JP2020070446A - Latent curing agent comprising silylamine compound - Google Patents

Abstract

To provide a latent curing agent that generates no aldehyde compound when reacting with an isocyanate compound.SOLUTION: A latent curing agent contains a silylamine compound represented by formula (1). (In formula (1), R-Rare each independently an alkyl group having 1-6 carbon atoms, Ris an alkylene group having 2-12 carbon atoms or an arylene group having 6-12 carbon atoms, and R- Rare each independently a hydrogen atom or an alkyl group having 1-6 carbon atoms. y and z are each independently an integer of 1-11, and n is an integer of 1-22.)SELECTED DRAWING: None

Description

  The present invention relates to a latent curing agent containing a silylamine compound and a curable composition containing the latent curing agent and an isocyanate compound.

  A curable composition containing an isocyanate group-containing urethane prepolymer is used in applications such as sealing materials and adhesives. The curable composition containing this isocyanate group-containing urethane prepolymer includes a one-pack type which contains an isocyanate group-containing urethane prepolymer and a latent curing agent and is reactively cured with moisture in the air, and an isocyanate group-containing urethane prepolymer. There is a two-pack type in which a main agent containing a polymer and a curing agent containing an active hydrogen-containing compound are mixed and cured at the time of use.

A curable composition containing a one-pack type isocyanate group-containing urethane prepolymer is a paste-like or viscous solution-like material containing an isocyanate group-containing prepolymer and a latent curing agent, and is a sealing material, a waterproof material, an adhesive agent. Used for paints, etc. Generally, the performance required of a latent curing agent includes storage stability, curability, and compatibility with a prepolymer.
As a latent curing agent, an oxazolidine-based latent curing agent in which an amine compound such as bisalkanolamine is protected with an aldehyde compound such as isobutyraldehyde is known (Patent Document 1).

  The oxazolidine-based latent curing agent is hydrolyzed into an aminoethanol derivative, which reacts with the isocyanate group of the urethane prepolymer to cure the curable composition. However, when the oxazolidine-based latent curing agent is hydrolyzed, an aldehyde compound is produced, and its odor and toxicity are problems (Reaction formula 1).

JP, 2016-113619, A

  The present invention has been made in view of the background art described above, and an object thereof is to provide a latent curing agent that does not generate an aldehyde compound when a reaction with an isocyanate compound is performed.

  The present inventors have found that the silylamine compound represented by the formula (1) functions as a latent curing agent when reacting with an isocyanate compound and does not generate an aldehyde compound, and completes the present invention. Came to.

That is, the present invention includes the following [1] to [7].
[1] A latent curing agent containing a silylamine compound represented by the following formula (1).

Formula (1):

（式（１）中、Ｒ^１〜Ｒ^１２はそれぞれ独立して炭素数１〜６のアルキル基、Ｒ^１３は炭素数２〜１２のアルキレン基または炭素数６〜１２のアリーレン基、Ｒ^１４〜Ｒ^２１はそれぞれ独立して水素原子または炭素数１〜６のアルキル基である。ｙおよびｚはそれぞれ独立して１〜１１の整数、ｎは１〜２２の整数である。）
［２］ｎが１〜５である［１］に記載の潜在性硬化剤。
［３］Ｒ^１〜Ｒ^１２がそれぞれ独立してメチル基およびエチル基から選択される［１］または［２］に記載の潜在性硬化剤。
［４］Ｒ^１３が炭素数２〜１２のアルキレン基である［１］〜［３］のいずれかに記載の潜在性硬化剤。
［５］［１］〜［４］のいずれかに記載の潜在性硬化剤及びイソシアネート化合物を含む硬化性組成物。
［６］［１］〜［４］のいずれかに記載の潜在性硬化剤、イソシアネート化合物及び酸性化合物を含む硬化性組成物。
［７］下記式（１）で表されるシリルアミン化合物の潜在性硬化剤としての使用。
式（１）：

（式（１）中、Ｒ^１〜Ｒ^１２はそれぞれ独立して炭素数１〜６のアルキル基、Ｒ^１３は炭素数２〜１２のアルキレン基または炭素数６〜１２のアリーレン基、Ｒ^１４〜Ｒ^２１はそれぞれ独立して水素原子または炭素数１〜６のアルキル基である。ｙおよびｚはそれぞれ独立して１〜１１の整数、ｎは１〜２２の整数である。）

(In the formula (1), R ^{1 to} R ¹² are each independently an alkyl group having 1 to 6 carbon atoms, R ¹³ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and R ¹⁴ to R ²¹ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, y and z are each independently an integer of 1 to 11, and n is an integer of 1 to 22.)
[2] The latent curing agent according to [1], wherein n is 1 to 5.
[3] The latent curing agent according to [1] or [2], wherein R ^{1 to} R ¹² are each independently selected from a methyl group and an ethyl group.
[4] The latent curing agent according to any one of [1] to [3], wherein R ¹³ is an alkylene group having 2 to 12 carbon atoms.
[5] A curable composition containing the latent curing agent according to any one of [1] to [4] and an isocyanate compound.
[6] A curable composition containing the latent curing agent according to any one of [1] to [4], an isocyanate compound and an acidic compound.
[7] Use of a silylamine compound represented by the following formula (1) as a latent curing agent.
Formula (1):

(In the formula (1), R ^{1 to} R ¹² are each independently an alkyl group having 1 to 6 carbon atoms, R ¹³ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and R ¹⁴ to R ²¹ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, y and z are each independently an integer of 1 to 11, and n is an integer of 1 to 22.)

  The silylamine compound of the present invention does not produce an aldehyde compound even when hydrolyzed with water. Therefore, it can be provided as a latent curing agent that does not generate the odor of an aldehyde compound when it reacts with an isocyanate compound. Further, the latent curing agent containing the silylamine compound of the present invention has excellent compatibility with the isocyanate group-containing urethane prepolymer.

  Hereinafter, modes for carrying out the present invention will be described in detail.

The latent curing agent of the present invention contains a silylamine compound represented by the formula (1). That is, the silylamine compound represented by the formula (1) can be used as a latent curing agent.

In formula (1), R ^{1 to} R ¹² are each independently an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, preferably a methyl group, an ethyl group, a propyl group, a butyl group, and more preferably Methyl group and ethyl group, particularly preferably methyl group.

R ¹³ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and preferably an alkylene group having 2 to 12 carbon atoms.

  The alkylene group having 2 to 12 carbon atoms may be linear or branched. Examples of the alkylene group having 2 to 12 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group and the like, preferably ethylene. Group, propylene group, butylene group, pentylene group, hexylene group, more preferably ethylene group, propylene group, butylene group.

  Examples of the arylene group having 6 to 12 carbon atoms include a phenylene group and a naphthylene group.

R ^{14 to} R ²¹ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms include the same groups as described above.

  y and z are each independently an integer of 1 to 11, preferably an integer of 1 to 3, and more preferably 1 or 2.

  n is an integer of 1 to 22, preferably an integer of 1 to 18, more preferably an integer of 1 to 14, and even more preferably an integer of 1 to 5.

  Specific examples of the silylamine compound represented by the formula (1) (hereinafter referred to as “silylamine compound (1)”) include N, N, N ′, N′-tetrakis (trimethylsilyl) -4,9-. Dioxa-1,12-dodecanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -3,6-dioxa-1,8-octanediamine, N, N, N', N'-tetrakis (trimethylsilyl) ) -4,7-Dioxa-1,10-decanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -4,7,10-trioxa-1,13-tridecanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -4,7,10,13-tetraoxa-1,16-hexadecanediamine, N, N, N', N'-tetrakis (trimethylsilyl) ) -4,7,10,13,16-Pentaoxa-1,19-nonadecanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -3,6,9-trioxa-1,11-undecane Diamine, N, N, N ', N'-tetrakis (trimethylsilyl) -3,6,9,12-tetraoxa-1,14-tetradecanediamine, N, N, N', N'-tetrakis (trimethylsilyl) -3 , 6,9,12,15-pentaoxa-1,17-heptadecanediamine, N, N, N ′, N′-tetrakis (trimethylsilyl) -3,6-dioxa-1,9-nonanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -3,6,9-trioxa-1,12-dodecanediamine, N, N, N', N'-tetrakis (trimethylsilyl) -3,6,9,12-Tetraoxa-1,15-pentadecanediamine, N, N, N ', N'-Tetrakis (trimethylsilyl) -3,6,9,12,15-pentaoxa-1,18-octadecane Diamine, N, N, N ', N'-tetrakis (trimethylsilyl) -3,8-dioxa-1,10-decanediamine, N, N, N', N'-tetrakis (trimethylsilyl) -3,8-dioxa -1,11-Undecanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -polyoxyethylenebisamine, N, N, N', N'-tetrakis (trimethylsilyl) -polyoxypropylenebisamine, etc. Is mentioned. Any of these may be used alone or in combination of two or more. Among these, N, N, N ', N'-tetrakis (trimethylsilyl) -4,9-dioxa-1,12-dodecanediamine, N, N, N', N'-tetrakis (trimethylsilyl) -3,6 -Dioxa-1,8-octanediamine, N, N, N ', N'-tetrakis (trimethylsilyl) -4,7-dioxa-1,10-decanediamine, N, N, N', N'-tetrakis ( Trimethylsilyl) -4,7,10-trioxa-1,13-tridecanediamine is preferred.

  The silylamine compound (1) includes an amine compound represented by the following formula (2) (hereinafter referred to as “amine compound (2)”) and a silane compound represented by the following formulas (3a) to (3d) (hereinafter It can be produced by reacting "silane compound (3)".

式（２）中、Ｒ^１３〜Ｒ^２１、ｙ、ｚ、およびｎは、式（１）で示すＲ^１３〜Ｒ^２１、ｙ、ｚ、およびｎと同じである。

In formula (2), R ^{13 to} R ²¹ , y, z, and n are the same as R ^{13 to} R ²¹ , y, z, and n shown in formula (1).

X-SiR ¹ R ² R ³ (3a)
X-SiR ⁴ R ⁵ R ⁶ (3b)
X-SiR ⁷ R ⁸ R ⁹ (3c)
X-SiR ¹⁰ R ¹¹ R ¹² (3d)
In formulas (3a) to (3d), R ^{1 to} R ¹² are the same as R ^{1 to} R ¹² shown in formula (1). X is a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonyloxy group, a perfluoroalkylsulfonyloxy group, an arylsulfonyloxy group, a perfluoroarylsulfonyloxy group, an aralkylsulfonyloxy group, a silylsulfate group, a bisperfluoroalkyl group. It is a group selected from the group consisting of sulfonylimide groups.

  The amine compound (2) will be described.

  Specific examples of the amine compound (2) include 4,9-dioxa-1,12-dodecanediamine, 3,6-dioxa-1,8-octanediamine, 4,7-dioxa-1,10-decane. Diamine, 4,7,10-trioxa-1,13-tridecanediamine, 4,7,10,13-tetraoxa-1,16-hexadecanediamine, 4,7,10,13,16-pentaoxa-1,19 -Nonadecanediamine, 3,6,9-trioxa-1,11-undecanediamine, 3,6,9,12-tetraoxa-1,14-tetradecanediamine, 3,6,9,12,15-pentaoxa-1 , 17-heptadecanediamine, 3,6-dioxa-1,9-nonanediamine, 3,6,9-trioxa-1,12-dodecanediamine, 3,6,9,12- Traoxa-1,15-pentadecanediamine, 3,6,9,12,15-pentaoxa-1,18-octadecanediamine, 3,8-dioxa-1,10-decanediamine, 3,8-dioxa-1,11 -Undecane diamine, polyoxyethylene bis amine, polyoxy propylene bis amine, etc. are mentioned. Of these, 4,9-dioxa-1,12-dodecanediamine, 4,7-dioxa-1,10-decanediamine, 3,6-dioxa-1,8-octanediamine, 4,7,10-trioxa -1,13-Tridecanediamine is preferred.

  As the amine compound (2), those which are generally available can be used, but those produced appropriately may be used. The following method is mentioned as a typical manufacturing method of amine compound (2). A diol compound represented by the following formula (4) is reacted with phosphorus halide, triphenylphosphine-carbon tetrahalide or the like to convert the terminal hydroxyl group into a halogen atom, and this is reacted with a metal azide to form an azide group. , How to further reduce. A method in which a terminal hydroxyl group of a diol compound represented by the following formula (4) is converted to a halogen atom, and then this is reacted with a metal cyanide to form a cyano group, and further reduced. A method of converting a terminal hydroxyl group of a diol compound represented by the following formula (4) into a halogen atom, reacting it with a phthalimide metal salt to further convert it into an imide group, and then performing deprotection. A manufacturing method including the following steps 1 and 2.

  The amine compound (2) produced by the production method including the following steps 1 and 2 is an amine compound represented by the formula (2a) (hereinafter referred to as “amine compound (2a)”).

アミン化合物（２ａ）は、式（２）で表されるアミン化合物のうち、Ｒ^１４〜Ｒ^１７、Ｒ^１９、およびＲ^２１が水素原子であり、ｙおよびｚが２である化合物である。

The amine compound (2a) is a compound in which R ^{14 to} R ¹⁷ , R ¹⁹ and R ²¹ are hydrogen atoms and y and z are 2 in the amine compound represented by the formula (2).

・ Process 1
Step 1 is a diol compound represented by the following formula (4) (hereinafter referred to as “diol compound (4)”) and a cyanated olefin compound represented by the following formula (5) (hereinafter referred to as “cyanated olefin compound”). (5) ”) is reacted to obtain a nitrile compound represented by the following formula (6) (hereinafter referred to as“ nitrile compound (6) ”).

式（４）中、Ｒ^１３およびｎは前記式（１）で示すＲ^１３およびｎと同じである。ジオール化合物（４）としては、具体的には、１，４−ブタンジオール、１，６−へキサンジオール、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ヘキサエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ジプロピレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、３−メチル−１，５−ペンタンジオール、ポリオキシエチレングリコール、ポリプロピレングリコール等が挙げられる。

In formula (4), R ¹³ and n are the same as R ¹³ and n shown in formula (1). Specific examples of the diol compound (4) include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol and hexaethylene. Glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, 9-nonanediol, 3-methyl-1,5-pentanediol, polyoxyethylene glycol, polypropylene glycol and the like can be mentioned.

式（５）中、Ｒ^ａおよびＲ^ｂは、前記式（１）で示すＲ^１８およびＲ^２０に相当し、それぞれ独立して水素原子または炭素数１〜６のアルキル基である。

In formula (5), R ^a and R ^b correspond to R ¹⁸ and R ²⁰ shown in the above formula (1), and each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the cyanide olefin compound (5) include acrylonitrile, methacrylonitrile, crotonitrile, and 2-pentenenitrile.

（式中、Ｒ^１３およびｎは前記式（１）で示すＲ^１３およびｎと同じであり、Ｒ^ａおよびＲ^ｂは前記式（５）で示すＲ^ａおよびＲ^ｂと同じである。）

^{(Wherein, R 13} and n are the same as ^{R 13} and n shown by the formula (1), ^{R a} and ^{R b} are the same as ^{R a} and ^{R b} shown by the formula (5).)

  Step 1 will be described.

  The reaction between the diol compound (4) and the cyanide olefin compound (5) in step 1 is usually carried out in the presence of a base. The amount of the cyanide olefin compound (5) used is usually 2 to 4 mol, preferably 2 to 3 mol, based on 1 mol of the diol compound (4).

  The base is not particularly limited as long as it does not react with the solvent or the cyanide olefin compound (5). Examples of the base used include alkali metal hydroxides, alkali metal carbonates, amidine compounds, guanidine compounds, aniline compounds, and the like, with alkali metal hydroxides being preferred.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, and sodium hydroxide is preferable. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, cesium carbonate and the like. Examples of the amidine compound include 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene. Examples of the guanidine compound include 1,5,7-triazabicyclo [4.4.0] dec-5-ene. Examples of the aniline compound include 1,8-bis (dimethylamino) naphthalene.

  The reaction of step 1 can be carried out without a solvent, but a solvent may be used if necessary. When a solvent is used, the solvent is not particularly limited as long as it does not inhibit this reaction. Examples of the solvent include ether solvents and aromatic hydrocarbon solvents, and ether solvents are preferable. Examples of the ether solvent include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, etc., and preferably tetrahydrofuran. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like. When an alkali metal hydroxide or alkali metal carbonate is used as the base, water may be added to dissolve them.

  When a solvent is used, the amount of the solvent used may be appropriately adjusted, and is generally 1 to 10 parts by mass, preferably 1 to 4 parts by mass with respect to 1 part by mass of the diol compound (4).

  The reaction pressure is not particularly limited, and the reaction may be carried out at normal pressure or may be carried out under pressure.

  The reaction temperature is not particularly limited, but is usually 0 to 100 ° C, preferably 10 to 50 ° C, and more preferably 25 to 30 ° C.

  The mixing order of the diol compound (4), the cyanide olefin compound (5), the solvent and the base is not particularly limited, and for example, the cyanide olefin compound (5) is added dropwise to the mixture of the solvent, the diol compound (4) and the base. There is a method of doing.

  After completion of the reaction, the desired nitrile compound (6) can be isolated through known purification operations such as distillation, filtration and extraction. Further, the nitrile compound (6) may be subjected to the step 2 without isolation.

・ Process 2
Step 2 is a step of reacting the nitrile compound (6) with a metal hydride (hereinafter referred to as a metal hydride (7)) to obtain an amine compound (2a).

  Step 2 will be described.

  As the metal hydride (7), lithium aluminum hydride, lithium borohydride, sodium borohydride, diisobutylaluminum hydride, lithium triethylborohydride, sodium bis (2-methoxyethoxy) aluminum hydride, tetrahydroborane, etc. And preferably lithium aluminum hydride, sodium borohydride, tetrahydroborane, and more preferably sodium borohydride.

  The amount of the metal hydride (7) used may be appropriately adjusted, and is generally 9 to 30 mol, preferably 9 to 18 mol with respect to 1 mol of the nitrile compound (6).

  The reaction of step 2 can be carried out without a catalyst, but a catalyst may be used if necessary. When a catalyst is used, examples of the catalyst include nickel chloride hexahydrate, cobalt chloride and the like, and nickel chloride hexahydrate is preferable.

  When a catalyst is used, the amount of the catalyst used is usually 0.1 to 9 mol, preferably 0.1 to 0.5 mol, based on 1 mol of the nitrile compound (6).

  The reaction of step 2 is usually carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit this reaction. Examples of the solvent used include alcohol solvents such as methanol and ethanol; ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbon solvents such as benzene, toluene and xylene. .. It is preferably an alcohol solvent, more preferably methanol.

  The amount of the solvent used may be appropriately adjusted, and is generally 10 to 50 parts by mass, preferably 10 to 20 parts by mass, and more preferably 12 to 15 parts by mass with respect to 1 part by mass of the nitrile compound (6). ..

  In the reaction of step 2, di-t-butyl dicarbonate may be further used for the purpose of reducing the catalyst and suppressing the dimerization reaction of the amine compound (2a). When di-t-butyl dicarbonate is used, the amount of di-t-butyl dicarbonate used may be appropriately adjusted, and is generally 2 to 8 mol, preferably 3 to 6 mol per 1 mol of the nitrile compound (6). , And more preferably 4 to 5 mol.

  After completion of the reaction, the amine compound (2a) can be isolated through known operations such as deprotection, distillation, filtration and extraction. When di-t-butyl dicarbonate is used in the reaction of step 2, since the terminal amino group of the amine compound (2a) is protected by t-butoxycarbonyl group, deprotection with an acid or the like may be performed. The amine compound (2a) can be obtained.

  The silane compound (3) will be described.

  Examples of the alkylsulfonyloxy group represented by X in the formulas (3a) to (3d) include a methanesulfonyloxy group, an ethanesulfonyloxy group, a propanesulfonyloxy group, a butanesulfonyloxy group, a pentanesulfonyloxy group and a hexanesulfonyloxy group. Is mentioned. It is preferably a methanesulfonyloxy group, an ethanesulfonyloxy group, a propanesulfonyloxy group, a butanesulfonyloxy group, more preferably a methanesulfonyloxy group.

  Examples of the perfluoroalkylsulfonyloxy group represented by X in the formulas (3a) to (3d) include a trifluoromethanesulfonyloxy group, a pentafluoroethanesulfonyloxy group, a heptafluoropropanesulfonyl group, a nonafluorobutanesulfonyl group, and undecafluoro. Examples thereof include a pentanesulfonyl group and a tridecafluorohexanesulfonyl group. It is preferably a trifluoromethanesulfonyloxy group, a pentafluoroethanesulfonyloxy group, a heptafluoropropanesulfonyl group, a nonafluorobutanesulfonyl group, and more preferably a trifluoromethanesulfonyl group.

  As the arylsulfonyloxy group represented by X in the formulas (3a) to (3d), a benzenesulfonyloxy group, a 2-chlorobenzenesulfonyloxy group, a 2-bromobenzenesulfonyloxy group, a 2-iodobenzenesulfonyloxy group, a 2- Methylbenzenesulfonyloxy group, 2-nitrobenzenesulfonyloxy group, 3-chlorobenzenesulfonyloxy group, 3-bromobenzenesulfonyloxy group, 3-iodobenzenesulfonyloxy group, 3-methylbenzenesulfonyloxy group, 3-nitrobenzenesulfonyloxy group , 4-chlorobenzenesulfonyloxy group, 4-bromobenzenesulfonyloxy group, 4-iodobenzenesulfonyloxy group, 4-methylbenzenesulfonyloxy group, 4-nitrobenzenesulfonyloxy group, - naphthalene sulfonyloxy group, such as 2-naphthalene sulfonyloxy group. A benzenesulfonyloxy group and a 4-methylbenzenesulfonyloxy group are preferable, and a 4-methylbenzenesulfonyloxy group is more preferable.

  Examples of the perfluoroarylsulfonyloxy group represented by X in the formulas (3a) to (3d) include a pentafluorobenzenesulfonyloxy group, a heptafluoro-1-naphthalenesulfonyloxy group, and a heptafluoro-2-naphthalenesulfonyloxy group. Can be mentioned. It is preferably a pentafluorobenzenesulfonyloxy group, a heptafluoro-1-naphthalenesulfonyloxy group, and more preferably a pentafluorobenzenesulfonyloxy group.

  Examples of the aralkylsulfonyloxy group represented by X in the formulas (3a) to (3d) include a benzylsulfonyloxy group, a phenethylsulfonyloxy group, a 1-naphthylsulfonyloxy group and a 2-naphthylsulfonyloxy group. It is preferably a pentafluorobenzenesulfonyloxy group, a benzylsulfonyloxy group, a phenethylsulfonyloxy group, more preferably a pentafluorobenzenesulfonyloxy group.

  Examples of the silylsulfate group represented by X in the formulas (3a) to (3d) include a trimethylsilylsulfate group, a triethylsilylsulfate group, a triisopropylsulfate group, and a tert-butyldimethylsilylsulfate group. Preferred are trimethylsilyl sulfate group, triethylsilyl sulfate group, triisopropyl sulfate group, tert-butyldimethylsilyl sulfate group, and more preferred is trimethylsilyl sulfate group.

  Examples of the bisperfluoroalkylsulfonylimide group represented by X in formulas (3a) to (3d) include a bistrifluoromethanesulfonylimide group, a bispentafluoroethanesulfonylimide group, a bisheptafluoropropanesulfonylimide group, and bisnonafluorobutane. Examples thereof include a sulfonylimide group, a bisundecafluoropentanesulfonylimide group, and a bistridecafluorohexanesulfonylimide group. A bistrifluoromethanesulfonylimide group, a bispentafluoroethanesulfonylimide group, a bisheptafluoropropanesulfonylimide group, a bisnonafluorobutanesulfonylimide group are preferred, and a bistrifluoromethanesulfonylimide group is more preferred.

  In formulas (3a) to (3d), X is preferably a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonyloxy group, a perfluoroalkylsulfonyloxy group, an arylsulfonyloxy group, a bisperfluoroalkylsulfonylimide group, Chlorine atom, bromine atom and iodine atom are more preferable, and chlorine atom is particularly preferable.

  Examples of the silane compound (3) include trimethylsilane compounds such as chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, trimethylsilyl trifluoromethanesulfonate, and bis (trimethylsilyl) sulfate; chlorotriethylsilane, bromotriethylsilane, iodotriethylsilane. Triethylsilane compounds such as triethylsilyl trifluoromethanesulfonate and bis (triethylsilyl) sulfate; tert-butyldimethylchlorosilane, tert-butyldimethylbromosilane, tert-butyldimethyliodosilane, tert-butyldimethylsilyl trifluoromethanesulfonate, etc. Tert-butyldimethylsilyl compound, etc., and a trimethylsilane compound is preferable, and chlorotrimethylsilane is particularly preferable. Down is preferable.

  The reaction between the amine compound (2) and the silane compound (3) is usually carried out in the presence of a base in order to capture an acid by-produced in the reaction. The base is not particularly limited as long as it does not affect the amine compound (2), the silane compound (3) and the silylamine compound (1) which is the product of this reaction. Examples of the base used include amidine compounds such as 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene; Guanidine compounds such as 7-triazabicyclo [4.4.0] dec-5-ene; aniline compounds such as 1,8-bis (dimethylamino) naphthalene; tert-butylimino-tris (dimethylamino) phosphorane, N- phosphine compounds such as tert-butyl-N, N, N ′, N ′, N ″, N ″ -hexamethylphosphorimidic acid triamide; amine compounds such as triethylamine and N, N-diisopropylethylamine. .. Of these, amidine compounds are preferable, and 1,8-diazabicyclo [5.4.0] -7-undecene is particularly preferable. In addition, in the reaction of the amine compound (2) and the silane compound (3), the base can be used alone or in combination of two or more kinds.

  The amount of the silane compound (3) used is generally 4 to 8 mol, preferably 4 to 6 mol, based on 1 mol of the amine compound (2).

  The reaction is usually performed in the presence of a solvent, and the solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent used include ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ester solvents such as ethyl acetate; dichloromethane, chloroform, Examples thereof include halogenated hydrocarbon solvents such as 1,2-dichloroethane; nitrile solvents such as acetonitrile. Among them, a nitrile solvent is preferable, and acetonitrile is more preferable.

  The amount of the solvent used may be appropriately adjusted, and is generally 1 to 100 parts by mass, preferably 3 to 6 parts by mass with respect to 1 part by mass of the amine compound (2).

  In order to prevent hydrolysis of the silylamine compound (1) and the silane compound (3), the reaction is preferably carried out under anhydrous conditions, in which case it can be carried out under an atmosphere of an inert gas such as nitrogen or argon.

  The reaction pressure is not particularly limited, and the reaction may be carried out at normal pressure or may be carried out under pressure.

  The reaction temperature is not particularly limited, but is usually 0 to 100 ° C, preferably 0 to 50 ° C, more preferably 5 to 30 ° C.

  The order of mixing the amine compound (2), the silane compound, the solvent, and the base is not particularly limited, and examples thereof include a method of dropping the silane compound into the mixture of the solvent, the amine compound (2), and the base.

  After completion of the reaction, the desired silylamine compound (1) can be isolated through known purification operations such as distillation, filtration and extraction.

  The silylamine compound (1) functions as a latent curing agent when reacting with an isocyanate compound or the like by reacting with water such as moisture and hydrolyzing to generate a primary or secondary amino group. .. In the latent curing agent of the present invention, two or more silylamine compounds (1) may be used in combination.

  Further, the latent curing agent of the present invention may contain a solvent, if necessary. When containing a solvent, the solvent is pentane, hexane, heptane, octane, cyclohexane, toluene, xylene, ethyl formate, butyl formate, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, acetonitrile, propionitrile, diethyl ether, diether. Butyl ether, tetrahydrofuran and the like can be preferably used.

  Furthermore, the latent curing agent of the present invention can be combined with an isocyanate compound to form a curable composition. The latent curing agent containing the silylamine compound (1) is useful because it does not produce an aldehyde compound even when hydrolyzed with water such as moisture, and does not produce an odor of the aldehyde compound when it reacts with an isocyanate compound. ..

  When the curable composition is used, the amount of the silylamine compound (1) used is usually 0.4 in terms of the molar ratio of the amino group generated by hydrolysis of the silylamine compound (1) to 1 mol of the isocyanate group of the isocyanate compound. Is about 1.3 mol, preferably 0.5 to 1.1 mol.

  Here, examples of the isocyanate compound include compounds having one or more, and preferably two or more isocyanate groups. As the isocyanate compound, both a low molecular weight isocyanate compound and a high molecular weight isocyanate compound can be used.

  Examples of low molecular weight isocyanate compounds include organic polyisocyanates and organic monoisocyanates. Organic polyisocyanate is a compound having two or more isocyanate groups in the compound. The organic monoisocyanate is a compound having one isocyanate group in the compound.

  Specific examples of the organic polyisocyanate include toluene polyisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and 2,2 ′. Diphenylmethane polyisocyanate such as diphenylmethane diisocyanate; 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6 -Phenylene polyisocyanates such as triisopropylphenyl-1,3-diisocyanate; naphthalene polyisols such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate Anate; chlorophenylene-2,4-diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. Aromatic polyisocyanates are mentioned. Further, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl- Aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, decamethylene diisocyanate and lysine diisocyanate; araliphatic polyisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate and p-xylylene diisocyanate; 1,4- Alicyclic polyisocyanates such as cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Door and the like. Further, there may be mentioned polymethylene polyphenyl polyisocyanate; polymeric isocyanates such as crude toluene diisocyanate. Furthermore, modified polyisocyanates obtained by modifying these organic polyisocyanates include one or more of uretdione bond, isocyanurate bond, allophanate bond, buret bond, uretonimine bond, carbodiimide bond, urethane bond or urea bond. .. Any of these may be used alone or in combination of two or more.

  Specific examples of the organic monoisocyanate include aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate and n-octadecyl monoisocyanate; p-isopropylphenyl monoisocyanate and p-isopropylphenyl monoisocyanate. -Aromatic mono-, such as benzyloxyphenyl monoisocyanate, phenyl isocyanate, p-tolyl isocyanate, m-tolyl isocyanate, m-tolyl isocyanate, 4-chlorophenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate Isocyanate may be mentioned. Any of these may be used alone or in combination of two or more. The organic monoisocyanate is preferably used in combination with the organic polyisocyanate.

  Examples of the high molecular weight isocyanate compound include an isocyanate group-containing resin. The isocyanate group-containing resin is a resin having one or more isocyanate groups in the resin, and the isocyanate group reacts with active hydrogen (group) to form a urethane bond, a urea bond, or the like and crosslink and cure. Suitable examples of the isocyanate group-containing resin include isocyanate group-containing urethane prepolymers.

  The isocyanate group-containing urethane prepolymer contains an organic polyisocyanate compound and an active hydrogen-containing compound in a batch or sequentially in an isocyanate group / active hydrogen molar ratio of 1.2 to 10, preferably 1.2 to 5. It can be produced by reacting so that the isocyanate group remains in the urethane prepolymer.

  The isocyanate group content in the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15% by mass, more preferably 0.5 to 5% by mass.

  The number average molecular weight of the isocyanate group-containing urethane prepolymer is preferably 1,500 or more, more preferably 1,500 to 20,000, further preferably 1,500 to 15,000, and particularly preferably 1,500 to 10,000. preferable. The number average molecular weight in the present invention is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

  The isocyanate group-containing urethane prepolymer can be produced by a conventionally known method. Specifically, a method of charging an organic isocyanate compound and an active hydrogen-containing compound into a reaction container made of glass or stainless steel, using a reaction catalyst or an organic solvent as necessary, and reacting with stirring at 50 to 120 ° C. Is mentioned. At this time, since the isocyanate group-containing urethane prepolymer thickens when the isocyanate group reacts with water such as moisture, it is preferable to replace the inside of the container with nitrogen gas in advance or to carry out the reaction under a nitrogen gas stream.

  An organic polyisocyanate can be mentioned as an organic isocyanate compound. Examples of the organic polyisocyanate include the same as those shown for the low molecular weight isocyanate compound. The organic polyisocyanates may be used either individually or in combination of two or more. Among the organic polyisocyanates, since the weatherability of the curable composition is excellent, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and modified polyisocyanates obtained by modifying these organic polyisocyanates. Is preferred.

  Moreover, an organic monoisocyanate can be used with an organic polyisocyanate. That is, a mixture of organic polyisocyanate and organic monoisocyanate can be used as the above-mentioned organic isocyanate compound. Examples of the organic monoisocyanate include the same as those shown for the low molecular weight isocyanate compound. The organic monoisocyanates may be used either individually or in combination of two or more.

  The active hydrogen-containing compound is a compound having at least one active hydrogen (group) in the compound. Specific examples include high molecular weight polyols, high molecular weight polyamines, low molecular weight polyols, low molecular weight polyamines, and high molecular weight and low molecular weight monools. Any of these active hydrogen-containing compounds can be used alone or in combination of two or more.

  The number average molecular weight of the polymer polyol and polymer polyamine is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000. The number average molecular weight of the high molecular weight monool is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 1,000 to 4,000.

  The molecular weight of the low molecular weight polyol, the low molecular weight polyamine, and the low molecular weight monool is preferably less than 1,000, more preferably 50 to 900. These molecular weights can be calculated from the structure. Moreover, when these have a molecular weight distribution such as a polymer, the molecular weight can be calculated as a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).

  Examples of the polymer polyol include polyester polyols, polycarbonate polyols, polyoxyalkylene-based polyols, poly (meth) acrylic polyols, hydrocarbon-based polyols, animal / vegetable polyols, and copolyols thereof. In the present invention, “(meth) acrylic” means “acrylic and / or methacrylic”.

  Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, etc. 1 or more of polycarboxylic acids and their anhydrides or carboxylic acids containing an alkyl ester such as methyl ester or ethyl ester, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8 -Octanediol, 1,9-nonane Obtained by a reaction with one or more low molecular weight polyols such as all, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, and pentaerythritol. Polyester polyols that can be mentioned.

  As the polycarbonate polyol, dehydrochlorination reaction of low molecular weight polyols and phosgene used in the synthesis of the above polyester polyol, or transesterification reaction of the above low molecular weight polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate The ones obtained in.

  Examples of the polyoxyalkylene-based polyol include low molecular weight polyols, low molecular weight polyamines, low molecular weight amino alcohols similar to those used in the above-mentioned polyester polyol synthesis; sorbitol, mannitol, sucrose, glucose and the like. Sugar-based low molecular weight polyhydric alcohols; one or more low molecular weight polyhydric phenols such as bisphenol A and bisphenol F as an initiator, and one or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Ring-opening addition polymerization or copolymerization, polyoxyethylene-based polyol, polyoxypropylene-based polyol, polyoxybutylene-based polyol, polyoxytetramethylene-based polyol, poly- (oxyethylene)-(oxypropylene - random or block copolymer polyols, further polyester polyether polyol initiator polyester polyols and polycarbonate polyols described above, polycarbonate polyol, and the like. Further, a polyol having a hydroxyl group at its molecular end is also exemplified by reacting these various polyols with an organic isocyanate compound in excess of hydroxyl groups with respect to isocyanate groups. The number of hydroxyl groups of the polyoxyalkylene-based polyol is preferably 2 or more on average in one molecule, more preferably 2 to 4, and particularly preferably 2 to 3.

  The polyoxyalkylene polyol has a dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of preferably 1.6 or less, more preferably 1.0 to 1.5. The weight average molecular weight in the present invention is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

  The catalyst for synthesizing the polyoxyalkylene polyol is a sodium catalyst, an alkali metal compound catalyst such as a potassium catalyst, a cationic polymerization catalyst, a complex metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex or a diglyme complex, Examples thereof include a phosphazene compound catalyst. Of these, alkali metal compound catalysts and complex metal cyanide complex catalysts are preferable. A polyoxyalkylene-based polyol synthesized using a complex cyanide complex catalyst is preferable because the total unsaturation degree is low and the viscosity of the polyol is low.

  Further, for modification of urethane prepolymer, polyoxypropylene-based compound obtained by ring-opening addition polymerization of the above-mentioned cyclic ether compound such as propylene oxide with low molecular weight monoalcohols such as methyl alcohol, ethyl alcohol and propyl alcohol as an initiator. A polyoxyalkylene-based monol such as monol can also be used.

  The "system" of the above-mentioned polyoxyalkylene-based polyol or polyoxyalkylene-based monool is 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass of the portion excluding the hydroxyl group in 1 mol of the molecule. Above, particularly preferably, if 95% by mass or more is composed of polyoxyalkylene, it means that the remaining portion may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. To do. In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”.

  A poly (meth) acrylic polyol is a radical polymerization such as a batch-type or continuous polymerization of a hydroxyl group-containing (meth) acrylic monomer and an ethylenically unsaturated compound other than the above, in the presence or absence of a solvent. It is obtained by copolymerization by the method of. What is obtained by carrying out a continuous block copolymerization reaction at a high temperature of 150 to 350 ° C., more preferably 210 to 250 ° C. in the absence of a solvent is preferable because the reaction product has a narrow molecular weight distribution and a low viscosity. In this copolymerization reaction, it is preferable to use the hydroxyl group-containing (meth) acrylic monomer so that the average hydroxyl functional number is 1.2 to 4 per molecule of the poly (meth) acrylic polyol. The glass transition point (Tg) of the poly (meth) acrylic polyol is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, further preferably −70 to −20 ° C., particularly preferably −70 to −30 ° C.

  The hydroxyl group-containing (meth) acrylic monomer is a (meth) acrylic monomer having one or more hydroxyl groups in the molecule. Specifically, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; pentaerythritol tri (meth) acrylate, glycerin mono (meth) acrylate, Mono (meth) acrylates or hydroxyl groups of polyhydric alcohols such as pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, polypropylene glycol mono (meth) acrylate Residual polyvalent (meth) acrylates may be mentioned. These can be used alone or in combination of two or more. Of these, hydroxyalkyl (meth) acrylates are preferable, and hydroxyethyl (meth) acrylate is more preferable, because the viscosity of the (meth) acrylic polyol is low and the reactivity with the isocyanate group is good.

  Examples of the ethylenically unsaturated compound other than the hydroxyl group-containing (meth) acrylic monomer include (meth) acrylic monomers and other ethylenically unsaturated compounds. Examples of the ethylenic compound other than the (meth) acrylic monomer include vinyl compounds such as ethylene, propylene, isobutylene, butadiene, chloroprene, styrene, chlorostyrene, 2-methylstyrene and divinylbenzene. Examples of (meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid. 2-ethylhexyl, benzyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, tridecyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glico Examples include rudi (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycidyl tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate. .. These can be used alone or in combination of two or more. Among these, the monomer of the (meth) acrylic acid ester compound is preferable in that the viscosity of the (meth) acrylic polyol is low, and further, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferred. In the present invention, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”.

  Examples of the hydrocarbon-based polyol include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; halogenated polyalkylene polyols such as chlorinated polypropylene polyol and chlorinated polyethylene polyol. Etc.

  Examples of animal and plant polyols include castor oil-based polyols and silk fibroin.

  The above-mentioned polymer polyols can be used alone or in combination of two or more. Among these, polyoxyalkylene-based polyols and poly (meth) acrylic polyols are preferable because they have good rubber physical properties after the curable composition is cured.

  A photoreactive unsaturated bond can be introduced into the isocyanate group-containing urethane prepolymer for the purpose of imparting weather resistance. The urethane prepolymer introduced with a photoreactive unsaturated bond acts as a curing component in the curable composition of the present invention and imparts good adhesion to the adhered surface and excellent weather resistance to the composition after curing. To do. The above-mentioned photoreactive unsaturated bond is an unsaturated bond that causes a chemical change such as polymerization in a relatively short time when exposed to light. Specific examples thereof include an unsaturated bond derived from a vinyl group, a vinylene group, and a (meth) acryloyl group. In the present invention, the “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”.

  The isocyanate group of the isocyanate group-containing urethane prepolymer having the photoreactive unsaturated bond introduced reacts with the active hydrogen-containing compound to crosslink and cure. Further, the photoreactive unsaturated bond of the isocyanate group-containing urethane prepolymer introduced with a photoreactive unsaturated bond, when exposed to light, undergoes a polymerization reaction to form a cured film having excellent weather resistance on the surface of the curable composition. Form. It is considered that this cured film imparts excellent weather resistance to the curable composition. The photoreactive unsaturated bond is preferably an unsaturated bond derived from a (meth) acryloyl group because of its high weather resistance imparting effect.

Examples of the method of introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer include the following methods.
(A) An organic isocyanate compound, a high molecular weight active hydrogen-containing compound (number average molecular weight of 1,000 or more), and a low molecular weight active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule (number And an average molecular weight of less than 1,000) under the condition of excess isocyanate groups with respect to the total amount of active hydrogen.
(B) An organic isocyanate compound and a polymer (number average molecular weight of 1,000 or more) of active hydrogen-containing compound having active hydrogen and a photoreactive unsaturated bond in the molecule (for example, polyoxyalkylene triol mono (meta ) Acrylate, alkylene oxide adduct of (meth) acrylic acid, polybutadiene polyol) under the condition of excess isocyanate groups with respect to the total amount of active hydrogen; and (c) Organic isocyanate compound and intramolecular A low molecular weight (number average molecular weight less than 1,000) active hydrogen-containing compound (for example, (meth) acryloyl isocyanate) having a photoreactive unsaturated bond and an isocyanate group, and a polymer (number average molecular weight of 1,000 or more) ) Active hydrogen-containing compound with respect to the total amount of active hydrogen under an isocyanate group excess condition. How obtainable by;
Among these methods, the method (a) is preferable in terms of availability of raw materials and easiness of reaction.

  The reaction for introducing the photoreactive unsaturated bond into the isocyanate group-containing urethane prepolymer may be performed by charging the raw materials all at once or by sequentially charging the raw materials. The molar ratio (isocyanate group / active hydrogen) of the isocyanate group of the organic isocyanate compound to the active hydrogen of the active hydrogen-containing compound (including the compound having active hydrogen and a photoreactive unsaturated bond) is 1.2 to 10. Is preferable, and 1.2-5 is more preferable. The isocyanate group content in the isocyanate group-containing urethane prepolymer having a photoreactive unsaturated bond introduced is preferably 0.3 to 15% by mass, more preferably 0.5 to 5% by mass.

  The concentration of the photoreactive unsaturated bond in the isocyanate group-containing urethane prepolymer having the photoreactive unsaturated bond introduced is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g, and particularly preferably 0.05 to 0.5 mmol / g is preferable.

  The active hydrogen-containing compound (of low molecular weight and high molecular weight) having the above-mentioned active hydrogen and a photoreactive unsaturated bond is a compound having active hydrogen (group) such as hydroxyl group, amino group and carboxyl group in the compound and vinyl group. , A vinylene group, a (meth) acryloyl group, and other photoreactive unsaturated bonds. A compound having a hydroxyl group and a (meth) acryloyl group in the compound is preferable from the viewpoint of easy reaction and high weather resistance imparting effect. Further, the molecular weight of the compound having active hydrogen (group) and the photoreactive unsaturated bond is preferably less than 1,000 in terms of number average molecular weight in terms of easy reaction.

  As the active hydrogen-containing compound having a hydroxyl group and a (meth) acryloyl group, 2-hydroxyethyl (meth) acrylate, which is a monoester of alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol and (meth) acrylic acid. , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, 6-hydroxyhexyl ( Monohydroxy mono (meth) acrylates such as (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, glycerin, trimethylolpropane, pentae Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth), which are polyesters such as monoesters or diesters of trifunctional or higher functional alkylene polyols such as thritol and (meth) acrylic acid, and triesters. ) Monohydropoly (meth) acrylates such as acrylates, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, polyhydroxymono (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di Examples thereof include polyhydroxy poly (meth) acrylates such as (meth) acrylate. In addition to these, dihydroxy glycols such as diethylene glycol, dipropylene glycol, polyoxyethylene polyols, polyoxypropylene polyols, and polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to bisphenol A and bisphenol F (meth ) Acrylates, polyhydroxymono (meth) acrylates, polyhydroxypoly (meth) acrylates and active hydrogens of hydroxyalkyl (meth) acrylates such as (meth) acrylic acid and hydroxyethyl (meth) acrylate, ethylene oxide, propylene oxide , Compounds having an alkylene oxide such as butylene oxide and having a hydroxyl group, caprolactone modified products of hydroxyethyl acrylate, etc. Compound has a hydroxyl group may also be mentioned. These can be used alone or in combination of two or more. Among these, monohydroxy poly (meth) acrylates and dihydroxy poly (meth) acrylates are preferable in that the viscosity of the urethane prepolymer can be suppressed to a low level and the weather resistance imparting effect can be enhanced.

  The curable composition may further contain an acidic compound. The acidic compound is used for the purpose of promoting hydrolysis of the silylamine compound and accelerating the curing of the curable composition. Examples of the acidic compound include a phosphoric acid ester compound, an organic carboxylic acid compound, an organic carboxylic acid anhydride compound, an organic sulfonic acid isocyanate compound, an organic sulfonic acid compound, and an organic sulfonimide compound. Any of these may be used alone or in combination of two or more.

  Examples of the phosphoric acid ester compound include an orthophosphoric acid ester compound and a phosphorous acid ester compound. Of these, orthophosphate compounds are preferred. Any of these may be used alone or in combination of two or more.

  Examples of the orthophosphoric acid ester compound include an orthophosphoric acid trialkyl ester compound, an orthophosphoric acid dialkyl ester compound, and an orthophosphoric acid monoalkyl ester compound.

  Examples of the trialkyl ester compound of orthophosphoric acid include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, cresyl di2,6-xylenyl phosphate and the like.

  Examples of monoalkyl ester compounds and dialkyl ester compounds (acidic phosphoric acid ester compounds) of orthophosphoric acid include ethyl acid phosphate, butyl acid phosphate, dibutyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, alkyl (C12, C14). , C16, C18) acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, and the like. Examples of the monoalkyl ester compound include monoethyl phosphate, monobutyl phosphate, monobutoxyethyl phosphate, mono n-octyl phosphate, mono 2-ethylhexyl phosphate, monolauryl phosphate, mono (2-hydroxyethyl methacrylate) phosphate and the like. Examples of the dialkyl ester compound include diethyl phosphate, dibutyl phosphate, dibutyl pyrophosphate, dibutoxyethyl phosphate, di-n-octyl phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate and the like. Any of these orthophosphate compounds may be used alone or in combination of two or more.

  Examples of the phosphite compound include triethylphosphite, triphenylphosphite, trisnonylphenylphosphite, tridecylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, and other phosphite triesters. Compounds: phosphite diester compounds such as dilauryl hydrogen phosphite, dioleyl hydrogen phosphite and diphenyl hydrogen phosphite. Any of these phosphite compounds can be used alone or in combination of two or more.

  Specific examples of the organic carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, and lauric acid. , Tridecyl acid, myristic acid, pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, mericinic acid, laxeric acid, acrylic acid, methacrylic acid, lactic acid , 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberculostearic acid, pivalic acid, neodecanoic acid, adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid, ethylmalonic acid, glutaric acid , Oxalic acid, malonic acid, succinic acid, oxydiacetic acid, maleic acid, fumar , Acetylene dicarboxylic acid, itaconic acid, benzoic acid, 9-anthracene carboxylic acid, anisic acid, isopropyl benzoic acid, toluic acid, phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl acetic acid, pyromellitic acid, salicylic acid. Any of these may be used alone or in combination of two or more.

  Specific examples of the organic carboxylic anhydride compound include maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Examples thereof include phthalic anhydride and methylcyclohexene tetracarboxylic acid anhydride. Any of these may be used alone or in combination of two or more.

  Specific examples of the organic sulfonic acid isocyanate compound include p-toluenesulfonyl isocyanate.

  Specific examples of the organic sulfonic acid compound include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, nonafluoro-1-butanesulfonic acid, and heptadeca. Examples thereof include fluorooctane sulfonic acid, (+)-10-camphor sulfonic acid, m-xylene-4-sulfonic acid anhydride and p-xylene-2-sulfonic acid anhydride.

  Specific examples of the organic sulfonimide compound include saccharin and N- (trifluoromethanesulfonyl) trifluoroacetamide.

  The amount of the acidic compound in the curable composition is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the isocyanate compound and the silylamine compound (1).

  The curable composition may contain various additives, if necessary. Specific examples of the additive include a curing accelerating catalyst, a plasticizer, a weather resistance stabilizer, a filler, a thixotropic agent, an adhesiveness improving agent, a storage stability improving agent (dehydrating agent), a colorant and an organic solvent. Can be mentioned. Any of these may be used alone or in combination of two or more.

  When using an organic solvent, as the organic solvent, specifically, pentane, hexane, heptane, octane, cyclohexane, toluene, xylene, ethyl formate, butyl formate, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, acetonitrile, propylene. Pionitrile, diethyl ether, dibutyl ether, tetrahydrofuran and the like can be mentioned.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited thereto. In the examples, ¹ H-NMR was measured at 400 MHz using AV400 manufactured by Bruker BioSpin Co., Ltd. The chemical shift of ¹ H-NMR was based on the chemical shift (7.20 ppm) of the peak of benzene in heavy benzene.

In the present specification, the degree of polymerization is the number average degree of polymerization unless otherwise specified, and the degree of polymerization n of the silylamine compounds E to J is the integral ratio of the etheric oxygen atom adjacent position and the nitrogen atom adjacent position in ¹ H-NMR analysis. I asked more.

  Further, in the examples, the “number of oxygen atoms in the molecule” refers to the number of etheric oxygen atoms in the silylamine compound. The “number of oxygen atoms in the molecule” of the silylamine compounds E to J was calculated by adding the number of oxygen atoms not included in the repeating unit to the polymerization degree n of each compound.

窒素置換した３Ｌ四つ口フラスコに４，９−ジオキサ−１，１２−ドデカンジアミン１６０．０ｇ（７８３ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン４７７．２ｇ（３１３５ｍｍｏｌ）、アセトニトリル８１０ｍＬを仕込み、得られた混合物を１０℃以下に冷却し、クロロトリメチルシラン３４３．１ｇ（３１５８ｍｍｏｌ）を滴下後、得られた反応混合物を２５℃で２４時間撹拌した。反応混合物に対してヘプタン１５０ｍＬによる抽出操作を３回行った。ヘプタン層を減圧下濃縮後、窒素下にて濾過し、上記式で表されるシリルアミン化合物Ａを３３９．１ｇ得た（収率８７．９％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 1 Synthesis of silylamine compound A

In a 3 L four-necked flask purged with nitrogen, 160.0 g (783 mmol) of 4,9-dioxa-1,12-dodecanediamine and 477.2 g (3135 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene. , 810 mL of acetonitrile were charged, the obtained mixture was cooled to 10 ° C. or lower, 343.1 g (3158 mmol) of chlorotrimethylsilane was added dropwise, and then the obtained reaction mixture was stirred at 25 ° C. for 24 hours. The extraction operation with 150 mL of heptane was performed on the reaction mixture three times. The heptane layer was concentrated under reduced pressure and then filtered under nitrogen to obtain 339.1 g of the silylamine compound A represented by the above formula (yield 87.9%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.28-3.25 (m, 4H), 3.23-3.21 (m, 4H), 2.98-2.94 (m , 4H), 1.68-1.65 (m, 8H), 0.17 (s, 36H).

窒素置換した５００ｍＬ四つ口フラスコに３，６−ジオキサ−１，８−オクタンジアミン２０．３ｇ（１３７ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン８３．６ｇ（５４９ｍｍｏｌ）、アセトニトリル１５５ｍＬを仕込み、得られた混合物を１０℃以下に冷却し、クロロトリメチルシラン５８．９ｇ（５４８ｍｍｏｌ）を滴下後、反応混合物を２５℃で２１時間撹拌した。反応混合物に対してヘプタン５０ｍＬによる抽出操作を４回行った。ヘプタン層を減圧下濃縮後、窒素下にて濾過し、上記式で表されるシリルアミン化合物Ｂを５２．８ｇ得た（収率８８．３％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 2 Synthesis of silylamine compound B

20.3 g (137 mmol) of 3,6-dioxa-1,8-octanediamine and 83.6 g (549 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene were placed in a 500 mL four-necked flask that had been purged with nitrogen. , 155 mL of acetonitrile were charged, the obtained mixture was cooled to 10 ° C. or lower, and 58.9 g (548 mmol) of chlorotrimethylsilane was added dropwise, and then the reaction mixture was stirred at 25 ° C. for 21 hours. The extraction operation with 50 mL of heptane was performed on the reaction mixture four times. The heptane layer was concentrated under reduced pressure and then filtered under nitrogen to obtain 52.8 g of the silylamine compound B represented by the above formula (yield 88.3%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.43 (s, 4H), 3.29 (t, J = 7.0 Hz, 4H), 2.98-2.94 (m, 4H). ), 0.15 (s, 36H)

窒素置換した４００ｍＬ四つ口フラスコに４，７−ジオキサ−１，１０−デカンジアミン１５．３ｇ（８７ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン５２．４ｇ（３４４ｍｍｏｌ）、アセトニトリル１５５ｍＬを仕込み、得られた混合物を１０℃以下に冷却し、クロロトリメチルシラン３７．４ｇ（３４４ｍｍｏｌ）を滴下後、反応混合物を２５℃で１４時間撹拌した。反応混合物に対してヘプタン５０ｍＬによる抽出操作を４回行った。ヘプタン層を減圧下濃縮後、窒素下にて濾過し、上記式で表されるシリルアミン化合物Ｃを３６．４ｇ得た（収率９０．１％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 3 Synthesis of silylamine compound C

Nitrogen-substituted 400 mL four-necked flask was charged with 4,7-dioxa-1,10-decanediamine (15.3 g, 87 mmol) and 1,8-diazabicyclo [5.4.0] -7-undecene (52.4 g, 344 mmol). Then, 155 mL of acetonitrile was charged, the obtained mixture was cooled to 10 ° C. or lower, and 37.4 g (344 mmol) of chlorotrimethylsilane was added dropwise, and then the reaction mixture was stirred at 25 ° C. for 14 hours. The extraction operation with 50 mL of heptane was performed on the reaction mixture four times. The heptane layer was concentrated under reduced pressure and then filtered under nitrogen to obtain 36.4 g of the silylamine compound C represented by the above formula (yield 90.1%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.42 (s, 4H), 3.29-3.26 (m, 4H), 2.98-2.94 (m, 4H), 1.72-1.65 (m, 4H), 0.15 (s, 36H)

窒素置換した５００ｍＬ四つ口フラスコに４，７，１０−トリオキサ−１，１３−トリデカンジアミン１５．０ｇ（６８ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン４１．５ｇ（２７３ｍｍｏｌ）、アセトニトリル１９０ｍＬを仕込み、得られた混合物を１０℃以下に冷却し、クロロトリメチルシラン３０．０ｇ（２７６ｍｍｏｌ）を滴下後、反応混合物を２５℃で２３時間撹拌した。反応混合物に対してヘプタン５０ｍＬによる抽出操作を５回行った。ヘプタン層を減圧下濃縮後、窒素下にて濾過し、上記式で表されるシリルアミン化合物Ｄを２９．５ｇ得た（収率８５．２％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 4 Synthesis of silylamine compound D

In a 500 mL four-necked flask purged with nitrogen, 15.0 g (68 mmol) of 4,7,10-trioxa-1,13-tridecanediamine and 41.5 g of 1,8-diazabicyclo [5.4.0] -7-undecene. (273 mmol) and 190 mL of acetonitrile were charged, the obtained mixture was cooled to 10 ° C. or lower, 30.0 g (276 mmol) of chlorotrimethylsilane was added dropwise, and then the reaction mixture was stirred at 25 ° C. for 23 hours. The extraction operation with 50 mL of heptane was performed 5 times on the reaction mixture. The heptane layer was concentrated under reduced pressure and then filtered under nitrogen to obtain 29.5 g of the silylamine compound D represented by the above formula (yield 85.2%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.54 to 3.52 (m, 4H), 3.44 to 3.42 (m, 4H), 3.27 to 3.24 (m. , 4H), 2.97-2.93 (m, 4H), 1.70-1.66 (m, 4H), 0.19 (s, 36H).

窒素置換した２００ｍＬ３つ口フラスコに２０．１ｇ（６７ｍｍｏｌ）のポリエチレングリコール３００（富士フイルム和光純薬株式会社製）、水５．０ｍＬ、４８％水酸化ナトリウム水溶液０．１ｇ（１ｍｍｏｌ）を仕込み、反応液の温度を２５〜３０℃に保ちながらアクリロニトリル１０．６ｇ（２００ｍｍｏｌ）を滴下した。得られた反応混合物を２５℃で２時間撹拌した後、トリフルオロ酢酸０．５ｇ（２ｍｍｏｌ）を加えて反応を停止した。混合物を減圧下濃縮し、上記式で表されるＰＥＧ３００−ＥｔＣＮを２７．５ｇ得た（収率９９．７％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 5 Synthesis of silylamine compound E (i) Synthesis of PEG300-EtCN

20.1 g (67 mmol) of polyethylene glycol 300 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 5.0 mL of water, and 0.1 g (1 mmol) of 48% sodium hydroxide aqueous solution were charged into a 200 mL three-necked flask whose atmosphere was replaced with nitrogen, and the reaction was performed. 10.6 g (200 mmol) of acrylonitrile was added dropwise while maintaining the temperature of the liquid at 25 to 30 ° C. The obtained reaction mixture was stirred at 25 ° C. for 2 hours, and then trifluoroacetic acid (0.5 g, 2 mmol) was added to stop the reaction. The mixture was concentrated under reduced pressure to obtain 27.5 g of PEG300-EtCN represented by the above formula (yield 99.7%). ^The results of ¹ H-NMR analysis are shown below.

^{_{1 H-NMR (C 6 D}} 6) δ (ppm): 3.66-3.22 (m, 76H), 2.73-2.69 (m, 4H), 1.86-1.78 (m , 4H)

窒素置換した５００ｍＬ四つ口フラスコにＰＥＧ３００−ＥｔＣＮ２０．０ｇ（４９ｍｍｏｌ）、メタノール３６８ｍＬ、二炭酸ジ−ｔｅｒｔ−ブチル４３．１ｇ（１９８ｍｍｏｌ）、塩化ニッケル六水和物２．３ｇ（１０ｍｍｏｌ）を仕込み、得られた混合物を１０℃以下に冷却し、窒素気流下にて水素化ホウ素ナトリウム２５．１ｇ（３１８ｍｍｏｌ）を２時間かけて加えた。得られた反応混合物を２５℃で５時間撹拌後、飽和炭酸ナトリウム水溶液５０ｍＬを加え、酢酸エチル１００ｍＬによる抽出操作を３度行った。酢酸エチル層を硫酸マグネシウムにより乾燥し、減圧下濃縮した。濃縮物に対して水１００ｍＬ、濃塩酸２０ｍＬを加え、２５℃で１３時間撹拌後、さらに濃塩酸２０ｍＬを加え６０℃で２時間攪拌した。反応混合物に４８％水酸化ナトリウム水溶液３０ｍＬを加え、得られた混合物を減圧下濃縮した。得られた残渣にテトラヒドロフラン２００ｍＬを加え、濾過をした。
濾液を減圧下濃縮し、残渣２０．０ｇに対してクロロトリメチルシラン４２．１ｇ（３８９ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン６１．１ｇ（４０１ｍｍｏｌ）、トルエン１０１ｍＬを加えた。得られた反応混合物を２５℃で７２時間撹拌し、ジエチルアミン１４．６ｇ（１５３ｍｍｏｌ）を滴下した。反応混合物を濾過し、濾液を減圧下濃縮することで、上記式で表されるシリルアミン化合物Ｅを２３．６ｇ得た（収率６９．５％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。また、^１Ｈ−ＮＭＲ分析結果より、シリルアミン化合物Ｅの重合度ｎは１１．０、分子中酸素原子数は１２．０であった。 (Ii) Synthesis of silylamine compound E

Into a 500 mL four-necked flask substituted with nitrogen, 20.0 g (49 mmol) of PEG300-EtCN, 368 mL of methanol, 43.1 g (198 mmol) of di-tert-butyl dicarbonate, and 2.3 g (10 mmol) of nickel chloride hexahydrate were charged, The obtained mixture was cooled to 10 ° C. or lower, and 25.1 g (318 mmol) of sodium borohydride was added over 2 hours under a nitrogen stream. The obtained reaction mixture was stirred at 25 ° C. for 5 hours, 50 mL of a saturated sodium carbonate aqueous solution was added, and extraction with 100 mL of ethyl acetate was performed 3 times. The ethyl acetate layer was dried over magnesium sulfate and concentrated under reduced pressure. To the concentrate, 100 mL of water and 20 mL of concentrated hydrochloric acid were added, and after stirring at 25 ° C for 13 hours, 20 mL of concentrated hydrochloric acid was further added and stirred at 60 ° C for 2 hours. 30 mL of 48% sodium hydroxide aqueous solution was added to the reaction mixture, and the obtained mixture was concentrated under reduced pressure. 200 mL of tetrahydrofuran was added to the obtained residue, and the mixture was filtered.
The filtrate was concentrated under reduced pressure, and 42.1 g (389 mmol) of chlorotrimethylsilane, 61.1 g (401 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene, and 101 mL of toluene were added to 20.0 g of the residue. added. The obtained reaction mixture was stirred at 25 ° C. for 72 hours, and 14.6 g (153 mmol) of diethylamine was added dropwise. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to give 23.6 g of the silylamine compound E represented by the above formula (yield 69.5%). ^The results of ¹ H-NMR analysis are shown below. Further, from the ¹ H-NMR analysis result, the degree of polymerization n of the silylamine compound E was 11.0, and the number of oxygen atoms in the molecule was 12.0.

^{_{1 H-NMR (C 6 D}} 6) δ (ppm): 3.66-3.16 (m, 48H), 2.95-2.91 (m, 4H), 1.70-1.63 (m , 4H), 0.17 (s, 36H)

窒素置換した２００ｍＬ３つ口フラスコに２０．０ｇ（５０ｍｍｏｌ）のポリエチレングリコール４００（富士フイルム和光純薬株式会社製）、水５．３ｍＬ、４８％水酸化ナトリウム水溶液０．１ｇ（１ｍｍｏｌ）を仕込み、反応液の温度を２５〜３０℃に保ちながらアクリロニトリル８．０ｇ（１５０ｍｍｏｌ）を滴下した。得られた反応混合物を２５℃で６時間撹拌した後、トリフルオロ酢酸０．５ｇ（２ｍｍｏｌ）を加えて反応を停止した。混合物を減圧下濃縮し、上記式で表されるＰＥＧ４００−ＥｔＣＮを２５．６ｇ得た（収率９９．２％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 6 Synthesis of silylamine compound F (i) Synthesis of PEG400-EtCN

20.0 g (50 mmol) of polyethylene glycol 400 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 5.3 mL of water, and 0.1 g (1 mmol) of 48% sodium hydroxide aqueous solution were charged into a 200 mL three-necked flask whose atmosphere was replaced with nitrogen, and the reaction was performed. 8.0 g (150 mmol) of acrylonitrile was added dropwise while maintaining the temperature of the liquid at 25 to 30 ° C. The obtained reaction mixture was stirred at 25 ° C for 6 hours, and then 0.5 g (2 mmol) of trifluoroacetic acid was added to stop the reaction. The mixture was concentrated under reduced pressure to obtain 25.6 g of PEG400-EtCN represented by the above formula (yield 99.2%). ^The results of ¹ H-NMR analysis are shown below.

^{_{1 H-NMR (C 6 D}} 6) δ (ppm): 3.59-3.02 (m, 171H), 2.76-2.73 (m, 4H), 1.69-1.66 (m , 4H)

窒素置換した５００ｍＬ四つ口フラスコにＰＥＧ４００−ＥｔＣＮ２０．０ｇ（３４ｍｍｏｌ）、メタノール２９３ｍＬ、二炭酸ジ−ｔｅｒｔ−ブチル３５．２ｇ（１６１ｍｍｏｌ）、塩化ニッケル六水和物１．９ｇ（８ｍｍｏｌ）を仕込み、得られた混合物を１０℃以下に冷却し、窒素気流下にて水素化ホウ素ナトリウム２７．０ｇ（３４３ｍｍｏｌ）を２時間かけて加えた。得られた反応混合物を２５℃で５時間撹拌後、飽和炭酸ナトリウム水溶液５０ｍＬを加え、酢酸エチル５５ｍＬによる抽出操作を３度行った。酢酸エチル層を硫酸マグネシウムにより乾燥し、減圧下濃縮した。濃縮物に対してメタノール６３ｍＬ、濃塩酸１０ｍＬを加え、２５℃で１３時間撹拌後、さらに濃塩酸２０ｍＬを加え５０℃で３時間攪拌した。反応混合物に４８％水酸化ナトリウム水溶液３０ｍＬを加え、得られた混合物を減圧下濃縮し、得られた残渣にテトラヒドロフラン２００ｍＬを加え、濾過をした。
濾液を減圧下濃縮し、残渣１８．４ｇに対してクロロトリメチルシラン３３．１ｇ（３０５ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン４４．１ｇ（２９０ｍｍｏｌ）、トルエン９４ｍＬを加えた。得られた反応混合物を２５℃で７２時間撹拌し、ジエチルアミン１１．２ｇ（１５３ｍｍｏｌ）を滴下した。反応混合物を濾過し、濾液を減圧下濃縮することで、上記式で表されるシリルアミン化合物Ｆを７．７３ｇ得た（収率２８．４％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。また、^１Ｈ−ＮＭＲ分析結果より、上記式中、重合度ｎは１３．９、分子中酸素原子数は１４．９であった。 (Ii) Synthesis of silylamine compound F

Into a 500 mL four-necked flask substituted with nitrogen, 20.0 g (34 mmol) of PEG400-EtCN, 293 mL of methanol, 35.2 g (161 mmol) of di-tert-butyl dicarbonate, and 1.9 g (8 mmol) of nickel chloride hexahydrate were charged, The resulting mixture was cooled to 10 ° C. or lower, and 27.0 g (343 mmol) of sodium borohydride was added over 2 hours under a nitrogen stream. The obtained reaction mixture was stirred at 25 ° C. for 5 hours, 50 mL of a saturated aqueous sodium carbonate solution was added, and extraction with 55 mL of ethyl acetate was performed 3 times. The ethyl acetate layer was dried over magnesium sulfate and concentrated under reduced pressure. To the concentrate, 63 mL of methanol and 10 mL of concentrated hydrochloric acid were added, and after stirring at 25 ° C for 13 hours, 20 mL of concentrated hydrochloric acid was further added and stirred at 50 ° C for 3 hours. 30 mL of 48% sodium hydroxide aqueous solution was added to the reaction mixture, the obtained mixture was concentrated under reduced pressure, 200 mL of tetrahydrofuran was added to the obtained residue, and the mixture was filtered.
The filtrate was concentrated under reduced pressure, and to the residue 18.4 g, 33.1 g (305 mmol) of chlorotrimethylsilane, 44.1 g (290 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene, and 94 mL of toluene were added. added. The obtained reaction mixture was stirred at 25 ° C. for 72 hours, and 11.2 g (153 mmol) of diethylamine was added dropwise. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 7.73 g of the silylamine compound F represented by the above formula (yield 28.4%). ^The results of ¹ H-NMR analysis are shown below. From the ¹ H-NMR analysis result, the degree of polymerization n was 13.9 and the number of oxygen atoms in the molecule was 14.9 in the above formula.

^{_{1 H-NMR (C 6 D}} 6) δ (ppm): 3.66-3.22 (m, 60H), 2.95-2.91 (m, 4H), 1.69-1.62 (m , 4H), 0.16 (s, 36H)

窒素置換した２００ｍＬ３つ口フラスコに２０．３ｇ（３３ｍｍｏｌ）のポリエチレングリコール６００（キシダ化学株式会社製）、水５ｍＬ、４８％水酸化ナトリウム水溶液０．１ｇ（１ｍｍｏｌ）を仕込み、反応液の温度を２５〜３０℃に保ちながらアクリロニトリル５．３ｇ（１００ｍｍｏｌ）を滴下した。得られた反応混合物を２５℃で２２時間撹拌した後、トリフルオロ酢酸０．５ｇ（２ｍｍｏｌ）を加えて反応を停止した。混合物を減圧下濃縮し、上記式で表されるＰＥＧ６００−ＥｔＣＮを３１．７ｇ得た（収率９８．３％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。
^１Ｈ−ＮＭＲ（Ｃ_６Ｄ_６）δ（ｐｐｍ）：３．５９−３．０２（ｍ，１０９Ｈ），２．６１−２．５８（ｍ，４Ｈ），１．５２−１．４９（ｍ，４Ｈ） Production Example 7 Synthesis of silylamine compound G (i) Synthesis of PEG600-EtCN

20.3 g (33 mmol) of polyethylene glycol 600 (manufactured by Kishida Chemical Co., Ltd.), 5 mL of water, and 0.1 g (1 mmol) of 48% sodium hydroxide aqueous solution were charged into a 200 mL three-necked flask which had been replaced with nitrogen, and the temperature of the reaction solution was adjusted to 25. 5.3 g (100 mmol) of acrylonitrile was added dropwise while maintaining at -30 ° C. The obtained reaction mixture was stirred at 25 ° C. for 22 hours, and then trifluoroacetic acid (0.5 g, 2 mmol) was added to stop the reaction. The mixture was concentrated under reduced pressure to obtain 31.7 g of PEG600-EtCN represented by the above formula (yield 98.3%). ^The results of ¹ H-NMR analysis are shown below.
¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.59-3.02 (m, 109H), 2.61-2.58 (m, 4H), 1.52-1.49 (m). , 4H)

窒素置換した５００ｍＬ四つ口フラスコにＰＥＧ６００−ＥｔＣＮ１０．０ｇ（８ｍｍｏｌ）、メタノール１０６ｍＬ、二炭酸ジ−ｔｅｒｔ−ブチル１２．４ｇ（５７ｍｍｏｌ）、塩化ニッケル六水和物０．７ｇ（３ｍｍｏｌ）を仕込み、得られた混合物を１０℃以下に冷却し、窒素気流下にて水素化ホウ素ナトリウム９．７１ｇを３０分かけて加えた。得られた反応混合物を２５℃で４．５時間撹拌し、飽和炭酸ナトリウム水溶液５０ｍＬを加え反応を停止した。反応混合物に対して、酢酸エチル５０ｇによる抽出操作を３度行った。酢酸エチル層を硫酸マグネシウムにより乾燥し、減圧下濃縮した。濃縮物に対してメタノール６３ｍＬ、濃塩酸３ｍＬを加え、２５℃で５日間撹拌後、水酸化ナトリウムを加えｐＨ１１以上とした。混合物を減圧下濃縮後、テトラヒドロフラン１５０ｍＬを加え、濾過をした。濾液を減圧下濃縮し、上記式で表されるＰＥＧＰＡ−６００を７．６６ｇ得た（収率９１．４％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 (Ii) Synthesis of PEGPA-600

Into a 500 mL four-necked flask substituted with nitrogen, 10.0 g (8 mmol) of PEG600-EtCN, 106 mL of methanol, 12.4 g (57 mmol) of di-tert-butyl dicarbonate and 0.7 g (3 mmol) of nickel chloride hexahydrate were charged, The obtained mixture was cooled to 10 ° C. or lower, and 9.71 g of sodium borohydride was added over 30 minutes under a nitrogen stream. The obtained reaction mixture was stirred at 25 ° C. for 4.5 hours, and 50 mL of saturated sodium carbonate aqueous solution was added to stop the reaction. The reaction mixture was extracted three times with 50 g of ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate and concentrated under reduced pressure. To the concentrate, 63 mL of methanol and 3 mL of concentrated hydrochloric acid were added, and after stirring at 25 ° C for 5 days, sodium hydroxide was added to adjust the pH to 11 or more. The mixture was concentrated under reduced pressure, 150 mL of tetrahydrofuran was added, and the mixture was filtered. The filtrate was concentrated under reduced pressure to obtain 7.66 g of PEGPA-600 represented by the above formula (yield 91.4%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.68-3.29 (m, 70H), 2.67-2.60 (m, 4H), 1.57-1.52 (m , 4H)

窒素置換した５００ｍＬナス型フラスコにＰＥＧＰＡ−６００を６．９ｇ（８ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン４．９ｇ（３２ｍｍｏｌ）、トルエン３５ｍＬを仕込み、得られた反応混合物に対してクロロトリメチルシラン３．５ｇ（３２ｍｍｏｌ）を滴下後、２５℃で２５時間撹拌した。反応混合物に対してクロロトリメチルシラン１０．０ｇ（９２ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン３．０ｇ（２０ｍｍｏｌ）をさらに加え２５℃で２０時間撹拌し、反応混合物に対してジエチルアミン３０．５ｇ（４１７ｍｍｏｌ）を滴下した。反応混合物を濾過して得られた濾液を減圧下濃縮することで、上記式で表されるシリルアミン化合物Ｇを８．４１ｇ得た（収率７７．１％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。^１Ｈ−ＮＭＲ分析結果より、上記式中、重合度ｎは１６．５、分子中酸素原子数は１７．５であった。 (Iii) Synthesis of silylamine compound G

A 500 mL eggplant-shaped flask whose nitrogen had been replaced was charged with 6.9 g (8 mmol) of PEGPA-600, 4.9 g (32 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene, and 35 mL of toluene, which were obtained. After 3.5 g (32 mmol) of chlorotrimethylsilane was added dropwise to the reaction mixture, the mixture was stirred at 25 ° C. for 25 hours. To the reaction mixture, 10.0 g (92 mmol) of chlorotrimethylsilane and 3.0 g (20 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene were further added, and the mixture was stirred at 25 ° C for 20 hours to give a reaction mixture. Then, 30.5 g (417 mmol) of diethylamine was added dropwise. The filtrate obtained by filtering the reaction mixture was concentrated under reduced pressure to obtain 8.41 g of the silylamine compound G represented by the above formula (yield 77.1%). ^The results of ¹ H-NMR analysis are shown below. ^{From the 1} H-NMR analysis result, the degree of polymerization n was 16.5 and the number of oxygen atoms in the molecule was 17.5 in the above formula.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.69-3.18 (m, 78H), 3.01-2.93 (m, 4H), 1.72-1.65 (m , 4H), 0.19 (s, 36H)

窒素置換した３Ｌナス型フラスコに１４７７．６ｇ（１４７８ｍｍｏｌ）のポリエチレングリコール１，０００（富士フイルム和光純薬株式会社製）、水３６７ｍＬを仕込み、得られた混合物を加熱した。混合物の温度が４７℃になった時点で、４８％水酸化ナトリウム水溶液１．２ｇ、水１．８ｇを混合物に加えた。混合物の温度を４７℃に保ち、１時間攪拌した後、２５℃へ冷却した。アクリロニトリル２３５．２ｇ（４４３３ｍｍｏｌ）を２時間かけて混合物へ滴下し、２５℃で３時間攪拌した。攪拌後、リン酸１．５ｇ、水１ｍＬを加えて反応を停止し、反応液２０７８．１ｇを得た。得られた反応液に水１２６ｍＬを加え、吸引濾過し、濾液２１９５．２ｇを得た。得られた濾液のうち２１７６．６ｇを５Ｌ四つ口フラスコへ移し、減圧下濃縮し、無色透明溶液２０５０．２ｇを得た。得られた無色透明溶液をトルエン２９２ｍＬに加え減圧下にて濃縮し、さらにトルエン１１６ｍＬを加え減圧下共沸脱水を行い、固体を１６７１．５ｇ得た。得られた固体を３７２．１ｇ採取し、残存した固体１２９９．４ｇにトルエン１２６８．２ｍＬを加え、反応混合物２３９７．９ｇを得た。得られた反応混合物の全量を５Ｌオートクレーブに仕込み、ＮＤＴ−６５（川研ファインケミカル株式会社製）３１６．４ｇ、トルエン２３１ｍＬをさらに加え、５Ｌオートクレーブ内を窒素置換した。窒素置換後、室温下アンモニアガスを導入し５Ｌオートクレーブ内の圧力を０．５ＭＰａとし、さらに水素を導入して圧力を３．０ＭＰａとした。続いて昇温し、反応液温度８０℃、反応器内部圧力４．４ＭＰａの条件で３時間反応を行った。反応後、反応液を室温まで冷却し、反応器内部圧力を常圧まで低下させた。得られた反応液にトルエン１４１ｍＬと水を加え、反応液を抜き出した。抜き出した反応液にさらにトルエン６４９ｍＬ、パーライト３５.０ｇを加え濾過をし、得られた濾液を減圧下濃縮し、無色透明液体１２１８．７ｇを得た。無色透明液体に水６００ｍＬを加えて得られた混合物を減圧下濃縮し、上記式で表されるＰＥＧＰＡ−１０００を１２０１.３ｇ得た。 Production Example 8 Synthesis of silylamine compound H (i) Synthesis of PEGPA-1000

A 3 L eggplant-shaped flask whose nitrogen was replaced was charged with 1477.6 g (1478 mmol) of polyethylene glycol 1,000 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 367 mL of water, and the obtained mixture was heated. When the temperature of the mixture reached 47 ° C., 1.2 g of 48% aqueous sodium hydroxide solution and 1.8 g of water were added to the mixture. The temperature of the mixture was kept at 47 ° C, stirred for 1 hour, and then cooled to 25 ° C. 235.2 g (4433 mmol) of acrylonitrile was added dropwise to the mixture over 2 hours, and the mixture was stirred at 25 ° C for 3 hours. After stirring, the reaction was stopped by adding phosphoric acid (1.5 g) and water (1 mL) to obtain a reaction liquid (2078.1 g). 126 mL of water was added to the obtained reaction liquid, and suction filtration was performed to obtain 2195.2 g of a filtrate. 2176.6 g of the obtained filtrate was transferred to a 5 L four-necked flask and concentrated under reduced pressure to obtain 2050.2 g of a colorless transparent solution. The obtained colorless transparent solution was added to 292 mL of toluene and concentrated under reduced pressure, 116 mL of toluene was further added, and azeotropic dehydration was performed under reduced pressure to obtain 1671.5 g of a solid. 372.1 g of the obtained solid was collected, and 1268.2 mL of toluene was added to 1299.4 g of the remaining solid to obtain 2397.9 g of a reaction mixture. The total amount of the obtained reaction mixture was charged into a 5 L autoclave, 316.4 g of NDT-65 (manufactured by Kawaken Fine Chemical Co., Ltd.) and 231 mL of toluene were further added, and the inside of the 5 L autoclave was replaced with nitrogen. After purging with nitrogen, ammonia gas was introduced at room temperature to bring the pressure in the 5 L autoclave to 0.5 MPa, and further hydrogen was introduced to bring the pressure to 3.0 MPa. Subsequently, the temperature was raised, and the reaction was carried out for 3 hours under the conditions of a reaction liquid temperature of 80 ° C. and a reactor internal pressure of 4.4 MPa. After the reaction, the reaction solution was cooled to room temperature and the internal pressure of the reactor was lowered to normal pressure. Toluene 141mL and water were added to the obtained reaction liquid, and the reaction liquid was extracted. Toluene (649 mL) and perlite (35.0 g) were added to the extracted reaction liquid and the mixture was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 1218.7 g of a colorless transparent liquid. 600 mL of water was added to the colorless transparent liquid, and the resulting mixture was concentrated under reduced pressure to obtain 1201.3 g of PEGPA-1000 represented by the above formula.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.49-3.29 (m, 90H), 2.66-2.60 (m, 4H), 1.57-1.54 (m , 4H)

窒素置換した４００ｍＬ四つ口フラスコに３１．７ｇ（２９ｍｍｏｌ）のＰＥＧＰＡ−１０００、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン１７．１ｇ（１１２ｍｍｏｌ）、トルエン１４０ｍＬを仕込み、得られた反応混合物に対してクロロトリメチルシラン１２．１ｇ（１１２ｍｍｏｌ）を滴下後、２５℃で４８時間撹拌した。反応混合物に対してテトラヒドロフラン２５ｍｌ、塩化メチレン２８ｍｌを加え、２４時間攪拌した。得られた反応混合物にクロロトリメチルシラン１２．７ｇ（１１７ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン１７．２ｇ（１１３ｍｍｏｌ）をさらに加え２５℃で２４時間撹拌し、反応混合物に対してプロピルアミン１６．７ｇ（２８２ｍｍｏｌ）を滴下し反応を停止した。反応混合物を濾過して得られた濾液を減圧下濃縮することで、上記式で表されるシリルアミン化合物Ｈを３１．６ｇ得た（収率７８．６％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。^１Ｈ−ＮＭＲ分析結果より、上記式中、重合度ｎは２２．１、分子中酸素原子数は２３．１であった。 (Ii) Synthesis of silylamine compound H

A nitrogen-substituted 400 mL four-necked flask was charged with 31.7 g (29 mmol) of PEGPA-1000, 1,8-diazabicyclo [5.4.0] -7-undecene (17.1 g, 112 mmol) and toluene (140 mL). 12.1 g (112 mmol) of chlorotrimethylsilane was added dropwise to the reaction mixture, and the mixture was stirred at 25 ° C for 48 hours. 25 ml of tetrahydrofuran and 28 ml of methylene chloride were added to the reaction mixture, and the mixture was stirred for 24 hours. 12.7 g (117 mmol) of chlorotrimethylsilane and 17.2 g (113 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene were further added to the obtained reaction mixture, and the mixture was stirred at 25 ° C. for 24 hours to carry out the reaction. 16.7 g (282 mmol) of propylamine was added dropwise to the mixture to stop the reaction. The filtrate obtained by filtering the reaction mixture was concentrated under reduced pressure to obtain 31.6 g of the silylamine compound H represented by the above formula (yield 78.6%). ^The results of ¹ H-NMR analysis are shown below. ^{From the 1} H-NMR analysis result, in the above formula, the degree of polymerization n was 22.1, and the number of oxygen atoms in the molecule was 23.1.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.52-3.41 (m, 88H), 3.25-3.22 (m, 4H), 2.94-2.90 (m. , 4H), 1.69-1.62 (m, 4H), 0.16 (s, 36H).

窒素置換した２Ｌ四つ口フラスコに４８０．２ｇ（３２０ｍｍｏｌ）のポリエチレングリコール１５００（シグマアルドリッチ社製）、水２４１ｍＬを仕込み、得られた混合物を加熱した。混合物の温度が５０℃になった時点で、４８％水酸化ナトリウム水溶液０．５ｇ、水４．５ｇ混合物に加えた。混合物の温度を５０℃に保ち、１時間攪拌した後、２７℃へ冷却した。アクリロニトリル５１．２ｇ（９６５ｍｍｏｌ）を２時間かけて混合物へ滴下し、２５℃で１６時間攪拌した。攪拌後、リン酸を０．７ｇ、水５ｍＬを加えて反応を停止し、２５℃で１．５時間攪拌した。得られた反応混合物に水７８ｍＬを加え、減圧下濃縮した。得られた混合物にトルエン１０１ｍＬを加え、減圧下共沸脱水し、さらにトルエン１０２ｍＬを加え、再び減圧下共沸脱水した。得られた混合物にさらにトルエン１０１ｍＬを加え、減圧下共沸脱水し得られた混合物５３２．８ｇにトルエン５４１ｍＬを加え、濃縮液Ａを１００１．６ｇ得た。
濃縮液Ａを４７０．２ｇ、ＮＤＴ−６５（川研ファインケミカル株式会社製）を５０．５ｇ、トルエン３５ｍＬを１Ｌオートクレーブに加え、１Ｌオートクレーブ内を窒素置換した。窒素置換後、室温下アンモニアガスを導入し１Ｌオートクレーブ内の圧力を０．５ＭＰａとした後、水素を導入して圧力を３．０ＭＰａとした。その後、反応器を加熱し、反応液温度８０℃、１Ｌオートクレーブ内の圧力４．４ＭＰａの条件で３時間反応を行った。反応後、反応液を室温まで冷却し、１Ｌオートクレーブ内の圧力を常圧まで低下させた。反応液にトルエン５８ｍＬを加え、反応液Ａを５９９．２ｇ得た。同様の方法で、４７０．２ｇの濃縮液Ａから、反応液Ｂを６０７．０ｇ得た。
５９９．２ｇの反応液Ａ、６０７．０ｇの反応液Ｂをトルエン４７６ｍＬに加え、得られた混合物を加圧濾過し、１６４７．８ｇの濾液を得た。得られた濾液に水２３０ｍＬを加え、減圧下濃縮し、上記式で表されるＰＥＧＰＡ−１５００を４７８．７ｇ得た（収率９２．６％）。 Production Example 9 Synthesis of silylamine compound I (i) Synthesis of PEGPA-1500

480.2 g (320 mmol) of polyethylene glycol 1500 (manufactured by Sigma-Aldrich) and 241 mL of water were charged into a nitrogen-substituted 2 L four-necked flask, and the obtained mixture was heated. When the temperature of the mixture reached 50 ° C., 0.5 g of a 48% aqueous sodium hydroxide solution and 4.5 g of water were added to the mixture. The temperature of the mixture was kept at 50 ° C, stirred for 1 hour, and then cooled to 27 ° C. 51.2 g (965 mmol) of acrylonitrile was added dropwise to the mixture over 2 hours, and the mixture was stirred at 25 ° C for 16 hours. After stirring, 0.7 g of phosphoric acid and 5 mL of water were added to stop the reaction, and the mixture was stirred at 25 ° C. for 1.5 hours. 78 mL of water was added to the obtained reaction mixture, and the mixture was concentrated under reduced pressure. Toluene 101mL was added to the obtained mixture, azeotropic dehydration was performed under reduced pressure, and further 102mL of toluene was added, and azeotropic dehydration was performed again under reduced pressure. 101 mL of toluene was added to the obtained mixture, and 541 mL of toluene was added to 532.8 g of the mixture obtained by azeotropic dehydration under reduced pressure to obtain 1001.6 g of concentrated liquid A.
470.2 g of the concentrate A, 50.5 g of NDT-65 (manufactured by Kawaken Fine Chemicals Co., Ltd.) and 35 mL of toluene were added to the 1 L autoclave, and the atmosphere in the 1 L autoclave was replaced with nitrogen. After purging with nitrogen, ammonia gas was introduced at room temperature to adjust the pressure in the 1 L autoclave to 0.5 MPa, and then hydrogen was introduced to adjust the pressure to 3.0 MPa. Then, the reactor was heated, and the reaction was carried out for 3 hours under the conditions of a reaction liquid temperature of 80 ° C. and a pressure of 4.4 MPa in a 1 L autoclave. After the reaction, the reaction solution was cooled to room temperature and the pressure in the 1 L autoclave was reduced to normal pressure. To the reaction solution, 58 mL of toluene was added to obtain 599.2 g of reaction solution A. By the same method, 607.0 g of the reaction solution B was obtained from 470.2 g of the concentrated solution A.
599.2 g of the reaction solution A and 607.0 g of the reaction solution B were added to 476 mL of toluene, and the resulting mixture was filtered under pressure to obtain 1647.8 g of a filtrate. 230 mL of water was added to the obtained filtrate and concentrated under reduced pressure to obtain 478.7 g of PEGPA-1500 represented by the above formula (yield 92.6%).

^{_{1 H-NMR (C 6 D}} 6) δ (ppm): 3.49-3.34 (m, 134H), 2.66-2.63 (m, 4H), 1.57-1.54 (m , 4H)

窒素置換した５００ｍＬ四つ口フラスコに３０．２ｇ（１９ｍｍｏｌ）のＰＥＧＰＡ−１５００、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン１７．５ｇ（１１２ｍｍｏｌ）、テトラヒドロフラン１３４ｍＬを仕込み、得られた反応混合物に対してクロロトリメチルシラン１３．０ｇ（１２０ｍｍｏｌ）を滴下後、２５℃で２４時間撹拌した。得られた反応混合物に１，８−ジアザビシクロ［５．４．０］−７−ウンデセン４．２ｇ（２８ｍｍｏｌ）、クロロトリメチルシラン３．１ｇ（２９ｍｍｏｌ）を加え２５℃で６時間攪拌後、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン８．８ｇ（５８ｍｍｏｌ）、クロロトリメチルシラン６．０ｇ（５５ｍｍｏｌ）を加え、２５℃で１６時間攪拌した。得られた反応混合物に対してプロピルアミン４．１ｇ（７０ｍｍｏｌ）を滴下し反応を停止した。反応混合物を濾過して得られた濾液を減圧下濃縮することで、上記式で表されるシリルアミン化合物Ｉを３３．１ｇ得た（収率９３．２％）。^１Ｈ−ＮＭＲ分析結果より、上記式中、重合度ｎは３０．７、分子中酸素原子数は３１．７であった。 (Ii) Synthesis of silylamine compound I

A 500 mL four-necked flask purged with nitrogen was charged with 30.2 g (19 mmol) of PEGPA-1500, 1,8-diazabicyclo [5.4.0] -7-undecene (17.5 g, 112 mmol) and tetrahydrofuran (134 mL). Chlorotrimethylsilane (13.0 g, 120 mmol) was added dropwise to the reaction mixture, and the mixture was stirred at 25 ° C. for 24 hours. To the obtained reaction mixture, 1,8-diazabicyclo [5.4.0] -7-undecene (4.2 g, 28 mmol) and chlorotrimethylsilane (3.1 g, 29 mmol) were added, and the mixture was stirred at 25 ° C for 6 hours. 8-diazabicyclo [5.4.0] -7-undecene 8.8 g (58 mmol) and chlorotrimethylsilane 6.0 g (55 mmol) were added, and the mixture was stirred at 25 ° C for 16 hours. 4.1 g (70 mmol) of propylamine was added dropwise to the obtained reaction mixture to stop the reaction. The filtrate obtained by filtering the reaction mixture was concentrated under reduced pressure to obtain 33.1 g of the silylamine compound I represented by the above formula (yield 93.2%). ^{From the 1} H-NMR analysis result, in the above formula, the degree of polymerization n was 30.7, and the number of oxygen atoms in the molecule was 31.7.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.53-3.16 (m, 127H), 2.97-2.93 (m, 4H), 1.72-1.65 (m , 4H), 0.18 (s, 36H)

Production Example 10 Synthesis of silylamine compound J (i) Synthesis of PEG2000-EtCN

  1493.3 g (747 mmol) of polyethylene glycol 2,000 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 747 mL of water were charged into a nitrogen-substituted 3 L four-necked flask, and the obtained mixture was heated. When the temperature of the mixture reached 43 ° C., 1.3 g of 48% aqueous sodium hydroxide solution and 1.3 g of water were added to the mixture. The temperature of the mixture was kept at 45 ° C, stirred for 1 hour, and then cooled to 20 ° C. Acrylonitrile 118.9 g (2241 mmol) was added dropwise to the mixture over 2 hours, and the mixture was stirred at 23 ° C. for 17 hours. 1.5 g of phosphoric acid and 2 mL of water were added, and the reaction was stopped by stirring at 25 ° C. for 0.5 hours. Toluene (146 mL) was added to the obtained reaction mixture and the mixture was concentrated under reduced pressure. Toluene (146 mL) was added and the mixture was concentrated under reduced pressure. Toluene (146 mL) was added again to the concentrated liquid obtained and the mixture was concentrated under reduced pressure to give 1669.5 g of PEG2000-EtCN.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.69-3.24 (m, 179H), 3.09-3.06 (m, 4H), 1.84-1.81 (m). , 4H)

得られた１３０２．５ｇのＰＥＧ２０００−ＥｔＣＮ、トルエン１５００ｍＬ、ＮＤＴ−６５（川研ファインケミカル株式会社製）２６０．０ｇを５Ｌオートクレーブに加え、５Ｌオートクレーブ内を窒素置換した。窒素置換後、室温下アンモニアガスを導入し５Ｌオートクレーブ内圧力を０．５ＭＰａとしたのち、さらに水素を導入して圧力を３．０ＭＰａとした。続いて昇温し、反応液温度８０℃、反応器内部圧力４．５ＭＰａの条件で３時間反応を行った。反応後、反応液を室温まで冷却し、反応器内部圧力を常圧まで低下させた。得られた反応混合物にトルエン８７８ｍＬを加えて得られる反応混合物を加圧濾過し、濾液３１７７．５ｇを得た。得られた濾液に水５９９ｍＬを加え減圧下濃縮し、上記式で表されるＰＥＧＰＡ−２０００を１２１９．６ｇ得た（収率９９．０％）。 (Ii) Synthesis of PEGPA-2000

The obtained 1302.5 g of PEG2000-EtCN, 1500 mL of toluene, and 260.0 g of NDT-65 (manufactured by Kawaken Fine Chemical Co., Ltd.) were added to a 5 L autoclave, and the inside of the 5 L autoclave was replaced with nitrogen. After purging with nitrogen, ammonia gas was introduced at room temperature to bring the internal pressure of the 5 L autoclave to 0.5 MPa, and then hydrogen was introduced to bring the pressure to 3.0 MPa. Subsequently, the temperature was raised, and the reaction was performed for 3 hours under the conditions of the reaction liquid temperature of 80 ° C. and the reactor internal pressure of 4.5 MPa. After the reaction, the reaction solution was cooled to room temperature and the internal pressure of the reactor was lowered to normal pressure. The reaction mixture obtained by adding 878 mL of toluene to the obtained reaction mixture was filtered under pressure to obtain 3177.5 g of a filtrate. Water (599 mL) was added to the obtained filtrate and the mixture was concentrated under reduced pressure to obtain 1219.6 g of PEGPA-2000 represented by the above formula (yield 99.0%).

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.66-3.35 (m, 179H), 2.66-2.63 (m, 4H), 1.57-1.54 (m , 4H)

窒素置換した５００ｍＬ四つ口フラスコにＰＥＧＰＡ−２０００を３０．０ｇ（１４ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン１４．０ｇ（９２ｍｍｏｌ）、トルエン１３９ｍＬを仕込み、得られた反応混合物に対してクロロトリメチルシラン１０．０ｇ（９２ｍｍｏｌ）を滴下後、２５℃で２４時間撹拌した。得られた反応混合物に塩化メチレン２１ｍＬを加え、２５℃で２４時間撹拌し、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン７．１ｇ（４７ｍｍｏｌ）、クロロトリメチルシラン４．９ｇ（４６ｍｍｏｌ）を加え、さらに２５℃で９６時間攪拌した。得られた反応混合物に対してプロピルアミン１０．０ｇ（１６９ｍｍｏｌ）を滴下し反応を停止した。反応混合物を濾過して得られた濾液を減圧下濃縮することで、上記式で表されるシリルアミン化合物Ｊを２７．１ｇ得た（収率７９．６％）。^１Ｈ−ＮＭＲ分析結果より、上記式中、重合度ｎは４２．５、分子中酸素原子数は４３．５であった。 (Iii) Synthesis of silylamine compound J

A 500 mL four-necked flask purged with nitrogen was charged with 30.0 g (14 mmol) of PEGPA-2000, 14.0 g (92 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene, and 139 mL of toluene. After 10.0 g (92 mmol) of chlorotrimethylsilane was added dropwise to the reaction mixture, the mixture was stirred at 25 ° C. for 24 hours. 21 mL of methylene chloride was added to the obtained reaction mixture, and the mixture was stirred at 25 ° C. for 24 hours, and 7.1 g (47 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene and 4.9 g of chlorotrimethylsilane ( 46 mmol) was added, and the mixture was further stirred at 25 ° C. for 96 hours. 10.0 g (169 mmol) of propylamine was added dropwise to the obtained reaction mixture to stop the reaction. The filtrate obtained by filtering the reaction mixture was concentrated under reduced pressure to obtain 27.1 g of the silylamine compound J represented by the above formula (yield 79.6%). ^{From the 1} H-NMR analysis result, the degree of polymerization n was 42.5 and the number of oxygen atoms in the molecule was 43.5 in the above formula.

^{_{1 H-NMR (C 6 D}} 6) δ (ppm): 3.65-3.42 (m, 174H), 2.95-2.91 (m, 4H), 1.68-1.64 (m , 4H)

窒素置換した５００ｍＬ四つ口フラスコに４−オキサ−１，７−ヘプタンジアミン９．８ｇ（７４ｍｍｏｌ）、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン４７．０ｇ（３０９ｍｍｏｌ）、アセトニトリル１２７ｍＬを仕込み、得られた混合物を１０℃以下に冷却し、クロロトリメチルシラン３３．ｇ（３０９ｍｍｏｌ）を滴下後、反応混合物を２５℃で２３時間撹拌した。反応混合物に対してヘプタン５０ｍＬによる抽出操作を４回行った。ヘプタン層を減圧下濃縮後、窒素下にて濾過し、上記式で表されるシリルアミン化合物Ｋを２２．４ｇ得た（収率７１．０％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 11 Synthesis of silylamine compound K

A nitrogen-substituted 500 mL four-necked flask was charged with 4-oxa-1,7-heptanediamine 9.8 g (74 mmol), 1,8-diazabicyclo [5.4.0] -7-undecene 47.0 g (309 mmol), acetonitrile. 127 mL was charged, the obtained mixture was cooled to 10 ° C. or lower, and chlorotrimethylsilane 33. After g (309 mmol) was added dropwise, the reaction mixture was stirred at 25 ° C. for 23 hours. The extraction operation with 50 mL of heptane was performed on the reaction mixture four times. The heptane layer was concentrated under reduced pressure and then filtered under nitrogen to obtain 22.4 g of the silylamine compound K represented by the above formula (yield 71.0%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 3.20-3.17 (m, 4H), 3.01-2.97 (m, 4H), 1.71-1.67 (m). , 4H), 0.20 (s, 36H)

窒素置換した４００ｍＬ四つ口フラスコにヘキサメチレンジアミン１０．０ｇ（８６ｍｍｏｌ）、１，５−ジアザビシクロ［４．３．０］−５−ノネン４２．７ｇ、アセトニトリル３９ｍＬを仕込み、得られた混合物を１０℃以下に冷却し、クロロトリメチルシラン３７．２ｇ（３４２ｍｍｏｌ）を滴下後、反応混合物を２５℃で１７時間撹拌した。反応混合物に対してヘプタン５０ｍＬによる抽出操作を３回行った。ヘプタン層を減圧下濃縮後、上記式で表されるシリルアミン化合物Ｌを２８．６ｇ得た（収率８２．１％）。^１Ｈ−ＮＭＲ分析結果を以下に示す。 Production Example 12 Synthesis of silylamine compound L

Hexamethylenediamine 10.0 g (86 mmol), 1,5-diazabicyclo [4.3.0] -5-nonene 42.7 g, and acetonitrile 39 mL were charged into a nitrogen-substituted 400 mL four-necked flask, and the resulting mixture was mixed with 10 After cooling to below ℃, after adding 37.2 g (342 mmol) of chlorotrimethylsilane dropwise, the reaction mixture was stirred at 25 ℃ for 17 hours. The extraction operation with 50 mL of heptane was performed on the reaction mixture three times. After the heptane layer was concentrated under reduced pressure, 28.6 g of the silylamine compound L represented by the above formula was obtained (yield 82.1%). ^The results of ¹ H-NMR analysis are shown below.

¹ H-NMR (C ₆ D ₆ ) δ (ppm): 2.80-2.75 (m, 4H), 1.33 to 1.17 (m, 8H), 0.19 (s, 36H).

Production Example 13 Synthesis of Oxazolidine-based Latent Curing Agent While flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device, 420 g of diethanolamine (molecular weight 105) and toluene were added. 177 g and 317 g of isobutyraldehyde (molecular weight 72.1) were charged, and the mixture was heated with stirring to remove the by-produced water (71.9 g) out of the system, and a reflux dehydration reaction was carried out at 110 to 150 ° C. After no more water was distilled off, the mixture was further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde, and an intermediate reaction product, N-hydroxyethyl-2-isopropyloxazolidine. Got Next, 336 g of hexamethylene diisocyanate (molecular weight 168) was added to 636 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture was heated at 80 ° C. for 8 hours, and the measured NCO content by titration was 0.0% by mass. The reaction was terminated at that point, and an oxazolidine-based latent curing agent having two oxazolidine rings in one molecule was obtained. The resulting oxazolidine-based latent curing agent was liquid at room temperature.

Production Example 14 Synthesis of Urethane Prepolymer Containing Isocyanate Group Polyoxypropylene diol (trade name: Sannix PP-4000, with nitrogen gas flowing into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, heating / cooling device) Sanyo Kasei Co., Ltd., number average molecular weight 5,570, dispersity Mw / Mn1.02) 421.5 g, polyoxypropylene triol (trade name: EXCENOL 5030F, AGC Co., number average molecular weight 5,140, 421.5 g of dispersity Mw / Mn1.02) and 0.05 g of 2-ethylhexyl acid phosphate (trade name: JP-508, manufactured by Johoku Chemical Co., Ltd.) were charged. Furthermore, while stirring, 156.7 g of isophorone diisocyanate (molecular weight 222.3, manufactured by Evonik Japan), zirconyl 2-ethylhexanoate (trade name: Nikka Octix Zirconium 12%, manufactured by Nippon Kagaku Sangyo Co., Ltd.) were used. 0.3 g was added, heated and reacted at 80 to 85 ° C. for 2 hours. The reaction was terminated when the isocyanate group content fell below the theoretical value (4.0% by mass) to synthesize an isocyanate group-containing urethane prepolymer.

Example 1 Storage stability test Under a nitrogen atmosphere, silylamine compound A or silylamine compound L as a latent curing agent, and isophorone diisocyanate and trifluoroacetic acid were put into a test tube with the composition shown in Table 1 and mixed by stirring until uniform. Then, a curable composition was prepared.
The curable composition was sealed and stored at 25 ° C. under a nitrogen atmosphere, and the test tube containing the curable composition was tumbled at 0 days, 1 day, 4 days, 6 days, and 12 days after starting storage, The fluidity of the sample was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 1.
A: The test tube was tumbled and flowed for 1 cm within 15 seconds. B: The test tube was tumbled and flowed for 1 cm within 1 minute. C: The test tube was tumbled for no more than 1 minute.

  As shown in Table 1, the curable composition containing the silylamine compound A had good fluidity even after 12 days from the start of storage, and showed excellent storage stability.

Example 2 Curing Performance Evaluation Test The curable composition prepared by using the silylamine compound A in Example 1 was hermetically stored at 25 ° C. for 1 day in a nitrogen atmosphere. The curable composition after storage was opened to the air, and the touch dry time (tack free time) was measured at a temperature of 16 ° C. and a humidity of 40% RH. As a result, the touch dry time was 6 hours.

＊ｍｏｌ比：イソシアネート基含有ウレタンプレポリマー中のイソシアネート基１ｍｏｌに対する潜在性硬化剤が加水分解して生じるアミノ基のｍｏｌ比 Examples 3 to 10, Comparative Example 1 Curing Test A test tube containing the isocyanate group-containing urethane prepolymer produced in Production Example 14, the latent curing agent shown in Table 2 and butoxyethyl acid phosphate (trade name: JP-506H, Johoku Chemical Co., Ltd.). (Manufactured by Kogyo Co., Ltd.) was blended with the composition shown in Table 2 and mixed by stirring until uniform, to produce a curable composition. The curable composition was opened under air, and the touch dry time (tack free time) was measured at a temperature of 16 ° C. and a humidity of 40% RH. The results are shown in Table 2. The fact that the tack free time of Comparative Example 1 is 96.0 or more indicates that the film did not cure even after 96.0 hours.

* Molar ratio: The molar ratio of amino groups generated by hydrolysis of the latent curing agent to 1 mol of isocyanate groups in the isocyanate group-containing urethane prepolymer.

Examples 11 to 17 and Comparative Examples 2 to 3 Storage stability test In a test tube, the isocyanate group-containing urethane prepolymer produced in Production Example 14, the latent curing agent and butoxyethyl acid phosphate shown in Table 3 (trade name: JP- 506H, manufactured by Johoku Chemical Industry Co., Ltd.) was blended in the composition shown in Table 3 and mixed by stirring until uniform, to produce a curable composition. The curable composition was stored in a closed system at 50 ° C. for 5 days, the viscosity was measured, and the storage stability was evaluated from the measured values according to the following three-level evaluation criteria. The viscosity was measured at 25 ° C. using EMS-1000 manufactured by Kyoto Electronics Manufacturing Co., Ltd. The results are shown in Table 3.
A: Viscosity less than 15,000 mPa · s after 5 days of storage B: Viscosity less than 35,000 mPa · s after 5 days of storage C: Viscosity of more than 35,000 mPa · s after 5 days of storage D: Viscosity measurement because a solid is present in the curable composition No (the silylamine compound does not dissolve).
Odor determination test After the storage stability test was completed, the upper part of the test tube containing the curable composition was looked up by hand, the odor was confirmed by the olfactory sense of the experimenter, and the evaluation was performed according to the following three-level evaluation criteria. The results are shown in Table 3.
A: No aldehyde smell is felt when holding an open test tube
B: An aldehyde odor is felt when holding an open test tube C: An aldehyde odor is strongly felt when holding an open test tube

＊ｍｏｌ比：イソシアネート基含有ウレタンプレポリマー中のイソシアネート基１ｍｏｌに対する潜在性硬化剤が加水分解して生じるアミノ基のｍｏｌ比

* Molar ratio: The molar ratio of amino groups generated by hydrolysis of the latent curing agent to 1 mol of isocyanate groups in the isocyanate group-containing urethane prepolymer.

Comparative Example 4 Odor Evaluation Test 5.00 g of the isocyanate group-containing urethane prepolymer produced in Production Example 14, 0.9641 g of the oxazolidine-based latent curing agent produced in Production Example 13 and butoxyethyl acid phosphate (trade name: JP 0.016 g (-506H, manufactured by Johoku Chemical Industry Co., Ltd.) was mixed and mixed with stirring until uniform to produce a curable composition. The odor of the curable composition produced was evaluated in the same manner as the odor determination test in Examples 11 to 17 and Comparative Examples 2 to 3. As a result, the result of the judgment test of the curable composition was C.

Comparative Example 5
In a test tube, 5.000 g of the isocyanate group-containing urethane prepolymer produced in Production Example 14, 0.952 g of silylamine compound L and butoxyethyl acid phosphate (trade name: JP-506H, manufactured by Johoku Chemical Co., Ltd.) were used. 013 g was blended and mixed with stirring until uniform to produce a curable composition. After the curable composition was stored in a closed system at 50 ° C. for 5 hours, the viscosity was measured. The viscosity was measured at 25 ° C. using EMS-1000 manufactured by Kyoto Electronics Manufacturing Co., Ltd. The viscosity of the curable composition immediately after production was 31,700 mPa · s, and the viscosity of the curable composition after storage for 5 hours was 66300 mPa · s.

Examples 18 to 25, Comparative Examples 6 to 10 Compatibility Test 2.0 g of the isocyanate group-containing urethane prepolymer produced in Production Example 14 and 1.0 g of the latent curing agent shown in Table 4 were blended into a test tube and uniformly mixed. The curable composition was manufactured by stirring and mixing until it became. The obtained curable composition was mixed by inversion at 25 ° C. (60 times / minute), and the compatibility at each elapsed time was visually evaluated according to the following evaluation criteria.
A: Completely mixed B: Interface not clear, but not completely compatible C: Clearly separated D: Solid exists in the curable composition (silylamine compound does not dissolve).

^＊オキサゾリジン系潜在性硬化剤：製造例１３で製造したオキサゾリジン系潜在性硬化剤

^* Oxazolidine-based latent curing agent: Oxazolidine-based latent curing agent produced in Production Example 13

From the results of Example 2, it was found that the composition prepared from the latent curing agent of the present invention and the isocyanate monomer exhibits curing performance. Further, from the results shown in Table 2, it was found that the composition prepared from the latent curing agent of the present invention and the isocyanate group-containing urethane prepolymer exhibits curing performance.
From the results shown in Table 3, it was found that the curable composition of the present invention had excellent storage stability and did not emit an aldehyde odor. On the other hand, it was found from the results of Comparative Example 4 that the oxazolidine-based curing agent emitted an aldehyde odor. Furthermore, from the results shown in Table 4, it was found that the latent curing agent of the present invention has excellent compatibility with the isocyanate compound (isocyanate group-containing urethane prepolymer). On the other hand, from the results of Comparative Example 5 and Comparative Example 10, the curable composition using the silylamine compound L containing no etheric oxygen atom in the molecule had a high initial viscosity, poor storage stability, and It was found that the compatibility with the compound (isocyanate group-containing urethane prepolymer) was poor. Further, from the results of Comparative Example 8, it was found that the oxazolidine-based latent curing agent had poor compatibility. From the results of Comparative Example 9, it was found that the silylamine compound K having one oxygen atom in the molecule had insufficient compatibility with the isocyanate compound (isocyanate group-containing urethane prepolymer). Further, from the results of Comparative Examples 6 and 7, the silylamine compounds I and J having the number of oxygen atoms in the molecule of 31.7 or 43.5 do not dissolve the silylamine compound in the isocyanate compound (isocyanate group-containing urethane prepolymer). I understood.

  From the results of Tables 1 to 4, it was found that the latent curing agent of the present invention is useful as a latent curing agent for a curable composition containing an isocyanate compound. Further, the latent curing agent of the present invention does not form an aldehyde compound even when hydrolyzed with water such as moisture as is clear from the structure of the silylamine compound represented by the formula (1), It is useful because the odor of the aldehyde compound does not occur during the reaction.

Claims (7)

A latent curing agent containing a silylamine compound represented by the following formula (1).

(In the formula (1), R ^{1 to} R ¹² are each independently an alkyl group having 1 to 6 carbon atoms, R ¹³ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and R ¹⁴ to R ²¹ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, y and z are each independently an integer of 1 to 11, and n is an integer of 1 to 22.)   The latent curing agent according to claim 1, wherein n is 1 to 5. The latent curing agent according to claim 1, wherein R ^{1 to} R ¹² are each independently selected from a methyl group and an ethyl group. The latent curing agent according to claim 1, wherein R ¹³ is an alkylene group having 2 to 12 carbon atoms.   A curable composition comprising the latent curing agent according to any one of claims 1 to 4 and an isocyanate compound.   A curable composition comprising the latent curing agent according to any one of claims 1 to 4, an isocyanate compound and an acidic compound. Use of a silylamine compound represented by the following formula (1) as a latent curing agent.

(In the formula (1), R ^{1 to} R ¹² are each independently an alkyl group having 1 to 6 carbon atoms, R ¹³ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, and R ¹⁴ to R ²¹ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, y and z are each independently an integer of 1 to 11, and n is an integer of 1 to 22.)