JP7209468B2 - Self-emulsifying polyisocyanate composition - Google Patents

Description

The present invention relates to a self-emulsifying polyisocyanate composition, a coating composition obtained therefrom and a coating film thereof.

Conventionally, polyisocyanate is known as a curable composition used as adhesives, paints, etc., but hydrophobic polyisocyanate having an isocyanurate structure is modified with a nonionic hydrophilic group-containing monofunctional alcohol compound, and is dissolved in water. Emulsified and dispersed for use. (See Patent Document 1, for example). In the case of such compositions, there has been the problem that the polyisocyanate must be uniformly incorporated into the aqueous medium by applying a strong shearing force such as by high-speed stirring. Moreover, the nonionic hydrophilic group-containing monofunctional alcohol compound has a polyether structure, which has the problem of lowering the hardness of the coating film. Therefore, by modifying the polyisocyanate with an anionic hydrophilic group-containing amine instead of a nonionic hydrophilic group-containing monofunctional alcohol, a self-emulsifying polyisocyanate that is easy to disperse in water was found (for example, Patent Document 2 reference). However, the resulting paint had insufficient water dispersion stability.

JP-A-61-291613 Japanese Patent Publication No. 2003-533566

The present invention has been made based on the above circumstances, and its object is to provide a self-emulsifying polyisocyanate composition capable of obtaining a coating film having excellent water dispersion stability, glossiness, and hardness. to provide.

As a result of intensive studies by the present inventors, the above problems have been solved by a self-emulsifying polyisocyanate composition which is a product obtained from a specific anionic compound (a), an organic polyisocyanate (b) and an amine compound (c). We have found a solution to this problem and arrived at the present invention.

That is, the present invention includes embodiments shown in [1] to [6] below.

[1] A hydrophilizing agent for producing a self-emulsifying polyisocyanate composition, comprising an anionic compound (a) represented by the following formula 1.

(wherein X represents a sulfo group or a hydroxysulfonyloxy group, R ¹ represents a linear or branched alkylene group, and R ² represents a linear or branched alkyl group. R ¹ and R The total number of carbon atoms contained in ² is 6 or more and less than 14, and one or more carbon atoms in the groups of R ¹ and R ² may be substituted with oxygen atoms.).

[2] A self-emulsifying polyisocyanate composition obtained from an anionic compound (a), an organic polyisocyanate (b) and an amine compound (c), wherein the anionic compound (a) is represented by the following formula 1 A self-emulsifying polyisocyanate composition characterized by:

(wherein X represents a sulfo group or a hydroxysulfonyloxy group, R ¹ represents a linear or branched alkylene group, and R ² represents a linear or branched alkyl group. R ¹ and R The total number of carbon atoms contained in ² is 6 or more and less than 14, and one or more carbon atoms in the groups of R ¹ and R ² may be substituted with oxygen atoms.).

[3] The self-emulsifying polyisocyanate composition according to [2] above, wherein the mass fraction of isocyanate groups in the organic polyisocyanate (b) is 10 to 35%.

[4] The self-emulsifying polyisocyanate composition according to [2] or [3] above, wherein the organic polyisocyanate (b) contains an isocyanurate-modified polyisocyanate of hexamethylene diisocyanate.

[5] A coating composition obtained from the self-emulsifying polyisocyanate composition according to any one of [2] to [4] above and a main agent.

[6] A coating film obtained from the coating composition described in [5] above.

ADVANTAGE OF THE INVENTION According to this invention, the self-emulsifying polyisocyanate composition which can form the coating film excellent in water-dispersion stability, glossiness, and hardness can be obtained.

The present invention will be described in detail below.

The self-emulsifying polyisocyanate composition of the present invention is obtained from an anionic compound (a), an organic polyisocyanate (b) and an amine compound (c).

<Anionic compound (a)>
In the present invention, the anionic compound (a) is a hydrophilizing agent for producing a self-emulsifying polyisocyanate composition represented by the following formula 1, which can impart hydrophilicity to the organic polyisocyanate (b).

(wherein X represents a sulfo group or a hydroxysulfonyloxy group, R ¹ represents a linear or branched alkylene group, and R ² represents a linear or branched alkyl group. R ¹ and R The total number of carbon atoms contained in ² is 6 or more and less than 14, and one or more carbon atoms in the groups of R ¹ and R ² may be substituted with oxygen atoms.).

Linear or branched alkylene groups represented by R ¹ include, for example, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group and 2,2-dimethyltetramethylene group. etc. can be exemplified. One or more carbon atoms in the alkylene group may be substituted with oxygen atoms, for example, 2-oxatrimethylene group, 2-oxatetramethylene group, 3-oxatrimethylene group, 2-oxa Pentamethylene group, 3-oxapentamethylene group, 3,6-dioxaoctamethylene group and the like can be exemplified.

Linear or branched alkyl groups represented by R ² include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Examples include a xyl group, a heptyl group, an octyl group and the like, and one or more carbon atoms in these alkyl groups may be substituted with oxygen atoms, for example, a 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-propoxypropyl group, 4-methoxybutyl group, 4-ethoxybutyl group, 4-propoxybutyl group, 2- (2-Methoxyethoxy)ethyl group, 2-(2-ethoxyethoxy)ethyl group and the like can be exemplified.

Examples of the anionic compound (a) to which R ¹ and R ² are applied include 3-(propylamino)propanesulfonic acid, 3-(butylamino)propanesulfonic acid, 3-[(3-methoxypropyl)amino ] Propanesulfonic acid, 3-[(3-ethoxypropyl)amino]propanesulfonic acid, 3-(hexylamino)propanesulfonic acid, 3-(octylamino)propanesulfonic acid, 3-(tert-butylamino)propanesulfone acid, 4-(propylamino)butanesulfonic acid, 4-(butylamino)butanesulfonic acid, 4-[(3-methoxypropyl)amino]butanesulfonic acid, 4-[(3-ethoxypropyl)amino]butanesulfone acid, 4-(hexylamino)butanesulfonic acid, 4-(octylamino)butanesulfonic acid, 4-(tert-butylamino)butanesulfonic acid, 5-(propylamino)pentanesulfonic acid, 5-(butylamino) Pentanesulfonic acid, 5-[(3-methoxypropyl)amino]pentanesulfonic acid, 5-[(3-ethoxypropyl)amino]pentanesulfonic acid, 5-(hexylamino)pentanesulfonic acid, 5-(octylamino) Pentanesulfonic acid, 5-(tert-butylamino)pentanesulfonic acid, 6-(propylamino)hexanesulfonic acid, 6-(butylamino)hexanesulfonic acid, 6-[(3-methoxypropyl)amino]hexanesulfonic acid , 6-[(3-ethoxypropyl)amino]hexanesulfonic acid, 6-(hexylamino)hexanesulfonic acid, 8-[(3-methoxypropyl)amino]octanesulfonic acid, 2-[2-(tert-butyl Amino)ethoxy]ethanesulfonic acid, 2-[2-(propylamino)ethoxy]ethanesulfonic acid, 2-[2-(butylamino)ethoxy]ethanesulfonic acid, 2-[2-[(3-methoxypropyl) amino]ethoxy]ethanesulfonic acid, 2-[2-[(3-ethoxypropyl)amino]ethoxy]ethanesulfonic acid, 2-[2-(hexylamino)ethoxy]ethanesulfonic acid, 2-[2-(octyl amino)ethoxy]ethanesulfonic acid, sulfate = 3-(propylamino)propyl, sulfate = 3-[(3-methoxypropyl)amino]propyl sulfate, sulfate = 3-[(3-ethoxypropyl)amino]propyl, sulfate = 3-(hexylamino)propyl, sulfate = 3-(tert-butylamino ) propyl, sulfate = 4-(propylamino) butyl, sulfate = 4-[(3-methoxypropyl) amino] butyl, sulfate = 4-[(3-ethoxypropyl) amino] butyl, sulfate = 4-(hexylamino ) butyl, 4-(tert-butylamino)butyl sulfate, etc., and it is preferable to use at least one selected from these groups.

The anionic compound (a) used in the present invention represented by formula (1) is an inner salt (1a) or An internal salt (1b) may be formed, but the anionic compound (a) of the present invention includes any internal salt. In this specification, the anionic compound (a) of the present invention is expressed as formula (1).

(In the formula, R ¹ , R ² and X have the same meanings as above).

The anionic compound (a) can be prepared with reference to methods described in literature (eg, US Patent Application Publication No. 20070010573).

<Organic polyisocyanate (b)>
Examples of the organic polyisocyanate (b) used in the present invention include organic polyisocyanates selected from aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. . These isocyanurate-modified polyisocyanates, allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, urethymine-modified polyisocyanates, acyl urea-modified polyisocyanates, etc. may be used alone or in combination of two or more. can do. Further, when considering weather resistance, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified polyisocyanates thereof are preferable, and from the viewpoint of durability of the coating film and adhesion to the substrate, aliphatic polyisocyanates, or It is preferable to use at least one selected from the group consisting of isocyanurate-modified polyisocyanates and allophanate-modified polyisocyanates of alicyclic polyisocyanates. From the viewpoint of glossiness, it is preferable to use at least one selected from the group consisting of isocyanurate-modified polyisocyanate of hexamethylene diisocyanate and allophanate-modified polyisocyanate.

<Aromatic polyisocyanate>
Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, 4,4′-diphenylmethane diisocyanate, 2 ,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4 ,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and the like.

<Aroliphatic polyisocyanate>
Examples of araliphatic polyisocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, or mixtures thereof; 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4 -bis(1-isocyanato-1-methylethyl)benzene, or mixtures thereof; ω,ω'-diisocyanato-1,4-diethylbenzene and the like.

<Aliphatic polyisocyanate>
Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate and ethylene diisocyanate. , trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5,7 -trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanate methyl ester , 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate and the like.

<Alicyclic polyisocyanate>
Examples of alicyclic polyisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate -n-butylidene)pentaerythritol, hydrogenated hydrogenated dimer acid diisocyanate, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2- isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2 .2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl )-5-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2 .2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2.2.1]-heptane, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]-heptane, hydrogen hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated hydrogenated tetramethylxylene diisocyanate, and the like.

Also, the mass fraction of isocyanate groups in the organic polyisocyanate (b) is preferably 10 to 35%, more preferably 15 to 24%.

<Amine compound (c)>
Examples of the amine compound (c) used in the present invention include trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N-methylpiperidine, N-ethylpiperidine and dimethylethanol. Amines, tertiary monoamines such as methyldiethanolamine and triethanolamine, tertiary diamines such as 1,3-bis(dimethylamino)propane, 1,4-bis(dimethylamino)butane or N,N'-dimethylpiperazine can be mentioned. In particular, tertiary monoamines are preferred, and tributylamine, dimethylcyclohexylamine, and N-methylmorpholine are more preferred, in terms of low reactivity to isocyanate.

Further, the amine compound (c) in the present invention is preferably used so that the molar equivalent ratio between the amino group contained in the amine compound (c) and the anionic compound (a) is 0.2 to 2.0. , 0.5 to 1.5.

<Method of Blending Self-Emulsifying Polyisocyanate Composition>
There are no particular restrictions on the mixing order of (a), (b), and (c), the mixing ratio, and the presence or absence of the use of a solvent during mixing.

<Paint composition>
Next, the coating composition in the present invention will be explained.

The coating composition of the present invention is obtained from the self-emulsifying polyisocyanate composition of the present invention and a main agent. Examples of coating compositions include urethane resins and polyurea resins.

As the main ingredient in the production of the coating composition of the present invention, a polymer compound which is liquid at room temperature and is insoluble in water or has no affinity for water can be preferably used. It is also possible to use water-soluble resins or water-based emulsions that are soluble in water or have a certain degree of affinity for water. These polymer compounds preferably contain hydroxyl groups, carboxyl groups or amino groups (hereinafter referred to as "nucleophilic groups") that react with isocyanate groups in the molecule, and in particular two or more nucleophilic groups per molecule. Those containing are preferred. Moreover, even if these polymer compounds do not contain nucleophilic groups capable of reacting with isocyanate groups, or even if they contain only a few nucleophilic groups, eventually the self-emulsifying polyisocyanate composition reacts with water. It becomes a polyurea compound, and a hard and tough coating film can be obtained. In addition, since the isocyanate group reacts with the nucleophilic groups present on the surface of the adherend, adhesion to the adherend is also improved. When a polymer compound containing a nucleophilic group capable of reacting with an isocyanate group at room temperature is used, the nucleophilic group in the polymer compound and the isocyanate group in the self-emulsifying polyisocyanate composition react to crosslink. Since it forms a structure, weather resistance, solvent resistance, etc. are further improved. The room temperature in the present invention is 5°C to 40°C.

Examples of such main agents include saturated or unsaturated polyester polyols, polycaprolactone polyols, saturated or unsaturated fatty acid-modified alkyd polyols, amino alkyd polyols, polycarbonate polyols, acrylic polyols, polyether polyols, epoxy polyols, fluorine-containing polyols, Further examples include saturated or unsaturated polyester resins, polycaprolactone resins, fatty acid-modified alkyd resins, aminoalkyd resins, polycarbonate resins, acrylic resins, polyether resins, epoxy resins, polyurethane resins, cellulose acetate butyrate resins, and fluorine-containing resins. be done.

In addition, water-soluble resins and water-based emulsions can also be suitably used as the main component. Epoxy resins, water-soluble cellulose derivatives, water-soluble polyesters, water-soluble lignin derivatives, water-soluble fluorine resins, water-soluble silicone resins, and the like.

The aqueous emulsion includes all so-called latexes and emulsions, such as styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methylmethacrylate-butadiene copolymer latex, chloroprene latex, polybutadiene latex, and the like. rubber latex, polyacrylate latex, polyvinylidene chloride latex, polybutadiene latex, or carboxyl-modified versions of these latexes, as well as polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, polyurethane emulsions, acrylic emulsions, and the like.

Among these, acrylic polyols, acrylic resins, water-soluble acrylic resins, acrylic emulsions, urethane-acrylic emulsions, and polyurethane emulsions can be particularly preferably used in terms of coating film properties such as gloss and weather resistance and adhesive strength.

The number average molecular weight of the polymer compound as the main agent is preferably 1,000 to 1,000,000, more preferably 10,000 to 100,000.

<Blending ratio>
The blending ratio of the self-emulsifying polyisocyanate composition and the main agent in the production of the coating composition of the present invention is set to The molar ratio of isocyanate groups in the product to active hydrogen groups in the main agent is preferably 9:1 to 1:9, more preferably 6:4 to 4:6. Within this range, a coating film having better performance can be obtained.

Further, when using a main agent containing no active hydrogen groups in the molecule or containing only a few active hydrogen groups, the mass ratio of the self-emulsifying polyisocyanate composition and the main agent is preferably 1:9 to 5:5. It is more preferably in the range of 1:9 to 3:7. Within this range, a coating film having better performance can be obtained.

<Formulation method>
Methods for blending the main agent and the self-emulsifying polyisocyanate composition include methods such as adding the composition as it is, dispersing the self-emulsifying polyisocyanate composition in water once, and dissolving it in a solvent commonly used in the urethane field. In the present invention, a method of dispersing the self-emulsifying polyisocyanate composition in water and then blending it with the main agent is preferred.

<Other additives>
The self-emulsifying polyisocyanate composition or coating composition in the present invention may optionally contain, for example, antioxidants, ultraviolet absorbers, pigments, dyes, flame retardants, hydrolysis inhibitors, lubricants, plasticizers, Additives such as agents, fillers, storage stabilizers, and film-forming aids can be appropriately added.

<Painting method>
The coating composition of the present invention can be applied by a conventional conventional coating method to obtain a coating film. For coating, an airless sprayer, an air sprayer, an electrostatic coating machine, immersion, a roll coater, a knife coater, a brush, or the like can be used.

The present invention will be described in more detail below with reference to synthesis examples, but the present invention should not be construed as being limited thereto.

[Production of anionic compound]
<Example 1>
1,3-Propanesultone (6.02 g, 49.1 mmol) and propylamine (4.00 mL, 48.5 mmol) were weighed into a 200 mL flask equipped with a reflux tube and dissolved in tetrahydrofuran (44 mL). After the reaction solution was refluxed under an argon atmosphere for 11 hours, the volatile components were removed. The obtained solid was recrystallized from ethanol, and the precipitated white precipitate was collected by filtration, washed with tetrahydrofuran, and dried at 60° C. under reduced pressure to give 3-(propylamino)propanesulfonic acid (A-1). Obtained (4.55 g, 25.1 mmol, 51%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.48 (br, 2H), 3.05 (t, J=6.7 Hz, 2H), 2.84 (m, 2H), 2. 62 (m, 2H), 1.93 (tt, J = 6.5, 6.7Hz, 2H), 1.57 (tq, J = 7.7, 7.5Hz, 2H), 0.91 (t , J=7.5 Hz, 3H).

<Example 2>
1,3-propanesultone (6.72 g, 55.0 mmol), butylamine (11.0 mL, 111 mmol) and tetrahydrofuran (60 mL) were added to a 200 mL flask equipped with a reflux tube, and 3 was obtained in the same manner as in Synthesis Example 1. -(Butylamino)propanesulfonic acid (A-2) was obtained (5.20 g, 26.6 mmol, 48%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.49 (brs, 2H), 3.04 (t, J=6.4 Hz, 2H), 2.87 (m, 2H), 2. 62 (m, 2H), 1.92 (m, 2H), 1.52 (m, 2H), 1.32 (m, 2H), 0.89 (t, J = 7.4Hz, 3H).

<Example 3>
1,3-propanesultone (10.1 g, 82.7 mmol) and (3-methoxypropyl)amine (12.6 mL, 123 mmol) were weighed into a 200 mL flask equipped with a reflux tube and dissolved in tetrahydrofuran (60 mL). . After the reaction solution was refluxed for 2 hours under an argon atmosphere, the volatile components were removed. The resulting solid was dissolved in methanol, and the solution was passed through a strongly acidic ion-exchange resin (Amberlyst 15JWET, manufactured by Organo), followed by a weakly basic ion-exchange resin (Amberlyst A21, manufactured by Organo) until the solution became neutral. Organo) was added. The weakly basic ion exchange resin was filtered off and volatile components were removed to give 3-[(3-methoxypropyl)amino]propanesulfonic acid (A-3) (8.82 g, 41.7 mmol, 51%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.48 (br, 2H), 3.38 (t, J=6.0 Hz, 2H), 3.24 (s, 3H), 3. 04 (m, 2H), 2.93 (m, 2H), 2.61 (m, 2H), 1.92 (m, 2H), 1.79 (m, 2H).

<Example 4>
1,3-Propanesultone (6.72 g, 55.0 mmol) and hexylamine (8.00 mL, 60.5 mmol) were weighed into a 200 mL flask equipped with a reflux tube and dissolved in tetrahydrofuran (60 mL). The reaction solution was refluxed for 2 hours under an argon atmosphere. After cooling to 25°C, the precipitated white precipitate was collected by filtration, washed with diethyl ether, and dried at 60°C under reduced pressure to obtain 3-(hexylamino)propanesulfonic acid (A-4) ( 6.73 g, 30.1 mmol, 55%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.47 (br, 2H), 3.03 (t, J=6.8 Hz, 2H), 2.86 (m, 2H), 2. 62 (m, 2H), 1.92 (m, 2H), 1.54 (m, 2H), 1.32-1.24 (m, 6H), 0.87 (t, J = 7.0Hz, 3H).

<Example 5>
1,3-propanesultone (6.11 g, 50.0 mmol), octylamine (8.53 mL, 51.5 mmol) and tetrahydrofuran (60 mL) were added to a 200 mL flask equipped with a reflux tube, and the same method as in Synthesis Example 1 was performed. to give 3-(octylamino)propanesulfonic acid (A-5) (6.35 g, 25.2 mmol, 51%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.40 (br, 2H), 3.03 (t, J=6.8 Hz, 2H), 2.86 (m, 2H), 2. 61 (t, J = 6.8Hz, 2H), 1.92 (m, 2H), 1.54 (m, 2H), 1.30-1.24 (m, 10H), 0.86 (t, J=6.8Hz, 3H).

<Example 6>
1,3,2-Dioxathiane 2,2-dioxide (4.00 g, 29.0 mmol) and propylamine (2.65 mL, 31.9 mmol) were weighed into a 100 mL flask equipped with a reflux tube and added to tetrahydrofuran (30 mL). Dissolved. After the reaction solution was heated under reflux for 2 hours under an argon atmosphere, the volatile components were removed. The obtained solid was dissolved in methanol, and diethyl ether was gradually added to precipitate a white precipitate. The precipitated white precipitate was collected by filtration, washed with diethyl ether, and dried at 60° C. under reduced pressure to obtain 3-(propylamino)propyl sulfate (A-6) (3.52 g, 17.9 mmol). , 62%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.23 (br, 2H), 3.83 (t, J=6.1 Hz, 2H), 2.98 (tt, J=5.5 , 7.2 Hz, 2H), 2.86 (tt, J = 6.2, 7.6 Hz, 2H), 1.85 (tt, J = 6.1, 7.2 Hz, 2H), 1.58 ( tq, J = 7.4, 7.6 Hz, 2H), 0.91 (t, 7.4 Hz, 3H).

<Example 7>
1,3,2-dioxathiane 2,2-dioxide (10.0 g, 72.4 mmol), (3-methoxypropyl)amine (8.20 mL, 80.1 mmol) and tetrahydrofuran (70 mL) were placed in a 200 mL flask equipped with a reflux tube. ) was added, and in the same manner as in Synthesis Example 3, 3-[(3-methoxypropyl)amino]propyl sulfate (A-7) was obtained (6.33 g, 27.9 mmol, 38%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.23 (br, 2H), 3.83 (t, J = 6.1 Hz, 2H), 3.38 (t, J = 6.0 Hz , 2H), 3.24 (s, 3H), 3.00-2.94 (m, 4H), 1.88-1.77 (m, 4H).

<Example 8>
1,3,2-dioxathiane 2,2-dioxide (4.00 g, 29.0 mmol), n-hexylamine (4.30 mL, 32.5 mmol) and tetrahydrofuran (40 mL) were added to a 100 mL flask equipped with a reflux tube. , 3-(hexylamino)propyl sulfate (A-8) was obtained in the same manner as in Synthesis Example 6 (6.04 g, 25.2 mmol, 87%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.20 (br, 2H), 3.83 (t, J = 6.1 Hz, 2H), 2.97 (m, 2H), 2. 89 (m, 2H), 1.85 (tt, J = 6.1, 7.3Hz, 2H), 1.58 (tt, J = 7.1, 7.5Hz, 2H), 1.34-1 .25 (m, 6H), 0.91 (t, 7.1 Hz, 3H).

<Example 9>
In a 200 mL flask fitted with a reflux tube, (3-methoxypropyl)amine (43.8 mL, 428 mmol) was dissolved in acetonitrile (60 mL) and 5-chloro-1-pentanol (10.5 g, 85.6 mmol) was added. The solution was added dropwise over 30 minutes while cooling with ice. After the temperature of the reaction solution was gradually raised to 25° C., it was refluxed for 24 hours under an argon atmosphere. Volatile components were removed, and an aqueous potassium hydroxide solution (20% by mass, 120 mL), saturated brine (120 mL) and diethyl ether (120 mL) were added to the obtained solid, and after liquid separation, the organic phase was recovered. Diethyl ether (60 mL) was added to the aqueous phase, and after liquid separation, the organic phase was recovered again. After drying the resulting organic phase over sodium sulfate, the volatile components were removed under reduced pressure to give the crude product of 5-(3-methoxypropyl)amino-1-pentanol as a colorless viscous solid (15 .0 g).

In a 200 mL flask equipped with a reflux tube, the resulting crude product of 5-(3-methoxypropyl)amino-1-pentanol (15.0 g) was dissolved in chloroform (70 mL) and thionyl chloride (8.1 mL). , 110 mmol) was added dropwise over 30 minutes while cooling with ice. After the reaction solution was gradually warmed to 25° C., it was refluxed for 3 hours under an argon atmosphere. Water (30 mL) was added to the reaction solution, neutralized with sodium carbonate, saturated brine (50 mL) was added, and after liquid separation, the organic phase was recovered. Chloroform (100 mL) was added to the aqueous phase, and after liquid separation, the organic phase was recovered again. The obtained organic phase was dried with sodium sulfate, and the volatile components were removed to obtain a brown solid. After dissolving the obtained brown solid in chloroform (20 mL), diethyl ether (100 mL) was gradually added to precipitate a white precipitate. The precipitated white precipitate was collected by filtration, washed with diethyl ether, and dried at 60° C. under reduced pressure to obtain N-(5-chloropentyl)-N-(3-methoxypropyl)amine hydrochloride (7 .10 g, 30.8 mmol, 2 steps 36%). ¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 9.44 (br, 2H), 3.55 (t, J=6.4 Hz, 2H), 3.52 (t, J=5.7 Hz, 2H), 3.35 (s, 3H), 3.10 (m, 2H), 2.97 (m, 2H), 2.15 (m, 2H), 1.93 (m, 2H), 1. 82 (m, 2H), 1.55 (m, 2H).

<Example 10>
N-(5-chloropentyl)-N-(3-methoxypropyl)amine hydrochloride (16.7 g, 72.6 mmol) obtained in Synthesis Example 9 and sodium sulfite (18.6 mmol) were placed in a 50 mL flask equipped with a reflux tube. 3 g, 145 mmol) and water (60 mL) were added and refluxed for 48 hours under an argon atmosphere. After the reaction solution was passed through a strongly acidic ion exchange resin (Amberlyst 15JWET, manufactured by Organo), a weakly basic ion exchange resin (Amberlyst A21, manufactured by Organo) was added until the solution became neutral. The weakly basic ion exchange resin was filtered off and volatile components were removed to give 5-[(3-methoxypropyl)amino]pentanesulfonic acid (A-9) (8.05 g, 33.6 mmol , 46%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.32 (br, 2H), 3.38 (t, J=6.0 Hz, 2H), 3.24 (s, 3H), 2. 92 (m, 2H), 2.87 (m, 2H), 2.44 (m, 2H), 1.83 (m, 2H), 1.63-1.53 (m, 4H), 1.41 -1.33 (m, 2H).

<Example 11>
In a 200 mL flask equipped with a reflux tube, (3-methoxypropyl)amine (25.6 mL, 250 mmol) was dissolved in acetonitrile (50 mL), and 8-chloro-1-octanol (8.23 g, 50 mmol) was ice-cooled. was added dropwise over 30 minutes. After the temperature of the reaction solution was gradually raised to 25° C., it was refluxed for 24 hours under an argon atmosphere. Removal of volatiles under reduced pressure gave crude 8-(3-methoxypropyl)amino-1-octanol as a white solid (11.0 g). This product was used in the next step without purification.

Subsequently, in a 100 mL flask equipped with a reflux tube, the obtained 8-(3-methoxypropyl)amino-1-octanol (11.0 g) was dissolved in chloroform (30 mL), and thionyl chloride (4.8 mL, 66 mmol) was dissolved. ) was added dropwise over 30 minutes while cooling with ice. After the reaction solution was gradually warmed to 25° C., it was refluxed for 1 hour under an argon atmosphere. Water (30 mL) was added to the reaction solution, neutralized with sodium carbonate, saturated brine (50 mL) was added, and after liquid separation, the organic phase was recovered. Chloroform (100 mL) was added to the aqueous phase, and after liquid separation, the organic phase was recovered again. The obtained organic phase was dried with sodium sulfate, and the volatile components were removed to obtain a brown solid. The resulting brown solid was recrystallized from chloroform/diethyl ether (100 mL), the precipitated white precipitate was collected by filtration, washed with diethyl ether, and dried at 60° C. under reduced pressure to give N-(8-chlorooctyl )-N-(3-Methoxypropyl)amine hydrochloride crude product was obtained (11.1 g).

Subsequently, N-(8-chlorooctyl)-N-(3-methoxypropyl)amine hydrochloride (11.1 g) and sodium sulfite (10.28 g, 81.6 mmol) obtained in a 100 mL flask equipped with a reflux tube ), ethanol (20 mL) and water (80 mL) were weighed and refluxed for 24 hours under an argon atmosphere. After the reaction solution was passed through a strongly acidic ion exchange resin (Amberlyst 15JWET, manufactured by Organo), a weakly basic ion exchange resin (Amberlyst A21, manufactured by Organo) was added until the solution became neutral. The crude product was obtained by filtering off the weakly basic ion exchange resin and removing the volatile components. The resulting crude product was dissolved in methanol, and acetonitrile was gradually added to precipitate a white precipitate. The precipitated white precipitate was collected by filtration, washed with acetonitrile, and dried at 60° C. under reduced pressure to obtain 8-[(3-methoxypropyl)amino]octanesulfonic acid (A-10) (9.74 g). , 34.6 mmol, 3 steps 69%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.23 (br, 2H), 3.38 (t, J=6.1 Hz, 2H), 3.24 (s, 3H), 2. 93 (m, 2H), 2.88 (m, 2H), 2.38 (m, 2H), 1.81 (tt, J = 6.1, 6.6Hz, 2H), 1.60-1. 51 (m, 4H), 1.35-1.23 (m, 8H).

<Comparative Example 1>
In a 200 mL flask equipped with a reflux tube, hexylamine (33.0 mL, 250 mmol) was dissolved in acetonitrile (50 mL), and 8-chloro-1-octanol (8.23 g, 50 mmol) was added over 30 minutes while cooling with ice. Dripped. After the temperature of the reaction solution was gradually raised to 25° C., it was refluxed for 24 hours under an argon atmosphere. Removal of volatiles under reduced pressure gave crude 8-hexylamino-1-octanol as a white solid (13.4 g).

Subsequently, in a 100 mL flask equipped with a reflux tube, the obtained 8-hexylamino-1-octanol (13.4 g) was dissolved in chloroform (30 mL), and thionyl chloride (4.8 mL, 66 mmol) was ice-cooled. was added dropwise over 30 minutes. After the reaction solution was gradually warmed to 25° C., it was refluxed for 1 hour under an argon atmosphere. Water (30 mL) was added to the reaction solution, neutralized with sodium carbonate, saturated brine (50 mL) was added, and after liquid separation, the organic phase was recovered. Chloroform (100 mL) was added to the aqueous phase, and after liquid separation, the organic phase was recovered again. The obtained organic phase was dried with sodium sulfate, and the volatile components were removed to obtain a brown solid. After dissolving the obtained brown solid in chloroform (20 mL), diethyl ether (100 mL) was gradually added to precipitate a white precipitate. The deposited white precipitate was collected by filtration, washed with diethyl ether, and dried at 60° C. under reduced pressure to obtain a crude product of N-(8-chlorooctyl)-N-hexylamine hydrochloride (15. 3g).

Subsequently, N-(8-chlorooctyl)-N-hexylamine hydrochloride (15.3 g), sodium sulfite (12.6 g, 100 mmol), ethanol (20 mL), and Water (80 mL) was weighed out and refluxed for 24 hours under an argon atmosphere. After the reaction solution was passed through a strongly acidic ion exchange resin (Amberlyst 15JWET, manufactured by Organo), a weakly basic ion exchange resin (Amberlyst A21, manufactured by Organo) was added until the solution became neutral. The crude product was obtained by filtering off the weakly basic ion exchange resin and removing the volatile components. The resulting crude product was dissolved in methanol, and acetonitrile was gradually added to precipitate a white precipitate. The precipitated white precipitate was collected by filtration, washed with acetonitrile, and dried at 60° C. under reduced pressure to obtain 8-(hexylamino)octanesulfonic acid (A-11) (3.76 g, 12.8 mmol, 3 steps 26%). ¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 8.46 (br, 2H), 2.94 (m, 2H), 2.89 (m, 2H), 2.83 (t, J = 7.5Hz, 2H), 1.86-1.72 (m, 6H), 1.48-1.25 (m, 14H), 0.86 (t, J = 6.9Hz, 3H).

[Production of self-emulsifying polyisocyanate]
<Example 12>
Coronate HXLV (isocyanurate-modified polyisocyanate of hexamethylene diisocyanate, isocyanate content 23.2% by mass, manufactured by Tosoh Corporation, 19.16 g ), A-1 (0.54 g, 0.15 mol) obtained in Synthesis Example 1, and dimethylcyclohexylamine (0.38 g, 0.15 mol) were added and stirred at 80° C. for 5 hours to obtain a self-emulsifying polyisocyanate. P-1 was obtained. The isocyanate content of P-1 was 21.5% by weight.

A self-emulsifying polyisocyanate composition synthesized in the same manner as in Example 12 is shown below.

・Dimethylcyclohexylamine: Reagent special grade, manufactured by Tokyo Chemical Industry Co., Ltd.

<Preparation of coating composition for gloss/hardness evaluation>
The main agent (acrylic emulsion, manufactured by DIC, WE-303, solid content 45% by mass, hydroxyl value is 84 (mg-KOH / g) in terms of solid content), and the obtained self-emulsifying polyisocyanate composition (P- 1 to 11) were blended so that the isocyanate group/hydroxyl group=1.5 (molar ratio). Water was added to this mixed liquid so that the solid content of the whole was 40% by mass, and the mixture was stirred at a high speed of 2000 rpm for 30 seconds using a homomixer to obtain a coating composition for evaluating glossiness/hardness.

<Preparation of coating film for gloss/hardness evaluation>
Each coating composition for glossiness/hardness evaluation was applied to a steel plate with an applicator, and cured in an atmosphere of 25° C. for 1 week to form a coating film with a dry film thickness of 40 μm.

<Gloss test>
Gloss 20° of each coating film obtained above was measured using BYK Micro-TRI-gloss. Tables 3 and 4 show the results. If the gloss 20° value is 80 or more, it can be said to be good.

<Hardness test>
The Martens hardness of each coating film obtained above was measured using HM-2000 manufactured by Fisher Instruments. Tables 3 and 4 show the results. If the Martens hardness is 100 (N/mm ² ) or more at 25° C., it can be said to be good.

<Water dispersibility evaluation>
The self-emulsifying polyisocyanate compositions (P-1 to 11) and water were mixed at a mass ratio of 1:9, respectively, and the aqueous dispersion prepared by stirring at 2000 rpm for 1 minute was allowed to stand at 25°C for 1 hour. , the state of dispersion at that time was visually evaluated. Tables 3 and 4 show the results.
・No separation or precipitation: ○
・There is precipitation: ×

Claims (6)

A hydrophilizing agent for producing a self-emulsifying polyisocyanate composition, comprising an anionic compound (a) represented by the following formula 1.

(wherein X represents a sulfo group or a hydroxysulfonyloxy group, R ¹ represents a linear or branched alkylene group, and R ² represents a linear or branched alkyl group. R ¹ and R The total number of carbon atoms contained in ² is 6 or more and less than 14, and one or two or more carbon atoms in the groups of R ¹ and R ² may be substituted with oxygen atoms.) A self-emulsifying polyisocyanate composition obtained from an anionic compound (a), an organic polyisocyanate (b) and an amine compound (c),
The anionic compound (a) is represented by the following formula 1 ,
the amine compound (c) is a tertiary monoamine or a tertiary diamine,
A self-emulsifying polyisocyanate composition characterized in that the molar equivalent ratio of amino groups contained in the amine compound (c) to the anionic compound (a) is 0.2 to 2.0 .

(wherein X represents a sulfo group or a hydroxysulfonyloxy group, R ¹ represents a linear or branched alkylene group, and R ² represents a linear or branched alkyl group. R ¹ and R The total number of carbon atoms contained in ² is 6 or more and less than 14, and one or two or more carbon atoms in the groups of R ¹ and R ² may be substituted with oxygen atoms.) 3. Self-emulsifying polyisocyanate composition according to claim 2, characterized in that the mass fraction of isocyanate groups in the organic polyisocyanate (b) is from 10 to 35%. 4. The self-emulsifying polyisocyanate composition according to claim 2, wherein the organic polyisocyanate (b) contains an isocyanurate-modified polyisocyanate of hexamethylene diisocyanate. A coating composition obtained from the self-emulsifying polyisocyanate composition according to any one of claims 2 to 4 and a main agent. A coating film obtained from the coating composition according to claim 5 .