JP6294136B2 - Polyisocyanate composition - Google Patents

Description

  The present invention relates to a polyisocyanate composition and a coating composition using the same.

  In recent years, from the viewpoint of environmental protection, it has been desired that a room temperature cross-linking type two-component urethane coating composition that has been conventionally used as a solvent-based paint is water-based. However, the polyisocyanate used as the curing agent in the two-component urethane coating composition is difficult to disperse in water, easily reacts with water, and generates carbon dioxide. Therefore, development of a polyisocyanate having high emulsifying properties and capable of suppressing the reaction between an isocyanate group and water in a water-dispersed state has been promoted.

  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 discloses a reaction product obtained by reacting a special aminoalkylsulfonic acid with a polyisocyanate. A modified polyisocyanate composition is disclosed.

JP-A-8-176267 Special table 2003-533666 gazette

  However, even the polyisocyanate compositions described in Patent Documents 1 and 2 are insufficient to achieve both emulsifying power and suppression of reaction between isocyanate groups and water.

  Accordingly, the present invention provides a polyisocyanate composition that exhibits high emulsifiability in water and that has a small decrease in isocyanate groups when blended with water or a main ingredient containing water, and a coating composition using the same. With the goal.

  The present inventors have found that a polyisocyanate composition containing a modified polyisocyanate obtained by reacting a sulfonic acid amine salt having a specific hydroxyl group with a polyisocyanate has excellent emulsifiability in water and good isocyanate groups. It has been found that it is possible to achieve both retention rates, and by using a water-based coating composition using the same, it is possible to form a coating film having a good appearance and good solvent resistance. The inventors have found that this is possible and have completed the present invention.

That is, the present invention is as follows.
[1]
Including a modified polyisocyanate obtained by reaction of a sulfonic acid amine salt having a hydroxyl group with a polyisocyanate,
The sulfonic acid amine salt having a hydroxyl group is at least one amine selected from a sulfonic acid having a hydroxyl group represented by the following general formula (1) and an amine compound having a ring structure represented by the following general formula (2) A polyisocyanate composition which is a salt with a compound.

（式（１）中、Ｒ¹は炭素原子数１から１０の炭化水素基またはアリール基であり、該炭化水素基またはアリール基は、エステル結合、水酸基、カルボニル基、三級アミノ基、窒素原子を２つ含む５員もしくは６員環、並びに窒素原子と酸素原子とを含む５員もしくは６員環からなる群より選ばれる少なくとも一種を含んでもよい。）

(In the formula (1), R ¹ is a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and the hydrocarbon group or aryl group includes an ester bond, a hydroxyl group, a carbonyl group, a tertiary amino group, a nitrogen atom. And may include at least one selected from the group consisting of a 5-membered or 6-membered ring containing 2 and a 5-membered or 6-membered ring containing nitrogen and oxygen atoms.)

（式（２）中、Ｒ²、Ｒ³およびＲ⁴は同じでも異なってもよく、炭素原子数１から１０の炭化水素基またはアリール基であり、Ｒ²、Ｒ³およびＲ⁴からなる群より選ばれる少なくとも一つが環構造を含み、該環構造は、アリール基、５員もしくは６員のシクロアルキル基、Ｒ²とＲ³とが互いに結合した５員もしくは６員環、Ｒ²とＲ³とが酸素原子を介して互いに結合した５員もしくは６員環、または、Ｒ²とＲ³とＲ⁴とが互いに結合した多員の多重環である。）
［２］
該ポリイソシアネートが、脂肪族ポリイソシアネート、脂環族ポリイソシアネートおよび芳香脂肪族ポリイソシアネートからなる群より選ばれる少なくとも一種である、［１］に記載のポリイソシアネート組成物。
［３］
水酸基を有するスルホン酸アミン塩と、ポリイソシアネートとを、イソシアネート基／水酸基の当量比が２から４００の範囲で反応させる工程を含み、
該水酸基を有するスルホン酸アミン塩が、下記一般式（１）で表される水酸基を有するスルホン酸と、下記一般式（２）で表される環構造を含むアミン化合物から選ばれる少なくとも一種のアミン化合物との塩である、変性ポリイソシアネートを含むポリイソシアネート組成物の製造方法。

(In the formula (2), R ² , R ³ and R ⁴ may be the same or different, and are a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and a group consisting of R ² , R ³ and R ^4. comprises at least one of the ring structures more selected, the ring system, aryl group, 5- or 6-membered cycloalkyl group, R ² and R ³ and is a 5- or 6-membered ring bonded to one another, R ² and R ³ is a 5- or 6-membered ring bonded to each other through an oxygen atom, or R ² , R ³ and R ⁴ are bonded to each other.
[2]
The polyisocyanate composition according to [1], wherein the polyisocyanate is at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates.
[3]
A step of reacting a sulfonic acid amine salt having a hydroxyl group with a polyisocyanate in an isocyanate group / hydroxyl group equivalent ratio of 2 to 400,
The sulfonic acid amine salt having a hydroxyl group is at least one amine selected from a sulfonic acid having a hydroxyl group represented by the following general formula (1) and an amine compound having a ring structure represented by the following general formula (2) The manufacturing method of the polyisocyanate composition containing modified polyisocyanate which is a salt with a compound.

（式（１）中、Ｒ¹は炭素原子数１から１０の炭化水素基またはアリール基であり、該炭化水素基またはアリール基は、エステル結合、水酸基、カルボニル基、三級アミノ基、窒素原子を２つ含む５員もしくは６員環、並びに窒素原子と酸素原子とを含む５員もしくは６員環からなる群より選ばれる少なくとも一種を含んでもよい。）

(In the formula (1), R ¹ is a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and the hydrocarbon group or aryl group includes an ester bond, a hydroxyl group, a carbonyl group, a tertiary amino group, a nitrogen atom. And may include at least one selected from the group consisting of a 5-membered or 6-membered ring containing 2 and a 5-membered or 6-membered ring containing nitrogen and oxygen atoms.)

（式（２）中、Ｒ²、Ｒ³およびＲ⁴は同じでも異なってもよく、炭素原子数１から１０の炭化水素基またはアリール基であり、Ｒ²、Ｒ³およびＲ⁴からなる群より選ばれる少なくとも一つが環構造を含み、該環構造は、アリール基、５員もしくは６員のシクロアルキル基、Ｒ²とＲ³とが互いに結合した５員もしくは６員環、Ｒ²とＲ³とが酸素原子を介して互いに結合した５員もしくは６員環、または、Ｒ²とＲ³とＲ⁴とが互いに結合した多員の多重環である。）
［４］
［１］または［２］に記載のポリイソシアネート組成物を含む、コーティング組成物。
［５］
［４］に記載のコーティング組成物によってコーティングされたコーティング基材。

(In the formula (2), R ² , R ³ and R ⁴ may be the same or different, and are a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and a group consisting of R ² , R ³ and R ^4. comprises at least one of the ring structures more selected, the ring system, aryl group, 5- or 6-membered cycloalkyl group, R ² and R ³ and is a 5- or 6-membered ring bonded to one another, R ² and R ³ is a 5- or 6-membered ring bonded to each other through an oxygen atom, or R ² , R ³ and R ⁴ are bonded to each other.
[4]
A coating composition comprising the polyisocyanate composition according to [1] or [2].
[5]
A coated substrate coated with the coating composition according to [4].

  When the polyisocyanate composition of the present invention is dispersed in water or a main agent containing water, the polyisocyanate composition can obtain excellent dispersibility with little decrease in isocyanate groups.

  The aqueous coating composition comprising the polyisocyanate composition of the present invention can form a coating film having excellent appearance and excellent solvent resistance.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following this embodiment. The present invention can be appropriately modified within the scope of the gist.

≪Polyisocyanate composition≫
The polyisocyanate composition of the present embodiment includes a modified polyisocyanate obtained by a reaction between a sulfonic acid amine salt having a hydroxyl group and a polyisocyanate,
The sulfonic acid amine salt having a hydroxyl group is at least one amine selected from a sulfonic acid having a hydroxyl group represented by the following general formula (1) and an amine compound having a ring structure represented by the following general formula (2) A salt with a compound.

（式（１）中、Ｒ¹は炭素原子数１から１０の炭化水素基またはアリール基であり、該炭化水素基またはアリール基は、エステル結合、水酸基、カルボニル基、三級アミノ基、窒素原子を２つ含む５員もしくは６員環、並びに窒素原子と酸素原子とを含む５員もしくは６員環からなる群より選ばれる少なくとも一種を含んでもよい。）

(In the formula (1), R ¹ is a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and the hydrocarbon group or aryl group includes an ester bond, a hydroxyl group, a carbonyl group, a tertiary amino group, a nitrogen atom. And may include at least one selected from the group consisting of a 5-membered or 6-membered ring containing 2 and a 5-membered or 6-membered ring containing nitrogen and oxygen atoms.)

（式（２）中、Ｒ²、Ｒ³およびＲ⁴は同じでも異なってもよく、炭素原子数１から１０の炭化水素基またはアリール基であり、Ｒ²、Ｒ³およびＲ⁴からなる群より選ばれる少なくとも一つが環構造を含み、該環構造は、アリール基、５員もしくは６員のシクロアルキル基、Ｒ²とＲ³とが互いに結合した５員もしくは６員環、Ｒ²とＲ³とが酸素原子を介して互いに結合した５員もしくは６員環、または、Ｒ²とＲ³とＲ⁴とが互いに結合した多員の多重環である。）
なお、本実施形態のポリイソシアネート組成物は、通常、未反応のポリイソシアネートを含む。また、後述する本実施形態のポリイソシアネート組成物の各種特性は、特段言及の無い限り、上記反応により得られる変性ポリイソシアネートと、未反応のポリイソシアネートとを含んだ状態での特性である。

(In the formula (2), R ² , R ³ and R ⁴ may be the same or different, and are a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and a group consisting of R ² , R ³ and R ^4. comprises at least one of the ring structures more selected, the ring system, aryl group, 5- or 6-membered cycloalkyl group, R ² and R ³ and is a 5- or 6-membered ring bonded to one another, R ² and R ³ is a 5- or 6-membered ring bonded to each other through an oxygen atom, or R ² , R ³ and R ⁴ are bonded to each other.
In addition, the polyisocyanate composition of this embodiment usually contains unreacted polyisocyanate. Further, various characteristics of the polyisocyanate composition of the present embodiment to be described later are characteristics in a state containing a modified polyisocyanate obtained by the above reaction and an unreacted polyisocyanate unless otherwise specified.

  In the polyisocyanate composition of the present embodiment, the ratio of unreacted polyisocyanate to modified polyisocyanate (modified polyisocyanate) is, for example, a hydroxyl group with respect to 100 equivalents of the isocyanate group of the starting polyisoisocyanate. It can calculate from the ratio by which the sulfonic acid amine salt which has is denatured.

<Polyisocyanate>
The polyisocyanate used in the present embodiment is not particularly limited. For example, at least one diisocyanate compound selected from aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and / or polyisocyanate derived from these diisocyanate compounds. Compounds. The polyisocyanate used in the present embodiment is preferably at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates and araliphatic polyisocyanates from the viewpoint of industrial availability.

  Although it does not specifically limit as aliphatic diisocyanate, For example, 1, 4- diisocyanato butane, 1, 5- diisocyanato pentane, ethyl (2, 6- diisocyanato) hexanoate, 1, 6- diisocyanato hexane (following , And 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. 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 “ Hydrogenated MDI "), 2,5- or 2,6-diisocyanatomethylnorbornane and the like. Although it does not specifically limit as aromatic diisocyanate, For example, xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate etc. are mentioned.

  Among these, HDI, IPDI, hydrogenated XDI, and hydrogenated MDI are preferable.

  The polyisocyanate compound derived from the diisocyanate is not particularly limited. For example, a polyisocyanate compound having a uretdione structure obtained by cyclizing and dimerizing two isocyanate groups, and cyclizing and trimerizing three isocyanate groups. Polyisocyanate compound having an isocyanurate structure or iminooxadiazinedione structure obtained in the above manner, a polyisocyanate compound having a biuret structure obtained by reacting three isocyanate groups with one water molecule, and two isocyanate groups A polyisocyanate compound having an oxadiazinetrione structure obtained by reacting carbon dioxide with one molecule of carbon, and a polyisocyanate having a plurality of urethane groups obtained by reacting one isocyanate group and one hydroxyl group Compound, polyisocyanate compound having an allophanate structure obtained by reacting two isocyanate groups and one hydroxyl group, polyisocyanate compound having an acylurea group obtained by reacting one isocyanate group and one carboxyl group, Examples thereof include polyisocyanate compounds having a urea structure obtained by reacting one isocyanate group with one primary or secondary amine.

  In addition, aliphatic triisocyanates such as 1,3,6-triisocyanatohexane, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl-2,6-diisocyanato-hexanoate can be used. It is.

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

  These may be used alone or in combination of two or more.

<Sulphonic acid amine salt having a hydroxyl group>
The sulfonic acid amine salt having a hydroxyl group used in the present embodiment is selected from a sulfonic acid having a hydroxyl group represented by the following general formula (1) and an amine compound having a ring structure represented by the following general formula (2). Preferred are salts with at least one amine compound.

（式（１）中、Ｒ¹は炭素原子数１から１０の炭化水素基またはアリール基であり、該炭化水素基またはアリール基は、エステル結合、水酸基、カルボニル基、三級アミノ基、窒素原子を２つ含む５員もしくは６員環、並びに窒素原子と酸素原子とを含む５員もしくは６員環からなる群より選ばれる少なくとも一種を含んでもよい。）
中でもＲ¹は炭素原子数１から６の炭化水素基、炭素原子数６から１０のアリール基が好ましい。

(In the formula (1), R ¹ is a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and the hydrocarbon group or aryl group includes an ester bond, a hydroxyl group, a carbonyl group, a tertiary amino group, a nitrogen atom. And may include at least one selected from the group consisting of a 5-membered or 6-membered ring containing 2 and a 5-membered or 6-membered ring containing nitrogen and oxygen atoms.)
Among these, R ¹ is preferably a hydrocarbon group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms.

  Specific examples of the sulfonic acid having a hydroxyl group represented by the general formula (1) are not particularly limited, and examples thereof include 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 4-hydroxybutanesulfonic acid, 5- Hydroxypentanesulfonic acid, 6-hydroxyhexanesulfonic acid, hydroxybenzenesulfonic acid, hydroxy (methyl) benzenesulfonic acid, 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid, 4- (2-hydroxyethyl)- Examples include 1-piperazinepropanesulfonic acid, 2-hydroxy-3-morpholinopropanesulfonic acid, and the like.

  Of these, 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, hydroxybenzenesulfonic acid, and hydroxy (methyl) benzenesulfonic acid are preferable.

（式（２）中、Ｒ²、Ｒ³およびＲ⁴は同じでも異なってもよく、炭素原子数１から１０の炭化水素基またはアリール基であり、Ｒ²、Ｒ³およびＲ⁴からなる群より選ばれる少なくとも一つが環構造を含み、該環構造は、アリール基、５員もしくは６員のシクロアルキル基、Ｒ²とＲ³とが互いに結合した５員もしくは６員環、Ｒ²とＲ³とが酸素原子を介して互いに結合した５員もしくは６員環、または、Ｒ²とＲ³とＲ⁴とが互いに結合した多員の多重環である。）
中でも、Ｒ²、Ｒ³およびＲ⁴のうち少なくとも一つが５員または６員のシクロアルキル基を含むか、Ｒ²とＲ³とが互いに結合した５員または６員環を形成するか、Ｒ²とＲ³とが酸素原子を介して互いに結合した５員または６員環を形成するのが好ましい。また、上記式（２）で表されるアミン化合物は、２つ以上の環構造を含んでいてもよい。

(In the formula (2), R ² , R ³ and R ⁴ may be the same or different, and are a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and a group consisting of R ² , R ³ and R ^4. comprises at least one of the ring structures more selected, the ring system, aryl group, 5- or 6-membered cycloalkyl group, R ² and R ³ and is a 5- or 6-membered ring bonded to one another, R ² and R ³ is a 5- or 6-membered ring bonded to each other through an oxygen atom, or R ² , R ³ and R ⁴ are bonded to each other.
Among them, at least one of R ² , R ³ and R ⁴ contains a 5-membered or 6-membered cycloalkyl group, R ² and R ³ are bonded to each other to form a 5-membered or 6-membered ring, ^It is preferable that ² and R ³ form a 5-membered or 6-membered ring bonded to each other through an oxygen atom. Moreover, the amine compound represented by the above formula (2) may contain two or more ring structures.

  Although it does not specifically limit as a specific example of the amine compound containing the ring structure represented by General formula (2), For example, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dibenzyl Methylamine, tribenzylamine, N, N-dimethyl-4-methylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dicyclohexylmethylamine, N, N-dicyclohexylethylamine, Tricyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N -Ethylmorpholine, N-propyl Ruhorin, N- butyl morpholine, N-sec-butyl morpholine, N-tert-butyl morpholine, N- isobutyl morpholine, quinuclidine or the like, or any mixtures of these.

  Among them, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, N-methylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, N-isobutylmorpholine, etc. Any mixtures of these are preferred.

  Particularly preferred is N, N-dimethylcyclohexylamine, N-methylpiperidine, N-ethylmorpholine, or any mixture thereof.

  As the salt using the amine compound containing the ring structure exemplified above, an amine compound containing a ring structure other than those exemplified above (for example, N-methylpyrrolidone, N-methylpiperidone, etc. combined with a carbonyl group) is used. There is a tendency that the compatibility with the polyisocyanate is further improved as compared with the prepared salt.

  The sulfonic acid amine salt having a hydroxyl group can be obtained, for example, by mixing and neutralizing a sulfonic acid having a hydroxyl group and an amine compound.

  In the neutralization reaction, the mixing ratio is preferably an equivalent ratio of sulfonic acid / amine compound having a hydroxyl group of 0.5 to 2, more preferably 0.8 to 1.5.

  In the neutralization reaction, the temperature and time are appropriately determined according to the progress of the reaction, but the temperature is usually preferably about 0 ° C. to 100 ° C., and the mixing time is preferably about 10 minutes to 24 hours. .

  The solvent used in the preparation of the sulfonic acid amine salt having a hydroxyl group is preferably water or a hydrophilic solvent. The hydrophilic solvent is not particularly limited. For example, alcohols such as methanol, ethanol, propanol, butanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Examples include ether alcohols such as butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. In addition, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone can be used.

  These can be used alone or in combination.

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

<Characteristics of polyisocyanate composition>
In the polyisocyanate composition of the present embodiment, the sulfonic acid amine salt having a hydroxyl group is from 0.25 to 50 equivalents of the isocyanate group of the raw polyisoisocyanate from the viewpoint of emulsifying properties and coating film properties. It is preferably modified at a rate, more preferably at a rate of 0.5 to 20 equivalents, and even more preferably at a rate of 1 to 10 equivalents.

  In addition, the isocyanate group content of the polyisocyanate composition of the present embodiment is 10 to 25% by weight from the viewpoints of emulsifiability and coating film properties in a state where the nonvolatile content is substantially 100% by weight. Preferably, it is 15 to 24% by weight. The method for controlling the isocyanate group content within the above range is not particularly limited, and examples thereof include a method of adjusting the blending ratio of the sulfonic acid amine salt and the polyisocyanate.

  In addition, the number average molecular weight of the polyisocyanate containing the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition of the present embodiment is 450 to 2,000 from the viewpoint of coating film properties and isocyanate group retention. It is preferably from 500 to 1800, more preferably from 550 to 1550. The method for controlling the number average molecular weight within the above range is not particularly limited, and examples thereof include a method of adjusting the blending ratio of the sulfonic acid amine salt and the polyisocyanate.

  In addition, the average number of functional groups of the polyisocyanate containing the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition of the present embodiment is from 1.8 to 6. Is preferably 2, is more preferably 2.0 to 5.6, and further preferably is 2.5 to 4.6. The method for controlling the average number of functional groups within the above range is not particularly limited, and examples thereof include a method of adjusting the blending ratio of the sulfonic acid amine salt and the polyisocyanate.

  In the present embodiment, the isocyanate group content, nonvolatile content, number average molecular weight, and average number of functional groups can be measured by the methods described in Examples described later.

<Polyisocyanate composition>
The polyisocyanate composition of this embodiment is a composition containing the above-mentioned modified polyisocyanate and unreacted polyisocyanate. The polyisocyanate composition of this embodiment may contain other components in addition to the above-described modified polyisocyanate and unreacted polyisocyanate. Although it does not specifically limit as another component, For example, a solvent, antioxidant, a light stabilizer, a polymerization inhibitor, and surfactant are mentioned.

  In the polyisocyanate composition of the present embodiment, the content of the solvent is preferably 0 to 90% by weight, more preferably 0 to 50% by weight, and further preferably 0 to 30% by weight. . In the polyisocyanate composition of the present embodiment, the content of the antioxidant, the light stabilizer, the polymerization inhibitor, and the surfactant is preferably 0 to 10% by weight, and 0 to 5% by weight. More preferably, it is more preferably 0 to 2% by weight.

≪Method for producing polyisocyanate composition≫
It is preferable that the manufacturing method of the polyisocyanate composition of this embodiment includes the process of mixing and reacting the sulfonic-acid amine salt which has the hydroxyl group mentioned above, and polyisocyanate, for example.

  In the reaction step, the mixing ratio of the above-mentioned sulfonic acid amine salt having a hydroxyl group and polyisocyanate is an isocyanate group / hydroxyl group equivalent ratio in the range of 2 to 400 from the viewpoint of emulsifying properties and coating film properties. Preferably, it is preferably in the range of 5 to 200, more preferably in the range of 10 to 100.

  In the reaction step, the reaction temperature and reaction time are appropriately determined according to the progress of the reaction, but the reaction temperature is preferably 0 ° C. to 150 ° C., and the reaction time is 0.5 to 48 hours. preferable.

  In the reaction step, a known ordinary catalyst may be used in some cases. The catalyst is not particularly limited, but, for example, tin octoate, tin 2-ethyl-1-hexanoate, tin ethylcaproate, tin laurate, tin palmitate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin Organotin compounds such as dimalate, dibutyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate; zinc chloride, zinc octoate, zinc 2-ethyl-1-hexanoate, zinc 2-ethylcaproate, zinc stearate, naphthenic acid Organic zinc compounds such as zinc and zinc acetylacetonate; organic titanium compounds; organic zirconium compounds; tertiary amines such as triethylamine, tributylamine, N, N-diisopropylethylamine, N, N-dimethylethanolamine S; triethylenediamine, tetramethylethylenediamine, 1,4-diazabicyclo [2.2.2] diamines such as octane. These may be used alone or in combination.

  In the method for producing the polyisocyanate composition of the present embodiment, a solvent may be used or may not be used. The solvent used in the method for producing the polyisocyanate composition of the present embodiment may be a hydrophilic solvent or a hydrophobic solvent.

  Although it does not specifically limit as a hydrophobic solvent, For example, ester, such as mineral spirit, solvent naphtha, LAWS (Low Aromatic White Spirit), HAWS (High Aromatic White Spirit), toluene, xylene, cyclohexane, ethyl acetate, butyl acetate, etc. And ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  Examples of the hydrophilic solvent include, but are not limited to, alcohols such as methanol, ethanol, propanol, isopropanol, and 2-ethylhexanol; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; 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, propylene glycol monomethyl ether acetate, dipropyle Esters of ether alcohols such as glycol monomethyl ether acetate. These can be used alone or in combination.

  Further, in the method for producing the polyisocyanate composition of the present embodiment, in addition to the sulfonic acid amine salt having a hydroxyl group and the polyisocyanate, a group further comprising an antioxidant, a light stabilizer, a polymerization inhibitor and a surfactant. At least one selected from the above can be added.

≪Coating composition≫
The coating composition of this embodiment contains the above-mentioned polyisocyanate composition.

  Although the coating composition of this embodiment can be used as an organic solvent-based coating composition, an aqueous coating composition in which resins as film-forming components are dissolved or dispersed in a medium mainly containing water. It is preferable to use as. In particular, architectural coatings, automotive coatings, automotive repair coatings, plastic coatings, adhesives, adhesives, building materials, household water-based coatings, other coating agents, sealing agents, inks, casting materials, elastomers, foams, plastic raw materials It can also be used for fiber treatment agents.

  The main resin is not particularly limited. For example, acrylic resins, polyester resins, polyether resins, epoxy resins, fluororesins, polyurethane resins, polyvinylidene chloride copolymers, polyvinyl chloride copolymers. Examples include polymers, vinyl acetate copolymers, acrylonitrile butadiene copolymers, polybutadiene copolymers, styrene butadiene copolymers, and the like.

  Although it does not specifically limit as acrylic resin, For example, (meth) acrylic acid methyl, (meth) ethyl acrylate, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid- (Meth) acrylic acid esters such as 2-ethylhexyl and lauryl (meth) acrylate; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2- (Meth) acrylic acid esters having active hydrogen such as hydroxybutyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl; acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc. Unsaturated carboxylic acids: acrylamide, N-methylolacrylamide, diacetone acrylic A single amide selected from glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, p-styrene sulfonic acid, allyl sulfosuccinic acid, etc. Or the acrylic resin obtained by polymerizing a mixture is mentioned.

  The polymerization method is generally emulsion polymerization, but can also be produced by suspension polymerization, dispersion polymerization, or solution polymerization. In emulsion polymerization, it can also be polymerized stepwise.

  Polyester resins are not particularly limited. For example, carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. Alone or in a mixture selected from the group of, for example, 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, Diols such as 2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, such as glycerin, Triols such as trimethylolpropane, for example polyester resins obtained by condensation reaction with polyhydric alcohols alone or in mixtures selected from the group of tetraols such as diglycerol, dimethylolpropane, pentaerythritol, and Obtained by ring-opening polymerization of ε-caprolactone to the hydroxyl group of molecular weight polyol Such as polycaprolactones.

  Polyether resins include, for example, polyhydric hydroxy compounds, alone or in mixture, using, for example, hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alcoholates and alkylamines, ethylene oxide and propylene oxide. , Polyether polyols obtained by adding a single or mixture of alkylene oxides such as butylene oxide, cyclohexene oxide, styrene oxide, and polyether polyols obtained by reacting an alkylene oxide with a polyfunctional compound such as ethylenediamine, Polyether polyols obtained by ring-opening polymerization of cyclic ethers such as tetrahydrofuran, and so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium. Le, and the like are included.

  These resins are preferably emulsified, dispersed or dissolved in water. Therefore, the carboxyl group, the sulfone group, etc. contained in the resins can be neutralized.

  The neutralizing agent for neutralizing the carboxyl group, the sulfone group and the like is not particularly limited. For example, ammonia, a water-soluble amino compound such as monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, One or more selected from dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, 2-ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, etc. Can be used. Preferably, tertiary amines such as triethylamine and dimethylethanolamine are used.

  Preferred resins are acrylic resins and polyester resins.

  If necessary, a resin such as a melamine curing agent, a urethane dispersion, or a urethane acrylic emulsion can be used in combination. In addition, inorganic pigments, organic pigments, extender pigments, silane coupling agents, titanium coupling agents, organic phosphates, organic phosphites, thickeners, leveling agents, thixotropic agents generally added to paints, Antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, anti-skinning agent, dispersant, wetting agent, filler, plasticizer, lubricant, reducing agent, preservative, antifungal agent, deodorant, You may combine with yellowing prevention agent, a ultraviolet absorber, an antistatic agent or a charge control agent, an anti-settling agent, etc. In order to improve the dispersibility in the paint, a surfactant may be further added, and in order to improve the storage stability of the paint, an antioxidant, a light stabilizer, and a polymerization inhibitor are further added. May be.

≪Coating substrate≫
In this embodiment, the coating substrate is a coating substrate coated with the above-described coating composition.

  The coating substrate of this embodiment includes any desired substrate, such as metal, wood, glass, stone, ceramic material, concrete, hard and flexible plastics, textiles, leather products and paper, optionally with a coating Ordinary primers may be provided before.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

  First, the measurement method will be described.

[Measuring method]
(Measurement of isocyanate group content)
The measurement of the isocyanate group content was carried out according to the method described in JIS K7301-1995 (Test method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer).

A specific method for measuring the isocyanate group content will be described below.
(1) 1 g of a sample was collected in a 200 mL Erlenmeyer flask, and 20 mL of toluene was added to the flask to dissolve the sample.
(2) Then, 20 mL of a 2.0 N di-n-butylamine / toluene solution was added to the flask and allowed to stand 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 with 1 mol / L hydrochloric acid to determine the sample titer.
(5) Even when the sample was not added, the measurement was performed in the same manner as in the above (1) to (3), and the blank titer was determined.

From the sample titration and blank titration determined above, the isocyanate group content was calculated by the following calculation method.
Isocyanate group content (% by weight) = (blank titer-sample titer) × 42 / [sample weight (g) × 1,000] × 100%.

(Measurement of non-volatile content)
The weight of the aluminum cup was precisely weighed, about 1 g of a sample was put, and the weight of the cup before heat drying was precisely weighed. The cup containing the sample was heated in a dryer at 105 ° C. for 3 hours. After the heated cup was cooled to room temperature, the weight of the cup was weighed again. The weight percent of the dry residue in the sample was defined as the nonvolatile content.

The calculation method of the nonvolatile content was as follows.
Nonvolatile content (% by weight) = (cup weight after heat drying−aluminum cup weight) / (cup weight before heat drying−aluminum cup weight) × 100%.

(Measurement of number average molecular weight)
The polystyrene-based number average molecular weight was measured by gel permeation chromatograph (GPC) using the following apparatus and conditions.

Device: HLC-8120GPC (trade name) manufactured by Tosoh Corporation
Column: Tosoh Co., Ltd. TSKgelSuperH1000 (trade name) x 1, TSKgel Super H2000 (trade name) x 1, TSKgel SuperH3000 (trade name) x 1,
Carrier: Tetrahydrofuran Detection method: Differential refractometer (Average number of functional groups)
The average number of functional groups is the number of isocyanate functional groups statistically possessed by one molecule of polyisocyanate, and was calculated from the number average molecular weight of the polyisocyanate and the isocyanate group content as follows.
Average number of functional groups = number average molecular weight of polyisocyanate × isocyanate group content (% by weight) / 42
[Production Example 1 (Production of sulfonic acid amine salt)]
10 parts by weight of 1-propanol was added to 20 parts by weight of a 70% by weight 2-hydroxyethanesulfonic acid aqueous solution and stirred to obtain a solution. Further, N-ethylmorpholine was weighed out so that the equivalent ratio was 1, and a solution diluted with 1 part by weight of 1-propanol was added dropwise to the stirring solution. Stirring was stopped 1 hour after the start of dropping, and dehydration and solvent removal were carried out using an evaporator to obtain N-ethylmorpholine salt of 2-hydroxyethanesulfonic acid having a solid content of 99.8% by weight.

[Production Example 2 (Production of sulfonic acid amine salt)]
A 2-hydroxyethanesulfonic acid N-methylpyrrolidine salt having a solid content of 99.9% by weight was obtained in the same manner as in Production Example 1 except that N-methylpyrrolidine was used instead of N-ethylmorpholine.

[Production Example 3 (Production of sulfonic acid amine salt)]
A 2-hydroxyethanesulfonic acid N-methylpiperidine salt having a solid content of 99.8% by weight was obtained in the same manner as in Production Example 1 except that N-methylpiperidine was used instead of N-ethylmorpholine.

[Production Example 4 (Production of sulfonic acid amine salt)]
A 2-hydroxyethanesulfonic acid N-methylmorpholine salt having a solid content of 99.8% by weight was obtained in the same manner as in Production Example 1 except that N-methylmorpholine was used instead of N-ethylmorpholine.

[Production Example 5 (Production of sulfonic acid amine salt)]
A 2-hydroxyethanesulfonic acid N, N-dimethylcyclohexylamine salt having a solid content of 99.7% by weight was obtained in the same manner as in Production Example 1 except that N, N-dimethylcyclohexylamine was used instead of N-ethylmorpholine. It was.

[Production Example 6 (Production of sulfonic acid amine salt)]
10 parts by weight of 1-propanol was added to 20 parts by weight of an 80% by weight aqueous solution of 3-hydroxypropanesulfonic acid and stirred to obtain a solution. Further, N, N-dimethylbenzylamine was weighed so that the equivalent ratio was 1, and a solution diluted with 1 part by weight of 1-propanol was added dropwise to the stirring solution. Stirring was stopped 1 hour after the start of dropping, and dehydration and solvent removal were carried out with an evaporator to obtain N, N-dimethylbenzylamine salt of 3-hydroxypropanesulfonic acid having a solid content of 99.8% by weight.

[Production Example 7 (Production of sulfonic acid amine salt)]
10 parts by weight of 1-propanol was added to 20 parts by weight of an aqueous solution of 85% by weight of 4-hydroxybenzenesulfonic acid and stirred to obtain a solution. Further, N, N-dicyclohexylmethylamine was weighed so that the equivalent ratio was 1, and a solution diluted with 1 part by weight of 1-propanol was dropped into the stirring solution. After 1 hour from the start of dropping, the stirring was stopped, and after dehydration and solvent removal using an evaporator, acetone was added to obtain N, N-dicyclohexylmethylamine salt of 4-hydroxybenzenesulfonic acid having a solid content of 50% by weight.

[Production Example 8 (Production of sulfonic acid amine salt)]
A 4-hydroxybenzenesulfonic acid N-isobutylmorpholine salt having a solid content of 50% by weight was obtained in the same manner as in Production Example 7, except that N-isobutylmorpholine was used instead of N, N-dicyclohexylmethylamine.

[Production Example 9 (Production of sulfonic acid amine salt)]
A 2-hydroxyethanesulfonic acid N-methylpyrrolidone salt having a solid content of 99.8% by weight was obtained in the same manner as in Production Example 1 except that N-methylpyrrolidone was used instead of N-ethylmorpholine.

[Production Example 10 (Production of sulfonic acid amine salt)]
A 2-hydroxyethanesulfonic acid triethylamine salt having a solid content of 99.8% by weight was obtained in the same manner as in Production Example 1 except that triethylamine was used instead of N-ethylmorpholine.

[Example 1]
Isocyanate prepolymer having an isocyanurate structure (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate TPA-100 (isocyanate group content: 23 wt%, nonvolatile content: 100 wt%)”) in Production Example 1 4.0 parts by weight of the obtained 2-hydroxyethanesulfonic acid N-ethylmorpholine salt (isocyanate group / hydroxyl group equivalent ratio: 33.3) and 20 parts by weight of acetone were added, and the mixture was refluxed at 70 ° C. under nitrogen. The reaction was carried out with stirring for 10 hours. Thereafter, the reflux was removed, and the reaction was continued by stirring at 100 ° C. for 1 hour. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 98.2% by weight and an isocyanate group content of 20.9% by weight. Moreover, the polyisocyanate in the obtained composition was number average molecular weight: 630 and average functional group number: 3.1.

[Example 2]
Isocyanate prepolymer having an isocyanurate structure (trade name “Duranate TPA-100 (isocyanate group content: 23 wt%, nonvolatile content: 100 wt%)” manufactured by Asahi Kasei Chemicals Corporation) with 2-ethyl- 10 parts by weight of 1-hexanol and 2.6 parts by weight of 2-hydroxyethanesulfonic acid N-methylpyrrolidine salt prepared in Production Example 2 (isocyanate group / hydroxyl group equivalent ratio: 33.3) were added under nitrogen. The reaction was carried out by stirring at 120 ° C. for 4 hours under reflux. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 100% by weight and an isocyanate group content of 16.3% by weight.

[Example 3]
Isocyanate prepolymer having an isocyanurate structure (product name “Duranate TPA-100 (isocyanate group content: 23 wt%, nonvolatile content: 100 wt%)” manufactured by Asahi Kasei Chemicals Corporation), 5 parts by weight of butanediol, 3.7 parts by weight of 2-hydroxyethanesulfonic acid N-methylpiperidine salt prepared in Production Example 3 (equivalent ratio of isocyanate group / hydroxyl group: 25), 20 parts by weight of acetone, and 0.2% of dibutyltin dilaurate. 005 parts by weight was added, and the reaction was carried out by stirring at 70 ° C. for 10 hours under reflux under nitrogen. Thereafter, the reflux was removed, and the reaction was continued by stirring at 100 ° C. for 1 hour. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The resulting composition had a nonvolatile content of 99.0% by weight and an isocyanate group content of 15.4% by weight. Moreover, the polyisocyanate in the obtained composition was number average molecular weight: 950 and average functional group number: 3.5.

[Example 4]
An isocyanate prepolymer having an isocyanurate structure (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate TLA-100 (isocyanate group content: 23.2 wt%, nonvolatile content: 100 wt%)”) 3.8 parts by weight of 2-hydroxyethanesulfonic acid N-methylmorpholine salt (isocyanate group / hydroxyl group equivalent ratio: 33.3), 20 parts by weight of acetone and 0.005 part by weight of dibutyltin dilaurate were added. The reaction was stirred for 10 hours at 70 ° C. under reflux under nitrogen. Thereafter, the reflux was removed, and the reaction was continued by stirring at 100 ° C. for 1 hour. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 98.8% by weight and an isocyanate group content of 21.0% by weight. Moreover, the polyisocyanate in the obtained composition was number average molecular weight: 550 and average functional group number: 2.8.

[Example 5]
An isocyanate prepolymer having an isocyanurate structure (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate TKA-100 (isocyanate group content: 21.7 wt%, nonvolatile content: 100 wt%)”) 5 parts by weight of 2-hydroxyethanesulfonic acid N, N-dimethylcyclohexylamine salt prepared in 5 (isocyanate group / hydroxyl group equivalent ratio: 25) was added and stirred at 120 ° C. for 4 hours under nitrogen. Went. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 100% by weight and an isocyanate group content of 19.6% by weight. Moreover, the polyisocyanate in the obtained composition was number average molecular weight: 680 and average functional group number: 3.2.

[Example 6]
An isocyanate prepolymer having a biuret structure (product name “Duranate 24A-100 (isocyanate group content: 23.5% by weight, nonvolatile content: 100% by weight)” manufactured by Asahi Kasei Chemicals Corporation) was prepared in Production Example 6 7.5 parts by weight of 3-hydroxypropanesulfonic acid N, N-dimethylbenzylamine salt (isocyanate group / hydroxyl group equivalent ratio: 20) prepared in Step 1 was added and stirred at 90 ° C. for 8 hours under nitrogen. went. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 100% by weight and an isocyanate group content of 20.7% by weight.

[Example 7]
70 parts by weight of an HDI prepolymer having an isocyanurate structure (product name “Duranate TPA-100 (isocyanate group content: 23 wt%, nonvolatile content: 100 wt%)” manufactured by Asahi Kasei Chemicals Corporation) isocyanurate structure 30 parts by weight of an IPDI prepolymer (made by Evonik Industries, trade name “VESTANAT T1890 (isocyanate group content: 17% by weight, nonvolatile content: 100% by weight)) and 30 parts by weight of propylene glycol monomethyl ether acetate Then, the solution was obtained by dissolving the pellet-shaped T1890 by heating to 120 ° C. Thereafter, the resulting solution was added to the 4-hydroxybenzenesulfonic acid N, N-dicyclohexylmethylamine salt solution prepared in Production Example 7. 15 parts by weight (isocyanate group / Hydroxyl equivalent ratio: 25) was added, and the reaction was carried out with stirring under nitrogen and reflux for 4 hours at 120 ° C. After completion of the reaction, a composition containing modified polyisocyanate was obtained. The non-volatile content was 79% by weight, and the isocyanate group content was 19.0% by weight.The polyisocyanate in the obtained composition had a number average molecular weight of 630 and an average number of functional groups of 2.9. there were.

[Example 8]
In Production Example 8 to 100 parts by weight of an isocyanate prepolymer having an isocyanurate structure (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate TPA-100 (isocyanate group content: 23 wt%, nonvolatile content: 100 wt%)”) 10.4 parts by weight of the produced 4-hydroxybenzenesulfonic acid N-isobutylmorpholine salt solution (isocyanate group / hydroxyl group equivalent ratio: 33.3), 20 parts by weight of acetone and 0.005 part by weight of dibutyltin dilaurate were added, The reaction was carried out by stirring at 70 ° C. for 10 hours under nitrogen and reflux. Thereafter, the reflux was removed, and the reaction was continued by stirring at 100 ° C. for 1 hour. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 99.2% by weight and an isocyanate group content of 21.0% by weight.

[Comparative Example 1]
An isocyanate prepolymer having an isocyanurate structure (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate TPA-100 (isocyanate group content 23 wt%, nonvolatile content 100 wt%)”) was produced in Production Example 9 in 100 parts by weight. 4.9 parts by weight of 2-hydroxyethanesulfonic acid N-methylpyrrolidone salt (isocyanate group / hydroxyl group equivalent ratio: 25) was added, and the mixture was stirred at 120 ° C. for 4 hours under nitrogen. When the stirring was stopped and observed, countless oil droplets were floating. Stirring was further continued for 2 hours, but no significant change was observed and a composition containing modified polyisocyanate was not obtained.

[Comparative Example 2]
Isocyanate prepolymer having an isocyanurate structure (product name “Duranate TPA-100 (isocyanate group content: 23 wt%, nonvolatile content: 100 wt%)” manufactured by Asahi Kasei Chemicals Corporation) in Production Example 10 The prepared 2-hydroxyethanesulfonic acid triethylamine salt (5.0 parts by weight (isocyanate group / hydroxyl equivalent ratio: 25)), acetone (20 parts by weight) and dibutyltin dilaurate (0.005 parts by weight) were added. The reaction was carried out with stirring at 70 ° C. for 10 hours. Thereafter, the reflux was removed, and the reaction was continued by stirring at 100 ° C. for 1 hour. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 98.5% by weight and an isocyanate group content of 20.5% by weight. Moreover, the polyisocyanate in the obtained composition was number average molecular weight: 600, average functional group number: 2.9.

[Comparative Example 3]
Isocyanurate structure-containing isocyanate prepolymer (manufactured by Asahi Kasei Chemicals Corporation, trade name “Duranate TPA-100 (isocyanate group content: 23 wt%, average number of functional groups: 3.2, nonvolatile content: 100 wt%)”) 100 4.8 parts by weight of 3-cyclohexylaminopropanesulfonic acid and 2.8 parts by weight of N, N-dimethylcyclohexylamine (equivalent ratio of isocyanate group / hydroxyl group: 25) are added to parts by weight, and the temperature is 120 ° C. under nitrogen. The reaction was carried out with stirring for 4 hours. After completion of the reaction, a composition containing a modified polyisocyanate was obtained. The composition obtained had a nonvolatile content of 100% by weight and an isocyanate group content of 20.5% by weight. Moreover, the polyisocyanate in the obtained composition was number average molecular weight: 600, average functional group number: 2.9.

≪Various evaluation≫
The compositions containing the modified polyisocyanates obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Table 1.

[Evaluation 1 (Appearance evaluation of composition containing modified polyisocyanate)]
The presence or absence of foreign matter and turbidity of the obtained modified polyisocyanate was visually evaluated. The judging method was as follows.

○: Transparent uniform liquid ×: Foreign matter or turbidity [Evaluation 2 (Emulsification ability evaluation of composition containing modified polyisocyanate)]
(1) The weight of a 100 mL flask and Yoshino paper was measured.
(2) A composition containing the modified polyisocyanate was collected in a 100 mL flask so as to be 16 g in terms of solid content, 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 Yoshino paper weighed in (1).
(4) The filtration residue remaining on Yoshino paper and the residue remaining on the 100 mL flask were combined and heated in a dryer at 105 ° C. for 1 hour to determine the weight (g).
(5) The ratio of the composition containing the modified polyisocyanate dispersed in water was determined by the following calculation method.
Percentage dispersed in water (% by weight) = 100%-(total weight of the 100 mL flask containing the residue determined in (4) and Yoshino paper (g) -total of 100 mL flask and Yoshino paper measured by (1) Weight (g)) / (weight of composition containing modified polyisocyanate collected in (2) (g) × nonvolatile content (% by weight)) × 100%
The judging method was as follows.

○: 80% by weight or more Δ: 60% by weight or more and less than 80% by weight ×: less than 60% by weight [Production Example 11 (Production of Acrylic Polyol Aqueous Dispersion)]
As the reactor, a four-necked separable flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was used. The reactor was filled with a nitrogen atmosphere, charged with 300 parts by weight of ethylene glycol monobutyl ether, and the reactor temperature was maintained at 80 ° C. with stirring. In the reactor, 146.3 parts by weight of methyl methacrylate, 105 parts by weight of styrene, 257.6 parts by weight of acrylate-n-butyl, 14 parts by weight of methacrylic acid, 177.1 parts by weight of 2-hydroxyethyl methacrylate Over a period of 4.5 hours, uniformly mixing 0.7 part by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator and 0.3 part by weight of n-dodecyl mercaptan as a chain transfer agent It was added continuously at a constant rate. Thereafter, the reactor internal temperature was maintained at 80 ° C. for 2 hours. Thereafter, the mixture in the reactor was cooled, 11.6 parts by weight of a 25% by weight aqueous ammonia solution was added, and the mixture was stirred for 15 minutes. Further, 1300 parts by weight of ion-exchanged water was added to the mixture in the reactor while stirring to obtain an aqueous dispersion. The resulting aqueous dispersion was concentrated using a rotary evaporator until the solid content was about 45% by weight. Thereafter, the resulting concentrate was adjusted to pH 8.0 with a 25 wt% ammonia aqueous solution to obtain an aqueous dispersion of an acrylic polyol. The obtained acrylic polyol aqueous dispersion has an average particle diameter of 90 nm of the particles in the aqueous dispersion, and the hydroxyl group concentration of the polyol resin is 3.3% by weight calculated from the charged raw materials. The number average molecular weight of the polyol resin was 9,600.

[Examples 9 to 16, Comparative Examples 4 to 6]
Using the compositions containing the modified polyisocyanates obtained in Examples 1 to 8 and Comparative Examples 1 to 3, coating compositions were prepared as follows.

[Preparation of coating composition]
40 g of the polyol aqueous dispersion prepared in Production Example 11 was weighed into a container, and the molar ratio of the isocyanate group in the composition containing the modified polyisocyanate to the hydroxyl group in the polyol aqueous dispersion was NCO / OH = 1.25. The composition containing the modified polyisocyanate was added to obtain a mixture. Furthermore, deionized water was added to the mixture so that the solid content of the coating composition was 42% by weight, and the mixture was stirred at 600 rpm for 10 minutes using a propeller blade to prepare a coating composition.

≪Various evaluation≫
The following evaluation was performed using the produced coating composition.

[Evaluation 1 (Retention rate of isocyanate group)]
The concentration change of the isocyanate group in the coating composition was measured by infrared absorption spectrum measurement using FT / IR-4200 type A (trade name) manufactured by JASCO Corporation (detector: TGS, number of integrations: 16 times, decomposition: 4 cm ^{− In 1} ), it was calculated from the intensity ratio of the isocyanate absorption peak (near wave number 2271 cm ⁻¹ ) to the isocyanurate absorption peak (near wave number 1686 cm ⁻¹ ). Immediately after preparation of the coating composition, 0 hour is set, and the isocyanate absorption peak intensity at that time / isocyanurate absorption peak intensity = X0, the peak intensity ratio after n hours = Xn is obtained, and the isocyanate group retention ratio = Xn / X0. Was calculated, and the time that could hold 80% or more was evaluated. The judging method was as follows.
○: 3 hours or more ×: less than 3 hours [Evaluation 2 (Coating Film Evaluation)]
A coating film was prepared using the above coating composition, and the appearance and solvent resistance were evaluated.

(Appearance evaluation of coating film)
A coating film having a thickness of 40 μm was applied on a glass plate using the above coating composition, and dried for 7 days in an atmosphere of 23 ° C./50% RH. The obtained coating film was visually evaluated. The judging method was as follows.

○: Transparent or no cretering △: Slightly cloudy or slightly cretered ×: Many cloudy or cretered (Evaluation of solvent resistance of coating film)
A coating film having a thickness of 40 μm was applied on a glass plate using the above coating composition, and dried for 7 days in an atmosphere of 23 ° C./50% RH. A cotton ball having a diameter of 10 mm containing 1 g of xylene was placed on the obtained coating film for 10 minutes, and the state of the coating film after removing xylene remaining on the surface was observed. The judging method was as follows.

○: Transparent, no depression Δ: Some cloudiness or some dent ×: Some cloudiness or dent Evaluation results are shown in Table 1.

Claims (5)

Including a modified polyisocyanate obtained by reaction of a sulfonic acid amine salt having a hydroxyl group with a polyisocyanate,
The sulfonic acid amine salt having a hydroxyl group is a sulfonic acid having a hydroxyl group represented by the following general formula (1): N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dibenzylmethyl Amine, tribenzylamine, N, N-dimethyl-4-methylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dicyclohexylmethylamine, N, N-dicyclohexylethylamine, tri Cyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N- Ethylmorpholine, N-propyl A polyisocyanate composition which is a salt with at least one amine compound selected from morpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutylmorpholine and quinuclidine .

(In the formula (1), R ¹ is a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and the hydrocarbon group or aryl group includes an ester bond, a hydroxyl group, a carbonyl group, a tertiary amino group, a nitrogen atom. And may include at least one selected from the group consisting of a 5-membered or 6-membered ring containing 2 and a 5-membered or 6-membered ring containing nitrogen and oxygen atoms.)   The polyisocyanate composition according to claim 1, wherein the polyisocyanate is at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates. A step of reacting a sulfonic acid amine salt having a hydroxyl group with a polyisocyanate in an isocyanate group / hydroxyl group equivalent ratio of 2 to 400,
The sulfonic acid amine salt having a hydroxyl group is a sulfonic acid having a hydroxyl group represented by the following general formula (1): N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dibenzylmethyl Amine, tribenzylamine, N, N-dimethyl-4-methylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dicyclohexylmethylamine, N, N-dicyclohexylethylamine, tri Cyclohexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-butylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-methylmorpholine, N- Ethylmorpholine, N-propyl Polyisocyanate composition comprising a modified polyisocyanate which is a salt with at least one amine compound selected from morpholine, N-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-isobutylmorpholine and quinuclidine Manufacturing method.

(In the formula (1), R ¹ is a hydrocarbon group or aryl group having 1 to 10 carbon atoms, and the hydrocarbon group or aryl group includes an ester bond, a hydroxyl group, a carbonyl group, a tertiary amino group, a nitrogen atom. And may include at least one selected from the group consisting of a 5-membered or 6-membered ring containing 2 and a 5-membered or 6-membered ring containing nitrogen and oxygen atoms.)   A coating composition comprising the polyisocyanate composition according to claim 1. A coated substrate coated with the coating composition of claim 4.