Polyuretonimine composition, water-dispersed composition, solution composition, curable composition, cured resin product, and method for producing a polyuretonimine composition

Abstract

To provide a polyuretonimine composition which achieves both excellent curability and excellent pot life, an aqueous dispersion composition, a solution composition, a curable composition, a cured resin product, and a method for producing a polyuretonimine composition.SOLUTION: A polyuretonimine composition contains a derivative of polyisocyanate having only a primary isocyanate group. The derivative contains a carbodiimide group and an uretonimine group. A derivatization rate (1) of polyisocyanate is 35-90 mol%. An intensity ratio of absorbance derived from stretching vibration of the carbodiimide group to absorbance derived from stretching vibration of the uretonimine group in infrared absorption spectra is less than 4.0. [ Derivatization rate (1)]=1-[(total moles of isocyanate group before uretonimine reaction after carbodiimide reaction of polyisocyanate) / (total moles of isocyanate group before carbodiimide reaction and uretonimine reaction of polyisocyanate)]×100(%).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyurethane imine composition, a water-dispersed composition, a solution composition, a curable composition, a cured resin product, and a method for producing a polyurethane imine composition. [Background technology]

[0002] In the fields of coating agents and adhesives, curable compositions containing a base agent and a curing agent are known. For example, uretonimine is known as a curing agent. More specifically, the following curing agents for coating compositions are known:

[0003] That is, the curing agent is obtained by carbodiimidation, uretonimination, and blocking of an isocyanate compound. More specifically, an isocyanate compound is carbodiimidized to obtain a carbodiimide. Next, the carbodiimide is uretonimined to obtain a uretonimine (polyisocyanate). Furthermore, the uretonimine (polyisocyanate) is blocked with an active hydrogen compound. This results in a curing agent containing uretonimine. 4,4'-diphenylmethane diisocyanate and isophorone diisocyanate have been proposed as the above isocyanate compound. Furthermore, in the above method, in the carbodiimidation of the isocyanate compound, the amount of isocyanate groups (residual amount) is reduced to two-thirds of the initial amount of isocyanate groups (see, for example, Patent Document 1 (Curing Agent Production Examples 1 and 2)). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2004-196955 A Summary of the Invention [Problem to be solved by the invention]

[0005] The curing agent is required to have further improved curing properties, but if the curing properties are too high, there is a problem that a sufficient pot life cannot be obtained.

[0006] The present invention relates to a polyurethane imine composition that combines excellent curability and excellent pot life, an aqueous dispersion composition and a solution composition that contain the polyurethane imine composition, a curable composition that contains the polyurethane imine composition, and a cured resin product obtained by curing the curable composition, as well as a method for producing the polyurethane imine composition. [Means for solving the problem]

[0007] The present invention [1] includes a derivative of a polyisocyanate having only a primary isocyanate group, the derivative containing a carbodiimide group and a uretonimine group, the following derivatization rate (1) of the polyisocyanate being 35 mol % or more and 90 mol % or less, and the infrared absorption spectrum shows a stretching vibration of 2120 cm due to the stretching vibration of the carbodiimide group. -1 Absorbance near IR CI The stretching vibration of the uretonimine group is at 1870 cm -1 Absorbance near IR UI Intensity ratio (IR CI / IR UI ) is less than 4.0.

[0008] [Derivatization rate (1)] = 1 - [(total moles of isocyanate groups after the carbodiimidation reaction of polyisocyanate and before the uretonimination reaction) / (total moles of isocyanate groups before the carbodiimidation reaction and the uretonimination reaction of polyisocyanate)] × 100 (%)

[0009] The present invention [2] includes the polyurethane imine composition according to the above [1], in which the following derivatization rate (2) of the polyisocyanate is 40 mol % or more and 90 mol % or less.

[0010] [Derivatization rate (2)] = 1 - [(total moles of isocyanate groups after the polyisocyanate undergoes the carbodiimidation reaction and the uretonimination reaction) / (total moles of isocyanate groups before the polyisocyanate undergoes the carbodiimidation reaction and the uretonimination reaction)] × 100 (%)

[0011] The present invention [3] includes the polyurethane imine composition according to the above [1] or [2], wherein the derivative further contains a urethane group.

[0012] The present invention [4] includes the polyurethane imine composition according to the above [3], in which the urethane group is obtained by reacting the polyisocyanate with an alcohol, and the alcohol contains an alcohol having three or more consecutive oxyethylene groups.

[0013] The present invention [5] includes the polyurethane imine composition according to any one of the above [1] to [4], wherein the derivative is capped and / or chain-extended with an amine compound.

[0014] The present invention [6] includes the polyurethane imine composition according to the above [5], in which the amine compound contains a polyamine.

[0015] The present invention [7] includes an aqueous dispersion composition, which is an aqueous dispersion liquid obtained by dispersing the polyurethane imine composition according to any one of the above [1] to [6] in water at a solids concentration of 5% by mass or more and 90% by mass or less.

[0016] The present invention [8] includes a solution composition in which the polyurethane imine composition according to any one of the above [1] to [6] is dissolved in an organic solvent at a solid content concentration of 5% by mass or more and 90% by mass or less.

[0017] The present invention [9] includes a curable composition containing a base agent having both a hydroxyl group and a carboxyl group, and a curing agent containing the polyurethaneimine composition according to any one of the above [1] to [6].

[0018] The present invention

[10] includes a resin cured product, which is a cured product of the curable composition described in the above [9].

[0019] The present invention

[11] comprises a carbodiimidation step of subjecting a polyisocyanate having only primary isocyanate groups and / or a urethane-modified product thereof to a carbodiimidation reaction to obtain a carbodiimidation reaction product, and a uretonimination step of subjecting the carbodiimidation reaction product to a uretonimination reaction to obtain a uretonimination reaction product, wherein in the carbodiimidation step, isocyanate groups of the polyisocyanate and / or a urethane-modified product thereof are subjected to the carbodiimidation reaction so that the following derivatization rate (1) is 35 mol % or more and 90 mol % or less, and a stretching vibration of 2120 cm 3 derived from the stretching vibration of the carbodiimide group is obtained in an infrared absorption spectrum. -1 Absorbance near IR CI The stretching vibration of the uretonimine group is at 1870 cm -1 Absorbance near IR UI Intensity ratio (IR CI / IR UI ) is less than 4.0.

[0020] [Derivatization rate (1)] = 1 - [(total moles of isocyanate groups after the carbodiimidation reaction of polyisocyanate and before the uretonimination reaction) / (total moles of isocyanate groups before the carbodiimidation reaction and the uretonimination reaction of polyisocyanate)] × 100 (%)

[0021] The present invention

[12] includes the method for producing a polyurethane imine composition according to the above item

[11] , wherein in the uretoniminization step, the isocyanate groups of the carbodiimidation reaction product are subjected to the uretoniminization reaction so that the following derivatization rate (2) is 40 mol % or more and 90 mol % or less:

[0022] [Derivatization rate (2)] = 1 - [(total moles of isocyanate groups after the polyisocyanate undergoes the carbodiimidation reaction and the uretonimination reaction) / (total moles of isocyanate groups before the polyisocyanate undergoes the carbodiimidation reaction and the uretonimination reaction)] × 100 (%)

[0023] The present invention

[13] includes the method for producing a polyuretonimine according to the above

[11] or

[12] , which includes a urethanization step, prior to the carbodiimidization step, of reacting the polyisocyanate having only primary isocyanate groups with an alcohol to obtain a urethane-modified product of the polyisocyanate, and / or a urethanization step, after the uretoniminization step, of reacting the uretoniminization reaction product with an alcohol to obtain a urethane-modified product of the uretoniminization reaction product.

[0024] The present invention

[14] comprises the method for producing a polyuretone imine according to any one of the above

[11] to

[13] , further comprising an amine reaction step after the uretone iminization step, in which the uretone iminization reaction product and / or a urethane modified product thereof is reacted with an amine compound, and the uretone iminization reaction product and / or a urethane modified product thereof is capped and / or chain-extended with the amine compound. [Effects of the Invention]

[0025] The polyurethane imine composition of the present invention contains a derivative of a polyisocyanate having only primary isocyanate groups, and the derivative contains a carbodiimide group and a uretonimine group. The polyisocyanate has the above-mentioned derivatization rate (1) within a predetermined range. Furthermore, in the infrared absorption spectrum, the 2120 cm stretching vibration due to the carbodiimide group is detected. -1 Absorbance near IR CI The stretching vibration of the uretonimine group is at 1870 cm -1 Absorbance near IR UI Intensity ratio (IR CI / IR UI ) is less than a predetermined value.

[0026] Therefore, the polyurethane imine composition of the present invention can achieve both excellent curability and an excellent pot life.

[0027] Furthermore, the aqueous dispersion composition, solution composition and curable composition of the present invention contain the above-mentioned polyurethane imine composition, and therefore can achieve both excellent curability and excellent pot life.

[0028] Furthermore, the cured resin product of the present invention is a cured product of the above-mentioned curable composition, and therefore has both excellent curability and an excellent pot life.

[0029] Furthermore, according to the method for producing a polyurethane imine composition of the present invention, the polyurethane imine composition of the present invention can be produced efficiently. DETAILED DESCRIPTION OF THE INVENTION

[0030] 1. Polyurethane imine composition The polyurethane imine composition contains a derivative of polyisocyanate and may be simply referred to as polyurethane imine.

[0031] The polyisocyanate derivative contains a carbodiimide group and a uretonimine group. Such a derivative can be obtained, for example, by the following method. First, the polyisocyanate is carbodiimidized (carbodiimidization step). Next, the reaction product after the carbodiimidization is uretonimidized (uretonimidization step). Furthermore, as will be described in detail later, the polyisocyanate can also be uretonized at any timing (uretonimidization step).

[0032] The polyisocyanate, the carbodiimidation step, the uretonimine formation step, and the urethanization step will be described in detail below.

[0033] (1) Polyisocyanate Polyisocyanate is a raw material monomer for the derivative. Polyisocyanate has two or more isocyanate groups in one molecule. Preferably, polyisocyanate has two isocyanate groups in one molecule.

[0034] Furthermore, the polyisocyanate has only a primary isocyanate group, and does not have a secondary isocyanate group or a tertiary isocyanate group.

[0035] A primary isocyanate group is an isocyanate group (-CH2NCO) in which the carbon atom (C) to which the isocyanate group (-NCO) is bonded has two hydrogen atoms (H).

[0036] A secondary isocyanate group is an isocyanate group (-CHR-NCO) in which the carbon atom (C) to which the isocyanate group (-NCO) is bonded has one hydrogen atom (H) and one group (R) other than a hydrogen atom.

[0037] A tertiary isocyanate group is a group in which the carbon atom (C) to which the isocyanate group (-NCO) is bonded does not have a hydrogen atom (H) and is bonded to two groups other than hydrogen atoms (R 1 and R 2 ) when the isocyanate group (-CR 1 R 2 -NCO).

[0038] Examples of polyisocyanates having only primary isocyanate groups include polyisocyanate monomers, such as aliphatic polyisocyanates having only primary isocyanate groups and araliphatic polyisocyanates having only primary isocyanate groups.

[0039] Aliphatic polyisocyanates having only primary isocyanate groups include linear (acyclic) aliphatic polyisocyanates having only primary isocyanate groups, and alicyclic polyisocyanates having only primary isocyanate groups. Here, linear refers to linear or branched.

[0040] Examples of chain aliphatic polyisocyanates having only primary isocyanate groups include chain aliphatic diisocyanates having only primary isocyanate groups. Examples of chain aliphatic diisocyanates having only primary isocyanate groups include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI). These can be used alone or in combination of two or more. Preferred are pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI), and more preferred is pentamethylene diisocyanate (PDI).

[0041] Examples of alicyclic polyisocyanates having only primary isocyanate groups include alicyclic diisocyanates having only primary isocyanate groups. Examples of alicyclic diisocyanates having only primary isocyanate groups include bis(isocyanatomethyl)cyclohexane (H6XDI). Examples of bis(isocyanatomethyl)cyclohexane (H6XDI) include 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) and 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI). These can be used alone or in combination of two or more. Preferred examples include 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) and 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI).

[0042] Examples of araliphatic polyisocyanates having only primary isocyanate groups include araliphatic diisocyanates having only primary isocyanate groups. Examples of araliphatic diisocyanates having only primary isocyanate groups include xylylene diisocyanate (XDI). Examples of xylylene diisocyanates include 1,3-xylylene diisocyanate (1,3-XDI) and 1,4-xylylene diisocyanate (1,4-XDI). These can be used alone or in combination of two or more. Preferred examples include 1,3-xylylene diisocyanate (1,3-XDI) and 1,4-xylylene diisocyanate (1,4-XDI).

[0043] Furthermore, examples of polyisocyanates having only primary isocyanate groups include modified products (excluding carbodiimide-modified products and uretonimine-modified products; the same applies hereinafter) obtained by modifying the above-mentioned polyisocyanate monomers having only primary isocyanate groups. In polyisocyanates having only primary isocyanate groups, the modified products do not contain carbodiimide groups or uretonimine groups. More specifically, examples of modified products include uretdione-modified products, isocyanurate-modified products, iminooxadiazinedione-modified products, biuret-modified products, allophanate-modified products, polyol adducts, and oxadiazinetrione-modified products. These can be used alone or in combination of two or more types.

[0044] The polyisocyanate having only primary isocyanate groups can be used alone or in combination of two or more types. Preferred examples include polyisocyanate monomers and isocyanurate derivatives, and more preferred examples include polyisocyanate monomers. Preferred examples of the polyisocyanate monomer include linear aliphatic polyisocyanates having only primary isocyanate groups, and aromatic aliphatic polyisocyanates having only primary isocyanate groups. More preferred examples include linear aliphatic diisocyanates having only primary isocyanate groups, and aromatic aliphatic diisocyanates having only primary isocyanate groups. Even more preferred examples include pentamethylene diisocyanate (PDI) and xylylene diisocyanate (XDI).

[0045] The polyisocyanate having only primary isocyanate groups has an isocyanate group concentration of, for example, 15% by mass or more, or preferably 20% by mass or more, and for example, 50% by mass or less, or preferably 45% by mass or less.

[0046] (2) Carbodiimidization process In the carbodiimidization step, the polyisocyanate having only primary isocyanate groups (and / or its urethane-modified product (described later, the same applies hereinafter)) is subjected to a carbodiimidization reaction.

[0047] More specifically, in the carbodiimidization step, for example, polyisocyanate is heated in the presence of a carbodiimidization catalyst.

[0048] Examples of the carbodiimidization catalyst include trialkyl phosphate ester compounds, phosphorene oxide compounds, phosphorene sulfide compounds, phosphine oxide compounds, and phosphine compounds. These can be used alone or in combination of two or more. A preferred example of the carbodiimidization catalyst is a phosphorene oxide compound.

[0049] Examples of phosphorene oxide compounds include phosphorene oxide compounds having 4 to 18 carbon atoms. Examples of phosphorene oxide compounds having 4 to 18 carbon atoms include 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phosphorene-1-oxide (EMPO), 1,3-dimethyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-methyl-2-phosphorene-1-oxide, 1-ethyl-2-phosphorene-1-oxide, and double bond isomers thereof. These compounds can be used alone or in combination of two or more. As the phosphorene oxide compound, preferably, a phosphorene oxide compound is used, more preferably, 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) and 1-ethyl-3-methyl-2-phosphorene-1-oxide (EMPO) are used, and particularly preferably, 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) is used.

[0050] The proportion of the carbodiimidization catalyst is appropriately set so that the derivatization rate (1) and the absorbance intensity ratio, which will be described later, fall within the ranges described later.

[0051] For example, the blending ratio of the carbodiimidization catalyst is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, per 100 parts by mass of polyisocyanate, and for example, 10 parts by mass or less, preferably 1 part by mass or less, per 100 parts by mass of polyisocyanate.

[0052] The reaction conditions in the carbodiimidization step are appropriately set according to the blending ratio of the carbodiimidization catalyst so that the derivatization rate (1) described below falls within the range described below.

[0053] The reaction conditions in the carbodiimidization step are determined based on the absorbance intensity ratio (IR CI / IR UI) is appropriately set so that it falls within the range described below.

[0054] The reaction conditions in the carbodiimidization step are preferably set appropriately so that the derivatization rate (2) described below falls within the range described below.

[0055] For example, the reaction temperature is, for example, 125°C or higher, preferably 130°C or higher, and more preferably 135°C or higher. The reaction temperature is, for example, 160°C or lower, preferably 155°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower. The reaction time is, for example, 1 hour or longer, preferably 3 hours or longer. The reaction time is, for example, 12 hours or shorter, preferably 9 hours or shorter, more preferably 7 hours or shorter, and even more preferably 6 hours or shorter. The reaction environment is atmospheric pressure and an inert gas (such as nitrogen gas) atmosphere.

[0056] In the carbodiimidization step, a known organic solvent may be added as needed, and the amount of the organic solvent added may be appropriately determined depending on the purpose and application.

[0057] In the carbodiimidation step, a carbodiimidation reaction terminator can be blended as needed. Examples of the carbodiimidation reaction terminator include a carbodiimidation catalyst deactivator. Examples of the carbodiimidation catalyst deactivator include known silylation acids. Examples of the silylation acids include trifluoromethanesulfonic acid trimethylsilyl triflate. The blending ratio of the carbodiimidation reaction terminator is appropriately set depending on the purpose and application.

[0058] Then, by the above method, the isocyanate groups of the polyisocyanate (and / or its urethane-modified product (described later)) are subjected to decarboxylation condensation (carbodiimidation reaction) to generate carbodiimide groups.

[0059] This produces a carbodiimidation reaction product having a carbodiimide group and an unreacted isocyanate group at the molecular terminal.

[0060] In the carbodiimidation step, a reaction product liquid containing the carbodiimidation reaction product (hereinafter referred to as carbodiimidation reaction product liquid) is obtained. The carbodiimidation reaction product liquid contains, for example, the carbodiimidation reaction product and unreacted polyisocyanate (and / or its urethane-modified product (described later)).

[0061] The carbodiimidation reaction product liquid has an isocyanate group concentration (solid content equivalent) of, for example, 1 mass % or more, or preferably 5 mass % or more, and for example, 30 mass % or less, or preferably 20 mass % or less.

[0062] More specifically, when a polyisocyanate (non-urethane-modified polyisocyanate) is carbodiimidized, the isocyanate group concentration (solid content equivalent) of the carbodiimidation reaction product liquid is, for example, 10% by mass or more, preferably 15% by mass or more. In this case, the isocyanate group concentration (solid content equivalent) of the carbodiimidation reaction product liquid is, for example, 30% by mass or less, preferably 20% by mass or less.

[0063] When a urethane-modified polyisocyanate is carbodiimidized, the isocyanate group concentration (solid content equivalent) of the carbodiimidation reaction product liquid is, for example, 1% by mass or more, preferably 5% by mass or more, and in this case, the isocyanate group concentration (solid content equivalent) of the carbodiimidation reaction product liquid is, for example, 20% by mass or less, preferably 10% by mass or less.

[0064] (3) Uretone iminization process In the uretonimination step, the carbodiimidation reaction product liquid is aged, and the carbodiimidation reaction product is subjected to a uretonimination reaction.

[0065] More specifically, in the uretoniminization step, for example, the carbodiimidization reaction product liquid is aged at an appropriate temperature to cause the uretoniminization reaction.

[0066] The aging conditions in the uretone iminization process are determined by the absorbance intensity ratio (IR CI / IR UI ) is appropriately set so that it falls within the range described below.

[0067] The aging conditions in the uretone imine step are preferably set appropriately so that the derivatization rate (2) described below falls within the range described below.

[0068] More specifically, the aging temperature is, for example, 5°C or higher, preferably 10°C or higher, and more preferably 15°C or higher. The aging temperature is, for example, 60°C or lower, preferably 50°C or lower, and more preferably 40°C or lower. The aging time is, for example, 1 hour or longer, preferably 3 hours or longer. The aging time is, for example, 50 hours or shorter, preferably 40 hours or shorter. The aging environment is normal pressure and an inert gas (such as nitrogen gas) atmosphere. The blending ratio of the organic solvent is set appropriately depending on the purpose and application.

[0069] In the uretone imine formation step, a known organic solvent may be added as needed, and the amount of the organic solvent added may be appropriately determined depending on the purpose and application.

[0070] Then, the carbodiimidation reaction product in the carbodiimidation reaction product liquid is subjected to a uretonimination reaction with unreacted polyisocyanate (and / or its urethane-modified product (described later)). That is, the carbodiimide group is reacted with the isocyanate group to generate a uretonimine group.

[0071] This produces a uretonimine reaction product having a carbodiimide group and a uretonimine group, and also having an isocyanate group at the molecular terminal.

[0072] That is, a polyisocyanate derivative is obtained as the uretone imine reaction product.

[0073] Furthermore, in the uretonimination reaction, a reaction product liquid containing the above-mentioned uretonimination reaction product (hereinafter referred to as uretonimination reaction product liquid) is obtained. The uretonimination reaction product liquid contains, for example, the above-mentioned uretonimination reaction product. Furthermore, the uretonimination reaction product liquid may contain unreacted polyisocyanate (and / or a urethane-modified product thereof (described later)).

[0074] That is, a polyurethaneimine composition is obtained as a uretone imine reaction product liquid.

[0075] The uretonimine reaction product liquid has an isocyanate group concentration (solid content equivalent) of, for example, 1 mass % or more, or preferably 5 mass % or more, and for example, 30 mass % or less, or preferably 20 mass % or less.

[0076] More specifically, when polyisocyanate (non-urethane-modified polyisocyanate) is carbodiimidized and uretoniminated, the isocyanate group concentration (solid content equivalent) of the uretoniminization reaction product liquid is, for example, 10% by mass or more, preferably 15% by mass or more. In this case, the isocyanate group concentration (solid content equivalent) of the uretoniminization reaction product liquid is, for example, 30% by mass or less, preferably 20% by mass or less.

[0077] When a urethane-modified polyisocyanate is carbodiimidized and uretoniminated, the isocyanate group concentration (solid content equivalent) of the uretonimin reaction product liquid is, for example, 1% by mass or more, preferably 5% by mass or more, and in this case, the isocyanate group concentration (solid content equivalent) of the uretonimin reaction product liquid is, for example, 20% by mass or less, preferably 10% by mass or less.

[0078] (4) Urethane formation process The polyisocyanate derivative (uretonimine reaction product) may optionally contain urethane groups in addition to carbodiimide groups and uretonimine groups.

[0079] The urethane group is formed in the urethanization step. The timing of the urethanization step is not particularly limited, and may be, for example, before the carbodiimidization step. Alternatively, the urethanization step may be performed after the carbodiimidization step and the uretonimine formation step. Furthermore, the urethane group may be formed after the carbodiimidization step and before the uretonimine formation step. Alternatively, these may be combined.

[0080] Preferably, the urethanization step is carried out before the carbodiimidization step, and more preferably, the urethanization step is carried out after the carbodiimidization step and the uretoniminization step.

[0081] The process of urethanizing polyisocyanate before the carbodiimidization process (hereinafter referred to as the pre-urethanization process) and the process of urethanizing the carbodiimidization reaction product after the carbodiimidization process and the uretoniminization process (hereinafter referred to as the post-urethanization process) will be described in detail below.

[0082] (a) Pre-urethane formation process In the pre-urethanization step, prior to the carbodiimide formation step, a polyisocyanate and an alcohol are subjected to a urethanization reaction (pre-urethanization reaction) to obtain a urethane-modified polyisocyanate.

[0083] Examples of alcohols include alcohols containing three or more consecutive oxyethylene groups (hereinafter referred to as three or more consecutive EO-containing alcohols), and other alcohols.

[0084] For example, when the polyurethane imine composition is dispersed in water, the alcohol is preferably an alcohol containing three or more consecutive EOs, and when the polyurethane imine composition is dissolved in an organic solvent, the alcohol is preferably another alcohol.

[0085] Examples of the alcohol containing three or more consecutive EO include a polyol containing three or more consecutive oxyethylene groups (hereinafter referred to as a polyol containing three or more consecutive EO) and a monol containing three or more consecutive oxyethylene groups (hereinafter referred to as a monol containing three or more consecutive EO).

[0086] A polyol containing three or more consecutive EOs is an organic compound having three or more consecutive oxyethylene groups and two or more hydroxyl groups in one molecule. An example of a polyol containing three or more consecutive EOs is polyoxyethylene polyol. Polyoxyethylene polyol can be obtained, for example, by subjecting a known low-molecular-weight polyol (initiator) to an addition reaction with ethylene oxide so that the number of repeating oxyethylene group units is three or more. The method for subjecting a low-molecular-weight polyol to an addition reaction with ethylene oxide is not particularly limited, and any known method can be used.

[0087] The polyol containing three or more consecutive EOs can be used alone or in combination of two or more. As the polyol containing three or more consecutive EOs, preferably, polyoxyethylene polyol is used, and more preferably, polyoxyethylene glycol is used.

[0088] The monool containing three or more consecutive EO groups is an organic compound having three or more consecutive oxyethylene groups and one hydroxyl group in one molecule. Examples of the monool containing three or more consecutive EO groups include one-end-capped polyoxyethylene glycol. Examples of the one-end-capped polyoxyethylene glycol include polyethylene glycol monoalkyl ether. In the polyethylene glycol monoalkyl ether, one of the terminal hydroxyl groups of the polyoxyethylene glycol is substituted with an alkoxy group. The number of carbon atoms in the alkoxy group is appropriately set. Preferred examples of the alkoxy group include a methoxy group and an ethoxy group. Specific examples of the polyethylene glycol monoalkyl ether include polyethylene glycol monomethyl ether (methoxypolyethylene glycol) and polyethylene glycol monoethyl ether (ethoxypolyethylene glycol).

[0089] The monool containing three or more consecutive EOs can be used alone or in combination of two or more. As the monool containing three or more consecutive EOs, preferably polyethylene glycol monoalkyl ether is used, and more preferably polyethylene glycol monomethyl ether is used.

[0090] The alcohol containing three or more consecutive EOs can be used alone or in combination of two or more. As the alcohol containing three or more consecutive EOs, preferably, a monool containing three or more consecutive EOs is used.

[0091] In the 3 or more consecutive EO-containing alcohol, the number of repeating oxyethylene groups (EO) is, for example, 3 or more, preferably 5 or more, and more preferably 10 or more. In addition, the number of repeating oxyethylene groups (EO) is, for example, 60 or less, preferably 50 or less. When the number of repeating oxyethylene groups is within the above range, the stability and water dispersibility of the polyurethaneimine composition can be improved.

[0092] The number average molecular weight (polystyrene equivalent molecular weight) of the copolymer containing three or more consecutive EOs is, for example, 100 or more, preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and particularly preferably 800 or more. The number average molecular weight (polystyrene equivalent molecular weight) of the copolymer containing three or more consecutive EOs is, for example, 5000 or less, preferably 3000 or less, more preferably 2000 or less, even more preferably 1500 or less, and particularly preferably 1200 or less. When the number average molecular weight is within the above range, the stability and water dispersibility of the polyurethane imine composition can be improved.

[0093] The other alcohols are alcohols that do not have three or more consecutive oxyethylene groups in the molecule, in other words, alcohols that do not contain an oxyethylene group or that contain three or more consecutive oxyethylene groups (two consecutive oxyethylene groups and / or a single oxyethylene group).

[0094] Specific examples of other alcohols include polyols other than the polyols containing three or more consecutive EOs (hereinafter referred to as other polyols), and monools other than the monools containing three or more consecutive EOs (hereinafter referred to as other monools).

[0095] The other polyol is an alcohol that does not have three or more consecutive oxyethylene groups in one molecule and has two or more hydroxyl groups in one molecule. Examples of other polyols include methanediol, ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, hexadecanediol, octadecanediol, eicosanediol, and diethylene glycol. These can be used alone or in combination of two or more.

[0096] The other monool is an alcohol that does not have three or more consecutive oxyethylene groups in one molecule and has one hydroxyl group in one molecule. Examples of the other monool include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol, pentanol, 2,2-dimethyl-1-propanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol (10 carbon atoms), lauryl alcohol (12 carbon atoms), cetyl alcohol (14 carbon atoms), stearyl alcohol (18 carbon atoms), oleyl alcohol (18 carbon atoms), eicosanol (20 carbon atoms), 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol monoethyl ether (also known as carbitol), phenol, benzyl alcohol, phenethyl alcohol, and naphthol. These can be used alone or in combination of two or more.

[0097] The other alcohols can be used alone or in combination of two or more. As the other alcohols, other monools are preferred, and 1-methoxy-2-propanol is more preferred.

[0098] The alcohols can be used alone or in combination of two or more types, i.e., the alcohols may contain only 3 or more consecutive EO-containing alcohols, only other alcohols, or a combination of 3 or more consecutive EO-containing alcohols and other alcohols.

[0099] From the viewpoint of improving water dispersibility, the alcohols preferably contain three or more consecutive EO-containing alcohols.

[0100] When the alcohols contain three or more consecutive EO-containing alcohols, the hydrophilicity is improved, that is, the dispersion of the polyurethane imine composition in water is improved, and an aqueous dispersion composition (described later) can be efficiently obtained.

[0101] Moreover, from the viewpoint of achieving both water dispersibility and water resistance, the alcohols more preferably contain an alcohol containing three or more consecutive EOs in combination with other alcohols.

[0102] When the alcohols contain three or more consecutive EO-containing alcohols and other alcohols, the content of the three or more consecutive EO-containing alcohols relative to the total moles of the alcohols is, for example, 10 mol% or more, preferably 50 mol% or more. The content of the three or more consecutive EO-containing alcohols is, for example, 99 mol% or less, preferably 95 mol% or less. The content of the other alcohols is, for example, 1 mol% or more, preferably 5 mol% or more. The content of the other alcohols is, for example, 90 mol% or less, preferably 50 mol% or less.

[0103] When the content ratio of the 3 or more consecutive EO-containing alcohols to the other alcohols is within the above range, the curability and water dispersibility of the polyurethane imine composition can be improved, and a cured resin product (described below) with excellent water resistance can be obtained.

[0104] Furthermore, when the alcohols contain three or more consecutive EO-containing alcohols, the polyurethane imine composition contains oxyethylene groups. The content of oxyethylene groups is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, based on the polyurethane imine composition. The content of oxyethylene groups is, for example, 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less, based on the polyurethane imine composition. The content of oxyethylene groups can be calculated from the charged amount.

[0105] On the other hand, when the alcohols do not contain three or more consecutive EO-containing alcohols and contain only other alcohols, lipophilicity is improved, i.e., the solubility of the polyurethane imine composition in organic solvents is improved, and a solution composition (described below) can be efficiently obtained.

[0106] In the urethanization step, the reaction ratio of the polyisocyanate and the alcohols is set so that the isocyanate groups are in excess relative to the hydroxyl groups. More specifically, the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the alcohols is, for example, greater than 1, preferably 2 or more, and more preferably 4 or more. Furthermore, the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the alcohols is, for example, 16 or less, preferably 14 or less, and more preferably 10 or less.

[0107] In this reaction, a known urethanization catalyst can be added in an appropriate proportion, if necessary. The reaction temperature is, for example, 30°C or higher, preferably 60°C or higher. The reaction temperature is, for example, 200°C or lower, preferably 180°C or lower. The reaction time is, for example, 1 hour or longer, preferably 3 hours or longer. The reaction time is, for example, 50 hours or shorter, preferably 40 hours or shorter. The reaction environment is, for example, atmospheric pressure and an inert gas (e.g., nitrogen gas) atmosphere.

[0108] In the pre-urethanization step, a known organic solvent may be added as needed, and the amount of the organic solvent added may be appropriately determined depending on the purpose and application.

[0109] Then, by the above-mentioned method, the isocyanate groups of the polyisocyanate and the hydroxyl groups of the alcohols are subjected to a urethane reaction (pre-urethane reaction) to generate urethane groups.

[0110] This produces a urethane-modified polyisocyanate (alcohol-modified polyisocyanate). The urethane-modified polyisocyanate has urethane groups. The urethane-modified polyisocyanate also has unreacted isocyanate groups at the molecular terminals.

[0111] In the pre-urethanization step, a reaction product liquid containing a urethane-modified polyisocyanate (hereinafter referred to as a pre-urethanization reaction product liquid) is obtained. The pre-urethanization reaction product liquid contains, for example, the above-mentioned urethane-modified polyisocyanate and unreacted polyisocyanate.

[0112] The isocyanate group concentration (solid content equivalent) of the pre-urethanization reaction product liquid is, for example, 15% by mass or more, or preferably 20% by mass or more, and for example, 50% by mass or less, or preferably 40% by mass or less.

[0113] The pre-urethanization reaction product liquid is used as a raw material in the carbodiimidation step and the uretonimination step, whereby the urethane-modified polyisocyanate is carbodiimidized and uretoniminated as described above.

[0114] As a result, a uretonimine reaction product is obtained, which has a carbodiimide group, a uretonimine group, and a urethane group, and also has an isocyanate group at the molecular terminal.

[0115] That is, a polyisocyanate derivative is obtained as the uretone imine reaction product.

[0116] (b) Post-urethane formation process In the post-urethanization step, after the above-mentioned uretoniminization step, the uretoniminization reaction product is subjected to a uretonization reaction (post-urethanization reaction) with alcohols to obtain a urethane-modified product of the uretoniminization reaction product.

[0117] That is, polyisocyanate (and / or its urethane-modified product) is first carbodiimidized and then uretoniminated, and then the resulting uretoniminated reaction product is subjected to a urethane-forming reaction with an alcohol.

[0118] Examples of alcohols include the alcohols described above. More specifically, examples include the alcohols containing three or more consecutive EOs and other alcohols. These can be used alone or in combination of two or more. Preferred examples of alcohols include alcohols containing three or more consecutive EOs.

[0119] The method for urethanizing the uretonimine reaction product is the same as the method for urethanizing the polyisocyanate described above.

[0120] In the post-urethanization step, the reaction ratio between the uretonimin reaction product and alcohols is set so that the isocyanate groups are in excess relative to the hydroxyl groups. More specifically, the equivalent ratio (NCO / OH) of the isocyanate groups of the uretonimin reaction product to the hydroxyl groups of the alcohols is, for example, greater than 1, preferably 2 or more, and more preferably 4 or more. Furthermore, the equivalent ratio (NCO / OH) of the isocyanate groups of the uretonimin reaction product to the hydroxyl groups of the alcohols is, for example, 16 or less, preferably 14 or less, and more preferably 10 or less.

[0121] In this reaction, a known urethanization catalyst can be added in an appropriate proportion, if necessary. The reaction temperature is, for example, 30°C or higher, preferably 60°C or higher. The reaction temperature is, for example, 200°C or lower, preferably 180°C or lower. The reaction time is, for example, 1 hour or longer, preferably 3 hours or longer. The reaction time is, for example, 50 hours or shorter, preferably 40 hours or shorter. The reaction environment is, for example, atmospheric pressure and an inert gas (e.g., nitrogen gas) atmosphere.

[0122] In the post-urethanization step, a known organic solvent may be added as needed, and the amount of the organic solvent added may be appropriately determined depending on the purpose and application.

[0123] Then, by the above-mentioned method, the isocyanate group of the uretone imine reaction product and the hydroxyl group of the alcohol are subjected to a urethane reaction (post-urethane reaction) to generate a urethane group.

[0124] This results in a urethane-modified uretonimine reaction product (alcohol-modified product). The urethane-modified uretonimine reaction product has a urethane group. The urethane-modified uretonimine reaction product also has unreacted isocyanate groups at the molecular terminals.

[0125] In the post-urethanization step, a reaction product liquid containing a urethane-modified product of the uretonimine reaction product (hereinafter referred to as a post-urethanization reaction product liquid) is obtained. The post-urethanization reaction product liquid contains, for example, the urethane-modified product and unreacted polyisocyanate.

[0126] The post-urethanization reaction product liquid has an isocyanate group concentration (solid content equivalent) of, for example, 15% by mass or more, or preferably 20% by mass or more, and the post-urethanization reaction product liquid has an isocyanate group concentration (solid content equivalent) of, for example, 50% by mass or less, or preferably 40% by mass or less.

[0127] The urethane-modified product of the uretonimine reaction has a carbodiimide group, a uretonimine group, and a urethane group, and also has an isocyanate group at the molecular terminal.

[0128] That is, a polyisocyanate derivative is obtained as a urethane-modified product of the uretone imine reaction product.

[0129] If necessary, a pre-urethanization step and a post-urethanization step can be used in combination. That is, a polyisocyanate may be subjected to a pre-urethanization reaction, then a carbodiimidization reaction and a uretoniminization reaction, and then a post-urethanization reaction.

[0130] (5) Amine reaction step The polyisocyanate derivative may have a free isocyanate group at the molecular end, and may be capped and / or chain-extended with an amine compound.

[0131] More specifically, the uretone imine reaction product and / or its urethane modified product can be reacted with an amine compound, and the uretone imine reaction product and / or its urethane modified product can be capped and / or chain-extended with the amine compound (amine reaction step).

[0132] The step of capping a polyisocyanate derivative with an amine compound (capping step) and the step of chain-extending a polyisocyanate derivative with an amine compound (chain-extension step) will be described in detail below.

[0133] (a) Sealing process The isocyanate groups at the molecular terminals of the polyisocyanate derivative may be blocked with an amine compound as a blocking agent, such as a monoamine.

[0134] Examples of monoamines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, 2-ethylhexylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxypropylamine), 3-(dodecyloxy)propylamine, and morpholine. These can be used alone or in combination of two or more.

[0135] In the sealing step, the amine compounds (monoamines) can be used alone or in combination of two or more kinds.

[0136] The method for capping a polyisocyanate derivative with an amine compound is not particularly limited. For example, a method of adding an amine compound dropwise to an organic solvent or water in which a polyisocyanate derivative is dispersed can be used. Another example is a method of adding a polyisocyanate derivative dropwise to an organic solvent or water in which an amine compound is dispersed. This allows the isocyanate groups at the molecular terminals of the polyisocyanate derivative to be capped with the amine compound.

[0137] In the capping step, the equivalent ratio of the isocyanate groups of the polyisocyanate derivative to the amino groups of the amine compound (isocyanate group / amino group) is, for example, 5 or less, preferably 3 or less, and more preferably 1 or less. The equivalent ratio of the isocyanate groups of the polyisocyanate derivative to the amino groups of the amine compound (isocyanate group / amino group) is, for example, 0.8 or more, preferably 0.9 or more. The reaction conditions are not particularly limited and are appropriately set depending on the purpose and application. For example, the reaction time is room temperature. The reaction time is, for example, 0.1 to 10 hours.

[0138] This allows the polyisocyanate derivative to be blocked with the amine compound, thereby improving the storage stability of the polyurethane imine composition.

[0139] In the capping step, if necessary, a monoamine and a polyamine, which will be described later, can be used in combination. In such a case, most of the polyisocyanate derivative is capped with the monoamine, and a part of the polyisocyanate derivative is chain-extended (described later) by the polyamine.

[0140] The ratio of the monoamine and polyamine used in combination is appropriately set depending on the purpose and application. For example, the polyamine is 10 mol% or less, preferably 5 mol% or less, based on the total amount of the monoamine and polyamine. Furthermore, the monoamine is 90 mol% or more, preferably 95 mol% or more, based on the total amount of the monoamine and polyamine.

[0141] In the sealing step, the amine compound and other known sealing agents can also be used in combination in an appropriate ratio.

[0142] (b) Chain elongation step The polyisocyanate derivative may be chain-extended with an amine compound as a chain extender, such as a polyamine.

[0143] Examples of polyamines include aromatic polyamines, araliphatic polyamines, alicyclic polyamines, aliphatic polyamines, amino alcohols, polyoxyethylene group-containing polyamines, alkoxysilyl compounds having a primary amino group, alkoxysilyl compounds having a primary amino group and a secondary amino group, hydrazines, and hydrazine derivatives.

[0144] Examples of aromatic polyamines include 4,4'-diphenylmethanediamine and tolylenediamine. Examples of araliphatic polyamines include 1,3-xylylenediamine and 1,4-xylylenediamine. Examples of alicyclic polyamines include 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis-(4-aminocyclohexyl)methane, diaminocyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane. Examples of aliphatic polyamines include ethylenediamine, propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane. These can be used alone or in combination of two or more.

[0145] Examples of amino alcohols include 2-((2-aminoethyl)amino)ethanol and 2-((2-aminoethyl)amino)-1-methylpropanol. Examples of polyoxyalkylene group-containing polyamines include polyoxyalkylene ether diamines and polyoxyalkylene ether triamines. Examples of polyoxyalkylene ether diamines include polyoxyethylene ether diamines. Examples of polyoxyalkylene ether triamines include trimethylolpropane poly(oxypropylene) triamine and glyceryl poly(oxypropylene) triamine. More specific examples include the JEFFAMINE D series, ED series, EDR series, RT series, and T series (all manufactured by HUNTSMAN). These can be used alone or in combination of two or more types.

[0146] Examples of alkoxysilyl compounds having a primary amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane. Examples of alkoxysilyl compounds having a primary amino group and a secondary amino group include N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, and N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane. Examples of hydrazines include hydrazine and hydrazine hydrate. Examples of hydrazine derivatives include succinic acid dihydrazide and adipic acid dihydrazide. These can be used alone or in combination.

[0147] In the chain extension step, the amine compounds (polyamines) can be used alone or in combination of two or more kinds.

[0148] The method for chain-extending a polyisocyanate derivative with an amine compound is not particularly limited. For example, a method of adding an amine compound dropwise to an organic solvent or water in which a polyisocyanate derivative is dispersed can be used. Another example is a method of adding a polyisocyanate derivative dropwise to an organic solvent or water in which an amine compound is dispersed. In this way, the polyisocyanate derivative is chain-extended by the amine compound.

[0149] In the chain elongation step, the equivalent ratio of the isocyanate groups of the polyisocyanate derivative to the amino groups of the amine compound (isocyanate groups / amino groups) is, for example, 5 or less, preferably 3 or less, and more preferably 1 or less. The equivalent ratio of the isocyanate groups of the polyisocyanate derivative to the amino groups of the amine compound (isocyanate groups / amino groups) is, for example, 0.3 or more, preferably 0.5 or more, and more preferably 0.9 or more. The reaction conditions are not particularly limited and are appropriately set depending on the purpose and application. For example, the reaction time is room temperature. The reaction time is, for example, 0.1 to 10 hours.

[0150] This allows the polyisocyanate derivative to be chain-extended by the amine compound, thereby improving the curability of the polyurethaneimine composition.

[0151] In the chain extension step, a polyamine and the monoamine may be used in combination, if necessary. In such a case, most of the polyisocyanate derivative is chain-extended by the polyamine, and a portion of the polyisocyanate derivative is capped with the monoamine.

[0152] The ratio of the monoamine and polyamine used in combination is appropriately set depending on the purpose and application. For example, the monoamine is 10 mol% or less, preferably 5 mol% or less, based on the total amount of the monoamine and polyamine. Furthermore, the polyamine is 90 mol% or more, preferably 95 mol% or more, based on the total amount of the monoamine and polyamine.

[0153] In the capping step, the amine compound and other known chain extenders can also be used in combination in an appropriate ratio.

[0154] (6) Derivatization rate (a) Derivatization rate (1) In the carbodiimidization step, the following derivatization rate (1) is adjusted to fall within a predetermined range.

[0155] [Derivatization rate (1)] = 1 - [(total moles of isocyanate groups after the carbodiimidation reaction of polyisocyanate and before the uretonimination reaction) / (total moles of isocyanate groups before the carbodiimidation reaction and the uretonimination reaction of polyisocyanate)] × 100 (%)

[0156] In the above formula (1), "the total moles of isocyanate groups before the polyisocyanate undergoes the carbodiimidation reaction and the uretonimine reaction" refers to the total moles of isocyanate groups immediately before the carbodiimidation step.

[0157] For example, when polyisocyanate is reacted with an alcohol (pre-urethanization reaction) before the carbodiimidization step, the "total moles of isocyanate groups before the carbodiimidization reaction and the uretoniminization reaction of polyisocyanate" refers to the total moles of isocyanate groups of the urethane-modified product of polyisocyanate and the isocyanate groups of unreacted polyisocyanate in the pre-urethanization reaction product liquid.

[0158] Furthermore, for example, when the polyisocyanate has not reacted with an alcohol before the carbodiimidization step, the "total moles of isocyanate groups before the polyisocyanate undergoes the carbodiimidization reaction and the uretonimine reaction" is the total moles of isocyanate groups of the unreacted polyisocyanate (monomer).

[0159] In the above formula (1), "the total moles of isocyanate groups after the carbodiimidation reaction of the polyisocyanate and before the uretonimine reaction" refers to the total moles of isocyanate groups immediately after the carbodiimidation step.

[0160] In other words, "the total moles of isocyanate groups after the carbodiimidation reaction of polyisocyanate and before the uretonimine reaction" refers to the total moles of isocyanate groups in the carbodiimidation reaction product of polyisocyanate (and / or its urethane-modified product) and isocyanate groups in unreacted polyisocyanate (and / or its urethane-modified product).

[0161] That is, the derivatization rate (1) is calculated from the reduction rate of the isocyanate groups after the carbodiimidization step relative to the isocyanate groups before the carbodiimidization step. If the derivatization rate (1) is within a predetermined range, excellent curability and pot life can be obtained.

[0162] More specifically, the derivatization rate (1) is 35 mol% or more, preferably 40 mol% or more, more preferably 45 mol% or more, even more preferably 50 mol% or more, even more preferably 55 mol% or more, even more preferably 60 mol% or more, even more preferably 65 mol% or more, and particularly preferably 70 mol% or more.

[0163] If the derivatization rate (1) is above the lower limit, a larger number of uretonimine groups can be obtained in the uretonimine formation step, resulting in a polyuretonimine composition with excellent curability.

[0164] More specifically, the derivatization rate (1) is 90 mol%. the following , preferably 85 mol % the following , more preferably 80 mol % the following , more preferably 75 mol% the following is.

[0165] If the derivatization rate (1) is below the upper limit, a sufficient amount of unreacted isocyanate groups can remain, thereby accelerating the conversion of carbodiimide groups to uretonimine, thereby reducing the amount of remaining carbodiimide groups and providing a polyurethaneimine composition with an excellent pot life.

[0166] The derivatization rate (1) is calculated based on the isocyanate group concentration (solid content basis). More specifically, the derivatization rate (1) is calculated based on the isocyanate group concentration (solid content basis (mass %)) before the carbodiimidation reaction and uretonimination reaction of the polyisocyanate (and / or its urethane-modified product) and the isocyanate group concentration (solid content basis (mass %)) after the carbodiimidation reaction of the polyisocyanate (and / or its urethane-modified product) and before the uretonimination reaction.

[0167] (b) Derivatization rate (2) In the above-mentioned uretone imine formation step, the following derivatization rate (2) is preferably adjusted to fall within a predetermined range.

[0168] [Derivatization rate (2)] = 1 - [(total moles of isocyanate groups after the polyisocyanate undergoes the carbodiimidation reaction and the uretonimination reaction) / (total moles of isocyanate groups before the polyisocyanate undergoes the carbodiimidation reaction and the uretonimination reaction)] × 100 (%)

[0169] In the above formula (2), "the total moles of isocyanate groups before the carbodiimidation reaction and uretonimine reaction of the polyisocyanate" is the total moles of isocyanate groups immediately before the carbodiimidation step, as in the above formula (1).

[0170] In the above formula (2), "the total moles of isocyanate groups after the polyisocyanate has undergone the carbodiimidation reaction and the uretonimination reaction" refers to the total moles of isocyanate groups immediately after the uretonimination step.

[0171] In other words, "the total moles of isocyanate groups after the carbodiimidation reaction and the uretonimination reaction of the polyisocyanate" refers to the total moles of isocyanate groups of the uretonimination reaction product of the polyisocyanate (and / or its urethane-modified product) and the isocyanate groups of the unreacted polyisocyanate (and / or its urethane-modified product).

[0172] That is, the derivatization rate (2) is calculated from the reduction rate of isocyanate groups after the uretoniminization step relative to the isocyanate groups before the carbodiimide formation step. If the derivatization rate (2) is within a predetermined range, excellent curability and pot life can be obtained.

[0173] More specifically, the derivatization rate (2) is, for example, 40 mol% or more, preferably 45 mol% or more, more preferably 50 mol% or more, even more preferably 55 mol% or more, even more preferably 60 mol% or more, still more preferably 65 mol% or more, and particularly preferably 70 mol% or more.

[0174] If the derivatization rate (2) is above the lower limit, a larger number of uretonimine groups can be obtained in the uretonimine formation step, thereby improving the curability of the polyuretonimine composition and the physical properties of the coating film.

[0175] More specifically, the derivatization rate (2) is, for example, 90 mol%. the following , preferably 85 mol % the following , more preferably 80 mol % the following , more preferably 75 mol% the following is.

[0176] When the derivatization rate (2) is below the upper limit, a polyurethane imine composition having an excellent pot life can be obtained.

[0177] The derivatization rate (2) is calculated based on the isocyanate group concentration (solid content basis). More specifically, the derivatization rate (2) is calculated based on the isocyanate group concentration (solid content basis (mass %)) before the carbodiimidation reaction and uretonimination reaction of the polyisocyanate (and / or its urethane-modified product) and the isocyanate group concentration (solid content basis (mass %)) after the carbodiimidation reaction and uretonimination reaction of the polyisocyanate (and / or its urethane-modified product).

[0178] (c)IR intensity ratio In the polyurethane imine composition, the polyisocyanate derivative contains a carbodiimide group and a uretonimine group. Therefore, the infrared absorption spectrum of the polyurethane imine composition contains a 2120 cm stretching vibration due to the carbodiimide group. -1 The absorption around 1870 cm originates from the stretching vibration of the uretonimine group. -1 Absorbance in the vicinity is confirmed.

[0179] In the polyurethane imine composition, the stretching vibration of the carbodiimide group is at 2120 cm -1 Absorbance near IR CI and 1870 cm due to the stretching vibration of the uretonimine group. -1 Absorbance near IR UI Intensity ratio (IR intensity ratio, IR CI / IR UI ) has been adjusted.

[0180] More specifically, in the polyurethane imine composition, the stretching vibration of 2120 cm originating from the carbodiimide group -1 Absorbance near IR CI The stretching vibration of the uretonimine group is at 1870 cm -1 Absorbance near IR UI Intensity ratio (IR CI / IR UI ) is less than 4.0, preferably 3.5 or less, more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.5 or less, even more preferably 1.0 or less, even more preferably 0.5 or less, and particularly preferably less than 0.1.

[0181] In the polyurethane imine composition, the above intensity ratio (IR CI / IR UI ) is below the upper limit, the amount of uretonimine groups is relatively large and the amount of carbodiimide groups is relatively small, so that sufficient curing properties due to the uretonimine groups can be obtained.

[0182] In addition, the stretching vibration of the carbodiimide group originates from 2120 cm -1 Absorbance near IR CI The stretching vibration of the uretonimine group is at 1870 cm -1 Absorbance near IR UI Intensity ratio (IR CI / IR UI ) typically exceeds 0.

[0183] The infrared absorption spectrum of the polyurethane imine composition can be measured in accordance with the examples described below.

[0184] (7) Additives The polyurethane imine composition may further contain known additives as needed. Examples of additives include storage stabilizers, plasticizers, antiblocking agents, heat stabilizers, light stabilizers, antioxidants, release agents, catalysts, pigments, dyes, lubricants, fillers, and hydrolysis inhibitors. The proportions and timing of addition of the additives are not particularly limited and may be appropriately determined depending on the purpose and application.

[0185] If necessary, unreacted components can be removed from the polyurethane imine composition. Examples of unreacted components include unreacted polyisocyanate and unreacted alcohols. Furthermore, organic solvents, carbodiimide catalysts, urethanization catalysts, and / or by-products can be removed from the polyurethane imine composition. The removal method is not particularly limited, and known methods can be used.

[0186] 2. Effects The above-mentioned polyurethane imine composition can achieve both excellent curability and an excellent pot life.

[0187] More specifically, it is required to increase the content of uretonimine groups in curing agents containing conventional polyurethane imine compositions to improve curability.

[0188] Therefore, in the production of a polyurethane imine composition, it has been attempted to increase the proportion of carbodiimidized isocyanate groups and, accordingly, increase the proportion of uretoniminated groups.

[0189] However, if the proportion of carbodiimidized isocyanate groups is excessively increased and the proportion of uretoniminated groups is correspondingly increased, the pot life becomes excessively short.

[0190] Furthermore, when a polyisocyanate contains a secondary or higher isocyanate group, steric hindrance is relatively large. Therefore, even if the carbodiimide conversion rate is increased, the reaction between the secondary or higher isocyanate group and the carbodiimide group is relatively difficult to proceed. As a result, the uretonimide conversion rate is difficult to increase, the number of carbodiimide groups is relatively large, and the pot life is relatively short.

[0191] In contrast, the above-mentioned polyurethane imine composition contains a derivative of polyisocyanate having only primary isocyanate groups, and the derivative contains a carbodiimide group and a uretonimine group. The above-mentioned derivatization rate (1) of the polyisocyanate is within a predetermined range. Furthermore, in the infrared absorption spectrum, the 2120 cm stretching vibration due to the stretching vibration of the carbodiimide group is present. -1 Absorbance near IR CI The stretching vibration of the uretonimine group is at 1870 cm -1 Absorbance near IR UI Intensity ratio (IR CI / IR UI ) is less than a predetermined value.

[0192] In such a polyurethane imine composition, the polyisocyanate has only primary isocyanate groups, so steric hindrance is relatively small. Therefore, the reaction between the primary isocyanate groups and the carbodiimide groups proceeds relatively easily. As a result, the number of carbodiimide groups is relatively small, and the pot life is relatively long.

[0193] In other words, the above-mentioned polyurethane imine composition can suppress a decrease in pot life even if the proportion of carbodiimidized isocyanate groups is excessively increased and the proportion of uretoniminated is increased accordingly, thereby achieving both excellent curability and excellent pot life.

[0194] Furthermore, according to the above-mentioned method for producing a polyurethane imine composition, the polyurethane imine composition can be produced efficiently.

[0195] 3. Use of Polyurethane Imine Composition Because the polyurethane imine composition has excellent curability and pot life, it is suitable for use as a curing agent in a reaction-curable resin composition (hereinafter referred to as a curable composition). The curable composition contains a curing agent including the polyurethane imine composition and a base agent having both a hydroxyl group and a carboxyl group.

[0196] The curing agent is not particularly limited as long as it contains a polyurethane imine composition, and examples thereof include an aqueous dispersion in which the polyurethane imine composition is dispersed in water (hereinafter referred to as an aqueous dispersion composition), and a solution in which the polyurethane imine composition is dissolved in an organic solvent (hereinafter referred to as a solution composition).

[0197] The aqueous dispersion composition contains a polyurethane imine composition and water.

[0198] The polyurethane imine composition in the water dispersion composition is preferably a polyurethane imine composition which has been pre-urethanized and / or post-urethanized with alcohols containing three or more consecutive EO-containing alcohols.

[0199] When the polyurethane imine composition is pre-urethanized and / or post-urethanized with alcohols containing three or more consecutive EO-containing alcohols, excellent hydrophilicity is obtained by the three or more consecutive EO-containing alcohols, and the polyurethane imine composition can be efficiently dispersed in water.

[0200] The method for dispersing the polyurethane imine composition in water is not particularly limited. For example, a method of adding water to the polyurethane imine composition and stirring the mixture, or a method of adding the polyurethane imine composition to water and stirring the mixture may be mentioned. Preferably, water is added to the polyurethane imine composition and stirring is carried out.

[0201] The ratio of the polyurethane imine composition to water is not particularly limited, and the solid content of the resin component (polyurethane imine composition) in the water-dispersed composition is, for example, 5% by mass or more, preferably 10% by mass or more. The solid content of the resin component (polyurethane imine composition) in the water-dispersed composition is, for example, 90% by mass or less, preferably 80% by mass or less.

[0202] If the curing agent is a water-dispersed composition, it is possible to improve compatibility with the water-based resin (main component). Furthermore, a cured product having excellent water resistance and solvent resistance can be obtained. Furthermore, since such a water-dispersed composition contains the above-mentioned polyurethane imine composition, it has excellent curability.

[0203] The solution composition contains a polyurethaneimine composition and an organic solvent.

[0204] The polyurethane imine composition in the solution composition is preferably a polyurethane imine composition produced without using an alcohol containing three or more consecutive oxyethylene groups. More specifically, the polyurethane imine composition is preferably a polyurethane imine composition that has not been pre- or post-urethanized with alcohols. Furthermore, the polyurethane imine composition is preferably a polyurethane imine composition that has not been pre- and / or post-urethanized with alcohols that do not contain three or more consecutive EO-containing alcohols and that contain only other alcohols.

[0205] When an alcohol containing three or more consecutive oxyethylene groups is not used in the production of a polyurethane imine composition, the polyurethane imine composition does not contain three or more consecutive oxyethylene groups. Such a polyurethane imine composition is hydrophobic. Therefore, the polyurethane imine composition can be efficiently dissolved in an organic solvent.

[0206] Examples of the organic solvent include the organic solvents described above, and preferred examples include propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.

[0207] The method for dissolving the polyurethane imine composition in the organic solvent is not particularly limited, and examples thereof include a method of adding an organic solvent to the polyurethane imine composition and stirring the mixture, and a method of adding the polyurethane imine composition to an organic solvent and stirring the mixture. Preferably, the method involves adding an organic solvent to the polyurethane imine composition and stirring the mixture.

[0208] The ratio of the polyurethane imine composition to the organic solvent is not particularly limited, but the solids concentration of the resin component (polyurethane imine composition) in the solution composition is, for example, 5% by mass or more, preferably 10% by mass or more, and the solids concentration of the resin component (polyurethane imine composition) in the solution composition is, for example, 90% by mass or less, preferably 80% by mass or less.

[0209] If the curing agent is a solution composition, it is possible to improve compatibility with the oil-based resin (main component), and to obtain a cured product with excellent water resistance and solvent resistance. Furthermore, such a solution composition has excellent curing properties because it contains the above-mentioned polyurethaneimine composition.

[0210] The above-described polyurethane imine composition may also be used in combination with other curing agents, such as carbodiimide curing agents, isocyanate curing agents, and epoxy curing agents.

[0211] The base material having both hydroxyl groups and carboxyl groups is not particularly limited, but examples thereof include resins having both hydroxyl groups and carboxyl groups. Examples of resins having both hydroxyl groups and carboxyl groups include polyester polyols having carboxyl groups, polyether polyols having carboxyl groups, and polyurethane polyols having carboxyl groups. These can be used alone or in combination of two or more types.

[0212] The base resin may further contain a resin having a hydroxyl group but not a carboxyl group.The base resin may further contain a resin having a carboxyl group but not a hydroxyl group.

[0213] Furthermore, the base resin may not contain a resin having both hydroxyl groups and carboxyl groups, and may contain a resin having hydroxyl groups but not carboxyl groups and a resin having carboxyl groups but not hydroxyl groups in an appropriate ratio.

[0214] The base resin may also contain a resin having no hydroxyl group or carboxyl group in an appropriate ratio.

[0215] The base resin preferably contains a resin having both a hydroxyl group and a carboxyl group.

[0216] Furthermore, the resin in the base resin may be a water-based resin or an oil-based resin. When the base resin contains a water-based resin, preferably, a water dispersion composition of a polyurethane imine composition is used as the curing agent. When the base resin contains an oil-based resin, preferably, a solution composition of a polyurethane imine composition is used as the curing agent.

[0217] That is, as for the base agent and the curing agent, a combination in which the base agent contains a water-based resin and the curing agent is a water-dispersed composition is preferably exemplified, and a combination in which the base agent contains an oil-based resin and the curing agent is a solution composition is also preferably exemplified.

[0218] From the viewpoint of reducing the amount of organic solvent and protecting the global environment, a combination of an aqueous base agent and a water-dispersed composition is preferred.

[0219] Furthermore, the curable composition is not particularly limited as long as it contains the above-mentioned base agent and the above-mentioned curing agent, and may be a two-component type in which the base agent and the curing agent are prepared separately and mixed at the time of use, or may be a one-component type in which the base agent and the curing agent are mixed in advance.

[0220] The curable composition is preferably a two-component type curable composition.

[0221] The content ratio of the base agent and the curing agent is appropriately set depending on the purpose and application. For example, the base agent is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, relative to 100 parts by mass of the total amount of the base agent and the curing agent. The base agent is, for example, 99.5 parts by mass or less, preferably 95.0 parts by mass or less. The curing agent is, for example, 0.5 parts by mass or more, preferably 5 parts by mass or more. The curing agent is, for example, 90 parts by mass or less, preferably 70 parts by mass or less.

[0222] The total moles of uretonimine groups and carbodiimide groups in the curing agent relative to the total moles of carboxyl groups and hydroxyl groups in the base resin is, for example, 0.1 or more, preferably 0.2 or more, and the total moles of uretonimine groups and carbodiimide groups in the curing agent relative to the total moles of carboxyl groups and hydroxyl groups in the base resin is, for example, 2.0 or less, preferably 1.5 or less.

[0223] The base resin and / or curing agent may contain known additives. Examples of additives include epoxy resins, catalysts, coating improvers, leveling agents, antifoaming agents, stabilizers, plasticizers, surfactants, pigments, fillers, organic fine particles, inorganic fine particles, antifungal agents, and silane coupling agents. The amount of additives and the timing of their addition are determined appropriately depending on the purpose and application.

[0224] Furthermore, since the above-mentioned aqueous dispersion composition, solution composition and curable composition contain the above-mentioned polyurethane imine composition, they can achieve both excellent curability and excellent pot life.

[0225] The method for producing a cured resin product is not particularly limited, but for example, if the curable composition is a one-component type, the curable composition is applied directly to the substrate or adherend. Alternatively, if the curable composition is a two-component type, the base agent and the curing agent are mixed, and the resulting mixture is applied to the substrate or adherend. The curable composition is then heated and cured to obtain a cured resin product.

[0226] The curing conditions for the curable composition are not particularly limited as long as the conditions are such that the uretonimine groups are thermally decomposed and the isocyanate groups and carbodiimide groups are regenerated.

[0227] For example, the curing temperature is the temperature at which uretonimine groups are thermally decomposed and isocyanate groups and carbodiimide groups are regenerated. The curing temperature is also the temperature at which the regenerated isocyanate groups react with hydroxyl groups in the base resin and / or the temperature at which the regenerated carbodiimide groups react with carboxyl groups in the base resin. Specifically, the curing temperature (dissociation temperature) is, for example, 40°C or higher, preferably 50°C or higher. The curing temperature (dissociation temperature) is, for example, 160°C or lower.

[0228] The curing time is the reaction time between the regenerated isocyanate groups and the hydroxyl groups in the base resin under heating conditions, and / or the reaction time between the regenerated carbodiimide groups and the carboxyl groups in the base resin under heating conditions. Specifically, the curing time is, for example, 10 minutes or more, preferably 20 minutes or more. The curing time is, for example, 60 minutes or less, preferably 30 minutes or less.

[0229] This thermally decomposes the uretonimine groups, regenerating isocyanate groups and carbodiimide groups. The regenerated isocyanate groups then react with hydroxyl groups in the base resin, and / or the regenerated carbodiimide groups react with carboxyl groups in the base resin. As a result, the curable composition cures.

[0230] If necessary, the heat-cured resin can be further dried. The drying temperature may be room temperature, for example, 10°C or higher, and preferably 15°C or higher. The drying temperature is, for example, 40°C or lower, and preferably 30°C or lower. The drying time is, for example, 1 minute or longer, and preferably 5 minutes or longer. The drying time is, for example, 2 hours or shorter, and preferably 1 hour or shorter.

[0231] Furthermore, the cured resin product is a cured product of the curable composition, and therefore can achieve both excellent curability and an excellent pot life.

[0232] Therefore, the curable composition and the cured resin product can be used in a wide range of industrial fields, including, more specifically, coating materials, adhesive materials, pressure-sensitive adhesive materials, inks, sealants, molding materials, foams, optical materials, and resin modifiers. [Example]

[0233] Next, the present invention will be described based on Production Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the "Description of the Invention" above.

[0234] The various measurement methods are described below.

[0235] <derivatization rate> In the carbodiimidization step, the isocyanate group concentration (mass %) before the carbodiimidization reaction was measured in accordance with the n-dibutylamine method of JIS K-1556 (2006).

[0236] Furthermore, the isocyanate group concentration (mass %) after the carbodiimidization reaction and before the uretoneimine reaction was measured in the same manner as above.

[0237] Furthermore, the isocyanate group concentration (mass %) after the uretone imine reaction was measured in the same manner as above.

[0238] The conversion rate (1) of the isocyanate group in the carbodiimidation reaction was calculated on a mass basis according to the following formula: The obtained conversion rate (1) of the isocyanate group was defined as the derivatization rate (1) below.

[0239] [Isocyanate group conversion rate (1)] = { 1-[(Isocyanate group concentration (mass%) after carbodiimidization reaction and before uretoniminization reaction) / (Isocyanate group concentration (mass%) before carbodiimidization reaction)] } ×100(%)

[0240] [derivatization rate(1)]= { 1-[(total moles of isocyanate groups after the carbodiimidization reaction of polyisocyanate and before the uretoniminization reaction) / (total moles of isocyanate groups before the carbodiimidization reaction and the uretoniminization reaction of polyisocyanate)] } ×100(%)

[0241] The conversion rate (2) of the isocyanate group in the uretone imine reaction was calculated on a mass basis according to the following formula: The obtained conversion rate (2) of the isocyanate group was defined as the derivatization rate (2) below.

[0242] [Isocyanate group conversion rate (2)] = {1 - [(isocyanate group concentration (mass %) after uretonimine formation reaction) / (isocyanate group concentration (mass %) before carbodiimidization reaction)] } × 100 (%)

[0243] [Derivatization rate (2)] = { 1 - [(total moles of isocyanate groups after the carbodiimidization reaction and uretonimine formation reaction of the polyisocyanate) / (total moles of isocyanate groups before the carbodiimidization reaction and uretonimine formation reaction of the polyisocyanate)] } × 100 (%)

[0244] <IR intensity ratio (IR CI / IR UI )> The polyurethaneimine composition (hereinafter referred to as "solvent - removed product") obtained by distilling off the organic solvent used in the reaction was measured for its IR spectrum according to a conventional method using the following apparatus and conditions.

[0245] And the intensity ratio (IR -1 / IR CI ) of the absorbance IR -1 near the stretching vibration of the carbodiimide group at 2120 cm<(0000060)>to the absorbance IR<(0000061)> / IR<(0000062)>near the C = O stretching vibration of the uretonimine group at 1870 cm was calculated.

[0246] IR measuring apparatus: Frontier FT - IR manufactured by Perkin Elmer Measurement method: ATR (reflection method) Wavenumber range: 4000 - 400 cm -1 Resolution: 4 cm -1

[0247] Example A1 <Pre - urethanization step> A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 100.0 parts by mass of xylylene diisocyanate (hereinafter, XDI (Mitsui Chemicals, Inc.)) as a polyisocyanate and 106.3 parts by mass of methoxypolyethylene glycol having a number average molecular weight of 1000 (hereinafter, MeOPEG1000) as an alcohol at room temperature.

[0248] While introducing nitrogen into the flask, the flask was heated to 75°C under normal pressure and stirred for 4 hours. This caused a urethane reaction between XDI and MeOPEG1000. The isocyanate group concentration of the content after the urethane reaction (urethane reaction product liquid) was 19.5 mass%.

[0249] <Carbodiimidization step> Next, 0.1 parts by mass of 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) as a carbodiimidization catalyst was placed in the flask.

[0250] The flask was heated to 141°C and stirred for 3 hours. This caused the urethanization reaction product liquid to undergo a carbodiimidation reaction. The isocyanate group concentration of the carbodiimidation reaction product liquid was 5.5 mass%.

[0251] The conversion rate of the isocyanate group in the carbodiimidization step was 72 mass %, that is, the derivatization rate (1) was 72 mol %.

[0252] <Uretone imine formation process> Thereafter, the flask was cooled to 70° C., and 196.0 parts by mass of propylene glycol monomethyl ether acetate (hereinafter, PMA) as an organic solvent was charged into the flask.

[0253] The flask was cooled to 25°C, and the contents of the flask were aged for 12 hours. The isocyanate group concentration of the contents (uretone imine reaction product liquid) after aging was 2.5% by mass. The isocyanate group concentration calculated as solid content was 5.1% by mass.

[0254] The conversion rate of the isocyanate group in the carbodiimidation step and the uretonimine step was 74 mass %, that is, the derivatization rate (2) was 74 mol %.

[0255] As a result, a polyurethane imine composition was obtained, which had a solids concentration of 50% by mass.

[0256] A portion of the polyurethane imine composition was taken out and the IR spectrum was measured. CI / IR UI ) was less than 0.1.

[0257] <Sealing process> The polyurethane imine composition was cooled to 30°C or below. The amine liquid was added dropwise to the polyurethane imine composition and mixed. This blocked the isocyanate groups at the molecular terminals of the polyurethane imine composition. That is, a water-dispersed composition of the polyurethane imine composition was obtained. The amine liquid was a mixed liquid of 30.5 parts by mass of dibutylamine and 30.5 parts by mass of propylene glycol monomethyl ether acetate (solvent). The color of the water-dispersed composition (JIS K 0071-2 (1998)) was Gardner 1.

[0258] <Curable composition> A water-dispersed composition of a polyurethane imine composition was prepared as a curing agent, and a carboxyl group-containing polyurethane polyol (water-based polyurethane dispersion, solid content 30% by mass, carboxyl group content 9 mg KOH / g in solid content) was prepared as a base resin.

[0259] A curing agent with a solid content of 10 parts by mass was mixed with a base agent with a solid content of 90 parts by mass. Next, water was added to the mixture of the curing agent and base agent so that the solid content concentration was 20% by mass. This resulted in a curable composition. No foreign matter was found in the curable composition. This confirmed that the composition had good water dispersibility.

[0260] Changes in the fluidity of the curable composition over time were also confirmed, and the time it took for the curable composition to gel was measured as the pot life (days).

[0261] <Cured resin> The curable composition was applied to a polypropylene plate using a 4-mil doctor blade. The resulting coating solution was heated at 150°C for 30 minutes. This dried and cured the coating solution, yielding a cured film made of a cured resin.

[0262] The cured film was immersed in a mixed solution of acetone and methanol (mass ratio 1 / 1) for 12 hours. The gel fraction was calculated as the ratio of the mass of the cured film after immersion to the mass of the cured film before immersion. The higher the gel fraction (the remaining rate of the cured film after immersion), the better the curability was judged to be.

[0263] Examples A2 to A24 and Comparative Examples A1 to A6 A polyurethaneimine composition, a curable composition, and a cured resin product were obtained in the same manner as in Example A1, except that the formulations and conditions were changed as shown in Table 1. The polyurethaneimine composition, the curable composition, and the cured resin product were evaluated in the same manner as in Example A1.

[0264] Example B1 <Pre-urethane process> A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 100.0 parts by mass of XDI (manufactured by Mitsui Chemicals, Inc.) as a polyisocyanate and 106.3 parts by mass of MeOPEG1000 as an alcohol at room temperature.

[0265] While introducing nitrogen into the flask, the flask was heated to 75°C under normal pressure and stirred for 4 hours. This caused a urethane reaction between XDI and MeOPEG1000. The isocyanate group concentration of the content after the urethane reaction (urethane reaction product liquid) was 19.5 mass%.

[0266] <Carbodiimidization step> Next, 0.1 parts by mass of 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) as a carbodiimidization catalyst was placed in the flask.

[0267] The flask was heated to 141°C and stirred for 4 hours. This caused the urethanization reaction product liquid to undergo a carbodiimidation reaction. The isocyanate group concentration of the content (carbodiimidation reaction product liquid) after the carbodiimidation reaction was 7.6 mass%.

[0268] The conversion rate of the isocyanate group in the carbodiimidization step was 61% by mass, i.e., the derivatization rate (1) was 61% by mole.

[0269] <Uretone imine formation process> Thereafter, the flask was cooled to 70° C., and 67.0 parts by mass of methyl ethyl ketone (MEK) as an organic solvent was charged into the flask.

[0270] The flask was cooled to 25°C, and the contents of the flask were aged for 12 hours. The isocyanate group concentration of the contents (uretonimine reaction product liquid) after aging was 5.4 mass%. The isocyanate group concentration calculated as solid content was 7.2 mass%.

[0271] The conversion rate of the isocyanate group in the carbodiimidation step and the uretonimine step was 63 mass %, that is, the derivatization rate (2) was 63 mol %.

[0272] As a result, a polyurethane imine composition was obtained, which had a solids concentration of 75% by mass.

[0273] A portion of the polyurethane imine composition was taken out and the IR spectrum was measured. CI / IR UI ) was less than 0.1.

[0274] <Chain extension process> The polyurethane imine composition obtained above was dispersed in 883.8 parts by mass of ion-exchanged water using a homodisper. An amine liquid was then added to the dispersion of the polyurethane imine composition to cause a chain extension reaction of the polyurethane imine composition. The amine liquid was a mixture of 10.2 parts by mass of ethylenediamine (EDA) and 49.0 parts by mass of ion-exchanged water.

[0275] The chain extension reaction product liquid was aged for 1 hour. Thereafter, methyl ethyl ketone and ion-exchanged water were distilled off from the chain extension reaction product liquid using an evaporator. Furthermore, ion-exchanged water was added to the chain extension reaction product liquid to adjust the solid content concentration to 15% by mass. This resulted in an aqueous dispersion composition of a chain-extended polyurethane imine composition. Furthermore, it was visually confirmed that the polyurethane imine composition was uniformly dispersed in the aqueous dispersion composition.

[0276] <Curable composition> A water-dispersed composition of a polyurethane imine composition was prepared as a curing agent, and a carboxyl group-containing polyurethane polyol (water-based polyurethane dispersion, solid content 30% by mass, carboxyl group content 9 mg KOH / g in solid content) was prepared as a base resin.

[0277] A curing agent with a solid content of 10 parts by mass was mixed with a base agent with a solid content of 90 parts by mass. Next, water was added to the mixture of the curing agent and base agent so that the solid content concentration was 20% by mass. This resulted in a curable composition. No foreign matter was found in the curable composition. This confirmed that the composition had good water dispersibility.

[0278] Changes in the fluidity of the curable composition over time were also confirmed, and the time it took for the curable composition to gel was measured as the pot life (days).

[0279] <Cured resin> The curable composition was applied to a polypropylene plate using a 4-mil doctor blade. The resulting coating solution was heated at 150°C for 30 minutes. This cured the coating solution, yielding a cured film made of a cured resin.

[0280] The cured film was immersed in a mixed solution of acetone and methanol (mass ratio 1 / 1) for 12 hours. The gel fraction was calculated as the ratio of the mass of the cured film after immersion to the mass of the cured film before immersion. The higher the gel fraction (the remaining rate of the cured film after immersion), the better the curability was judged to be.

[0281] Examples B2 to B4 and Comparative Examples B1 to B2 A polyurethaneimine composition, a curable composition, and a cured resin product were obtained in the same manner as in Example B1, except that the formulations and conditions were changed as shown in Table 6. The polyurethaneimine composition, the curable composition, and the cured resin product were evaluated in the same manner as in Example B1.

[0282] Example C1 <Carbodiimidization step> A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged at room temperature with 100.0 parts by mass of XDI (manufactured by Mitsui Chemicals, Inc.) as a polyisocyanate and 0.1 parts by mass of 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) as a carbodiimidization catalyst. The isocyanate group concentration of the XDI before the carbodiimidization reaction was 44.6% by mass.

[0283] The flask was heated to 141°C and stirred for 3 hours. This caused the polyisocyanate to undergo a carbodiimidation reaction. The isocyanate group concentration of the carbodiimidation reaction product liquid was 18.8 mass%.

[0284] The conversion rate of the isocyanate group in the carbodiimidization step was 58 mass %, that is, the derivatization rate (1) was 58 mol %.

[0285] <Uretone imine formation process> Thereafter, the flask was cooled to 70°C, and 72.0 parts by mass of MEK as an organic solvent was charged into the flask.

[0286] The flask was cooled to 25°C, and the contents of the flask were aged for 12 hours. The isocyanate group concentration of the contents (uretonimine reaction product liquid) after aging was 8.9 mass%. The isocyanate group concentration calculated as solid content was 17.9 mass%.

[0287] The conversion rate of the isocyanate group in the carbodiimidation step and the uretonimine step was 60 mass %, that is, the derivatization rate (2) was 60 mol %.

[0288] As a result, a polyurethane imine composition was obtained, which had a solids concentration of 50% by mass.

[0289] A portion of the polyurethane imine composition was taken out and the IR spectrum was measured. CI / IR UI ) was less than 0.1.

[0290] <Post-urethane formation process> Next, 76.1 parts by mass of methoxypolyethylene glycol having a number average molecular weight of 400 (hereinafter, MeOPEG400) was placed in the flask.

[0291] While introducing nitrogen into the flask, the flask was heated to 75°C under normal pressure and stirred for 4 hours. This caused a urethane reaction between XDI and MeOPEG400. The isocyanate group concentration of the content after the urethane reaction (urethane reaction product liquid) was 3.2 mass%.

[0292] <Sealing process> The post-urethanized polyurethane imine composition was cooled to 30°C or below. An amine liquid was added dropwise to the polyurethane imine composition and mixed. This blocked the isocyanate groups at the molecular ends of the polyurethane imine composition. That is, an aqueous dispersion of the polyurethane imine composition was obtained. The amine liquid was a mixture of 25.3 parts by mass of dibutylamine and 25.3 parts by mass of methyl ethyl ketone (solvent).

[0293] <Curable composition> A water-dispersed composition of a polyurethane imine composition was prepared as a curing agent, and a carboxyl group-containing polyurethane polyol (water-based polyurethane dispersion, solid content 30% by mass, carboxyl group content 9 mg KOH / g in solid content) was prepared as a base resin.

[0294] A curing agent with a solid content of 10 parts by mass was mixed with a base agent with a solid content of 90 parts by mass. Next, water was added to the mixture of the curing agent and base agent so that the solid content concentration was 20% by mass. This resulted in a curable composition. No foreign matter was found in the curable composition. This confirmed that the composition had good water dispersibility.

[0295] Changes in the fluidity of the curable composition over time were also confirmed, and the time it took for the curable composition to gel was measured as the pot life (days).

[0296] <Cured resin> The curable composition was applied to a polypropylene plate using a 4-mil doctor blade. The resulting coating solution was heated at 150°C for 30 minutes. This cured the coating solution, yielding a cured film made of a cured resin.

[0297] The cured film was immersed in a mixed solution of acetone and methanol (mass ratio 1 / 1) for 12 hours. The gel fraction was calculated as the ratio of the mass of the cured film after immersion to the mass of the cured film before immersion. The higher the gel fraction (the remaining rate of the cured film after immersion), the better the curability was judged to be.

[0298] Examples C2 to C4 A polyurethaneimine composition, a curable composition, and a cured resin product were obtained in the same manner as in Example C1, except that the formulations and conditions were changed as shown in Table 7. The polyurethaneimine composition, the curable composition, and the cured resin product were evaluated in the same manner as in Example C1.

[0299] Example D1 <Carbodiimidization step> A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged at room temperature with 100.0 parts by mass of XDI (manufactured by Mitsui Chemicals, Inc.) as a polyisocyanate and 0.1 parts by mass of 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) as a carbodiimidization catalyst. The isocyanate group concentration of the XDI before the carbodiimidization reaction was 44.57% by mass.

[0300] The flask was heated to 141°C and stirred for 3 hours. This caused the polyisocyanate to undergo a carbodiimidation reaction. The isocyanate group concentration of the carbodiimidation reaction product liquid was 18.8 mass%.

[0301] The conversion rate of the isocyanate group in the carbodiimidization step was 58 mass %, that is, the derivatization rate (1) was 58 mol %.

[0302] <Uretone imine formation process> Thereafter, the flask was cooled to 70°C, and 72.0 parts by mass of MEK as an organic solvent was charged into the flask.

[0303] The flask was cooled to 25°C, and the contents of the flask were aged for 12 hours. The isocyanate group concentration of the contents (uretonimine reaction product liquid) after aging was 8.9 mass%. The isocyanate group concentration calculated as solid content was 17.9 mass%.

[0304] The conversion rate of the isocyanate group in the carbodiimidation step and the uretonimine step was 60 mass %, that is, the derivatization rate (2) was 60 mol %.

[0305] As a result, a polyurethane imine composition was obtained, which had a solids concentration of 50% by mass.

[0306] A portion of the polyurethane imine composition was taken out and the IR spectrum was measured. CI / IR UI) was less than 0.1.

[0307] <Post-urethane formation process> Next, 33.1 parts by mass of MeOPEG1000 as an alcohol was placed in the flask.

[0308] While introducing nitrogen into the flask, the flask was heated to 75°C under normal pressure and stirred for 4 hours. This caused a urethane reaction between XDI and MeOPEG1000. The isocyanate group concentration of the content after the urethane reaction (urethane reaction product liquid) was 6.9 mass%.

[0309] <Chain extension process> The post-urethanized polyurethane imine composition was dispersed in 2261.9 parts by mass of ion-exchanged water using a homodisper. An amine liquid was then added to the polyurethane imine composition dispersion, and the polyurethane imine composition was subjected to a chain extension reaction. The amine liquid was a mixture of 10.6 parts by mass of ethylenediamine (EDA) and 201.6 parts by mass of ion-exchanged water.

[0310] The chain extension reaction product liquid was aged for 1 hour. Thereafter, methyl ethyl ketone and ion-exchanged water were distilled off from the chain extension reaction product liquid using an evaporator. Furthermore, ion-exchanged water was added to the chain extension reaction product liquid to adjust the solid content concentration to 15% by mass. This resulted in an aqueous dispersion composition of a chain-extended polyurethane imine composition. Furthermore, it was visually confirmed that the polyurethane imine composition was uniformly dispersed in the aqueous dispersion composition.

[0311] <Curable composition> A water-dispersed composition of a polyurethane imine composition was prepared as a curing agent, and a carboxyl group-containing polyurethane polyol (water-based polyurethane dispersion, solid content 30% by mass, carboxyl group content 9 mg KOH / g in solid content) was prepared as a base resin.

[0312] A curing agent with a solid content of 10 parts by mass and a main agent with a solid content of 90 parts by mass were mixed. Next, water was added to the mixed solution of the curing agent and the main agent so that the solid content concentration became 20% by mass. Thereby, a curable composition was obtained. No foreign matter was confirmed in the curable composition. Thereby, it was confirmed that the water dispersibility was good.

[0313] Also, the change in the fluidity of the curable composition over time was confirmed. The time until the curable composition gelled was measured as the pot life (day).

[0314] <Resin cured product> The curable composition was applied to a polypropylene plate using a 4-mil doctor blade. The obtained coating solution was heated at 150 °C for 30 minutes. Thereby, the coating solution was cured to obtain a cured film made of a resin cured product.

[0315] The cured film was immersed in a mixed solution of acetone and methanol (mass ratio 1 / 1) for 12 hours. And the mass of the cured film after immersion was calculated with respect to the mass of the cured film before immersion as the gel fraction. It was judged that the higher the gel fraction (the residual rate of the cured film after immersion), the better the curability.

[0316] Examples D2 to D7 A polyurethane imine composition, a curable composition, and a resin cured product were obtained in the same manner as in Example D1, except that the formulations and conditions shown in Tables 8 to 9 were changed. Also, the polyurethane imine composition, the curable composition, and the resin cured product were evaluated in the same manner as in Example D1.

[0317] Example D8 <Synthesis of XDI isocyanurate A> Hydrogen chloride was added to 1,3-xylylene diisocyanate (m-XDI, manufactured by Mitsui Chemicals, Inc.) to adjust the acidity (conforming to JIS K-1603-2:2007) to 50 ppm. Thereby, a raw material component consisting of an XDI composition with a predetermined acidity was obtained (preparation step). <H

[0318] Under a nitrogen atmosphere, 787.470 parts by mass of the XDI composition and 0.161 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (hindered phenol-based antioxidant, trade name: Irganox 1076, manufactured by Ciba Japan) were mixed at 60°C to 65°C.

[0319] Next, a propylene glycol methyl ether acetate solution (active ingredient concentration 50% by mass) of dodecylbenzenesulfonic acid (DDBSA, catalyst deactivator) was added to the mixture. The amount of DDBSA added was adjusted to 0.064 parts by mass (80 ppm relative to the total amount of raw material components).

[0320] Next, 15.726 parts by mass of 1,3-butanediol was added to the mixture at 70°C to 75°C and mixed to carry out a urethane-forming reaction. Next, a propylene glycol methyl ether acetate solution (solids concentration 3.7% by mass) of tetrabutylammonium hydroxide (isocyanuration catalyst, TBAOH (37% methanol solution)) was added to the obtained urethane reaction liquid. The amount of TBAOH (37% methanol solution) added was adjusted to 0.803 parts by mass (0.3 parts by mass as active ingredient). Next, while mixing the urethane reaction liquid, the XDI was subjected to an isocyanuration reaction at 70°C to 75°C until the NCO concentration reached 37.7% (reaction step).

[0321] Next, a propylene glycol methyl ether acetate solution (active ingredient concentration 50% by mass) of dodecylbenzenesulfonic acid (DDBSA, catalyst deactivator) was added to the obtained isocyanurate reaction solution to terminate the isocyanurate reaction. The amount of DDBSA added was adjusted to 0.415 parts by mass (the proportion of DDBSA added was 500 ppm relative to the isocyanurate reaction solution). This produced an isocyanurate-modified product of XDI (hereinafter referred to as XDI Isocyanurate A).

[0322] A polyurethaneimine composition, a curable composition, and a cured resin were obtained in the same manner as in Example D1, except that XDI isocyanurate A was used and the formulation and conditions were changed as shown in Table 9. The polyurethaneimine composition, the curable composition, and the cured resin were evaluated in the same manner as in Example D1.

[0323] Example E1 <Carbodiimidization step> A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged at room temperature with 100.0 parts by mass of XDI (manufactured by Mitsui Chemicals, Inc.) as a polyisocyanate and 0.1 parts by mass of 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) as a carbodiimidization catalyst. The isocyanate group concentration of the XDI before the carbodiimidization reaction was 44.57% by mass.

[0324] The flask was heated to 141°C and stirred for 3 hours. This caused the polyisocyanate to undergo a carbodiimidation reaction. The isocyanate group concentration of the carbodiimidation reaction product liquid was 18.8 mass%.

[0325] The conversion rate of the isocyanate group in the carbodiimidization step was 58 mass %, that is, the derivatization rate (1) was 58 mol %.

[0326] <Uretone imine formation process> Thereafter, the flask was cooled to 70°C, and 72.0 parts by mass of MEK was charged into the flask as an organic solvent.

[0327] The flask was cooled to 25°C, and the contents of the flask were aged for 12 hours. The isocyanate group concentration of the contents (uretonimine reaction product liquid) after aging was 8.9 mass%. The isocyanate group concentration calculated as solid content was 17.9 mass%.

[0328] The conversion rate of the isocyanate group in the carbodiimidation step and the uretonimine step was 60 mass %, that is, the derivatization rate (2) was 60 mol %.

[0329] As a result, a polyurethane imine composition was obtained, which had a solids concentration of 50% by mass.

[0330] A portion of the polyurethane imine composition was taken out and the IR spectrum was measured. CI / IR UI ) was less than 0.1.

[0331] <Sealing process> The polyurethane imine composition was cooled to 30°C or below. An amine liquid was added dropwise to the polyurethane imine composition and mixed therewith. This blocked the isocyanate groups at the molecular ends of the polyurethane imine composition. That is, a solution composition of the polyurethane imine composition was obtained. The amine liquid was a mixture of 49.8 parts by mass of dibutylamine and 49.8 parts by mass of methyl ethyl ketone (solvent).

[0332] <Curable composition> A solution composition of a polyurethaneimine composition was prepared as a curing agent, and polyol 1 was prepared as a base resin.

[0333] That is, 283 parts by mass of isophthalic acid, 352 parts by mass of 1,3-butanediol, and 191 parts by mass of neopentyl glycol were charged into a reactor, and an esterification reaction was carried out at 190 to 220° C. under a nitrogen stream.

[0334] Thereafter, a predetermined amount of water was distilled off, and 124 parts by mass of adipic acid, 172 parts by mass of sebacic acid, and 0.01 parts by mass of titanium tetrabutoxide were added to the reactor, and an esterification reaction was carried out at 180° C. to 220° C. under a nitrogen stream. Polyester diol A was thereby obtained.

[0335] The polyester diol A had an average functionality of 2.0 and a hydroxyl equivalent weight of 250.

[0336] Next, 5.8 parts by mass of trimellitic anhydride was added to 75.0 parts by mass of polyester diol A, and the terminals were partially acid-modified at 150° C. Thus, acid-modified polyester diol A was obtained.

[0337] Acid-modified polyester diol A and 17.1 g of polypropylene polyol (propylene oxide adduct using glycerin as an initiator, hydroxyl value 530) were uniformly mixed to obtain polyol 1.

[0338] Polyol 1 had an average functionality of 2.29, a hydroxyl equivalent of 231 mg KOH / g, an acid value of 33 mg KOH / g, and a carboxyl equivalent of 1,650.

[0339] Then, 10 parts by mass of the curing agent with a solid content of 90 parts by mass of the base agent were mixed. Next, a mixed solvent was added to the mixed solution of the curing agent and base agent so that the solid content concentration was 20% by mass, and the mixture was mixed for 10 minutes. The mixed solvent was a mixture of butyl acetate, propylene glycol monomethyl ether acetate, and ethyl acetate (mass ratio 1 / 1 / 1). This resulted in a curable composition. No foreign matter was found in the curable composition. This confirmed that the solvent dispersibility was good.

[0340] Changes in the fluidity of the curable composition over time were also confirmed, and the time it took for the curable composition to gel was measured as the pot life (days).

[0341] <Cured resin> The curable composition was applied to a polypropylene plate using a 4-mil doctor blade. The resulting coating solution was heated at 150°C for 30 minutes. This cured the coating solution, yielding a cured film made of a cured resin.

[0342] The cured film was immersed in a mixed solution of acetone and methanol (mass ratio 1 / 1) for 12 hours. The gel fraction was calculated as the ratio of the mass of the cured film after immersion to the mass of the cured film before immersion. The higher the gel fraction (the remaining rate of the cured film after immersion), the better the curability was judged to be.

[0343] Examples E2 to E3 and Comparative Examples E1 to E2 A polyurethaneimine composition, a curable composition, and a cured resin product were obtained in the same manner as in Example E1, except that the formulations and conditions were changed as shown in Table 10. In addition, the polyurethaneimine composition, the curable composition, and the cured resin product were evaluated in the same manner as in Example E1.

[0344] Example F1 <Pre-urethane formation process> A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 100.0 parts by mass of XDI (manufactured by Mitsui Chemicals, Inc.) as a polyisocyanate and 19.2 parts by mass of 1-methoxy-2-propanol as an alcohol at room temperature.

[0345] While introducing nitrogen into the flask, the flask was heated to 75°C under normal pressure and stirred for 4 hours. This caused a urethane reaction between XDI and 1-methoxy-2-propanol. The isocyanate group concentration of the content after the urethane reaction (urethane reaction product liquid) was 37.5% by mass.

[0346] <Carbodiimidization step> Next, 0.1 parts by mass of 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO) as a carbodiimidization catalyst was placed in the flask.

[0347] The flask was heated to 141°C and stirred for 4 hours. This caused the urethanization reaction product liquid to undergo a carbodiimidation reaction. The isocyanate group concentration of the content (carbodiimidation reaction product liquid) after the carbodiimidation reaction was 7.5 mass%.

[0348] The conversion rate of the isocyanate group in the carbodiimidization step was 80% by mass, i.e., the derivatization rate (1) was 80% by mole.

[0349] <Uretone imine formation process> Thereafter, the flask was cooled to 70° C., and 106.5 parts by mass of ethyl acetate (EtOAc) as an organic solvent was placed in the flask.

[0350] The flask was cooled to 25°C, and the contents of the flask were aged for 12 hours. The isocyanate group concentration of the contents (uretone imine reaction product liquid) after aging was 3.4 mass%. The isocyanate group concentration calculated as solid content was 6.7 mass%.

[0351] The conversion rate of the isocyanate group in the carbodiimidation step and the uretonimine step was 82 mass %, that is, the derivatization rate (2) was 82 mol %.

[0352] As a result, a polyurethane imine composition was obtained, which had a solids concentration of 50% by mass.

[0353] A portion of the polyurethane imine composition was taken out and the IR spectrum was measured. CI / IR UI ) was 0.2.

[0354] <Sealing process> The polyurethane imine composition was cooled to 30°C or below. An amine liquid was added dropwise to the polyurethane imine composition and mixed. This blocked the isocyanate groups at the molecular terminals of the polyurethane imine composition. That is, a solution composition of the polyurethane imine composition was obtained. The amine liquid was a mixture of 22.1 parts by mass of dibutylamine and 22.1 parts by mass of ethyl acetate (EtOAc).

[0355] <Curable composition> A solution composition of a polyurethaneimine composition was prepared as a curing agent, and the above-mentioned polyol 1 was prepared as a base resin.

[0356] Then, 10 parts by mass of the curing agent with a solid content of 90 parts by mass of the base agent were mixed. Next, a mixed solvent was added to the mixed solution of the curing agent and base agent so that the solid content concentration was 20% by mass, and the mixture was mixed for 10 minutes. The mixed solvent was a mixture of butyl acetate, propylene glycol monomethyl ether acetate, and ethyl acetate (mass ratio 1 / 1 / 1). This resulted in a curable composition. No foreign matter was found in the curable composition. This confirmed that the solvent dispersibility was good.

[0357] Changes in the fluidity of the curable composition over time were also confirmed, and the time it took for the curable composition to gel was measured as the pot life (days).

[0358] <Cured resin> The curable composition was applied to a polypropylene plate using a 4-mil doctor blade. The resulting coating solution was heated at 150°C for 30 minutes. This cured the coating solution, yielding a cured film made of a cured resin.

[0359] The cured film was immersed in a mixed solution of acetone and methanol (mass ratio 1 / 1) for 12 hours. The gel fraction was calculated as the ratio of the mass of the cured film after immersion to the mass of the cured film before immersion. The higher the gel fraction (the remaining rate of the cured film after immersion), the better the curability was judged to be.

[0360] Examples F2 to F5 and Comparative Examples F1 to F2 A polyurethaneimine composition, a curable composition, and a cured resin product were obtained in the same manner as in Example F1, except that the formulations and conditions were changed as shown in Table 11. In addition, the polyurethaneimine composition, the curable composition, and the cured resin product were evaluated in the same manner as in Example F1.

[0361] [Table 1]

[0362]

Table 2

[0363]

Table 3

[0364]

Table 4

[0365]

Table 5

[0366]

Table 6

[0367]

Table 7

[0368]

Table 8

[0369]

Table 9

[0370]

Table 10

[0371]

Table 11

[0372] Details of the abbreviations in the table are given below. XDI: 1,3-xylylene diisocyanate PDI: Pentamethylene diisocyanate HDI: Hexamethylene diisocyanate TDI: 2,4-tolylene diisocyanate IPDI: Isophorone diisocyanate 1,3BG: 1,3-butanediol MeOPEG1000: methoxypolyethylene glycol, number average molecular weight 1000 MeOPEG400: methoxypolyethylene glycol, number average molecular weight 400 MPPO: 3-methyl-1-phenyl-2-phosphorene-1-oxide PMA: Propylene glycol monomethyl ether acetate AN: Acetonitrile MEK: Methyl ethyl ketone EtOAc: ethyl acetate DBA: Dibutylamine DEA: Diethylamine JEFFAMINEt 403: Trimethylolpropane (polyoxypropylene) triamine, manufactured by HUNTSMAN EDA: ethylenediamine

Claims

1. including derivatives of polyisocyanates having only primary isocyanate groups, The derivative contains a carbodiimide group and a uretonimine group, The following derivatization rate (1) of the polyisocyanate is 35 mol% or more and 90 mol% or less, In the infrared absorption spectrum, 2120 cm due to the stretching vibration of the carbodiimide group －１ Absorbance IR near ＣＩ of, 1870 cm due to the stretching vibration of the uretonimine group －１ Absorbance IR near ＵＩ Intensity ratio (IR ＣＩ / IR ＵＩ ) is less than 4.

0. [Derivatization rate (1)] = {1 - [(total moles of isocyanate groups after the carbodiimidation reaction of polyisocyanate and before the uretonimination reaction) / (total moles of isocyanate groups before the carbodiimidation reaction and the uretonimination reaction of polyisocyanate)]} × 100 (%)

2. 2. The polyurethaneimine composition according to claim 1, wherein the following derivatization rate (2) of the polyisocyanate is 40 mol % or more and 90 mol % or less. [Derivatization rate (2)] = {1 - [(total moles of isocyanate groups after the polyisocyanate has undergone the carbodiimidation reaction and the uretonimination reaction) / (total moles of isocyanate groups before the polyisocyanate has undergone the carbodiimidation reaction and the uretonimination reaction)]} × 100 (%)

3. The polyuretoneimine composition according to claim 1 or 2, wherein the derivative further comprises a urethane group.

4. the urethane group is obtained by reacting the polyisocyanate with an alcohol, 4. The polyurethaneimine composition according to claim 3, wherein the alcohols include an alcohol containing three or more consecutive oxyethylene groups.

5. The polyurethane imine composition according to any one of claims 1 to 4, wherein the derivative is capped and / or chain extended with an amine compound.

6. The polyurethane imine composition according to claim 5 , wherein the amine compound comprises a polyamine.

7. The polyurethane imine composition according to any one of claims 1 to 6, The water-dispersed composition is an aqueous dispersion liquid dispersed in water at a solid content concentration of 5% by mass or more and 90% by mass or less.

8. The polyurethane imine composition according to any one of claims 1 to 6, A solution composition in which a solid content is dissolved in an organic solvent at a ratio of 5% by mass to 90% by mass.

9. A base agent having both a hydroxyl group and a carboxyl group, A curing agent comprising the polyurethaneimine composition according to any one of claims 1 to 6. A curable composition comprising:

10. A cured resin product, which is a cured product of the curable composition according to claim 9.

11. a carbodiimidization step of subjecting a polyisocyanate having only primary isocyanate groups and / or a urethane-modified polyisocyanate thereof to a carbodiimidization reaction to obtain a carbodiimidation reaction product; a uretonimination step of subjecting the carbodiimidation reaction product to a uretonimination reaction to obtain a uretonimination reaction product, In the carbodiimidization step, the isocyanate groups of the polyisocyanate and / or its urethane-modified product are subjected to the carbodiimidization reaction so that the following derivatization rate (1) is 35 mol % or more and 90 mol % or less, In the infrared absorption spectrum, the stretching vibration of the carbodiimide group at 2120 cm －１ Absorbance IR near ＣＩ 1870 cm resulting from the stretching vibration of the uretonimine group －１ Absorbance IR near ＵＩ Intensity ratio (IR ＣＩ / IR ＵＩ ) is less than 4.

0. [Derivatization rate (1)] = {1 - [(total moles of isocyanate groups after the carbodiimidation reaction of polyisocyanate and before the uretonimination reaction) / (total moles of isocyanate groups before the carbodiimidation reaction and the uretonimination reaction of polyisocyanate)]} × 100 (%)

12. 12. The method for producing a polyurethaneimine composition according to claim 11, wherein in the uretoniminization step, the isocyanate groups of the carbodiimidation reaction product are subjected to the uretoniminization reaction so that the following derivatization rate (2) is 40 mol % or more and 90 mol % or less: [Derivatization rate (2)] = {1 - [(total moles of isocyanate groups after the polyisocyanate has undergone the carbodiimidation reaction and the uretonimination reaction) / (total moles of isocyanate groups before the polyisocyanate has undergone the carbodiimidation reaction and the uretonimination reaction)]} × 100 (%)

13. a urethane-forming step of reacting the polyisocyanate having only primary isocyanate groups with an alcohol to obtain a urethane-modified product of the polyisocyanate, prior to the carbodiimidization step; and / or The method for producing a polyurethane imine composition according to claim 11 or 12, further comprising, after the uretone iminization step, a urethanization step of reacting the uretone iminization reaction product with an alcohol to obtain a urethane-modified product of the uretone iminization reaction product.

14. The method further includes an amine reaction step after the uretone iminization step, In the amine reaction step, The method for producing a polyurethane imine composition according to any one of claims 11 to 13, comprising reacting the uretone imine reaction product and / or a urethane-modified product thereof with an amine compound, and capping and / or chain-extending the uretone imine reaction product and / or the urethane-modified product thereof with the amine compound.

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