JP7377613B2 - Polyisocyanate compositions, coating compositions and coating substrates - Google Patents

Description

The present invention relates to polyisocyanate compositions, coating compositions and coating substrates.

In recent years, from the viewpoint of environmental protection, it has been desired to convert the room-temperature crosslinking two-component urethane coating composition, which has conventionally been used as a solvent-based paint, into a water-based one. However, polyisocyanates used as curing agents in two-component urethane coating compositions have the problem of being difficult to disperse in water and easily reacting with water, generating carbon dioxide. Therefore, efforts are being made to develop polyisocyanates that have high emulsifying properties and can suppress the reaction between isocyanate groups and water in a water-dispersed state.

Patent Document 1 discloses a reaction product of a polyisocyanate compound and a compound having at least one sulfonic acid group and an isocyanate reactive group.
Patent Document 2 and Patent Document 3 disclose a polyisocyanate composition containing a modified polyisocyanate obtained by reacting a sulfonic acid amine salt having a hydroxyl group with a polyisocyanate.
Patent Documents 4 and 5 disclose modified polyisocyanates obtained by reacting aminosulfonic acids with specific structures with polyisocyanates.

Japanese Unexamined Patent Publication No. 8-176267 Japanese Patent Application Publication No. 2015-205957 Japanese Patent Application Publication No. 2016-017157 Patent No. 4806511 International Publication No. 2015/035673

Water-based two-component urethane coating compositions are used for painting furniture and building materials, residential woodwork, wooden floors of houses and school facilities, trains and construction machinery, agricultural vehicles, and the like. For these uses, polyisocyanate compositions that provide coating films with excellent appearance, hardness, and water resistance are required.

Patent Documents 1 to 3 disclose that the dispersibility in water is improved by using a polyisocyanate containing a sulfonic acid group. However, since the compatibility between the sulfonic acid group and the polyisocyanate is poor, there is a problem in that the synthetic product becomes cloudy. In order to improve this turbidity, if a highly organic sulfonic acid or an amine salt of a highly organic sulfonic acid is used, the appearance of the coating will deteriorate and the hydrophilicity will decrease. There was also the problem that the hardness of the coating film decreased due to the need for a large amount of modification.

Patent Documents 4 and 5 disclose that the hardness of the coating film and the solvent resistance of the coating film can be improved by using a modified polyisocyanate obtained by reaction with an aminosulfonic acid having a specific structure. On the other hand, since the aminosulfonic acid having a specific structure has relatively high hydrophobicity, there is a problem in that the appearance of the coating film becomes poor. In addition, there was also the problem that the water resistance was poor despite the relatively high hydrophobicity of aminosulfonic acid.

As described above, it has been difficult for any of the polyisocyanate compositions disclosed in Patent Documents 1 to 5 to satisfy the requirements of achieving both good appearance, hardness, and water resistance when used as a coating film.

The present invention was made in view of the above circumstances, and it is possible to obtain excellent dispersibility when dispersed in water or a main agent containing water, and to obtain a coating film with excellent appearance, hardness, and water resistance. A polyisocyanate composition, a coating composition containing the polyisocyanate composition, and a coated substrate using the coating composition are provided.

The present inventors have developed a polyisocyanate containing a sulfonic acid anion group in the molecule, a tertiary ammonium cation of two or more amine compounds, and a polyisocyanate containing a uretdione dimer of a diisocyanate in a specific range of content. The present inventors have discovered that the composition has excellent water dispersibility, and that when used in a coating composition, a coating film with excellent appearance, hardness, and water resistance can be obtained, and the present invention has been completed.

That is, the present invention includes the following aspects.
The polyisocyanate composition according to the first aspect of the present invention comprises a polyisocyanate containing a sulfonic acid anion group in the molecule and a tertiary ammonium cation of one or more amine compounds represented by the following general formula (1). and one or more tertiary ammonium cations of amine compounds represented by the following general formula (2), or two or more types of R ¹¹ , R ¹² and R ¹³ having different total carbon numbers from each other ( A polyisocyanate composition comprising a tertiary ammonium cation of an amine compound represented by 1) and a uretdione dimer of a diisocyanate monomer, wherein the content of the uretdione dimer is greater than the total content of the composition. The polyisocyanate is 2.0% by mass or more and 20.0% by mass or less based on the mass, and the polyisocyanate containing the sulfonic acid anion group in the molecule contains two or more amine salts of sulfonic acid having active hydrogen groups. It is obtained by reaction with polyisocyanate. The amine salt of a sulfonic acid having an active hydrogen group comprises a sulfonic acid having an active hydrogen group, one or more amine compounds represented by the general formula (1), and one or more of the general formula (2). or the sulfonic acid having an active hydrogen group and the general formula (1) in which the total number of carbon atoms of the two or more types of R ¹¹ , R ¹² and R ¹³ are different from each other; It is a salt with the represented amine compound. The sulfonic acid having an active hydrogen group is a compound represented by the following general formula (3) .

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)

(In general formula (3), R ³¹ is a hydrocarbon group having 1 or more and 10 or less carbon atoms which may contain at least one selected from the group consisting of a hydroxyl group, an ether bond, an ester bond, a carbonyl group, and an imino group. R ³¹ may include a ring structure. The ring structure is an aromatic ring, a 5- or 6-membered ring containing two nitrogen atoms, or a 5- or 6-membered ring containing a nitrogen atom and an oxygen atom. )

The polyisocyanate composition according to the second aspect of the present invention comprises a polyisocyanate containing a sulfonic acid anion group in the molecule and a tertiary ammonium cation of one or more amine compounds represented by the general formula (1). and one or more tertiary ammonium cations of the amine compound represented by the general formula (2), or two or more R ¹¹ ,R ¹² and R ¹³ A polyisocyanate composition comprising a tertiary ammonium cation of an amine compound represented by the general formula (1) having different total carbon numbers, and a uretdione dimer of a diisocyanate monomer, wherein the uretdione dimer The content of polyisocyanate is 2.0% by mass or more and 20.0% by mass or less based on the total mass of the composition, and the polyisocyanate containing the sulfonic acid anion group in the molecule has an active hydrogen group. It is obtained by the reaction between a sulfonic acid and a polyisocyanate. The sulfonic acid having an active hydrogen group is a compound represented by the following general formula (4).

(In general formula (4), R ⁴¹ and R ⁴³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and which may contain a hydroxyl group. R ⁴¹ is a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group, R ⁴³ is a hydrogen atom, and R ⁴³ is a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group, R ⁴¹ is a hydrogen atom. R ⁴² is a hydrocarbon group having 1 or more and 12 or less carbon atoms that may contain a hydroxyl group. )

The polyisocyanate compositions according to the first and second aspects have an isocyanurate group, and the ratio of the molar amount of the isocyanurate group to the molar amount of the uretdione group in the composition is 2.5 or more and 10. It may be 0 or less.
The polyisocyanate compositions according to the first and second aspects have a uretdione dimer content of 2.0% by mass or more and 5.0% by mass or less based on the total mass of the composition. Good too.

In the polyisocyanate composition according to the first aspect and the second aspect , the amine compound represented by the general formula (1) is a cyclic amine compound, an amine compound containing a chain aliphatic hydrocarbon group, and a cycloaliphatic carbonized The amine compound is at least one selected from the group consisting of amine compounds containing a hydrogen group, and the amine compound represented by the general formula (2) is an amine compound containing a chain aliphatic hydrocarbon group and a cyclic aliphatic carbonization group. It may be at least one selected from the group consisting of amine compounds containing hydrogen groups.
In the polyisocyanate composition according to the first aspect and the second aspect , the polyisocyanate is at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates. It's okay.

The method for producing a polyisocyanate composition according to the third aspect of the present invention comprises (A) two or more amine salts of sulfonic acid having active hydrogen groups , and one or more polyisocyanates represented by the following general formula (1). and one or more amine compounds represented by the following general formula (2), or two or more types of R ¹¹ , R ¹² and R ¹³ of the above general formula ( A method in which the amine compound represented by 1) is reacted with the molar amount of the isocyanate group to the molar amount of the active hydrogen group in a range of 2 to 400, and the amine salt of the sulfonic acid having the active hydrogen group is is a salt of the sulfonic acid having the active hydrogen group and one or more amine compounds represented by the general formula (1) and one or more amine compounds represented by the general formula (2), Alternatively, it is a salt of the sulfonic acid having an active hydrogen group and two or more amine compounds represented by the general formula (1) in which the total carbon numbers of R ¹¹ , R ¹² and R ¹³ are different from each other, The sulfonic acid having an active hydrogen group is a compound represented by the following general formula (3), and the polyisocyanate composition according to the first aspect is manufactured.

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)
(In general formula (3), R ³¹ is a hydrocarbon group having 1 to 10 carbon atoms that may contain at least one selected from the group consisting of a hydroxyl group, an ether bond, an ester bond, a carbonyl group, and an imino group. R ³¹ may include a ring structure. The ring structure is an aromatic ring, a 5-membered ring or 6-membered ring containing two nitrogen atoms, or a 5-membered ring or 6-membered ring containing a nitrogen atom and an oxygen atom. It is a member ring.)

The method for producing a polyisocyanate composition according to the fourth aspect of the present invention comprises (B) a sulfonic acid having an active hydrogen group, a polyisocyanate, one or more amine compounds represented by the general formula (1), and one or more amine compounds represented by the general formula (2), or two or more R ¹¹ ,R ¹² and R ¹³ A method in which amine compounds represented by the general formula (1) having different total carbon numbers are reacted in a ratio of the molar amount of isocyanate groups to the molar amount of active hydrogen groups in the range of 2 to 400, The sulfonic acid having an active hydrogen group is a compound represented by the following general formula (4), and the polyisocyanate composition according to the second aspect is manufactured.

(In general formula (4), R ⁴¹ and R ⁴³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group. Even if R ⁴¹ contains a hydroxyl group When R 43 is a hydrocarbon group having 1 to 12 carbon atoms, R ⁴³ is a hydrogen atom, and when R ⁴³ is a hydrocarbon group having 1 to 12 carbon atoms which may include a hydroxyl group, R ⁴¹ is a hydrogen atom. ( ^R42 is a hydrocarbon group having 1 or more and 12 or less carbon atoms that may contain a hydroxyl group.)

In the method for producing a polyisocyanate composition according to the third aspect, the amine represented by the general formula (2) relative to the molar amount of the amine compound represented by the general formula (1) in the amine salt of the sulfonic acid. The molar ratio of the compounds may be 10/90 or more and 90/10 or less.

The coating composition according to the fifth aspect of the present invention includes the polyisocyanate composition according to the first aspect or the second aspect .

The coated substrate according to the sixth aspect of the present invention is coated with the coating composition according to the fifth aspect.

The polyisocyanate composition of the above embodiment has excellent dispersibility in water and a water-containing main ingredient, and provides a coating film with excellent appearance, hardness, and water resistance. According to the coating composition of the above embodiment, a coating film having excellent appearance, hardness, and water resistance can be obtained. The coated substrate of the above embodiment has excellent appearance, hardness, and water resistance.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment. The present invention can be implemented with appropriate modifications within the scope of its gist.

≪Polyisocyanate composition≫
The polyisocyanate composition of the present embodiment includes a polyisocyanate containing a sulfonic acid anion group in the molecule, and one or more amine compounds represented by the following general formula (1) (hereinafter referred to as "amine compound (1)"). The tertiary ammonium cation of one or more amine compounds represented by the following general formula (2) (hereinafter sometimes referred to as "amine compound (2)") cation, or the tertiary ammonium cation of the amine compound (1) in which two or more types of R ¹¹ , R ¹² and R ¹³ have different total carbon numbers, and a uretdione dimer of a diisocyanate monomer.

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)

From the viewpoint of hardness when formed into a coating film, the content of the uretdione dimer is 2.0% by mass or more and 20.0% by mass or less, based on the total mass of the polyisocyanate composition, and 2.0% by mass or less It is preferably at least 10.0% by mass, and more preferably at least 2.0% by mass and at most 5.0% by mass.
The method for controlling the content of the uretdione dimer within the above range is not particularly limited, but for example, in the above "method for producing a polyisocyanate containing a uretdione group", the yield or heating time of the polyisocyanate is adjusted. One method is to do so.
The content of uretdione dimer in the diisocyanate monomer can be measured by the method described in Examples below.

The polyisocyanate composition of this embodiment includes a polyisocyanate containing a sulfonic acid anion group in the molecule and a tertiary ammonium cation of two or more types of amine compounds. Thereby, as shown in Examples below, the water dispersibility of the polyisocyanate composition of this embodiment can be kept high.
In addition, the polyisocyanate composition of this embodiment has a content of uretdione dimer in the diisocyanate within the above range, so that the polyisocyanate composition has a coating film that has both excellent appearance, hardness, and water resistance, as shown in the examples below. is obtained.

Note that the polyisocyanate composition of the present embodiment usually includes an unmodified polyisocyanate, that is, a polyisocyanate that does not contain a sulfonic acid anion group in the molecule. In addition, various properties of the polyisocyanate composition of the present embodiment described below are based on polyisocyanate containing a sulfonic acid anion group in the molecule and unmodified polyisocyanate (having a sulfonic acid anion group in the molecule) unless otherwise specified. This is the property in a state containing polyisocyanate).

In the polyisocyanate composition of the present embodiment, the ratio of unmodified polyisocyanate to polyisocyanate containing a sulfonic acid anion group in the molecule is, for example, sulfonate to 100 moles of isocyanate groups in the raw material polyisocyanate. It can be calculated from the proportion of isocyanate groups containing acid anion groups in the molecule.

<Polyisocyanate containing sulfonic acid anion group in the molecule>
The polyisocyanate containing a sulfonic acid anion group in the molecule contained in the polyisocyanate composition of the present embodiment is a reaction product obtained by reacting a sulfonic acid having an active hydrogen group or an amine salt thereof with a polyisocyanate. .

[Polyisocyanate]
The polyisocyanate used in the polyisocyanate containing a sulfonic acid anion group in the molecule is not particularly limited, but for example, at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Examples include polyisocyanates derived from. The polyisocyanate used for the polyisocyanate containing a sulfonic acid anion group in the molecule is selected from the group consisting of aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate from the viewpoint of industrial availability. It is preferable that it is at least one type.

Examples of aliphatic diisocyanates include, but are not limited to, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato)hexanoate, 1,6-diisocyanatohexane ( (hereinafter also referred to as "HDI"), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane etc.

The alicyclic diisocyanate is not particularly limited, but includes, for example, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter also referred to as "hydrogenated XDI"), 1,3- or 1,4 -diisocyanatocyclohexane, 3,5,5-trimethyl 1-isocyanato-3-(isocyanatomethyl)cyclohexane (hereinafter also referred to as "IPDI"), 4-4'-diisocyanato-dicyclohexylmethane (hereinafter referred to as "hydrogenated MDI), 2,5- or 2,6-diisocyanatomethylnorbornane, and the like.

Examples of aromatic diisocyanates include, but are not limited to, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and the like.

Among these, preferred diisocyanates are HDI, IPDI, hydrogenated XDI, and hydrogenated MDI.

Polyisocyanates derived from the above diisocyanates are not particularly limited, but include, for example, the polyisocyanates shown in (a) to (h) below. Moreover, since the polyisocyanate composition of this embodiment contains the uretdione dimer of diisocyanate, it contains the above (a).
(a) A polyisocyanate having a uretdione group obtained by cyclizing and dimerizing two isocyanate groups;
(b) a polyisocyanate having an isocyanurate group or an iminooxadiazinedione group obtained by cyclizing and trimerizing three isocyanate groups;
(c) a polyisocyanate having a biuret group obtained by reacting three isocyanate groups and one water molecule;
(d) a polyisocyanate having an oxadiazinetrione group obtained by reacting two isocyanate groups with one molecule of carbon dioxide;
(e) polyisocyanate having a plurality of urethane groups obtained by reacting one isocyanate group with one hydroxyl group;
(f) a polyisocyanate having an allophanate group obtained by reacting two isocyanate groups and one hydroxyl group;
(g) a polyisocyanate having an acylurea group obtained by reacting one isocyanate group and one carboxyl group;
(h) A polyisocyanate having a urea group obtained by reacting one isocyanate group with one primary or secondary amine.

Among these, from the viewpoint of hardness, water resistance, drying properties, and weather resistance when formed into a coating film, it is preferable that the polyisocyanate contains an isocyanurate group in addition to a uretdione group. That is, the polyisocyanate composition of this embodiment preferably contains the above (a) and the above (b). The uretdione group and the isocyanurate group may be contained within the same polyisocyanate molecule or within different polyisocyanate molecules, but are preferably contained within different polyisocyanate molecules. In particular, the polyisocyanate composition of the present embodiment preferably contains a uretdione dimer of the diisocyanate and an isocyanurate trimer of the diisocyanate.
The "uretdione dimer and isocyanurate trimer" herein refer to those containing a sulfonic acid anion group in the molecule and those containing no sulfonic acid anion group in the molecule (unmodified uretdione dimer and isocyanurate trimer). nurate trimer).

Further, the polyisocyanate used for the polyisocyanate containing a sulfonic acid anion group in the molecule may include an aliphatic triisocyanate. Examples of the aliphatic triisocyanate include 1,3,6-triisocyanatohexane, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl-2,6-diisocyanato-hexanoate, and the like. It will be done.

Further, these polyisocyanates may be modified with a nonionic hydrophilic group such as alkoxypolyalkylene glycol or a vinyl polymer having a hydroxyl group and a nonionic hydrophilic group.

Further, these polyisocyanates can be used alone or in combination of two or more.

[Production method of polyisocyanate]
(Method for producing polyisocyanate containing isocyanurate groups)
The method for producing polyisocyanate containing an isocyanurate group is not particularly limited, but for example, diisocyanate is subjected to an isocyanurate reaction using a catalyst, etc., and when a predetermined conversion rate is reached, the reaction is stopped, and unreacted A method for removing diisocyanate may be mentioned.

The catalyst used in the above-mentioned isocyanurate reaction is not particularly limited, but it is preferable to use one that shows basicity. Examples include weak acid salts, alkali metal salts of alkylcarboxylic acids, metal alcoholates, aminosilyl group-containing compounds, Mannich bases, combinations of tertiary amines and epoxy compounds, phosphorus compounds, and the like.
Examples of the tetraalkylammonium include tetramethylammonium and tetraethylammonium.
Examples of organic weak acids include acetic acid, capric acid, and the like.
Examples of the hydroxyalkylammonium include trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium.
Examples of alkylcarboxylic acids include acetic acid, caproic acid, octylic acid, myristic acid, and the like.
Examples of the alkali metal salt include tin, zinc, and lead.
Examples of the metal alcoholate include sodium alcoholate and potassium alcoholate.
Examples of the aminosilyl group-containing compound include hexamethyldisilazane.
Examples of the phosphorus compound include tributylphosphine.

The amount of these catalysts used is preferably 10 ppm or more and 1.0% or less based on the total mass of the diisocyanate and alcohol as raw materials. Further, in order to terminate the isocyanurate reaction, the catalyst may be inactivated by addition of an acidic substance that neutralizes the catalyst, thermal decomposition, chemical decomposition, or the like. Examples of the acidic substance that neutralizes the catalyst include phosphoric acid, acidic phosphoric acid ester, and the like.

The yield of polyisocyanate generally tends to be 10% by mass or more and 70% by mass or less. Polyisocyanates obtained in higher yields tend to have higher viscosities. The yield can be measured by the method described in Examples below.

The reaction temperature of the isocyanurate reaction is not particularly limited, but is preferably 50°C or higher and 200°C or lower, more preferably 50°C or higher and 150°C or lower. When the reaction temperature is 50° C. or higher, the reaction tends to proceed more easily, and when the reaction temperature is 200° C. or lower, side reactions that cause coloring tend to be suppressed.

After the isocyanurate-forming reaction is completed, it is preferable to remove unreacted diisocyanate monomer by a thin film evaporator, extraction, or the like. Even if the polyisocyanate contains unreacted diisocyanate, it preferably contains 3.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass or less of diisocyanate. Even more preferable. When the concentration of residual unreacted diisocyanate monomer is within the above range, curability tends to be excellent.

(Method for producing polyisocyanate containing uretdione group)
The method for producing a polyisocyanate containing a uretdione group is not particularly limited, but includes, for example, a method in which a diisocyanate is subjected to a uretdiionization reaction using a uretdioneation catalyst or the like.
Examples of the uretdiionization reaction catalyst include, but are not limited to, tertiary phosphines such as trialkylphosphines, tris(dialkylamino)phosphine, and cycloalkylphosphines.
Examples of the trialkylphosphine include tri-n-butylphosphine and tri-n-octylphosphine.
Examples of tris(dialkylamino)phosphine include tris(dialkylamino)phosphine such as tris-(dimethylamino)phosphine.
Examples of the cycloalkylphosphine include cyclohexyl-di-n-hexylphosphine.
Many of these compounds also promote the isocyanurate reaction at the same time, producing isocyanurate group-containing polyisocyanates in addition to uretdione group-containing polyisocyanates.
When the desired yield is reached, a deactivator for the uretodionation reaction catalyst, such as phosphoric acid or methyl p-toluenesulfonate, is added to stop the uretodionation reaction.

Moreover, a uretdione group-containing polyisocyanate can also be obtained by heating a diisocyanate monomer without using the above-mentioned uretdione conversion reaction catalyst.
When the above-mentioned uretdiionization reaction catalyst is not used, the heating temperature can be 120°C or higher, preferably 150°C or higher and 170°C or lower. Moreover, the heating time can be 1 hour or more and 4 hours or less.

[Sulfonic acid with active hydrogen group]
In the sulfonic acid having an active hydrogen group used in a polyisocyanate containing a sulfonic acid anion group in the molecule, examples of the active hydrogen group include an amino group, a carboxy group, and a hydroxyl group. Among these, the active hydrogen group is preferably at least one selected from the group consisting of amino groups and hydroxyl groups.

(Sulfonic acid (3))
When the active hydrogen group is a hydroxyl group, examples of the sulfonic acid having a hydroxyl group include a compound represented by the following general formula (3) (hereinafter abbreviated as "sulfonic acid (3)").

In the general formula (3), R ³¹ is a hydrocarbon group having 1 to 10 carbon atoms that may contain at least one selected from the group consisting of a hydroxyl group, an ether bond, an ester bond, a carbonyl group, and an imino group. be. R ³¹ may include a ring structure. The ring structure is an aromatic ring, a 5- or 6-membered ring containing two nitrogen atoms, or a 5- or 6-membered ring containing a nitrogen atom and an oxygen atom.

・R ³¹
In general formula (3), R ³¹ is a hydroxyl group, an ester bond (-COO-), an ether bond (-O-), a carbonyl group (-C(=O)-), an imino group (-NR-), and It is a hydrocarbon group having 1 or more and 10 or less carbon atoms which may include at least one member selected from the group consisting of ring structures.

The hydrocarbon group having 1 to 10 carbon atoms may be a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. There may be. The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably a chain alkylene group having 1 to 6 carbon atoms. In the case of a chain alkylene group having 1 to 6 carbon atoms, a part of the chain alkylene group may include a ring structure. The alkylene group having 1 or more and 6 or less carbon atoms may be linear or branched.

Among these, ^R31 is a chain alkylene group having 1 or more carbon atoms and 6 or less carbon atoms, a divalent aromatic hydrocarbon group (arylene group) having 6 or more carbon atoms and 10 or less carbon atoms, and a divalent carbon number 1 or more containing an aromatic ring. An alkylene group of 6 or less, a divalent alkylene group having 1 or more and 6 or less carbon atoms, including a 5-membered ring or 6-membered ring containing two nitrogen atoms, or a 5- or 6-membered ring containing a nitrogen atom and an oxygen atom. It is preferably a divalent alkylene group containing a ring and having 1 or more and 6 or less carbon atoms.

Preferred examples of the sulfonic acid (3) include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 4-hydroxybutanesulfonic acid, 5-hydroxypentanesulfonic acid, 6-hydroxyhexanesulfonic acid, and hydroxybenzene. Sulfonic acid, hydroxy(methyl)benzenesulfonic acid, 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazinepropanesulfonic acid, 2-hydroxy-3-morpholino Examples include propanesulfonic acid.
Note that these compounds are only some of the preferred sulfonic acids (3), and the preferred sulfonic acids (3) are not limited to these.
Further, these sulfonic acids (3) may be used alone or in combination of two or more.

Among them, the sulfonic acid having a hydroxyl group is at least one selected from the group consisting of 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, hydroxybenzenesulfonic acid, and hydroxy(methyl)benzenesulfonic acid. is preferred.

In addition, when the polyisocyanate composition of this embodiment contains two or more types of amine salts of sulfonic acids, the sulfonic acids (3) may be the same or different.

Further, the sulfonic acid used in the polyisocyanate containing a sulfonic acid anion group in the molecule may form a salt with an amine compound described below.

(Sulfonic acid (4))
When the active hydrogen group is an amino group, examples of the sulfonic acid having an amino group include a compound represented by the following general formula (4) (hereinafter abbreviated as "sulfonic acid (4)"), etc. .

In general formula (4), R ⁴¹ and R ⁴³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and which may contain a hydroxyl group. R ⁴¹ and R ⁴³ may be the same or different. At least one of R ⁴¹ and R ⁴³ is a hydrogen atom. R ⁴² is a hydrocarbon group having 1 or more and 12 or less carbon atoms that may include a hydroxyl group.

・R ⁴¹ and R ⁴³
In general formula (4), R ⁴¹ and R ⁴³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and which may contain a hydroxyl group. R ⁴¹ and R ⁴³ may be the same or different. At least one of R ⁴¹ and R ⁴³ is a hydrogen atom. That is, when R ⁴¹ is a hydrocarbon group having 1 to 12 carbon atoms that may include a hydroxyl group, R ⁴³ is a hydrogen atom. Further, when R ⁴³ is a hydrocarbon group having 1 or more and 12 or less carbon atoms which may include a hydroxyl group, R ⁴¹ is a hydrogen atom. Further, both R ⁴¹ and R ⁴³ may be hydrogen atoms.

The hydrocarbon group having 1 to 12 carbon atoms may be a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. There may be. The monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferably a chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms. The chain alkyl group having 1 to 6 carbon atoms may be linear or branched.

Among these, each of R ⁴¹ and R ⁴³ is preferably a hydrogen atom, a chain alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms.

・^R42
R ⁴² is a hydrocarbon group having 1 or more and 12 or less carbon atoms that may include a hydroxyl group.
The hydrocarbon group having 1 to 12 carbon atoms may be a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. There may be. The divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferably a chain alkylene group having 1 to 12 carbon atoms. The chain alkyl group having 1 to 12 carbon atoms may be linear or branched.
Among these, R ⁴² is preferably a divalent chain alkylene group having 1 to 6 carbon atoms or a divalent aromatic hydrocarbon group (arylene group) having 6 to 10 carbon atoms.

Preferred sulfonic acids (4) include, for example, 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, 2-methylaminoethanesulfonic acid, 3-methylaminopropanesulfonic acid, and 2-cyclohexylaminoethanesulfonic acid. , 3-cyclohexylaminopropanesulfonic acid, 3-cyclohexylaminoisobutylsulfonic acid, 4-cyclohexylaminobutanesulfonic acid, 2-cyclohexylmethylaminoethanesulfonic acid, 3-cyclohexylmethylaminopropanesulfonic acid, 3-cyclohexylmethylaminoisobutylsulfonic acid Acid, 4-cyclohexylmethylaminobutanesulfonic acid, 2-methylcyclohexylaminoethanesulfonic acid, 3-methylcyclohexylaminopropanesulfonic acid, 3-methylcyclohexylaminoisobutylsulfonic acid, 4-methylcyclohexylaminobutanesulfonic acid, 2-dimethyl Cyclohexylaminoethanesulfonic acid, 3-dimethylcyclohexylaminopropanesulfonic acid, 3-dimethylcyclohexylaminoisobutylsulfonic acid, 4-dimethylcyclohexylaminobutanesulfonic acid, 2-trimethylcyclohexylaminoethanesulfonic acid, 3-trimethylcyclohexylaminopropanesulfonic acid , 3-trimethylcyclohexylaminoisobutylsulfonic acid, 4-trimethylcyclohexylaminobutanesulfonic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-(methylamino)benzenesulfonic acid, Examples include 3-(methylamino)benzenesulfonic acid, 4-(methylamino)benzenesulfonic acid, amino-methylbenzenesulfonic acid, amino-dimethylbenzenesulfonic acid, and aminonaphthalenesulfonic acid.
Note that these compounds are only some of the preferred sulfonic acids (4), and the preferred sulfonic acids (4) are not limited to these.
Further, these sulfonic acids (4) may be used alone or in combination of two or more.

Among them, sulfonic acids having an amino group include 2-cyclohexylaminoethanesulfonic acid, 3-cyclohexylaminopropanesulfonic acid, 4-cyclohexylaminobutanesulfonic acid, 3-cyclohexylmethylaminopropanesulfonic acid, 3-(p-methyl Cyclohexylamino)propanesulfonic acid, 3-(3,3,5-trimethylcyclohexylamino)propanesulfonic acid, 4-(p-methylcyclohexylamino)butanesulfonic acid, 2-aminobenzenesulfonic acid, 2-amino-5- Methylbenzenesulfonic acid, 2-amino-3,5-dimethylbenzenesulfonic acid, 5-amino-2-methylbenzenesulfonic acid (4-aminotoluene-2-sulfonic acid), 4-amino-2-methylbenzenesulfonic acid (5-aminotoluene-2-sulfonic acid) and 2-aminonaphthalene-4-sulfonic acid.

In addition, when the polyisocyanate composition of this embodiment contains two or more types of amine salts of sulfonic acids, the sulfonic acids (4) may be the same or different.

<Amine compound>
The polyisocyanate composition of the present embodiment includes a tertiary ammonium cation of one or more amine compounds (1) and a tertiary ammonium cation of one or more amine compounds (2), or two or more R ¹¹ , a tertiary ammonium cation of an amine compound (1) in which the total number of carbon atoms of R ¹² and R ¹³ is different from each other.

In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. At least one selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ are bonded to each other to form a ring structure. may be formed. The ring structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5-membered ring or a 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a bond in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring connected to each other. The total carbon number of R ¹¹ , R ¹² and R ¹³ is 8 or less.

In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. At least one selected from the group consisting of R ²¹ , R ²² and R ²³ may contain a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ are bonded to each other to form a ring structure. may be formed. The ring structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5-membered ring or a 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a 5- or 6-membered ring in which R ²¹ and ^{R 22 are} bonded to each other. It is a multi-membered multi-ring connected to each other. The total carbon number of R ²¹ , R ²² and R ²³ is 9 or more.

Note that the "tertiary ammonium cation of amine compound (1)" and "tertiary ammonium cation of amine compound (2)" as used herein refer to the tertiary ammonium cation of amine compound (1) and amine compound (2). A proton (H ⁺ ) is coordinated to "N" of "N" to mean protonation.

Moreover, in the polyisocyanate composition of this embodiment, the amine compound (1) and the amine compound (2) may form a salt with the above-mentioned sulfonic acid.

[Amine compound (1)]
(R ¹¹ , R ¹² and R ¹³ )
In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ may be the same or different.

Further, the total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less. That is, the total carbon number of R ¹¹ , R ¹² and R ¹³ is 3 or more and 8 or less.

The hydrocarbon group having 1 to 6 carbon atoms may be a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 carbon atoms. good. The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferably a chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms. The chain alkyl group having 1 to 6 carbon atoms may be linear or branched.

Preferred amine compounds (1) include, for example, those shown in (a) to (d) below. Note that these compounds are only some of the preferred amine compounds (1), and the preferred amine compounds (1) are not limited to these.
(a) Trimethylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylisopropylamine, N,N-dimethylbutylamine, N,N-dimethylisobutylamine, N,N-dimethylpentylamine , N,N-dimethylhexylamine, N,N-diethylmethylamine, triethylamine, N,N-diethylpropylamine, N,N-diethylisopropylamine, N,N-diethylbutylamine, N,N-diethylisobutylamine, Tertiary amines having a chain aliphatic hydrocarbon group such as N,N-diisopropylmethylamine, N,N-diisopropylethylamine, N,N-dimethylallylamine, N-methyldiallylamine;
(b) Tertiary amines having a cycloaliphatic hydrocarbon group such as N,N-dimethylcyclohexylamine;
(c) Tertiary amines having an aromatic hydrocarbon group such as N,N-dimethylphenylamine;
(d) N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-methylmorpholine, N-ethylmorpholine, N- Cyclic amines such as propylmorpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutylmorpholine, and quinuclidine.

Moreover, one type of these amine compounds may be used, or two or more types may be used in combination.
Among these, the amine compound (1) is at least one selected from the group consisting of a cyclic amine compound, an amine compound containing a chain aliphatic hydrocarbon group, and an amine compound containing a cyclic aliphatic hydrocarbon group. is preferred.

Among them, examples of the amine compound (1) include N,N-dimethylbutylamine, N,N-diethylmethylamine, triethylamine, N,N-diisopropylethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, -More preferably at least one selected from the group consisting of -methylmorpholine, N-ethylpiperidine, N-ethylmorpholine, and N-isobutylmorpholine.

Among them, examples of the amine compound (1) include N,N-diethylmethylamine, triethylamine, N,N-diisopropylethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, N-methylmorpholine, and -More preferably at least one selected from the group consisting of -methylpyrrolidine. Salts using these amine compounds tend to have further improved emulsifying power.

[Amine compound (2)]
(R ²¹ , R ²² and R ²³ )
In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ may be the same or different.

Further, the total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more. That is, the total carbon number of R ²¹ , R ²² and R ²³ is 9 or more and 57 or less.

The hydrocarbon group having 1 to 19 carbon atoms may be a monovalent aliphatic hydrocarbon group having 1 to 19 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 19 carbon atoms, etc. It may be. The monovalent aliphatic hydrocarbon group having 1 to 19 carbon atoms is preferably a chain alkyl group having 1 to 19 carbon atoms, or a cyclic alkyl group having 3 to 19 carbon atoms. In the case of a chain alkyl group having 1 or more and 19 or less carbon atoms, a part of the alkyl group may include an aromatic hydrocarbon. The chain alkyl group having 1 to 19 carbon atoms may be linear or branched.

Preferred examples of the amine compound (2) include those shown in (e) to (g) below. Note that these compounds are only some of the preferred amine compounds (2), and the preferred amine compounds (2) are not limited to these.
(e) N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethyl-2-ethylhexylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, N,N- Dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethylstearylamine, N,N-diethylpentylamine, N,N-diethylhexylamine, N,N- Diethylheptylamine, N,N-diethyloctylamine, N,N-diethyl-2-ethylhexylamine, N,N-diethylnonylamine, N,N-diethyldecylamine, N,N-diethylundecylamine, N, N-diethyldodecylamine, N,N-diethyltridecylamine, N,N-diethylstearylamine, tripropylamine, N,N-diisopropylbutylamine, N,N-diisopropyl-2-ethylhexylamine, N,N-dibutyl Methylamine, N,N-dibutylethylamine, N,N-dibutylpropylamine, tributylamine, N,N-dibutylpentylamine, N,N-dibutylhexylamine, N,N-dibutylheptylamine, N,N-dibutyl Octylamine, N,N-dibutyl-2-ethylhexylamine, N,N-dibutylnonylamine, N,N-dibutyldecylamine, N,N-dibutylundecylamine, N,N-dibutyldodecylamine, N,N - Tertiary amines having a chain aliphatic hydrocarbon group such as dibutyltridecylamine, N,N-dibutylstearylamine, triamylamine, trihexylamine;
(f) Tertiary amines having a cycloaliphatic hydrocarbon group such as N,N-diethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-dicyclohexylethylamine, tricyclohexylamine;
(g) N,N-dimethylbenzylamine, N,N-diethylbenzylamine, N,N-dibenzylmethylamine, tribenzylamine, N,N-dimethyl-4-methylbenzylamine, N,N-dimethylphenyl Tertiary amines having an aromatic hydrocarbon group such as amine, N,N-diethylphenylamine, and N,N-diphenylmethylamine.

Moreover, one type of these amine compounds may be used, or two or more types may be used in combination.
Among these, the amine compound (2) is preferably at least one selected from the group consisting of amine compounds containing a chain aliphatic hydrocarbon group and amine compounds containing a cyclic aliphatic hydrocarbon group.

Among them, examples of the amine compound (2) include N,N-dimethyl-2-ethylhexylamine, N,N-diisopropyl-2-ethylhexylamine, tripropylamine, tributylamine, N,N-diethylcyclohexylamine, , N-dicyclohexylmethylamine, N,N-dimethylbenzylamine, and N,N-diethylbenzylamine.

Among them, the amine compound (2) is at least one selected from the group consisting of N,N-diisopropyl-2-ethylhexylamine, tripropylamine, tributylamine, and N,N-dicyclohexylmethylamine. It is even more preferable that there be. Salts using these amine compounds tend to have further improved compatibility with polyisocyanates and a longer pot life.

Further, the polyisocyanate composition of the present embodiment includes one or more tertiary ammonium cations of the amine compound (1), one or more tertiary ammonium cations of the amine compound (2), or It contains two or more types of tertiary ammonium cations of the above amine compound (1) in which R ¹¹ , R ¹² and R ¹³ have different total carbon numbers.

Further, when the polyisocyanate composition of the present embodiment contains one or more tertiary ammonium cations of the amine compound (1) and one or more tertiary ammonium cations of the amine compound (2), The molar ratio between the amine compound (1) and the amine compound (2) is preferably 10/90 or more and 90/10 or less, more preferably 20/80 or more and 80/20 or less, and 30/70 or more and 70/20 or less. More preferably, it is 30 or less.

Further, in the polyisocyanate composition of the present embodiment, when two or more types of tertiary ammonium cations of the above amine compound (1) having different total carbon numbers of R ¹¹ , R ¹² and R ¹³ are included, R ¹¹ , R 13 The amine compound (1) preferably contains the above amine compound (1) in which the total carbon number of R ¹² and R ¹³ is 6 or less, and the above amine compound (1) in which the total carbon number of R ¹¹ , R ¹² and R ¹³ is 7 or more. . Further, the above amine compound (1) in which the total carbon number of R ¹¹ , R ¹² and R ¹³ is 5 or less, and the above amine compound (1) in which the total carbon number of R ¹¹ , R ¹² and R ¹³ is 7 or more It is more preferable to include. Further, the above amine compound (1) in which the total carbon number of R ¹¹ , R ¹² and R ¹³ is 5 or less, and the above amine compound (1) in which the total carbon number of R ¹¹ , R ¹² and R ¹³ is 8; It is further preferable to include.

<Method for producing amine salt of sulfonic acid>
When the sulfonic acid forms a salt with the amine compound, that is, when it is an amine salt of sulfonic acid, for example, by mixing the sulfonic acid having an active hydrogen group and the amine compound and causing a neutralization reaction. can get.

The neutralization reaction may be performed in advance before reacting with the polyisocyanate. Alternatively, the reaction may be performed simultaneously with the polyisocyanate. Alternatively, the amine compound may be added after the polyisocyanate and the sulfonic acid having an active hydrogen group are reacted.

When the active hydrogen group is a hydroxyl group, the neutralization reaction is preferably carried out in advance before reacting with the polyisocyanate. In addition, when the active hydrogen group is an amino group, the neutralization reaction is carried out simultaneously with the reaction with the polyisocyanate, or the amine compound is added after the polyisocyanate and the sulfonic acid having an active hydrogen group are reacted. It is preferable to do so.

Further, when the active hydrogen group is a hydroxyl group, in the neutralization reaction, the ratio of mixing the sulfonic acid having a hydroxyl group and the amine compound is such that the molar ratio of the sulfonic acid having a hydroxyl group/amine compound is 0.5 or more and 2 or less. It is preferable that it is, and it is more preferable that it is 0.8 or more and 1.5 or less.

When the neutralization reaction is carried out in advance, the temperature and time can be determined as appropriate depending on the progress of the reaction, but the temperature is usually preferably about 0°C or more and 100°C or less, and the mixing time is 10 minutes or more. It is preferably about 24 hours or less.

The solvent used in the preparation of the amine salt of the sulfonic acid having an active hydrogen group is preferably water or a hydrophilic solvent. Examples of the hydrophilic solvent include, but are not limited to, alcohols, ether alcohols, ketones, amide solvents, and the like. These solvents can be used alone or in combination.
Examples of alcohols include methanol, ethanol, propanol, butanol, isopropanol, and the like.
Examples of ether alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, etc. can be mentioned.
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Examples of the amide solvent include N,N-dimethylformamide and N,N-dimethylacetamide.

After the neutralization reaction, it is preferable to remove water or the hydrophilic solvent.

<Characteristics of polyisocyanate composition>
[Ratio of molar amount of isocyanurate group to molar amount of uretdione group (isocyanurate group/uretdione group)]
When the polyisocyanate composition of this embodiment has isocyanurate groups in addition to uretdione groups, the ratio of the molar amount of isocyanurate groups to the molar amount of uretdione groups in the composition (isocyanurate groups/uretdione groups) is From the viewpoint of appearance, hardness, and water resistance when formed into a coating film, it is 2.5 or more and 10.0 or less, preferably 3.0 or more and 9.0 or less, and more preferably 4.0 or more and 9.0 or less.
The method for controlling the isocyanurate group/uretdione group within the above range is not particularly limited, but for example, the yield in the method for producing a polyisocyanate containing an isocyanurate structure, the above "method for producing a polyisocyanate containing a uretdione group" In this case, a method of adjusting the yield or heating time of the polyisocyanate can be mentioned.
Note that the isocyanurate group/uretdione group can be measured by the method described in Examples below.

[Denaturation rate]
From the viewpoint of water dispersibility and coating film properties, the polyisocyanate composition of the present embodiment has a sulfonic acid having an active hydrogen group in an amount of 0.25 mol or more based on 100 mol of isocyanate groups of the raw material polyisocyanate. It is preferable that the isocyanate groups are modified in a proportion of 50 molar or less, more preferably that the isocyanate groups are modified in a proportion of 0.5 to 20 molar, and 1 to 10 molar. It is more preferable that the isocyanate groups are modified in the following proportions.
Note that the modification rate can be measured by the method described in Examples below.

[Isocyanate group content]
The isocyanate group content of the polyisocyanate composition of the present embodiment is preferably 10% by mass or more and 25% by mass or less, from the viewpoint of solvent resistance of the coating film, when the nonvolatile content is 100% by mass. More preferably, the content is 15% by mass or more and 24% by mass or less.
The method for controlling the isocyanate group content within the above range is not particularly limited, but includes, for example, a method of adjusting the blending ratio of sulfonic acid and polyisocyanate.
Note that the isocyanate group content can be measured by the method described in Examples below.

[Number average molecular weight]
In addition, the number average molecular weight of the polyisocyanate (including polyisocyanate containing a sulfonic acid anion group in the molecule and unmodified polyisocyanate) used in the polyisocyanate composition of the present embodiment is determined from the viewpoint of the physical properties of the coating film. It is preferably 450 or more and 2000 or less, more preferably 500 or more and 1800 or less, and even more preferably 550 or more and 1550 or less.
A method for controlling the number average molecular weight within the above range is not particularly limited, but includes, for example, a method of adjusting the blending ratio of sulfonic acid, amine compound, and polyisocyanate.
Note that the number average molecular weight can be measured by gel permeation chromatography (hereinafter sometimes referred to as "GPC").

[Average number of functional groups (average number of NCO groups)]
The average number of functional groups (average number of NCO groups) of the polyisocyanate (including modified polyisocyanate and unmodified polyisocyanate) used in the polyisocyanate composition of this embodiment is determined from the viewpoint of solvent resistance of the coating film and the isocyanate group retention rate. From this viewpoint, it is preferably 1.8 or more and 6.2 or less, more preferably 2.0 or more and 5.6 or less, and even more preferably 2.5 or more and 4.6 or less. The method for controlling the average number of functional groups within the above range is not particularly limited, but includes, for example, a method of adjusting the blending ratio of sulfonic acid, amine compound, and polyisocyanate.
Note that the average number of functional groups can be calculated from the isocyanate group content and the number average molecular weight.

[Sulfur atom content]
In the polyisocyanate composition of the present embodiment, the sulfur atom content is preferably 0.1% by mass or more and 10% by mass or less, and 0.2% by mass or more from the viewpoint of water dispersibility and physical properties of the coating film. It is more preferably 5.0% by mass or less, and preferably 0.3% by mass or more and 2.0% by mass or less.
Note that the sulfur atom content can be measured by ion chromatography (IC).

<Other ingredients>
The polyisocyanate composition of the present embodiment includes a polyisocyanate containing the above-mentioned sulfonic acid anion group in the molecule, an unmodified polyisocyanate, two or more types of tertiary ammonium cations of an amine compound, and a uretdione dimer of a diisocyanate. A composition comprising: The polyisocyanate composition of this embodiment includes a polyisocyanate containing the above-mentioned sulfonic acid anion group in the molecule, an unmodified polyisocyanate, two or more types of tertiary ammonium cations of an amine compound, and a uretdione dimer of a diisocyanate. It may also contain other components. Other components include, but are not particularly limited to, solvents, antioxidants, light stabilizers, polymerization inhibitors, surfactants, and the like.

The solvent used in the polyisocyanate composition of this embodiment may be a hydrophilic solvent or a hydrophobic solvent. These solvents can be used alone or in combination.
Examples of hydrophobic solvents include, but are not limited to, mineral spirits, solvent naphtha, LAWS (Low Aromatic White Spirit), HAWS (High Aromatic White Spirit), toluene, xylene, cyclohexane, esters, ketones, and amides. Can be mentioned.
Examples of esters include ethyl acetate and butyl acetate.
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide.
Examples of the hydrophilic solvent include, but are not limited to, alcohols, ethers, and esters of ether alcohols.
Examples of alcohols include methanol, ethanol, propanol, isopropanol, and 2-ethylhexanol.
Examples of the ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether.
Examples of esters of ether alcohols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol. Examples include monomethyl ether acetate and dipropylene glycol monomethyl ether acetate.

In the polyisocyanate composition of this embodiment, the content of the solvent is preferably 0% by mass or more and 90% by mass or less, and 0% by mass or more and 50% by mass or less, based on the total mass of the polyisocyanate composition of this embodiment. It is more preferably not more than 0% by mass, and even more preferably not less than 0% by mass and not more than 30% by mass.

Examples of the antioxidant and light stabilizer include those shown in (a) to (e) below. These may be contained alone or in combination of two or more kinds.
(a) Aliphatic, aromatic or alkyl group-substituted aromatic esters of phosphoric acid or phosphorous acid and hypophosphorous acid derivatives;
(b) Phosphorus compounds such as phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite;
(c) phenolic derivatives (especially hindered phenol compounds);
(d) Compounds containing sulfur such as thioether compounds, dithioate salt compounds, mercaptobenzimidazole compounds, thiocarbanilide compounds, thiodipropionic acid esters;
(e) Tin-based compounds such as tin malate and dibutyltin monoxide.

Examples of the polymerization inhibitor include hydroquinones, phenols, cresols, catechols, and benzoquinones. Specific examples of the polymerization inhibitor include benzoquinone, p-benzoquinone, p-torquinone, p-xyloquinone, naphthoquinone, 2,6-dichloroquinone, hydroquinone, trimethylhydroquinone, catechol, pt-butylcatechol, 2, Examples include 5-di-t-butylhydroquinone, monomethylhydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, and hydroquinone monomethyl ether. These may be contained alone or in combination of two or more kinds.

Examples of the surfactant include known anionic surfactants, cationic surfactants, and amphoteric surfactants.

In the polyisocyanate composition of this embodiment, the total content of the antioxidant, light stabilizer, polymerization inhibitor, and surfactant is 0% by mass or more with respect to the total mass of the polyisocyanate composition of this embodiment. The content is preferably 10% by mass or less, more preferably 0% by mass or more and 5% by mass or less, and even more preferably 0% by mass or more and 2% by mass or less.

≪Method for producing polyisocyanate composition≫
The method for producing a polyisocyanate composition of the present embodiment preferably includes, for example, a step of (A) mixing and reacting two or more amine salts of sulfonic acid having active hydrogen groups with a polyisocyanate.
Alternatively, the method for producing the polyisocyanate composition of the present embodiment may include, for example, (B) a sulfonic acid having an active hydrogen group, a polyisocyanate, one or more of the above amine compounds (1), and the above amine compounds (2). ) or two or more of the above amine compounds (1) in which the total carbon numbers of R ¹¹ , R ¹² and R ¹³ are different from each other.

In step (A), the amine salt of sulfonic acid is preferably prepared in advance and then added to the polyisocyanate.
Moreover, in step (B), the sulfonic acid having an active hydrogen group and the amine compound may be added to the polyisocyanate simultaneously or sequentially.
Among these, when the active hydrogen group is a hydroxyl group, step (A) is preferable, and it is more preferable that the sulfonic acid amine salt is prepared in advance and then added to the polyisocyanate.
Among these, when the active hydrogen group is an amino group, step (B) is preferable.
Note that hereinafter, step (A) and step (B) may be collectively referred to as a "reaction step."

In the reaction step, the mixing ratio of the sulfonic acid or its amine salt having an active hydrogen group and the polyisocyanate is determined by the molar amount of the isocyanate group relative to the molar amount of the active hydrogen group, from the viewpoint of water dispersibility and coating film properties. The ratio (isocyanate group/active hydrogen group) is preferably in the range of 2 or more and 400 or less, more preferably in the range of 5 or more and 200 or less, and even more preferably in the range of 10 or more and 100 or less.

In the reaction step, the reaction temperature and reaction time are appropriately determined depending on the progress of the reaction, but the reaction temperature is preferably 0°C or more and 150°C or less, and the reaction time is 30 minutes or more and 48 hours or less. is preferred.

Further, in the reaction step, a known common catalyst may be used depending on the case. The catalyst is not particularly limited, but includes, for example, those shown in (a) to (f) below. These may be used alone or in combination.
(a) Tin octoate, tin 2-ethyl-1-hexanoate, tin ethyl caproate, tin laurate, tin palmitate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dimalate, dibutyltin dilaurate, dioctyltin dichloride Organotin compounds such as acetate and dioctyltin dilaurate;
(b) organic zinc compounds such as zinc chloride, zinc octoate, zinc 2-ethyl-1-hexanoate, zinc 2-ethylcaproate, zinc stearate, zinc naphthenate, zinc acetylacetonate;
(c) organic titanium compound;
(d) organic zirconium compound;
(e) Tertiary amines such as triethylamine, tributylamine, N,N-diisopropylethylamine, N,N-dimethylethanolamine;
(f) Diamines such as triethylenediamine, tetramethylethylenediamine, and 1,4-diazabicyclo[2.2.2]octane.

Further, after the above reaction step, an addition step of further adding and mixing unmodified polyisocyanate may be included.

In the method for producing a polyisocyanate composition of this embodiment, a solvent may or may not be used. The solvent used in the method for producing the polyisocyanate composition of this embodiment may be a hydrophilic solvent or a hydrophobic solvent. Examples of the hydrophilic solvent and hydrophobic solvent include those exemplified above for other components.

In addition, in the method for producing a polyisocyanate composition of the present embodiment, in addition to the sulfonic acid having an active hydrogen group, the polyisocyanate, and the amine compound, an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant are further added. At least one selected from the group consisting of agents may be added. Examples of the antioxidant, light stabilizer, polymerization inhibitor, and surfactant include those exemplified above as other components.

≪Coating composition≫
The coating composition of this embodiment includes the above-mentioned polyisocyanate composition.
The coating composition of this embodiment can also be used as an organic solvent-based coating composition, but it may also be used as an aqueous coating composition in which resins as coating film-forming components are dissolved or dispersed in a medium mainly composed of water. It is preferable to use it as In particular, architectural paints, automotive paints, automotive refinish paints, plastic paints, pressure-sensitive adhesives, building materials, household water-based paints, other coating agents, sealants, inks, casting materials, elastomers, foams, and plastic raw materials. , it can also be used as a fiber treatment agent.

<Resins>
The main resins are not particularly limited, but examples include acrylic resins, polyester resins, polyether resins, epoxy resins, fluororesins, polyurethane resins, polyvinylidene chloride copolymers, polyvinyl chloride, etc. Polymers, vinyl acetate copolymers, acrylonitrile butadiene copolymers, polybutadiene copolymers, styrene butadiene copolymers, and the like.
Among these, acrylic resins or polyester resins are preferred as the resins.

(Acrylic resin)
Acrylic resins are not particularly limited, but include, for example, acrylic resins obtained by polymerizing single or mixtures of polymerizable monomers shown in (a) to (e) below. These acrylic resins may be used alone or in combination.
(a) Methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate (meth)acrylic acid esters such as;
(b) 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) (meth)acrylic acid esters with active hydrogen such as 4-hydroxybutyl acrylate;
(c) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid;
(d) Unsaturated amides such as acrylamide, N-methylolacrylamide, diacetone acrylamide;
(e) Other polymerizable monomers such as glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, dibutyl fumarate, p-styrenesulfonic acid, and allylsulfosuccinic acid.

As a polymerization method, emulsion polymerization is generally used, but it can also be produced by suspension polymerization, dispersion polymerization, and solution polymerization. Emulsion polymerization can also be carried out in stages.

(Polyester resins)
Examples of polyester resins include, but are not limited to, polyester resins obtained by a condensation reaction of carboxylic acids alone or in mixtures with polyhydric alcohols alone or in mixtures.

Examples of the carboxylic acid include succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

Examples of the polyhydric alcohol include diols, triols, and tetraols.
Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1, 6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propane Examples include diol.
Examples of triols include glycerin, trimethylolpropane, and the like.
Examples of the tetraols include diglycerin, dimethylolpropane, and pentaerythritol.

Alternatively, for example, polycaprolactones obtained by ring-opening polymerization of ε-caprolactone to the hydroxyl group of a low molecular weight polyol can also be used as the polyester resin.

(Polyether resins)
Examples of polyether resins include those shown in (a) to (d) below.
(a) Polyether polyols obtained by adding alkylene oxide alone or as a mixture to polyhydric hydroxy compounds alone or as a mixture using a strong basic catalyst.
Examples of the polyhydric hydroxy compound include those shown in (i) to (vi) below.
(i) diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.;
(ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, rhamnitol;
(iii) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesose;
(iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose;
(v) trisaccharides such as raffinose, gentianose, meletitose;
(vi) Tetrasaccharides such as stachyose.
Examples of the strong basic catalyst include hydroxides of lithium, sodium, potassium, etc., alcoholates, alkylamines, and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
(b) Polyether polyols obtained by reacting a polyamine compound with an alkylene oxide.
Examples of the polyamine compound include ethylenediamines.
(c) Polyether polyols obtained by ring-opening polymerization of cyclic ethers.
Examples of the cyclic ethers include tetrahydrofuran.
(d) So-called polymer polyols obtained by polymerizing acrylamide or the like using the polyether polyols obtained in (a) to (c) as a medium.

Furthermore, in the coating composition of the present embodiment, these resins may be used in combination with resins such as a melamine curing agent, urethane dispersion, and urethane acrylic emulsion, if necessary.

Moreover, these resins are preferably emulsified, dispersed, or dissolved in water. For this purpose, carboxyl groups, sulfone groups, etc. contained in resins can be neutralized.

Examples of the neutralizing agent for neutralizing carboxyl groups, sulfone groups, etc. include, but are not limited to, ammonia, water-soluble amino compounds, and the like.

Examples of water-soluble amino compounds include monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, 2-ethylhexylamine, and ethylenediamine. , propylene diamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine and the like. These may be used alone or in combination of two or more.

Among these, the neutralizing agent is preferably a tertiary amine, more preferably triethylamine or dimethylethanolamine.

<Other ingredients>
In addition to the polyisocyanate composition and resins described above, the coating composition of the present embodiment further includes inorganic pigments, organic pigments, extender pigments, silane coupling agents, titanium coupling agents, Organic phosphates, organic phosphites, thickeners, leveling agents, thixotizing agents, antifoaming agents, freeze stabilizers, matting agents, crosslinking reaction catalysts (catalysts for accelerating curing), anti-skinning agents, Dispersants, wetting agents, fillers, plasticizers, lubricants, reducing agents, preservatives, antifungal agents, deodorants, antiyellowing agents, ultraviolet absorbers, antistatic agents or charge control agents, antisettling agents etc. may be combined or included.

Examples of catalysts for accelerating curing include, but are not limited to, those shown in (a) or (b) below.
(a) Metal salts such as dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt salts;
(b) 3 such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N'-endoethylenepiperazine, N,N'-dimethylpiperazine, etc. class amines.

The coating composition of this embodiment may further contain a surfactant in addition to the above-mentioned polyisocyanate composition and resins in order to improve dispersibility in the paint.

The coating composition of this embodiment may further contain an antioxidant, a light stabilizer, and a polymerization inhibitor in addition to the polyisocyanate composition and resins described above, in order to improve the storage stability of the paint.

≪Coating base material≫
The coated base material of this embodiment is a coated base material coated with the above-mentioned coating composition. The coated base material of this embodiment preferably has a coating layer containing the above-mentioned coating composition.

The coated substrate of this embodiment may include the desired substrate and optionally a conventional primer before coating.
Examples of the material for the base material include metal, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textile products, leather products, and paper.

Hereinafter, this embodiment will be described in more detail by giving specific examples and comparative examples, but this embodiment is not limited in any way by the following examples and comparative examples unless it exceeds the gist thereof. isn't it. The physical properties and evaluation of the polyisocyanate compositions in Examples and Comparative Examples were measured as follows. Note that unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass."

<Measurement method>
[Physical Properties 1] Viscosity The viscosity of the polyisocyanate components obtained in Examples and Comparative Examples was measured at 25° C. using an E-type viscometer (manufactured by Tokimec). A standard rotor (1°34'×R24) was used for the measurement. The rotation speed is as follows.

(number of rotations)
100rpm (for less than 128mPa・s)
50 rpm (for 128 mPa・s or more and less than 256 mPa・s)
20rpm (for 256mPa・s or more and less than 640mPa・s)
10 rpm (for 640 mPa・s or more and less than 1280 mPa・s)
5 rpm (for 1280 mPa・s or more and less than 2560 mPa・s)
2.5 rpm (for 2560 mPa・s or more and less than 5120 mPa・s)

[Physical properties 2] Isocyanate group content (NCO group content)
Using the polyisocyanate compositions obtained in Examples and Comparative Examples as samples, the isocyanate group content was measured according to the method described in JIS K7301-1995 (Test method for tolylene diisocyanate type prepolymers for thermosetting urethane elastomers). carried out. A more specific method for measuring the isocyanate group content is shown below.
(1) 1 g of the sample was taken into a 200 mL Erlenmeyer flask, and 20 mL of toluene was added to the flask to dissolve the sample.
(2) Thereafter, 20 mL of a 2.0N di-n-butylamine toluene solution was added to the flask, and the flask was left standing for 15 minutes.
(3) 70 mL of 2-propanol was added to the flask and dissolved to obtain a solution.
(4) The solution obtained in (3) above was titrated using 1 mol/L hydrochloric acid to determine the sample titer.
(5) Even when no sample was added, measurements were performed in the same manner as in (1) to (3) above to determine the blank titer.

The isocyanate group content was calculated from the sample titer and blank titer determined above using the formula shown below.

Isocyanate group content [mass%]
= (blank titer - sample titer) x 42/[sample mass (1g) x 1,000] x 100%

[Physical Properties 3] Modification Rate The modification rate is the ratio of isocyanate groups modified by sulfonic acid or its amine salt to 100 moles of isocyanate groups in the raw material polyisocyanate. Using the polyisocyanate compositions obtained in Examples and Comparative Examples as samples, unmodified isocyanurate trimer, 1-modified isocyanurate trimer, and 2-modified isocyanurate trimer were measured at 220 nm by liquid chromatography (LC). , and the peak area ratio of the tri-modified isocyanurate trimer. The equipment and conditions used are as follows.

(Measurement condition)
LC device: Manufactured by Waters, UPLC (product name)
Column: Waters, ACQUITY UPLC HSS T3 1.8μm C18 inner diameter 2.1mm x length 50mm
Flow rate: 0.3mL/min
Mobile phase: x = 10mM ammonium acetate aqueous solution, y = acetonitrile Gradient conditions: The initial mobile phase composition was x/y = 98/2, and after sample injection, the ratio of y was increased linearly, and after 10 minutes, x/y was increased. y=0/100.
Detection method: Photodiode array detector, measurement wavelength is 220nm

[Physical properties 4] Qualitative properties of amine compounds The amine compounds contained in the modified polyisocyanates obtained in the examples and comparative examples were separated by pyrolysis gas chromatography and then measured by mass spectrometry using the following equipment and conditions. It was qualitatively determined.

(Measurement condition)
Pyrolysis device: FRONTIER LAB Py3030D
Heating temperature: 600℃
Heating atmosphere: He
GC/MS device: Agilent6890/MSD5975C
Column: DB-1
Column temperature: 40°C (5 minutes) → 20°C/min temperature increase → 300°C (held for 11 minutes)
Column flow rate: 1.0mL/min Inlet temperature: 320℃
Injection method: Split method (split ratio: 1/50)
Ion source temperature: 230℃
Interface temperature: 300℃
Ionization method: Electron ionization method Sample amount: 0.3mg

[Physical property 5] Uretdione dimer content of diisocyanate monomer Using a polyisocyanate composition as a sample, the amount of uretdione dimer in the diisocyanate monomer relative to the area of the entire polyisocyanate composition was measured by gel permeation chromatography using the following apparatus. The area ratio of the body was determined.

(Measurement condition)
Equipment: HLC-802A (manufactured by Tosoh Corporation)
Column: G1000HXL x 1 (manufactured by Tosoh)
G2000HXL x 1 (manufactured by Tosoh)
G3000HXL x 1 (manufactured by Tosoh)
Carrier: Tetrahydrofuran Flow rate: 0.6 mL/min Sample concentration: 1.0% by mass
Injection volume: 20μL
Temperature: 40℃
Detection method: differential refractometer

[Physical property 6] Ratio of the molar amount of isocyanurate groups to the molar amount of uretdione groups in the composition (isocyanurate group/uretdione group)
The ratio of the molar amount of isocyanurate groups to the molar amount of uretdione groups in the composition (isocyanurate groups/uretdione groups) was determined by ¹³ C-NMR measurement under the conditions shown below.

(Measurement condition)
Device: AVANCE600 (product name) (manufactured by Bruker Biospin)
Cryoprobe: CP DUL 600S3 C/HD-05 Z
(Manufactured by Bruker Biospin)
Resonance frequency: 150MHz
Concentration: 60wt/vol%
Shift standard: CDCl3 (77ppm)
Integration number: 10,000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 seconds)

In addition, in the above measurement, the integral value of the following signals was divided by the number of carbons being measured, and each molar amount was determined from that value. The isocyanurate group/uretdione group was calculated using each obtained molar amount.

Isocyanurate group: around 148.5 ppm: integral value ÷ 3
Uretdione group: around 157.5 ppm: integral value ÷ 2

[Physical Property 7] Yield The yield of polyisocyanate was determined by measuring the refractive index of the polyisocyanate reaction solution obtained in each production example.

[Evaluation 1] Water dispersibility of polyisocyanate composition Using the polyisocyanate compositions obtained in Examples and Comparative Examples as samples, water dispersibility was evaluated using the method shown below.
(1) The total mass (W1 g) of the 100 mL flask and Yoshino paper was measured.
(2) The polyisocyanate composition was collected in a 100 mL flask so as to have a solid content of 16 g (W2 g), and 24 g of deionized water was added.
(3) Using a propeller blade, the solution in the 100 mL flask was stirred at 200 rpm for 3 minutes, and then filtered through the Yoshino paper weighed in (1).
(4) The filtration residue remaining on the Yoshino paper and the residue remaining on the 100 mL flask were combined and heated in a dryer at 105° C. for 1 hour, and the mass (W3 g) of the Yoshino paper and the 100 mL flask was measured.
(5) The proportion of the polyisocyanate composition dispersed in water was determined using the following formula.

Percentage dispersed in water (mass%) = {1-(W3(g)-W1(g))/(W2(g)×nonvolatile content (mass%))}×100%

Moreover, the evaluation criteria for water dispersibility were as follows.

(Evaluation criteria)
○: 80% by mass or more △: 60% by mass or more and less than 80% by mass ×: less than 60% by mass

[Evaluation 2] Appearance of coating film (1) Production of coating composition 40 g of an aqueous acrylic polyol dispersion (product name: Setaqua 6510, hydroxyl value per resin: 138 mgKOH/g, manufactured by Allnex) was weighed into a container. Next, the ratio (NCO/OH) of the molar amount of isocyanate groups in the polyisocyanate compositions obtained in Examples and Comparative Examples to the molar amount of hydroxyl groups in the aqueous acrylic polyol dispersion was 1.25. , each polyisocyanate composition was added. Further, deionized water was added so that the solid content in the coating composition was 42% by mass, and the mixture was stirred for 10 minutes at 600 rpm using a propeller blade to obtain each coating composition.

(2) Appearance evaluation of coating film A coating film with a thickness of 40 μm was coated on a glass plate using the coating composition obtained in (1). Next, it was dried in an atmosphere of 23° C. and 50% RH, and the resulting coating film was visually evaluated on the next day. The evaluation criteria for appearance were as follows.

(Evaluation criteria)
○: Transparent, no bumps, good smoothness.
△: Transparent, no bumps, poor smoothness.
×: Cloudy or with spots.

[Evaluation 3] Hardness of coating film (1) Production of coating composition A coating composition was prepared using the same method as in (1) of "Evaluation 2".

(2) Evaluation of hardness of coating film A coating film with a thickness of 40 μm was coated on a mild steel plate using the coating composition obtained in (1). Next, it was dried in an atmosphere of 23° C. and 50% RH, and after 7 days, the pencil hardness of the resulting coating film was measured according to JIS K 5600-5-4. Note that the hardness increases in the following order. Those with pencil hardness of B or higher were evaluated as having good hardness.

B<HB<F<H

[Evaluation 4] Water resistance of coating film (1) Production of coating composition A coating composition was prepared using the same method as in (1) of "Evaluation 2".

(2) Evaluation of water resistance of coating film The coating composition obtained in (1) was coated on a glass plate with an applicator to a thickness of 40 μm. Next, it was dried in an atmosphere of 23° C. and 50% RH for 7 days to obtain a coating film. Next, a silicone O-ring having a diameter of 20 mm was placed on the resulting coating film, and 0.5 g of water was poured into the O-ring. Next, it was left at 23° C. for 24 hours, and the appearance of the coating film after removing water remaining on the surface was observed. The water resistance of the coating film was evaluated according to the following evaluation criteria. However, if the appearance of the coating film in "Evaluation 2" was "x", visual evaluation was impossible, so it was determined that it could not be measured.

(Evaluation criteria)
○: No change.
△: No cloudiness or blister generation.
×: Blistering occurred, clouding or coating film dissolution.

Note that the term "blister" here refers to blisters or blisters that occur on the surface of a coating film.

[Production Example 1] Production of polyisocyanate P-1 A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was made into a nitrogen atmosphere, and 1000 g of HDI and 4.0 g of isobutanol were added. 0 g was charged, and the temperature inside the reactor was maintained at 70° C. while stirring. Tetramethylammonium capriate was added to this, and when the yield reached 50%, phosphoric acid was added to stop the reaction. Next, the temperature was raised to 160°C and held for 1 hour. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain polyisocyanate P-1. The resulting polyisocyanate P-1 had a viscosity of 900 mPa·s and an isocyanate group content of 22.3% at 25°C.

[Production Example 2] Production of Polyisocyanate P-2 Polyisocyanate P-2 was obtained in the same manner as Production Example 1, except that phosphoric acid was added to stop the reaction when the yield reached 55%. Ta. The resulting polyisocyanate P-2 had a viscosity of 1200 mPa·s and an isocyanate group content of 22.6% at 25°C.

[Production Example 3] Production of polyisocyanate P-3 1000 g of HDI and 1.5 g of 2-ethylhexanol were charged into the same apparatus as in Production Example 1, and the temperature inside the reactor was maintained at 70° C. while stirring. Tetramethylammonium capriate was added to this, and when the yield reached 18%, phosphoric acid was added to stop the reaction. Next, the temperature was raised to 160°C and held for 1 hour. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain polyisocyanate P-3. The resulting polyisocyanate P-3 had a viscosity of 500 mPa·s and an isocyanate group content of 23.3% at 25°C.

[Production Example 4] Production of Polyisocyanate P-4 Polyisocyanate P-4 was obtained in the same manner as Production Example 3, except that phosphoric acid was added to stop the reaction when the yield reached 16%. Ta. The resulting polyisocyanate P-4 had a viscosity of 300 mPa·s and an isocyanate group content of 23.0% at 25°C.

[Production Example 5] Production of Polyisocyanate P-5 1000 g of HDI and 3.5 g of isobutanol were charged into the same apparatus as in Production Example 1, and the temperature inside the reactor was maintained at 70° C. while stirring. Tetramethylammonium capriate was added to this, and when the yield reached 40%, phosphoric acid was added to stop the reaction. Next, after filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain polyisocyanate P-5. The resulting polyisocyanate P-5 had a viscosity of 2700 mPa·s at 25°C and an isocyanate group content of 21.7%.

[Production Example 6] Production of Polyisocyanate P-6 Polyisocyanate P-6 was obtained in the same manner as Production Example 5, except that phosphoric acid was added to stop the reaction when the yield reached 20%. . The resulting polyisocyanate P-6 had a viscosity of 1000 mPa·s at 25°C and an isocyanate group content of 22.8%.

[Production Example 7] Production of Polyisocyanate P-7 1000 g of HDI and 10 g of 1,3-butanediol were charged into the same apparatus as in Production Example 1, and the temperature inside the reactor was maintained at 60° C. while stirring. Tri-n-butylphosphine was added to this, and when the yield reached 25%, methyl p-toluenesulfonate was added to stop the reaction. Next, the temperature was raised to 80°C and held for 1 hour. Unreacted HDI was removed using a thin film evaporator. Next, 63 g of IPDI isocyanurate (product name: VESTANAT T1890, manufactured by Evonik) was added and mixed to obtain polyisocyanate P-7. The obtained polyisocyanate P-7 had a viscosity of 3000 mPa·s at 25°C and an isocyanate group content of 20.0%.

[Production Example 8] Production of Polyisocyanate P-8 1000 g of HDI and 1.5 g of 2-ethylhexanol were charged into the same apparatus as in Production Example 1, and the temperature inside the reactor was maintained at 70° C. while stirring. Tetramethylammonium capreate was added to this, and when the yield reached 24%, phosphoric acid was added to stop the reaction. Next, the temperature was raised to 160°C and held for 1 hour. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain polyisocyanate P-8. The resulting polyisocyanate P-8 had a viscosity of 1100 mPa·s at 25°C and an isocyanate group content of 22.6%.

[Production Example 9] Production of Polyisocyanate P-9 Polyisocyanate P-9 was obtained in the same manner as Production Example 5, except that phosphoric acid was added to stop the reaction when the yield reached 25%. . The resulting polyisocyanate P-9 had a viscosity of 1500 mPa·s at 25°C and an isocyanate group content of 22.3%.

[Production Example 10] Production of amine salt of sulfonic acid 1
To 20 parts by mass of an aqueous solution containing 70% by mass of 2-hydroxyethanesulfonic acid, 10 parts by mass of 1-propanol was added and stirred to obtain a solution. Furthermore, N,N-dimethylcyclohexylamine was weighed out so that the molar ratio to 2-hydroxyethanesulfonic acid was 1, and diluted with 10 parts by mass of 1-propanol. Then, a diluted solution of N,N-dimethylcyclohexylamine was added dropwise to the stirring 2-hydroxyethanesulfonic acid solution. One hour after the start of the dropwise addition, stirring was stopped, water was removed and the solvent removed using an evaporator, and 2-hydroxyethanesulfonic acid N,N-dimethylcyclohexylamine salt (hereinafter abbreviated as "HES/DMCHA") with a solid content of 99.8% by mass was prepared. ).

[Production Example 11] Production of amine salt of sulfonic acid 2
Using the same method as in Production Example 10 except that tributylamine was used instead of N,N-dimethylcyclohexylamine, 2-hydroxyethanesulfonic acid tributylamine salt (hereinafter referred to as "HES /TBA") was obtained.

[Production Example 12] Production of amine salt of sulfonic acid 3
Using the same method as in Production Example 10 except that N,N-diisopropylethylamine was used instead of N,N-dimethylcyclohexylamine, N,N-2-hydroxyethanesulfonic acid with a solid content of 99.7% by mass was prepared. Diisopropylethylamine salt (hereinafter sometimes abbreviated as "HES/DIPEA") was obtained.

[Production Example 13] Production of amine salt of sulfonic acid 4
Using the same method as in Production Example 10 except that N,N-dicyclohexylmethylamine was used instead of N,N-dimethylcyclohexylamine, 2-hydroxyethanesulfonic acid N,N with a solid content of 99.8% by mass was prepared. -dicyclohexylmethylamine salt (hereinafter sometimes abbreviated as "HES/DCHMA") was obtained.

[Example 1] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-1 obtained in Production Example 1, 2-hydroxyethanesulfonic acid N,N-dimethylcyclohexylamine salt obtained in Production Example 10 ( 2.4 parts by mass of HES/DMCHA) and 3.0 parts by mass of 2-hydroxyethanesulfonic acid tributylamine salt (HES/TBA) obtained in Production Example 11 were added. Next, the mixture was stirred at 120°C for 3 hours under a nitrogen atmosphere so that the molar ratio of each amine was 1/1 and the ratio of the molar amount of isocyanate groups to the molar amount of hydroxyl groups (isocyanate group/hydroxyl group) was 25. The reaction was carried out to obtain a polyisocyanate composition.
The obtained polyisocyanate composition had a non-volatile content of 100% by mass, a viscosity at 25°C of 1800 mPa·s, an isocyanate group content of 20.4% by mass, a modification rate of 4.0%, and a diisocyanate monomer containing uretdione diamolet. The body content was 9.7% by mass, and the ratio of isocyanurate groups/uretdione groups was 6.1. In addition, each physical property is also shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Examples 2, 5 to 6] Production of polyisocyanate compositions Polyisocyanate compositions were prepared using the same method as in Example 1 except that the formulations and molar ratio of amine in the amine salt of sulfonic acid were set as shown in Table 1. A composition was obtained. The physical properties of the obtained polyisocyanate composition were measured using the method described above. The results are shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Example 3] Production of polyisocyanate composition 3-cyclohexylaminopropanesulfonic acid (hereinafter sometimes abbreviated as "CAPS")6. 1 part by mass, 2.7 parts by mass of N,N-dimethylcyclohexylamine (hereinafter sometimes abbreviated as "DMCHA"), and 0.7 parts by mass of triethylamine (hereinafter sometimes abbreviated as "TEA"). part was added. Next, the reaction was carried out by stirring at 80° C. for 5 hours under reflux under a nitrogen atmosphere so that the ratio of the molar amount of isocyanate groups to the molar amount of amino groups (isocyanate group/amino group) was 20. An isocyanate composition was obtained. The physical properties of the obtained polyisocyanate composition were measured using the method described above. The results are shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Example 4] Production of polyisocyanate composition 4-cyclohexylaminobutanesulfonic acid (hereinafter sometimes abbreviated as "CABS")7. 9 parts by mass, 3.2 parts by mass of N,N-diisopropylethylamine (hereinafter sometimes abbreviated as "DIPEA"), and 1.5 parts by mass of tributylamine (hereinafter sometimes abbreviated as "TBA"). part was added. Next, the reaction was carried out by stirring at 100° C. for 5 hours under reflux under a nitrogen atmosphere so that the molar ratio of each amine was 3/1 and the ratio of isocyanate groups/amino groups was 16.7, thereby changing the polyisocyanate composition. I got something. The physical properties of the obtained polyisocyanate composition were measured using the method described above. The results are shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Example 7] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-5 obtained in Production Example 5, 5.2 parts by mass of HES/DMCHA obtained in Production Example 10 and 5.2 parts by mass of HES/DMCHA obtained in Production Example 11 were added. 6.4 parts by mass of HES/TBA was added. Next, the mixture was stirred at 120° C. for 3 hours under a nitrogen atmosphere to carry out a reaction such that the molar ratio of each amine was 1/1 and the ratio of isocyanate group/hydroxyl group was 12.5. After the reaction was completed, 110 parts by mass of polyisocyanate P-4 obtained in Production Example 4 was added and mixed to obtain a polyisocyanate composition. The obtained polyisocyanate composition had a non-volatile content of 100% by mass, a viscosity at 25°C of 2000 mPa·s, an isocyanate group content of 20.3% by mass, a modification rate of 4.0%, and a diisocyanate monomer containing uretdione dimer. The body content was 10.0% by mass, and the isocyanurate group/uretdione group content was 7.0. In addition, each physical property is also shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Example 8] Production of polyisocyanate composition 2-hydroxyethanesulfonic acid N,N-diisopropylethylamine salt (HES) obtained in Production Example 12 was added to 100 parts by mass of polyisocyanate P-5 obtained in Production Example 5. /DIPEA) and 6.4 parts by mass of HES/TBA obtained in Production Example 11 were added. Next, the mixture was stirred at 120° C. for 3 hours under a nitrogen atmosphere to carry out a reaction such that the molar ratio of each amine was 1/1 and the ratio of isocyanate group/hydroxyl group was 12.5. After the reaction was completed, 110 parts by mass of polyisocyanate P-3 obtained in Production Example 3 was added and mixed to obtain a polyisocyanate composition. The obtained polyisocyanate composition has a non-volatile content of 100% by mass, a viscosity at 25°C of 2500 mPa·s, an isocyanate group content of 20.7% by mass, a modification rate of 4.0%, and a diisocyanate monomer containing uretdione dimer. The body content was 7.8% by mass, and the isocyanurate group/uretdione group content was 8.4. In addition, each physical property is also shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Example 9] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-5 obtained in Production Example 5, 5.2 parts by mass of HES/DMCHA obtained in Production Example 10 and 5.2 parts by mass of HES/DMCHA obtained in Production Example 11 were added. 6.4 parts by mass of HES/TBA was added. Next, the mixture was stirred at 120° C. for 3 hours under a nitrogen atmosphere to carry out a reaction such that the molar ratio of each amine was 1/1 and the ratio of isocyanate group/hydroxyl group was 12.5. After the reaction was completed, 110 parts by mass of polyisocyanate P-8 obtained in Production Example 8 was added and mixed to obtain a polyisocyanate composition. The obtained polyisocyanate composition has a non-volatile content of 100% by mass, a viscosity at 25°C of 3000 mPa·s, an isocyanate group content of 20.4% by mass, a modification rate of 4.0%, and a diisocyanate monomer containing uretdione dimer. The body content was 4.5% by mass, and the isocyanurate group/uretdione group content was 13.0. In addition, each physical property is also shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Example 10] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-5 obtained in Production Example 5, 5.2 parts by mass of HES/DMCHA obtained in Production Example 10 and 5.2 parts by mass of HES/DMCHA obtained in Production Example 11 were added. 6.4 parts by mass of HES/TBA was added. Next, the mixture was stirred at 120° C. for 3 hours under a nitrogen atmosphere to carry out a reaction such that the molar ratio of each amine was 1/1 and the ratio of isocyanate group/hydroxyl group was 12.5. After the reaction was completed, 110 parts by mass of polyisocyanate P-9 obtained in Production Example 9 was added and mixed to obtain a polyisocyanate composition. The obtained polyisocyanate composition had a non-volatile content of 100% by mass, a viscosity at 25°C of 3500 mPa·s, an isocyanate group content of 20.1% by mass, a modification rate of 4.0%, and a diisocyanate monomer containing uretdione dimer. The body content was 2.5% by mass, and the isocyanurate group/uretdione group content was 22.0. In addition, each physical property is also shown in Table 1.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 1.

[Comparative Example 1] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-5 obtained in Production Example 5, 3.9 parts by mass of HES/DMCHA obtained in Production Example 10 and 3.9 parts by mass of HES/DMCHA obtained in Production Example 11 were added. 1.6 parts by mass of HES/TBA was added. Next, the mixture was stirred at 120° C. for 3 hours under a nitrogen atmosphere to carry out a reaction such that the molar ratio of each amine was 3/1 and the ratio of isocyanate groups to hydroxyl groups was 25, thereby obtaining a polyisocyanate composition. The obtained polyisocyanate composition has a non-volatile content of 100% by mass, a viscosity at 25°C of 4000 mPa·s, an isocyanate group content of 20.4% by mass, a modification rate of 4.0%, and a diisocyanate monomer containing uretdione dimer. The body content was 0.2% by mass, and the isocyanurate group/uretdione group content was 154.3. In addition, each physical property is also shown in Table 2.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 2.

[Comparative Example 2] Production of polyisocyanate composition A polyisocyanate composition was obtained using the same method as in Comparative Example 1 except that the formulations and molar ratio of amine in the amine salt of sulfonic acid were respectively shown in Table 1. Ta. The physical properties of the obtained polyisocyanate composition were measured using the method described above. The results are shown in Table 2.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 2.

[Comparative Example 3] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-5 obtained in Production Example 5, 5.1 parts by mass of 3-cyclohexylaminopropanesulfonic acid (CAPS) and N,N-dimethyl were added. 3.0 parts by mass of cyclohexylamine (DMCHA) were added. Next, the mixture was stirred at 80° C. for 5 hours under reflux under a nitrogen atmosphere to conduct a reaction such that the ratio of isocyanate groups/amino groups was 22, thereby obtaining a polyisocyanate composition. The physical properties of the obtained polyisocyanate composition were measured using the method described above. The results are shown in Table 2.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 2.

[Comparative Example 4] Production of polyisocyanate composition To 100 parts by mass of polyisocyanate P-7 obtained in Production Example 7, 10.9 parts by mass of 4-cyclohexylaminobutanesulfonic acid (CABS) and N,N-diisopropyl were added. 6.0 parts by mass of ethylamine (DIPEA) were added. Next, the mixture was stirred at 100° C. for 5 hours under reflux under a nitrogen atmosphere to conduct a reaction such that the ratio of isocyanate groups to amino groups was 11.1, thereby obtaining a polyisocyanate composition. The physical properties of the obtained polyisocyanate composition were measured using the method described above. The results are shown in Table 2.
Further, the obtained polyisocyanate composition was evaluated by the method described above. The results are shown in Table 2.

From Tables 1 and 2, 2.5% by mass or more of the polyisocyanate containing a sulfonic acid anion group in the molecule, the tertiary ammonium cation of two or more amine compounds, and the total mass of the composition13 It has been confirmed that the polyisocyanate compositions (Examples 1 to 10) containing uretdione dimers of diisocyanate of .5 mass or less have excellent water dispersibility and provide coating films with excellent appearance, hardness and water resistance. Ta.
Furthermore, the polyisocyanate compositions using an amine salt of sulfonic acid (Examples 1, 2, 5 to 10) had a higher level of The water resistance of the resulting coating film was particularly good.
Furthermore, the polyisocyanate compositions (Examples 1, 2, 7 to 10) in which the isocyanurate group/uretdione group is 6.1 or more are different from the polyisocyanate compositions in which the molar ratio is less than 6.1 (Example 3). -6) The pencil hardness of the resulting coating film was better.
In addition, the polyisocyanate compositions (Examples 9 to 10) in which the content of uretdione dimer is 2.5% by mass or more and 4.5% by mass or less have a content of uretdione dimer of 4.5% by mass. The pencil hardness of the resulting coating film was particularly better than that of the polyisocyanate compositions (Examples 1 to 8).

The polyisocyanate composition of this embodiment has excellent dispersibility in water and a water-containing main ingredient, and provides a coating film with excellent appearance, hardness, and water resistance. The coating composition of the present embodiment includes the above polyisocyanate composition, and includes architectural paints, automotive paints, automotive repair paints, plastic paints, adhesives, adhesives, building materials, household water-based paints, and other coating agents. , sealants, inks, casting materials, elastomers, foams, plastic raw materials, and fiber processing agents.

Claims (11)

A polyisocyanate containing a sulfonic acid anion group in the molecule,
A tertiary ammonium cation of one or more amine compounds represented by the following general formula (1) and a tertiary ammonium cation of one or more amine compounds represented by the following general formula (2), or 2 A tertiary ammonium cation of an amine compound represented by the general formula (1) in which the total carbon numbers of R ¹¹ , R ¹² and R ¹³ are different from each other;
A polyisocyanate composition comprising a uretdione dimer of a diisocyanate monomer,
The content of the uretdione dimer is 2.0% by mass or more and 20.0% by mass or less based on the total mass of the composition,
The polyisocyanate containing the sulfonic acid anion group in the molecule is obtained by reacting two or more amine salts of sulfonic acid having active hydrogen groups with the polyisocyanate,
The amine salt of a sulfonic acid having an active hydrogen group comprises a sulfonic acid having an active hydrogen group, one or more amine compounds represented by the general formula (1), and one or more of the general formula (2). is a salt with an amine compound represented by the formula, or
A salt of the sulfonic acid having an active hydrogen group and an amine compound represented by the general formula (1) in which two or more of the R ¹¹ , R ¹² and R ¹³ have different total carbon numbers,
A polyisocyanate composition , wherein the sulfonic acid having an active hydrogen group is a compound represented by the following general formula (3) .

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)

(In general formula (3), R ³¹ is a hydrocarbon group having 1 to 10 carbon atoms that may contain at least one selected from the group consisting of a hydroxyl group, an ether bond, an ester bond, a carbonyl group, and an imino group. R ³¹ may include a ring structure. The ring structure is an aromatic ring, a 5-membered ring or 6-membered ring containing two nitrogen atoms, or a 5-membered ring or 6-membered ring containing a nitrogen atom and an oxygen atom. It is a member ring.) A polyisocyanate containing a sulfonic acid anion group in the molecule,
A tertiary ammonium cation of one or more amine compounds represented by the following general formula (1) and a tertiary ammonium cation of one or more amine compounds represented by the following general formula (2), or 2 A tertiary ammonium cation of an amine compound represented by the general formula (1) in which the total carbon numbers of R ¹¹ , R ¹² and R ¹³ are different from each other;
A polyisocyanate composition comprising a uretdione dimer of a diisocyanate monomer,
The content of the uretdione dimer is 2.0% by mass or more and 20.0% by mass or less based on the total mass of the composition,
The polyisocyanate containing a sulfonic acid anion group in the molecule is obtained by a reaction between a sulfonic acid having an active hydrogen group and a polyisocyanate,
A polyisocyanate composition , wherein the sulfonic acid having an active hydrogen group is a compound represented by the following general formula (4) .

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)

(In general formula (4), R ⁴¹ and R ⁴³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group. Even if R ⁴¹ contains a hydroxyl group When R 43 is a hydrocarbon group having 1 to 12 carbon atoms, R ⁴³ is a hydrogen atom, and when R ⁴³ is a hydrocarbon group having 1 to 12 carbon atoms which may include a hydroxyl group, R ⁴¹ is a hydrogen atom. ( ^R42 is a hydrocarbon group having 1 or more and 12 or less carbon atoms that may contain a hydroxyl group.) The polyisocyanate composition has an isocyanurate group,
The polyisocyanate composition according to claim 1 or 2, wherein the ratio of the molar amount of isocyanurate groups to the molar amount of uretdione groups in the composition is 2.5 or more and 10.0 or less. The polyisocyanate composition according to any one of claims 1 to 3 , wherein the content of the uretdione dimer is 2.0% by mass or more and 5.0% by mass or less based on the total mass of the composition. thing. The amine compound represented by the general formula (1) is at least one selected from the group consisting of a cyclic amine compound, an amine compound containing a chain aliphatic hydrocarbon group, and an amine compound containing a cyclic aliphatic hydrocarbon group. and the amine compound represented by the general formula (2) is at least one selected from the group consisting of an amine compound containing a chain aliphatic hydrocarbon group and an amine compound containing a cyclic aliphatic hydrocarbon group. A polyisocyanate composition according to any one of claims 1 to 4 . The polyisocyanate composition according to any one of claims 1 to 5, wherein the polyisocyanate is at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates. thing. (A) two or more amine salts of sulfonic acid having active hydrogen groups and a polyisocyanate ,
The reaction is carried out at a ratio of the molar amount of isocyanate groups to the molar amount of active hydrogen groups in the range of 2 to 400,
The amine salt of the sulfonic acid having an active hydrogen group comprises the sulfonic acid having the active hydrogen group, one or more amine compounds represented by the general formula (1), and one or more of the general formula (2). is a salt with an amine compound represented by the formula, or
A salt of the sulfonic acid having an active hydrogen group and two or more amine compounds represented by the general formula (1) in which the total carbon numbers of R ¹¹ , R ¹² and R ¹³ are different from each other,
The sulfonic acid having an active hydrogen group is a compound represented by the following general formula (3),
A method for producing a polyisocyanate composition, comprising producing the polyisocyanate composition according to claim 1.

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)

(In general formula (3), R ³¹ is a hydrocarbon group having 1 to 10 carbon atoms that may contain at least one selected from the group consisting of a hydroxyl group, an ether bond, an ester bond, a carbonyl group, and an imino group. R ³¹ may include a ring structure. The ring structure is an aromatic ring, a 5-membered ring or 6-membered ring containing two nitrogen atoms, or a 5-membered ring or 6-membered ring containing a nitrogen atom and an oxygen atom. It is a member ring.)
In the amine salt of the sulfonic acid, the ratio of the molar amount of the amine compound represented by the general formula (2) to the molar amount of the amine compound represented by the general formula (1) is 10/90 or more and 90/10 or less The method for producing a polyisocyanate composition according to claim 7 . ( B) a sulfonic acid having an active hydrogen group, a polyisocyanate,
one or more amine compounds represented by the following general formula (1) and one or more amine compounds represented by the following general formula (2), or
An amine compound represented by the general formula (1) in which two or more types of R ¹¹ , R ¹² and R ¹³ have different total carbon numbers,
The reaction is carried out at a ratio of the molar amount of isocyanate groups to the molar amount of active hydrogen groups in the range of 2 to 400,
The sulfonic acid having an active hydrogen group is a compound represented by the following general formula (4),
A method for producing a polyisocyanate composition, comprising producing the polyisocyanate composition according to claim 2 .

(In general formula (1), R ¹¹ , R ¹² and R ¹³ are each independently a hydrocarbon group having 1 to 6 carbon atoms and which may contain an ether bond. R ¹¹ , R ¹² and R ¹³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ¹¹ and R ¹² are bonded to each other, or a structure in which R ¹¹ , R ¹² , and R ¹³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ¹¹ , R ¹² and R ¹³ is 8 or less.)

(In general formula (2), R ²¹ , R ²² and R ²³ are each independently a hydrocarbon group having 1 to 19 carbon atoms and which may contain an ether bond. R ²¹ , R ²² and R ²³ At least one selected from the group consisting of may include a ring structure, and two or more selected from the group consisting of R ²¹ , R ²² and R ²³ may be bonded to each other to form a ring structure. The structure is an aromatic ring, a cycloalkyl group having 5 or 6 carbon atoms, a 5- or 6-membered ring in which R ²¹ and R ²² are bonded to each other, or a structure in which R ²¹ , R ²² , and R ²³ are bonded to each other. It is a multi-membered multi-ring. The total number of carbon atoms of R ²¹ , R ²² and R ²³ is 9 or more.)

(In general formula (4), R ⁴¹ and R ⁴³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms that may contain a hydroxyl group. Even if R ⁴¹ contains a hydroxyl group When R 43 is a hydrocarbon group having 1 to 12 carbon atoms, R ⁴³ is a hydrogen atom, and when R ⁴³ is a hydrocarbon group having 1 to 12 carbon atoms which may include a hydroxyl group, R ⁴¹ is a hydrogen atom. ( ^R42 is a hydrocarbon group having 1 or more and 12 or less carbon atoms that may contain a hydroxyl group.) A coating composition comprising a polyisocyanate composition according to any one of claims 1 to 6 . A coated substrate coated with the coating composition according to claim 10 .