.), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica ( 10 parts of a product name “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) was blended to prepare an epoxy resin composition.

Comparative Example 1
In the same manner as in Example 1, a reaction product containing a ketimine compound (sometimes referred to as “reaction product (H1)”) was obtained (ketiminization rate 89.40%). 50 parts of reaction product (H1), 100 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Japan Epoxy Resin), 40 parts of epoxy silane (trade name “KBM403”, manufactured by Shin-Etsu Silicone), silica (trade name “ 10 parts of “RY200S” (manufactured by Nippon Aerosil Co., Ltd.) were blended to prepare an epoxy resin composition.

Comparative Example 2
154 parts of amine (A1) (norbornanediamine) and 129 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 8 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 ketimine conversion rate was 76.00%). 90 parts of the urethane prepolymer (G1) obtained in Preparation Example 1 are reacted with 40 parts of the reaction product (H1) under a nitrogen atmosphere at 70 ° C. for 1 hour to obtain a urethanized ketimine composition. It was.

Evaluation test About the epoxy resin composition obtained in the Example and the comparative example, the physical property evaluation test was done as follows.

[Method of measuring internal curability]
The epoxy resin composition was put in a polypropylene cup up to a height of 7 mm, and allowed to stand for 7 days in an atmosphere of 23 ° C. and 50% RH, and the curing depth (mm) from the surface was measured.

  None of Examples 1 to 25 gelled, but Comparative Example 2 gelled because the ketiminization rate was low. Moreover, although the epoxy resin composition of Examples 1-25 was excellent in internal curability (deep part curability), the comparative example 1 was inferior in the point of internal curability (deep part curability). The above results are summarized in Table 1, Table 2, Table 3, and Table 4.

Claims (16)

Following formula (1)

(In the formula, R ¹ represents an organic group, and n represents an integer of 2 or more)
A primary amine compound A represented by 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 primary amine compound A has a ketimination rate of 80% or more,

(Wherein 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 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. A ring may be formed with a carbon atom)
For the reaction product containing at least one of the ketimine compound D having a primary amino group represented by formula (1) and the unreacted primary amine compound A, the following formula (5):

(Wherein R ⁴ is a polyvalent organic group containing at least a hetero atom, 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 containing a ketimine compound C and a urethane-modified ketimine compound obtained by reacting a urethane prepolymer G having an isocyanate group at the molecular chain end obtained by reaction with the polyisocyanate compound F represented by   The urethane prepolymer G is reacted at a ratio of 1 to 5 moles of isocyanate groups with respect to 1 mole of the total amount of primary amino groups of the ketimine compound D having a primary amino group and the unreacted primary amine compound A. The ketimine composition according to claim 1 obtained by   The ketimine composition according to claim 1 or 2, wherein the polyisocyanate compound F is a non-aromatic polyisocyanate compound.   The ketimine composition according to any one of claims 1 to 3, wherein the polyisocyanate compound F is isophorone diisocyanate.   The ketimine composition according to any one of claims 1 to 4, wherein the primary amine compound A has a ketiminization rate of 90 to 99.5%. The ketimine composition according to any one of claims 1 to 5, wherein R ² and R ³ in the ketone compound B are both hydrocarbon groups having 2 or more carbon atoms. The ketimine composition according to any one of claims 1 to 6, wherein R ² and R ³ in the ketone compound B are both ethyl groups.   The ketimine composition according to any one of claims 1 to 7, wherein the polyol compound E is at least one polyol compound selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol.   The ketimine composition according to any one of claims 1 to 8, wherein the polyol compound E is a polyether polyol containing 5 to 40% by mass of oxyethylene units.   The ketimine composition according to any one of claims 1 to 9, wherein the polyol compound E is a copolymer of polyethylene glycol and polypropylene glycol.   The ketimine composition according to any one of claims 1 to 10, wherein the polyol compound E is a block copolymer of polyethylene glycol / polypropylene glycol / polyethylene glycol.   The acrylic polymer containing ketimine composition obtained by superposing | polymerizing an acrylic monomer in the ketimine composition in any one of Claims 1-11.   The acrylic polymer-containing ketimine composition according to claim 12, wherein at least an acrylic monomer containing a reactive silyl group is used as the acrylic monomer.   An epoxy resin composition comprising the ketimine composition according to any one of claims 1 to 13 and an epoxy resin.   The epoxy resin composition according to claim 14, which is a one-component resin composition further containing a dehydrating agent in addition to the ketimine composition and the epoxy resin.   The epoxy resin composition according to claim 15, wherein the dehydrating agent is a silane compound.