JP6600508B2 - Polyisocyanate composition, coating composition, water-based coating composition, and coating substrate - Google Patents

Description

  The present invention relates to a polyisocyanate composition, a coating composition, an aqueous coating composition, and a coating substrate.

  In recent years, from the viewpoint of environmental protection, it is desired that a room temperature cross-linking type two-component urethane coating composition used as a solvent-based paint is water-based. However, in the two-component urethane coating composition, polyisocyanate used as a curing agent is difficult to disperse in water and easily reacts with water, and carbon dioxide is generated by the reaction. For this reason, development of polyisocyanates having emulsifying properties and suppressing the reaction between isocyanate groups and water even in a water-dispersed state is underway.

  For example, Patent Document 1 discloses a polyisocyanate mixture dispersible in water, which contains a polyisocyanate compound and a polyether containing an ethylene oxide unit. Patent Document 2 discloses a low-viscosity aqueous polyisocyanate composition containing an isocyanurate group and a uretdione group that can be dissolved or dispersed in water. Furthermore, Patent Document 3 discloses a polyisocyanate composition having high emulsifiability, obtained by reacting an isocyanate prepolymer obtained from an aliphatic or alicyclic diisocyanate and a monoalcohol with a nonionic hydrophilic component. . In addition, in Patent Document 4, water obtained by reacting a prepolymer obtained from an aliphatic or alicyclic diisocyanate with a nonionic hydrophilic component consisting of ethylene oxide repeating units having an average of 3.0 to 4.9 is obtained. A polyisocyanate composition which is easily dispersible is disclosed.

JP 05-222150 A JP 2007-332193 A JP 2000-178335 A JP 2000-248044 A

  However, even the polyisocyanate compositions described in Patent Documents 1 to 4 are insufficient to satisfy both the water dispersibility and the film crosslinkability.

  Accordingly, an object of the present invention is to provide a polyisocyanate composition exhibiting at least good water dispersibility and water dispersion stability and good coating crosslinkability.

  The inventors include a modified polyisocyanate obtained by reacting a polyisocyanate with a specific range amount of a polyalkylene glycol alkyl ether having a specific structure, the isocyanate average functional group number within a specific range, and a viscosity within a specific range. The present inventors have found that the polyisocyanate composition exhibits good water dispersibility, water dispersion stability, and coating film crosslinkability, thereby completing the present invention.

（式（１）中、Ｒ₁は炭素原子数１から４のアルキレン基であり、Ｒ₂は炭素数１から４のアルキル基である。ｎの平均数は５．０以上２０以下である。）
［２］一般式（１）中、前記Ｒ₁はエチレン基であり、前記ｎの平均数は５．０以上１１以下である、［１］に記載のポリイソシアネート組成物。
［３］前記平均イソシアネート官能基数は、２．５以上３．２以下である、［１］又は［２］に記載のポリイソシアネート組成物。
［４］ゲルパーミエーションクロマトグラフィーでの示差屈折率計検出によって求められる、前記ポリイソシアネート及び前記変性ポリイソシアネートの全ピーク面積に対する、ジイソシアネート三量体の面積割合が、全面積１００％に対して、４５％以上６５％以下である、［１］〜［３］のいずれかに記載のポリイソシアネート組成物。
［５］ゲルパーミエーションクロマトグラフィーでの示差屈折率計検出によって求められる、前記ポリイソシアネート及び前記変性ポリイソシアネートの全ピーク面積に対する、ジイソシアネート三量体の面積割合が、全面積１００％に対して、４７％以上６０％以下である、［１］〜［４］のいずれかに記載のポリイソシアネート組成物。
［６］［１］〜［５］のいずれか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。
［７］［６］に記載のコーティング組成物と水とを含む、水系コーティング組成物。
［８］［６］に記載のコーティング組成物又は［７］に記載の水系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。 That is, the present invention is as follows.
[1] A polyisocyanate composition comprising a modified polyisocyanate obtained from a polyisocyanate and a polyalkylene glycol alkyl ether represented by the following general formula (1):
The portion derived from the polyalkylene glycol alkyl ether is 1.0% by mass or more and less than 13% by mass with respect to 100% by mass of the polyisocyanate composition.
The average isocyanate functional group number is 2.3 or more and 3.3 or less,
The polyisocyanate composition whose viscosity in 23 degreeC is 330 mPa * s or more and 1000 mPa * s or less.

(In Formula (1), R ₁ is an alkylene group having 1 to 4 carbon atoms, and R ₂ is an alkyl group having 1 to 4 carbon atoms. The average number of n is 5.0 or more and 20 or less. )
[2] The polyisocyanate composition according to [1], wherein in general formula (1), R ₁ is an ethylene group, and the average number of n is 5.0 or more and 11 or less.
[3] The polyisocyanate composition according to [1] or [2], wherein the average number of isocyanate functional groups is 2.5 or more and 3.2 or less.
[4] The area ratio of the diisocyanate trimer to the total peak area of the polyisocyanate and the modified polyisocyanate obtained by differential refractometer detection by gel permeation chromatography is 100% of the total area. The polyisocyanate composition according to any one of [1] to [3], which is 45% or more and 65% or less.
[5] The area ratio of the diisocyanate trimer to the total peak area of the polyisocyanate and the modified polyisocyanate obtained by differential refractometer detection in gel permeation chromatography is 100% of the total area. The polyisocyanate composition according to any one of [1] to [4], which is 47% or more and 60% or less.
[6] A coating composition comprising the polyisocyanate composition according to any one of [1] to [5].
[7] An aqueous coating composition comprising the coating composition according to [6] and water.
[8] A coating substrate coated with the coating composition according to [6] or the aqueous coating composition according to [7].

  According to the polyisocyanate composition of the present invention, excellent water dispersibility and water dispersion stability and excellent coating crosslinkability can be obtained.

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

（式（１）中、Ｒ₁は炭素原子数１から４のアルキレン基であり、Ｒ₂は炭素数１から４のアルキル基である。ｎの平均数は５．０以上２０以下である。） [Polyisocyanate composition]
The polyisocyanate composition of this embodiment contains a modified polyisocyanate obtained from a polyisocyanate and a polyalkylene glycol alkyl ether represented by the following general formula (1). Moreover, the polyisocyanate composition of this embodiment is 1.0 mass% in the part derived from the polyalkylene glycol alkyl ether represented by the following general formula (1) with respect to 100 mass% of the polyisocyanate composition. The average isocyanate functional group number is 2.3 or more and 3.3 or less, and the viscosity at 23 ° C. is 330 mPa · s or more and 1000 mPa · s or less.

(In Formula (1), R ₁ is an alkylene group having 1 to 4 carbon atoms, and R ₂ is an alkyl group having 1 to 4 carbon atoms. The average number of n is 5.0 or more and 20 or less. )

  The polyisocyanate composition of the present embodiment may contain the polyisocyanate that has not reacted with the polyalkylene glycol alkyl ether (hereinafter also referred to as “unreacted polyisocyanate”). Further, various physical properties or characteristics of the polyisocyanate composition of the present embodiment to be described later are also referred to as modified polyisocyanate (hereinafter simply referred to as “modified polyisocyanate”) obtained from the above polyalkylene glycol alkyl ether unless otherwise specified. ) And unreacted polyisocyanate.

  Moreover, in the polyisocyanate composition of this embodiment, the ratio of unreacted polyisocyanate and modified polyisocyanate can be specifically determined by measurement by liquid chromatography.

<Polyisocyanate>
Specific examples of the polyisocyanate used in the present embodiment include at least one diisocyanate compound selected from aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polyisocyanate compounds derived from these diisocyanate compounds. . The polyisocyanate used in the present embodiment is preferably at least one diisocyanate compound selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates from the viewpoint of industrial availability.

  Specific examples of the aliphatic diisocyanate include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato) hexanoate, 1,6-diisocyanatohexane (hereinafter, “ HDI ”), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane and the like. Can be mentioned.

  Specific examples of the alicyclic diisocyanate include 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (hereinafter, also referred to as “hydrogenated XDI”), 1,3- or 1,4-diis. Isocyanatocyclohexane, 3,5,5-trimethyl 1-isocyanato-3- (isocyanatomethyl) cyclohexane (hereinafter also referred to as “IPDI”), 4-4′-diisocyanato-dicyclohexylmethane (hereinafter “hydrogenated MDI”) And 2,5- or 2,6-diisocyanatomethylnorbornane and the like.

  Specific examples of the aromatic diisocyanate include xylylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.

  Among these, HDI, IPDI, hydrogenated XDI, and hydrogenated MDI are more preferable because they tend to hardly yellow.

  As the polyisocyanate compound derived from the above diisocyanate, specifically, 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 isocyanurate structure, iminooxadiazinedione structure, polyisocyanate compound having biuret structure obtained by reacting three isocyanate groups and one water molecule, two isocyanate groups and one molecule of dioxide A polyisocyanate compound having an oxadiazine trione structure obtained by reacting with carbon, a polyisocyanate compound having a plurality of urethane groups obtained by reacting one isocyanate group and one hydroxyl group, and two isocyanate groups Polyisocyanate compound having an allophanate structure obtained by reacting one hydroxyl group, polyisocyanate compound having an acylurea group obtained by reacting one isocyanate group and one carboxyl group, one isocyanate group and one primary Or the polyisocyanate compound etc. which have a urea structure obtained by making a secondary amine react are mentioned. In addition, aliphatic triisocyanates such as 1,3,6-triisocyanatohexane, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl-2,6-diisocyanato-hexanoate, and the like are also included.

  These polyisocyanates may be modified with a sulfonic acid amine salt having a hydroxyl group, a vinyl polymer having a hydroxyl group and a nonionic hydrophilic group, or the like. These can also be used 1 type or in combination of 2 or more types.

（式（１）中、Ｒ₁は炭素原子数１から４のアルキレン基であり、Ｒ₂は炭素数１から４のアルキル基である。ｎの平均数は５．０以上２０以下である。） <Polyalkylene glycol alkyl ether>
The polyalkylene glycol alkyl ether used in the present embodiment has a structure represented by the following formula (1).

(In Formula (1), R ₁ is an alkylene group having 1 to 4 carbon atoms, and R ₂ is an alkyl group having 1 to 4 carbon atoms. The average number of n is 5.0 or more and 20 or less. )

Specifically, as the polyalkylene glycol alkyl ether, R ₁ is an alkylene group having 1 to 4 carbon atoms from the viewpoint of imparting hydrophilicity. From the viewpoint of imparting more hydrophilicity, ethylene having 2 carbon atoms is preferable. From the viewpoint of imparting hydrophilicity, R ₂ is an alkyl group having 1 to 4 carbon atoms. From the viewpoint of imparting more hydrophilicity, methyl having 1 carbon atom is preferable. Furthermore, n is 5.0 or more and 20 or less from the viewpoint of water dispersibility. From the viewpoint of water dispersibility and dispersibility in the main agent, n is preferably 5.0 or more and 11 or less.

  Specific examples of the compound include polyethylene glycol (mono) methyl ether, poly (ethylene, propylene) glycol (mono) methyl ether, polyethylene glycol (mono) ethyl ether, and the like. From the viewpoint of imparting hydrophilicity, polyethylene glycol (mono) methyl ether is preferable.

  The number of hydroxyl groups in the polyalkylene glycol alkyl ether is preferably one from the viewpoint of reducing the viscosity of the polyisocyanate composition.

The polyalkylene glycol alkyl ether contains an alkylene oxide repeating unit — (R ₁ O) _n — therein. The average number of alkylene oxide repeating units of the polyalkylene glycol alkyl ether, that is, the average number of n is preferably 5.0 or more and 20 or less, more preferably from the viewpoint of water dispersibility, dispersibility in the main agent, and coating film appearance. Is 5.0 or more and 11 or less, more preferably 5.0 or more and 10 or less. When the average number of n is 5.0 or more, the emulsifying power is increased, so that the dispersibility tends to be improved. When the average number is 20 or less, the viscosity is prevented from increasing, so that it can be easily dispersed. The said polyalkylene glycol alkyl ether can also use the thing from which the average number of n differs 1 type or in combination of 2 or more types. The average number of n of the raw material polyalkylene glycol alkyl ether is measured by the method described in the examples described later.

The polyalkylene glycol alkyl ether in the polyisocyanate composition also contains an alkylene oxide repeating unit — (R ₁ O) _n —. The average number of alkylene oxide repeating units of the polyalkylene glycol alkyl ether, that is, the average number of n is 5.0 or more and 20 or less, preferably 5. from the viewpoints of water dispersibility, dispersibility in the main agent, and coating film appearance. It is 0 or more and 11 or less, more preferably 5.0 or more and 10 or less. When the average number of n is 5.0 or more, the emulsifying power is increased, so that the dispersibility tends to be improved. When the average number is 20 or less, the viscosity is prevented from increasing, so that it can be easily dispersed. The average number of n of the polyalkylene glycol alkyl ether in the polyisocyanate composition is measured by the method described in Examples described later.

In the polyalkylene glycol alkyl ether in the polyisocyanate composition, in general formula (1), R ₁ is an ethylene group, and the average number of n is 5.0 or more and 11 or less. From the viewpoint of obtaining

  In the polyisocyanate composition, the proportion of the polyalkylene glycol alkyl ether modified (hereinafter also referred to as “modification rate”) is such that the polyalkylene glycol alkyl ether is 100 equivalents of the isocyanate group of the raw polyisoisocyanate. Denatured ratio. The modification rate is preferably 0.5% or more and 15% or less, more preferably 1.0% or more and 10% or less, and further preferably 2.0% or more and 10% or less. When the modification rate is 0.5% or more, there is a tendency to exhibit better water dispersibility due to a decrease in interfacial tension. When the modification rate is 15% or less, it is used for crosslinking. Due to an increase in the number of isocyanate groups, the crosslinkability tends to be better.

  The method for controlling the modification rate within the above range is not limited to the following, and examples thereof include a method of adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate. The modification rate is measured by the method described in the examples.

  The content of the part derived from the polyalkylene glycol alkyl ether is 1.0% by mass or more with respect to 100% by mass of the polyisocyanate composition from the viewpoints of water dispersibility, isocyanate group retention, and coating film properties. It is less than 13% by mass, preferably 2.0% by mass or more and 12% by mass or less. When the portion derived from the polyalkylene glycol alkyl ether is 1.0% by mass or more, the interfacial tension is lowered, so that dispersibility is improved, and when it is less than 13% by mass, contact between water and an isocyanate group is achieved. Therefore, the retention of isocyanate groups is high, and the physical properties of the coating film (hardness, solvent resistance, water resistance) are improved. The said content rate is measured by the method as described in the Example mentioned later.

  Specific examples of the method of reacting the polyisocyanate with the polyalkylene glycol alkyl ether include a method of reacting the terminal isocyanate group of the polyisocyanate with the hydroxyl group of the polyalkylene glycol alkyl ether.

  The viscosity at 23 ° C. of the polyisocyanate composition of the present embodiment is 330 mPa · s or more and 1000 mPa · s or less, and 350 mPa · s or more from the viewpoint of water dispersion stability and dispersibility in the main agent (coating film appearance). It is preferably 950 mPa · s or less, and more preferably 350 mPa · s 900 mPa · s or less. When the viscosity at 23 ° C. is 330 mPa · s or higher, the thixotropy is improved, so that the appearance of the coating film is improved, and when it is 1000 mPa · s or lower, the particles are easily formed into fine particles when dispersed in water. Property is improved.

  As a method for controlling the viscosity at 23 ° C. within the above range, specifically, a method for adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate, and a polyisocyanate having a viscosity within an appropriate range is used as a raw material. Examples thereof include a method, a method of adjusting a conversion rate when producing a raw material polyisocyanate. The viscosity at 23 ° C. is measured by the method described in the examples.

  The isocyanate group content of the polyisocyanate composition of the present embodiment is preferably 16% by mass or more and 24% by mass or less from the viewpoint of coating film properties in a state where the nonvolatile content is substantially 100% by mass. It is more preferably 16.5% by mass or more and 23% by mass or less, and further preferably 17% by mass or more and 23% by mass or less. When the isocyanate group content is 16% by mass or more and 24% by mass or less, the number of isocyanate groups used for crosslinking increases, and the ease of movement of the molecules during curing of the polyisocyanate molecules is improved. It tends to be good.

  Specific examples of the method for controlling the isocyanate group content within the above range include a method for adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate. The isocyanate group content is measured by the method described in the examples.

  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 or more and 700 or less from the viewpoint of water dispersion stability and dispersibility in the main agent. It is preferably 500 or more and 700 or less, and more preferably 500 or more and 650 or less. Since the number average molecular weight of the polyisocyanate is 450 or more and 700 or less, the number of trimer components used for crosslinking increases, and the ease of movement of the molecules during curing of the polyisocyanate molecules is improved. It tends to be good.

  Specific examples of the method of controlling the number average molecular weight within the above range include a method of adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate. The number average molecular weight of the polyisocyanate is measured by the method described in the examples.

  Diisocyanate trimer in unreacted polyisocyanate obtained by differential refractometer detection in gel permeation chromatography of polyisocyanate containing modified polyisocyanate and unreacted polyisocyanate in polyisocyanate composition of this embodiment The body area ratio (area percentage) is preferably 45% or more and 65% or less, more preferably 47% or more and 60% or less, and 50% from the viewpoint of water dispersion stability and physical properties of the coating film. More preferably, it is 60% or less. When the area ratio is 45% or more, components having high chemical stability increase, and thus the strength of the coating film tends to increase. When the area ratio is 65% or less, there are many components that are micellar and exist stably, and thus the water dispersion stability tends to be good.

  As a method for controlling the area ratio of the diisocyanate trimer in the unreacted polyisocyanate to the above range, specifically, a method for adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate, Examples thereof include a method of modifying polyisocyanate having an appropriate content as a raw material, a method of adjusting the conversion rate when producing the raw material polyisocyanate, and the like. Moreover, the area ratio of a diisocyanate trimer is measured by the method described in an Example.

  The average number of isocyanate functional groups in the polyisocyanate composition containing the modified polyisocyanate and the unreacted polyisocyanate of the present embodiment (hereinafter also referred to as “average isocyanate functional group number”) is 2. 3 or more and 3.3 or less, preferably 2.5 or more and 3.2 or less, and more preferably 2.6 or more and 3.1 or less. When the average isocyanate functional group number is 2.3 or more and 3.3 or less, the crosslinking efficiency of the coating film is improved, and the ease of movement of the molecules during curing of the polyisocyanate molecules is improved. Become.

  Specific examples of a method for controlling the average number of isocyanate functional groups within the above range include a method for adjusting the blending ratio of the polyalkylene glycol alkyl ether and the polyisocyanate. The average number of isocyanate functional groups is measured by the method described in the examples.

  The polyisocyanate composition of this embodiment may contain other components in addition to the above-described modified polyisocyanate and unreacted polyisocyanate. Specific examples of other components include a solvent, an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant.

  The content of the solvent is preferably 0.0% by mass or more and 90% by mass or less, more preferably 0.0% by mass or more and 50% by mass or less, with respect to 100% by mass of the polyisocyanate composition. More preferably, it is 0.0 mass% or more and 30 mass% or less. Further, the antioxidant, light stabilizer, polymerization inhibitor, and surfactant are preferably 0.0% by mass or more and 10% by mass or less with respect to 100% by mass of the polyisocyanate composition, and 0.0% by mass. % To 5.0% by mass, more preferably 0.0% to 2.0% by mass.

[Method for producing polyisocyanate composition]
It is preferable that the manufacturing method of the polyisocyanate composition of this embodiment includes the process (reaction process) of carrying out the mixing reaction of the said polyalkylene glycol alkyl ether and polyisocyanate.

  In the reaction step, the mixing ratio of the polyalkylene glycol alkyl ether and the polyisocyanate is 100% by mass with respect to 100% by mass of the polyisocyanate composition from the viewpoint of water dispersibility, isocyanate group retention and coating film properties. The polyalkylene glycol alkyl ether is preferably reacted so as to be 1.0% by mass or more and less than 13% by mass, more preferably 2.0% by mass or more and 12% by mass or less. preferable.

  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 0.0 ° C. or higher and 150 ° C. or lower, and the reaction time is 0.5 hour or longer and 48 hours or shorter. It is preferable that

  In the reaction step, a known catalyst may be used in some cases. Specific examples of catalysts include tin octoate, tin 2-ethyl-1-hexanoate, tin ethylcaproate, tin laurate, tin palmitate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dimaleate and dibutyltin. Organotin compounds such as dilaurate, dioctyltin diacetate, dioctyltin dilaurate; zinc chloride, zinc octoate, zinc 2-ethyl-1-hexanoate, zinc 2-ethylcaproate, zinc stearate, zinc naphthenate, acetylacetonic acid Organic zinc compounds such as zinc; organic titanium compounds; organic zirconium compounds; tertiary amines such as triethylamine, tributylamine, N, N-diisopropylethylamine, N, N-dimethylethanolamine; triethylenedia Emissions, tetramethylethylenediamine, 1,4-diazabicyclo [2.2.2] diamines such as octane. You may use these individually or in mixture.

  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.

  Specific examples of the hydrophobic solvent include mineral spirits, solvent naphtha, LAWS (Low Aromatic White Spirit), HAWS (High Aromatic White Spirit), toluene, xylene, cyclohexane, etc .; esters such as ethyl acetate and butyl acetate; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  Specific examples of hydrophilic solvents include 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, dipropylene glycol monomethyl Esters of ether alcohols such as ether acetate. These can be used alone or in combination.

  In the method for producing a polyisocyanate composition of the present embodiment, in addition to the polyalkylene glycol alkyl ether and the polyisocyanate, the polyisocyanate composition is selected from the group consisting of an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant. At least one kind may be further added.

[Coating composition]
The coating composition of the present embodiment is not particularly limited as long as it contains the above-described polyisocyanate composition, and an organic solvent-based coating composition is a film-forming component in a medium mainly composed of water. An aqueous coating composition in which resins are dissolved or dispersed may be used, and an aqueous coating composition is preferred from the viewpoint of reducing the amount of organic solvent used. Specifically, architectural paints, automotive paints, automotive repair paints, plastic paints, adhesives, adhesives, building materials, household water-based paints, other coating agents, sealing agents, inks, casting materials, elastomers, foams It can be used for plastic raw materials, fiber treatment agents and the like.

  Specifically, the main resins in the aqueous coating composition include acrylic resins, polyester resins, polyether resins, epoxy resins, fluororesins, polyurethane resins, polyvinylidene chloride copolymers, polychlorinated resins. Examples thereof include vinyl copolymers, vinyl acetate copolymers, acrylonitrile butadiene copolymers, polybutadiene copolymers, and styrene butadiene copolymers.

  Specific examples of acrylic resins include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (n-butyl) (meth) acrylate, and 2-ethylhexyl (meth) acrylate. (Meth) acrylic acid esters such as lauryl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meth) acrylic acid esters having active hydrogen such as (meth) acrylic acid-3-hydroxypropyl and (meth) acrylic acid-4-hydroxybutyl; unsaturated such as acrylic acid, methacrylic acid, maleic acid and itaconic acid Carboxylic acids; unsaturated amides such as acrylamide, N-methylol acrylamide and diacetone acrylamide Obtained by polymerizing a single or a mixture selected from other polymerizable monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, p-styrene sulfonic acid, allyl sulfosuccinic acid, etc. Acrylic resins and the like. 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.

  Specific examples of polyester resins include succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. Selected one or a mixture with ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, , 3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, , 6-hexanediol, 1,2-hexanediol, 2,5- Xanthdiol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2, Diols such as 2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol; triols such as glycerin and trimethylolpropane; Polyester resins obtained by a condensation reaction with a single or mixture of polyhydric alcohols selected from the group of tetraols such as diglycerin, dimethylolpropane, pentaerythritol, etc., and ε- Examples thereof include polycaprolactones obtained by ring-opening polymerization of caprolactone.

  Specific examples of the polyether resins include ethylene oxide using a polyhydric hydroxy compound alone or in a mixture thereof with a hydroxide such as lithium, sodium or potassium; a strongly basic catalyst such as alcoholate or alkylamine. , Polyether polyols obtained by adding a single or mixture of alkylene oxides such as propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide; 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; so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium; That.

  Among these resins, acrylic resins and polyester resins are preferable. Moreover, resin, such as a melamine type hardening | curing agent, a urethane dispersion, and a urethane acrylic emulsion, can be used together as needed.

  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.

  Specific examples of neutralizing agents for neutralizing carboxyl groups, sulfone groups and the like include ammonia, water-soluble amino compounds such as monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, Use of at least one selected from isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, 2-ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, etc. it can. The neutralizing agent is preferably a tertiary amine such as triethylamine or dimethylethanolamine.

  In addition, inorganic pigments, organic pigments, extender pigments, silane coupling agents, titanium coupling agents, organic phosphates, organic phosphites, thickeners, leveling agents, thixotropic agents commonly 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 a 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 added, and in order to improve the storage stability of the paint, an antioxidant, a light stabilizer, and a polymerization inhibitor may be added. Also good.

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

  Specific examples of the coating substrate of the present embodiment include metals, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textile products, leather products, paper, and the like. . In some cases, a normal primer may be provided before coating.

  Hereinafter, the present embodiment will be described more specifically with specific examples and comparative examples. However, the present embodiment is not limited to the following examples and comparative examples unless they exceed the gist of the present embodiment. Absent. The physical properties of the polyisocyanate compositions in Examples and Comparative Examples were measured as follows.

(Physical property 1) Viscosity at 23 ° C. The viscosity was measured at 23 ° C. using an E-type viscometer (manufactured by Tokimec). In the measurement, a standard rotor (1 ° 34 ′ × R24) was used. The number of rotations was as follows.
100 rpm (less than 112 mPa · s)
50 rpm (in the case of 112 mPa · s or more and less than 280 mPa · s)
20 rpm (when 280 mPa · s or more and less than 560 mPa · s)
10 rpm (in the case of 560 mPa · s or more and less than 1120 mPa · s)
5 rpm (1120 mPa · s or more and less than 2240 mPa · s)
In addition, the non volatile matter of the polyisocyanate composition manufactured by each Example mentioned later and each comparative example was investigated by the below-mentioned method, and the thing whose value was 98 mass% or more was used for the measurement of a viscosity.

(Physical Property 2) Isocyanate Group Content The measurement of the isocyanate group content was performed according to the method described in JIS K7301-1995 (Test Method for Tolylene Diisocyanate Type Prepolymer for Thermosetting Urethane Elastomer). Below, the more specific measuring method of isocyanate group content rate is shown.

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

(Physical property 3) Number average molecular weight of polyisocyanate The number average molecular weight of the polyisocyanate containing the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition is determined by gel permeation chromatography (GPC) using the following apparatus and conditions. ) Was used to measure the polystyrene-based number average molecular weight.
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

(Physical property 4) Area ratio of unreacted diisocyanate trimer in modified polyisocyanate and unreacted polyisocyanate With respect to the total peak area of polyisocyanate containing modified polyisocyanate and unreacted polyisocyanate detected by GPC measurement of property 3. The ratio of the area of a mountain centered on the peak corresponding to the molecular weight three times that of the diisocyanate monomer was defined as the area ratio of the unreacted diisocyanate trimer in the modified polyisocyanate and unreacted polyisocyanate.

(Physical property 5) Average number of isocyanate functional groups The average number of functional groups is the number of isocyanate functional groups statistically possessed by one molecule of polyisocyanate. The number of molecular weight of polyisocyanate measured in physical property 3 and isocyanate group content measured in physical property 2 From the rate, it was calculated as follows.
Average number of functional groups = number average molecular weight of polyisocyanate × isocyanate group content (mass%) / 42

(Physical Property 6) Nonvolatile Content When the solvent was diluted, the mass of the aluminum cup was precisely weighed, about 1 g of a sample was put, and the mass 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 mass of the cup was weighed again. The mass% of the dry residue in the sample was defined as the nonvolatile content. The calculation method of the nonvolatile content is as follows. In the case of no solvent dilution, the nonvolatile content was treated as 100%.
Nonvolatile content (mass%) = (cup mass after heat drying−aluminum cup mass) / (cup mass before heat drying−aluminum cup mass) × 100%.

(Physical property 7) Conversion rate of isocyanuration reaction It was determined by measuring the refractive index of the reaction solution.

(Physical property 8) Average number of n of polyalkylene glycol alkyl ether in polyisocyanate composition Using polyisocyanate composition as a sample, the average number of n is determined by proton nuclear magnetic resonance (NMR) using the following apparatus and conditions. Asked. Here, by making the integral value of the relative intensity corresponding to the alkylene group correspond to the integral value of the relative intensity corresponding to the alkyl group, the alkylene oxide repeating unit in the polyalkylene glycol alkyl ether in the polyisocyanate composition-( The average number of n in R ₁ O) _n − was determined.
NMR apparatus: Bruker Biospin Avance 600 (trade name)
Observation nucleus: 1H
Frequency: 600MHz
Solvent: CDCl ₃
Integration count: 256 times

(Physical property 9) The average number of n of the raw material polyalkylene glycol alkyl ether Using the raw material polyalkylene glycol alkyl ether as a sample, the average number of n of the alkylene oxide repeating unit-(R ₁ O) _n- is the raw material polyalkylene glycol The alkyl ether was determined from the hydroxyl value of the sample. Specifically, it calculated | required as follows.

  The hydroxyl value is measured by JIS K 0070-1992 (Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products) and JIS K 1557-1 (plastic-polyurethane raw material). Polyol test method-Part 1: Determination of hydroxyl value).

From the hydroxyl value measured above, the molecular weight of the polyalkylene glycol alkyl ether was determined using the following formula. Using the molecular weight, the average number of n was calculated by the following calculation method.
Molecular weight of polyalkylene glycol alkyl ether = 56.1 × 1000 / [hydroxyl value (mgKOH / g)]

Next, the average number of n was calculated from the following formula from the molecular weight of the polyalkylene glycol alkyl ether calculated above.
Average number of n = (molecular weight of polyalkylene glycol alkyl ether−molecular weight of alkyl group−molecular weight of hydroxyl group) / (molecular weight of alkylene oxide)

For example, when the polyalkylene glycol alkyl ether used was polyethylene glycol (mono) methyl ether, the average number of n was determined as follows.
Average number of n = (molecular weight of polyethylene glycol (mono) methyl ether−molecular weight of methyl group (15) −molecular weight of hydroxyl group (17)) / (molecular weight of ethylene oxide (44))

(Physical property 10) Ratio of polyalkylene glycol alkyl ether modified (modification rate)
Using the polyisocyanate composition as a sample, the modification rate is the ratio of the polyalkylene glycol alkyl ether modified with respect to 100 equivalents of the isocyanate group of the starting polyisoisocyanate, and at a measurement wavelength of 220 nm in liquid chromatography (LC). The unmodified isocyanurate trimer, the 1 modified isocyanurate trimer, the 2 modified isocyanurate trimer, and the peak area ratio of the 3 modified isocyanurate trimer. The equipment and conditions used are as follows.
LC device: manufactured by Waters, UPLC (trade name),
Column: manufactured by Waters, ACQUITY UPLC HSS T3 1.8 μm C18 inner diameter 2.1 mm × length 50 mm
Flow rate: 0.3 mL / min
Mobile phase: A = 10 mM ammonium acetate aqueous solution, B = acetonitrile Gradient condition: Initial mobile phase composition is A / B = 98/2, the ratio of B increases linearly after sample injection, and A / B B = 0/100.
Detection method: photodiode array detector, measurement wavelength is 220 nm

(Physical Property 11) Content of Part Derived from Polyalkylene Glycol Alkyl Ether Using Polyisocyanate Composition as Sample, Content of Part Derived from Polyalkylene Glycol Alkyl Ether of Modified Polyisocyanate in Polyisocyanate Composition is ( The molecular weight of the polyalkylene glycol alkyl ether calculated from the isocyanate group content measured in the physical property 2) and the average number of n of the polyalkylene glycol alkyl ether obtained in the physical property 8 and the physical property 10 The following calculation was performed based on the denaturation rate.
Content (%) = isocyanate group content (% by mass) / 100% / 42 / (100-modification rate (%)) × modification rate (%) × molecular weight of polyalkylene glycol alkyl ether × 100%

For example, when the polyalkylene glycol alkyl ether used was polyethylene glycol (mono) methyl ether, it was determined as follows.
Molecular weight of polyethylene glycol (mono) methyl ether = molecular weight of methyl group (15) + molecular weight of hydroxyl group (17) + (molecular weight of ethylene oxide (44) × n average number)

[Production Example 1 (Production of polyisocyanate)]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was placed in a nitrogen atmosphere, and 600 parts of HDI and 0.6 part of isobutanol were charged. C. for 2 hours. Thereafter, tetramethylammonium capryate was added as an isocyanurate-forming catalyst, an isocyanurate-forming reaction was carried out, and phosphoric acid was added to stop the reaction when the conversion rate reached 13%. Thereafter, the reaction solution was further maintained at 160 ° C. for 1 hour. This heating produced a polyisocyanate containing uretdione groups. After cooling and filtering the reaction liquid, unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate composition (1) containing a uretdione group.

[Production Example 2 (Production of polyisocyanate)]
A polyisocyanate composition (2) was obtained in the same manner as in Production Example 1 except that the conversion of the isocyanurate reaction was changed from 13% to 17%.

[Production Example 3 (Production of polyisocyanate)]
In addition to 0.6 part of isobutanol, 2.0 parts of 2-ethylhexanol was further added, and the conversion of the isocyanurate reaction was carried out in the same manner as in Production Example 1 except that the conversion rate was changed from 13% to 12%. 3) was obtained.

[Production Example 4 (Production of polyisocyanate)]
Manufacture except that isobutanol is changed from 0.6 parts to 3.0 parts of 2-ethylhexanol, the conversion of isocyanurate reaction is from 13% to 21%, and the reaction solution is heated from 160 ° C for 1 hour to 160 ° C for 30 minutes. In the same manner as in Example 1, a polyisocyanate composition (4) was obtained.

[Production Example 5 (Production of polyisocyanate)]
Manufactured except that 0.6 part of isobutanol to 18.0 parts of 2-ethylhexanol, the conversion of isocyanurate reaction is 13% to 28%, and the reaction liquid is heated at 160 ° C for 1 hour to 90 ° C for 1 hour. In the same manner as in Example 1, a polyisocyanate composition (5) was obtained.

[Production Example 6 (Production of polyisocyanate)]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel is placed in a nitrogen atmosphere, 1000 parts of HDI, 10 parts of 1,3-butanediol, 3 parts of tri-n-butylphosphine The reactor was heated to 60 ° C. with stirring and reacted for 4 hours. Then, p-toluenesulfonic acid methyl ester was added and the reaction was stopped by heating at 80 ° C. for 1 hour. Thereafter, the reaction solution was further maintained at 160 ° C. for 1 hour. After cooling and filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain a polyisocyanate composition (6) containing a large amount of uretdione groups.

[Production Example 7 (Production of polyisocyanate)]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was placed in a nitrogen atmosphere, 600 parts of HDI, 1.0 part of 1,3-butanediol, and tetraisocyanate forming catalyst. Methylammonium capryate was charged, the temperature in the reactor was heated to 70 ° C. with stirring, and the reaction was carried out for 3 hours. Thereafter, p-toluenesulfonic acid methyl ester was added to stop the reaction. Thereafter, the reaction solution was further maintained at 100 ° C. for 1 hour. The reaction solution was cooled, filtered, and unreacted HDI was removed using a thin-film evaporator to obtain a polyisocyanate composition (7).

[Production Example 8 (Production of polyisocyanate)]
0.93 parts by mass of 1,3-butanediol was added to 100 parts by mass of HDI-based polyisocyanate (product name “Duranate TKA”, manufactured by Asahi Kasei Chemicals Corporation), and the mixture was reacted at 80 ° C. for 2 hours under nitrogen. To obtain a polyisocyanate composition (8).

[Production Example 9 (Production of polyethylene glycol monomethyl ether)]
After the inside of a 1000 ml autoclave reactor was purged with nitrogen, 128 g (4.0 mol) of methanol and 0.56 g (9.8 mmol) of potassium hydroxide were charged. After raising the temperature to 110 ° C., 1320 g (30.0 mol) of ethylene oxide was reacted under pressure for 2.5 hours while maintaining this temperature, and further aged for 1 hour. The obtained reaction mixture was neutralized by adding 1.16 g (10.0 mmol) of 85% by mass of phosphoric acid, the precipitated potassium salt of phosphoric acid was removed by filtration, and the average number of ethylene oxide repeating units: 7.0 Of polyethylene glycol monomethyl ether (1) was obtained.

[Production Example 10 (Production of polyethylene glycol monomethyl ether)]
Average number of ethylene oxide repeating units: Polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units of 9.4 in 85 parts by mass of polyethylene glycol monomethyl ether of 4.2 (trade name “MPG” manufactured by Nippon Emulsifier Co., Ltd.) 15 parts by mass (manufactured by Nippon Emulsifier Co., Ltd., trade name “MPG-130”) was added and mixed and stirred at room temperature for 30 minutes. Got.

[Example 1]
To 97 parts by mass of the polyisocyanate composition (1) obtained in Production Example 1, polyethylene glycol monomethyl ether having a number average molecular weight of 550 (manufactured by NOF Corporation, trade name “Uniox M-550 (average of ethylene oxide repeating units) Number: 11.8) ") 3 parts by mass were added, and the reaction was performed by stirring at 100 ° C for 4 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a non-volatile content of 100%, an isocyanate group content of 22.7% by mass, and a viscosity of 450 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 550 and an average of The number of functional groups: 2.97, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 61.3.

  The average number of ethylene oxide repeating units detected from NMR was 11.9, and the modification rate of polyethylene glycol monomethyl ether in the resulting composition was 1.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 3.0%.

[Example 2]
In 94 parts by mass of the polyisocyanate composition (2) obtained in Production Example 2, polyethylene glycol monomethyl ether having a number average molecular weight of 400 (manufactured by NOF Corporation, trade name “Uniox M-400 (average of ethylene oxide repeating units) Number: 8.4) ") 6 parts by mass were added, and the reaction was carried out by stirring at 100 ° C for 4 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a nonvolatile content of 100%, an isocyanate group content of 21.2% by mass, and a viscosity of 630 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 600 and an average of The number of functional groups: 3.01, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 53.9.

  The average number of ethylene oxide repeating units detected from NMR was 8.3, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 3.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 6.2%.

[Example 3]
In 90 parts by mass of the polyisocyanate composition (2) obtained in Production Example 2, an average number of ethylene oxide repeating units: 9.4 polyethylene glycol monomethyl ether (trade name “MPG-130”, manufactured by Nippon Emulsifier Co., Ltd.) 10 parts by mass was added, and the reaction was performed by stirring at 90 ° C. for 6 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a non-volatile content of 100%, an isocyanate group content of 19.9% by mass, and a viscosity of 670 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 620, an average of The number of functional groups: 2.96, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 47.0.

  The average number of ethylene oxide repeating units detected from NMR was 9.4, and the modification ratio of polyethylene glycol monomethyl ether in the obtained composition was 4.5%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 9.9%.

[Example 4]
To 95 parts by mass of the polyisocyanate composition (3) obtained in Production Example 3, 5 parts by mass of polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Production Example 9 of 7.0 is added. The reaction was carried out with stirring at 90 ° C. for 6 hours. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained had a non-volatile content of 100%, an isocyanate group content of 21.3% by mass, and a viscosity of 350 mPa · s. The polyisocyanate in the composition obtained had a number average molecular weight of 560 and an average of The number of functional groups: 2.82, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 59.9.

  The average number of ethylene oxide repeating units detected from NMR was 7.2, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 2.8%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 5.0%.

[Example 5]
To 90 parts by mass of the polyisocyanate composition (3) obtained in Production Example 3, 10 parts by mass of polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units: 4.2 (trade name “MPG” manufactured by Nippon Emulsifier Co., Ltd.) Part was added, and the reaction was performed by stirring at 80 ° C. for 6 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a non-volatile content of 100%, an isocyanate group content of 18.9% by mass, and a viscosity of 360 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 590 and an average of Functional group number: 2.63, The area ratio of the unreacted diisocyanate trimer in the obtained composition was 51.4.

  The average number of ethylene oxide repeating units detected from NMR was 4.1, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 9.4%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 9.9%.

[Example 6]
In 96 parts by mass of the polyisocyanate composition (4) obtained in Production Example 4, an average number of ethylene oxide repeating units: 15.0 polyethylene glycol monomethyl ether (manufactured by Nippon Emulsifier Co., Ltd., trade name “MPG-081”) 4 parts by mass were added, and the reaction was performed by stirring at 110 ° C. for 4 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The obtained composition has a nonvolatile content of 100%, an isocyanate group content of 21.8% by mass, and a viscosity of 900 mPa · s. The polyisocyanate in the obtained composition has a number average molecular weight of 570 and an average of The number of functional groups: 2.97, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 65.2.

  The average number of ethylene oxide repeating units detected from NMR was 15.0, and the modification ratio of polyethylene glycol monomethyl ether in the obtained composition was 1.2%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 4.3%.

[Example 7]
To 95 parts by mass of the polyisocyanate composition (4) obtained in Production Example 4, 5 parts by mass of polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Production Example 10 of 5.0 is added. The reaction was carried out with stirring at 110 ° C. for 4 hours. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a nonvolatile content of 100%, an isocyanate group content of 21.0% by mass, and a viscosity of 850 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 580 and an average of The number of functional groups: 2.89, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 62.0.

  The average number of ethylene oxide repeating units detected from NMR was 5.1, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 3.7%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 4.9%.

[Example 8]
To 98 parts by mass of the polyisocyanate composition (5) obtained in Production Example 5, polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units: 9.4 (trade name “MPG-130”, manufactured by Nippon Emulsifier Co., Ltd.) 2 parts by mass were added, and the reaction was performed by stirring at 110 ° C. for 3 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a non-volatile content of 100%, an isocyanate group content of 20.2% by mass, and a viscosity of 510 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 570 and an average of Functional group number: 2.74, The area ratio of the unreacted diisocyanate trimer in the obtained composition was 67.0.

  The average number of ethylene oxide repeating units detected from NMR was 9.4, and the modification rate of polyethylene glycol monomethyl ether in the resulting composition was 1.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 2.1%.

[Example 9]
To 88 parts by mass of the polyisocyanate composition (5) obtained in Production Example 5, 12 parts by mass of polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Production Example 10 of 5.0 is added. The reaction was carried out with stirring at 110 ° C. for 4 hours. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a nonvolatile content of 100%, an isocyanate group content of 16.3% by mass, and a viscosity of 630 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 640 and an average of Functional group number: 2.47, The area ratio of the unreacted diisocyanate trimer in the obtained composition was 52.0.

  The average number of ethylene oxide repeating units detected from NMR was 5.1, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 11.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 12.3%.

[Example 10]
To 90 parts by mass of the polyisocyanate composition (5) obtained in Production Example 5, 10 parts by mass of an average number of ethylene oxide repeating units: 4.2 polyethylene glycol monomethyl ether (trade name “MPG” manufactured by Nippon Emulsifier Co., Ltd.) Part was added, and it reacted by stirring at 110 degreeC under nitrogen for 4 hours. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained had a non-volatile content of 100%, an isocyanate group content of 16.8% by mass, and a viscosity of 650 mPa · s. The polyisocyanate in the composition obtained had a number average molecular weight of 620 and an average of The number of functional groups: 2.48, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 53.0.

  The average number of ethylene oxide repeating units detected from NMR was 4.1, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 10.5%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 10.0%.

[Comparative Example 1]
To 100 parts by mass of the polyisocyanate composition (1) obtained in Production Example 1, polyethylene glycol monomethyl ether having an average molecular weight of 550 (manufactured by NOF Corporation, trade name “Uniox M-550 (average number of ethylene oxide repeating units) 11.8) ") 15.4 parts by mass were added, and the reaction was carried out by stirring at 80 ° C for 6 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a non-volatile content of 100%, an isocyanate group content of 19.1% by mass, and a viscosity of 470 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 600 and an average of The number of functional groups: 2.73, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 48.4.

  The average number of ethylene oxide repeating units detected from NMR was 11.9, and the modification rate of polyethylene glycol monomethyl ether in the resulting composition was 5.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 13.3%.

[Comparative Example 2]
To 100 parts by mass of the polyisocyanate composition (2) obtained in Production Example 2, polyethylene glycol monomethyl ether having an average molecular weight of 550 (manufactured by NOF Corporation, trade name “Uniox M-550 (average number of ethylene oxide repeating units) 11.8) ") 15.2 parts by mass were added, and the reaction was carried out by stirring at 80 ° C for 6 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The obtained composition has a nonvolatile content of 100%, an isocyanate group content of 18.6% by mass, and a viscosity of 690 mPa · s. The polyisocyanate in the obtained composition has a number average molecular weight of 640 and an average of The number of functional groups: 2.83, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 45.6.

  The average number of ethylene oxide repeating units detected from NMR was 11.9, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 5.1%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 13.2%.

[Comparative Example 3]
20 parts by mass of 100 parts by mass of the polyisocyanate composition (4) obtained in Production Example 4 and polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units: 4.2 (trade name “MPG” manufactured by Nippon Emulsifier Co., Ltd.) Part was added, and the reaction was performed by stirring at 90 ° C. for 8 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained had a non-volatile content of 100%, an isocyanate group content of 16.0% by mass, and a viscosity of 1100 mPa · s. The polyisocyanate in the composition obtained had a number average molecular weight of 680 and an average of The number of functional groups: 2.49, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 43.3.

  The average number of ethylene oxide repeating units detected from NMR was 4.1, and the modification ratio of polyethylene glycol monomethyl ether in the obtained composition was 17.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 16.6%.

[Comparative Example 4]
To 100 parts by mass of the polyisocyanate composition (5) obtained in Production Example 5, polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units: 9.4 (trade name “MPG-130”, manufactured by Nippon Emulsifier Co., Ltd.) 20 parts by mass was added, and the reaction was carried out by stirring at 90 ° C. for 8 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained had a non-volatile content of 100%, an isocyanate group content of 15.5% by mass, and a viscosity of 740 mPa · s. The polyisocyanate in the obtained composition had a number average molecular weight of 680 and an average of The number of functional groups: 2.52, and the area ratio of unreacted diisocyanate trimer in the obtained composition was 45.0.

  The average number of ethylene oxide repeating units detected from NMR was 9.4, and the modification ratio of polyethylene glycol monomethyl ether in the obtained composition was 9.2%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 16.7%.

[Comparative Example 5]
To 100 parts by mass of the polyisocyanate composition (6) obtained in Production Example 6, 9.5 parts by mass of polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Production Example 9 of 7.0 was added. The reaction was carried out with stirring at 100 ° C. for 2.5 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained had a non-volatile content of 100%, an isocyanate group content of 18.9% by mass, and a viscosity of 320 mPa · s. The polyisocyanate in the composition obtained had a number average molecular weight of 510 and an average of Functional group number: 2.27, The area ratio of the unreacted diisocyanate trimer in the obtained composition was 15.8.

  The average number of ethylene oxide repeating units detected from NMR was 7.2, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 5.3%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 8.8%.

[Comparative Example 6]
To 100 parts by mass of the polyisocyanate composition (7) obtained in Production Example 7, 5.6 parts by mass of polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units obtained in Production Example 9 of 7.0 was added. The reaction was conducted with stirring at 100 ° C. for 2 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained has a nonvolatile content of 100%, an isocyanate group content of 20.7% by mass, and a viscosity of 1100 mPa · s. The polyisocyanate in the composition obtained has a number average molecular weight of 650 and an average of Functional group number: 3.20, The area ratio of the unreacted diisocyanate trimer in the obtained composition was 62.6.

  The average number of ethylene oxide repeating units detected from NMR was 7.2, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 3.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 5.3%.

[Comparative Example 7]
To 99.5 parts by mass of the polyisocyanate composition (1) obtained in Production Example 1, polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units: 9.4 (manufactured by Nippon Emulsifier Co., Ltd., trade name “MPG-130”) ]) 0.5 parts by mass was added, and the reaction was carried out by stirring at 100 ° C. for 4 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The composition obtained had a non-volatile content of 100%, an isocyanate group content of 23.4% by mass, and a viscosity of 410 mPa · s. The polyisocyanate in the obtained composition had a number average molecular weight of 530 and an average of The number of functional groups: 2.99, and the area ratio of the unreacted diisocyanate trimer in the obtained composition was 64.3.

  The average number of ethylene oxide repeating units detected from NMR was 9.4, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 0.2%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 0.5%.

[Comparative Example 8]
Polyethylene glycol monomethyl ether having an average number of ethylene oxide repeating units: 9.4 (manufactured by Nippon Emulsifier Co., Ltd., trade name “MPG-130”) in 90 parts by mass of the polyisocyanate composition (8) obtained in Production Example 8 10 parts by mass was added, and the reaction was performed by stirring at 120 ° C. for 3 hours under nitrogen. After completion of the reaction, a composition containing a modified polyisocyanate was obtained.

  The obtained composition has a nonvolatile content of 100%, an isocyanate group content of 17.6% by mass, and a viscosity of 6000 mPa · s. The polyisocyanate in the obtained composition has a number average molecular weight of 800 and an average of The number of functional groups: 3.40, the area ratio of the unreacted diisocyanate trimer in the obtained composition was 30.2.

  The average number of ethylene oxide repeating units detected from NMR was 9.4, and the modification rate of polyethylene glycol monomethyl ether in the obtained composition was 5.0%. Therefore, the content of polyethylene glycol monomethyl ether was calculated to be 9.8%.

  Evaluation of the polyisocyanate composition containing the modified polyisocyanate obtained in Examples 1 to 10 and Comparative Examples 1 to 8 was performed as follows. The evaluation results are shown in Table 1.

(Evaluation 1) Water dispersibility (1) The mass 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 the Yoshino paper and the residue remaining on the 100 mL flask were combined and heated in a dryer at 105 ° C. for 1 hour to determine the mass (g).
(5) The ratio of the composition containing the modified polyisocyanate dispersed in water was determined by the following calculation method.
Ratio (mass%) dispersed in water = 100% − (total mass of 100 mL flask containing the residue determined in (4) and Yoshino paper (g) −total of 100 mL flask and Yoshino paper measured by (1) Mass (g)) / (mass of composition containing modified polyisocyanate collected in (2) (g) × nonvolatile content (mass%)) × 100%
The judging method was as follows.
○: 80% by mass or more ×: less than 80% by mass

(Evaluation 2) Water dispersion stability 0.1 g of composition containing modified polyisocyanate and 100 g of deionized water are weighed into a 200 mL flask, and the solution in the 200 mL flask is stirred at 600 rpm for 5 minutes using propeller blades. An aqueous dispersion was obtained. Then, it transferred to the 50 mL glass bottle, and the dispersion state was observed with the naked eye.
The judging method was as follows.
○: No change was observed after 2 hours.
○ Δ: Slight precipitation or separation was observed after 2 hours.
Δ: Slight precipitation or separation was observed after 1 hour.
X: Precipitation or separation was observed within 1 hour.

(Evaluation 3) Retention of isocyanate group In a 100 mL flask, weigh 15 g of a composition containing modified polyisocyanate and 45 g of deionized water, and use a propeller blade to stir the solution in the 100 mL flask at 600 rpm for 10 minutes. An aqueous dispersion was obtained. The retention rate of isocyanate groups in this aqueous dispersion was evaluated as follows.

The change in the concentration of the isocyanate group was determined by measuring the infrared absorption spectrum using FT / IR-4200type A (trade name) manufactured by JASCO Corporation (detector: TGS, number of integrations: 16 times, decomposition: 4 cm ⁻¹ ). It was calculated from the intensity ratio of absorption peaks of isocyanurate isocyanate absorption peaks for (wavenumber 1686cm around ^-1) (wavenumber of around 2271cm ^-1).

Immediately after the preparation of the aqueous dispersion, 0 hour is set, the absorption peak intensity of isocyanate at that time / absorption peak intensity of isocyanurate = X0, the peak intensity ratio after n hours = Xn is obtained, and the retention rate of isocyanate group = Xn / X0 And the retention after 6 hours was evaluated. The judging method was as follows.
○: 80% or more ×: less than 80%

[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 inside of the reactor was put into a nitrogen atmosphere, 300 parts by mass of ethylene glycol monobutyl ether was charged, and the temperature in the reactor was kept 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 A mixture obtained by uniformly mixing 0.7 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator and 0.3 parts by weight of n-dodecyl mercaptan as a chain transfer agent over 4.5 hours It was added continuously at a constant rate. Thereafter, the temperature in the reactor was kept at 80 ° C. for 2 hours. Thereafter, the mixture in the reactor was cooled, 11.6 parts by mass of a 25% by mass aqueous ammonia solution was added, and the mixture was stirred for 15 minutes. Furthermore, 1300 parts by mass of ion-exchanged water was added to the mixture in the reactor while stirring to obtain an aqueous dispersion. The obtained aqueous dispersion was concentrated using a rotary evaporator until the solid content was about 45% by mass. Thereafter, the obtained concentrate was adjusted to pH 8.0 with 25% by mass aqueous ammonia to obtain an aqueous dispersion of an acrylic polyol. The obtained acrylic polyol aqueous dispersion has an average particle diameter of 90 nm of particles in the aqueous dispersion, and the hydroxyl group concentration of the polyol resin is 3.3% by mass as calculated from the raw materials used. The number average molecular weight of the polyol resin was 9,600.

[Examples 11 to 20, Comparative Examples 9 to 16]
Using the compositions containing modified polyisocyanates obtained in Examples 1 to 10 and Comparative Examples 1 to 8, coating compositions were prepared as follows.

[Preparation of coating composition]
A 40 g container of the aqueous polyol dispersion prepared in Production Example 11 was weighed, and the molar ratio of the isocyanate group in the composition containing 4 g of propylene glycol monomethyl ether acetate and the modified polyisocyanate to the hydroxyl group in the aqueous polyol dispersion was NCO. A composition containing a modified polyisocyanate was added so that /OH=1.25 was obtained. Furthermore, deionized water was added to the above mixture so that the solid content of the coating composition was 45% by mass, and the mixture was stirred at 1000 rpm for 5 minutes using a disper feather to prepare a coating composition. The following coating film evaluation was performed using the produced coating composition. The evaluation results are shown in Table 2.

(Evaluation 4) Appearance of coating film Using the above coating composition, a coating film having a thickness of 40 μm was applied on a glass plate and baked at 60 ° C. for 30 minutes. The obtained coating film was visually evaluated. The judging method was as follows.
○: Transparent, no foreign matter △: Slightly cloudy, somewhat foreign matter, smoothness slightly low ×: White turbidity, many foreign matters, low smoothness

(Evaluation 5) Crosslinkability of coating film A coating film having a thickness of 40 μm was applied on a PP plate using the above coating composition and baked at 60 ° C. for 30 minutes. The film was cooled in an atmosphere of 23 ° C./50% RH, and the resulting coating film was immersed in acetone at 23 ° C. for 24 hours, then taken out and dried. The crosslinkability of the coating film was calculated by the following calculation method.
Crosslinkability of coating film (%) = (mass of coating film remaining without being dissolved) / (mass of coating film before immersion in acetone) × 100%
The judging method was as follows.
○: 92% or more △: 90% or more, less than 92% ×: less than 90%

(Evaluation 6) Hardness of coating film Using the above coating composition, a coating film having a thickness of 40 μm was applied on a glass plate and baked at 60 ° C. for 30 minutes. The film was cooled in an atmosphere of 23 ° C./50% RH, and the obtained film was measured the next day using a König hardness meter (manufactured by BYK Garder, trade name “Pendulum hardness tester”). The judging method was as follows.
○: 40 or more ×: less than 40

(Evaluation 7) Solvent resistance of coating film Using the above coating composition, a coating film having a thickness of 40 μm was applied on a glass plate and baked at 60 ° C. for 30 minutes, and then 23 ° C./50% RH. Dry for 7 days under atmosphere. 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 △: Some cloudiness or some dent ×: Some cloudiness or dent

(Evaluation 8) Water resistance of coating film Using the above coating composition, a coating film having a thickness of 40 μm was applied on an aluminum plate and baked at 60 ° C. for 30 minutes, and then an atmosphere of 23 ° C./50% RH. On the next day, a silicon O-ring having a diameter of 20 mm was placed on the obtained coating film, and 0.5 g of water was poured therein. The state of the coating film was observed after leaving at 23 ° C. for 24 hours and removing water remaining on the surface. The judging method was as follows.
○: No change ×: Blister generation, cloudiness, or dissolution of coating film

[Production Example 12 (Preparation of coating main agent)]
92 parts by mass of water-based acrylic polyol (product name “Macrynal VSM2521w / 42WA” manufactured by Allnex Co., Ltd.), 0.5 part by mass of antifoaming agent (product name “BYK028” manufactured by BYK Co., Ltd.), and thickener (product manufactured by Dow Chemical Co., Ltd., product) Name “SCT275”) 0.5 parts by mass, thickener (manufactured by Dow Chemical, trade name “RM5000”) 0.5 parts by mass and 7 parts by mass of deionized water are stirred and mixed to obtain a coating base (1). It was.

[Examples 21 to 30, Comparative Examples 17 to 24]
Using the compositions containing the modified polyisocyanates obtained in Examples 1 to 10 and Comparative Examples 1 to 8, coating compositions were prepared as follows according to the correspondence in Table 3.

[Preparation of coating composition]
40 g of the coating main agent (1) produced in Production Example 12 was weighed into a container, and the molar ratio of isocyanate groups in the composition containing each modified polyisocyanate to hydroxyl groups in the polyol aqueous dispersion was NCO / OH = 1. The composition containing the modified polyisocyanate was added so as to obtain a mixture of 3 to obtain a mixture. Deionized water was added to the resulting mixture so that the solid content of the coating composition was 45% by mass, and the mixture was stirred at 600 rpm for 5 minutes using a disper feather to prepare a coating composition. The following coating film evaluation was performed using the produced coating composition. The evaluation results are shown in Table 3.

(Evaluation 9) Drying property of coating film Using the above coating composition, a coating film having a thickness of 40 μm was coated on a glass plate, dried in an atmosphere of 23 ° C./50% RH, and after 3 hours, A cylindrical cotton having a diameter of 2.5 cm and a height of 2.0 cm was placed on the obtained coating film, and 100 g of a weight was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the cotton marks remaining on the coating film were observed.
The judging method was as follows.
○: Slight or no cotton marks △: Slightly cotton marks ×: Many cotton marks

(Evaluation 10) Pencil hardness of the coating film Using the above coating composition, a coating film having a thickness of 40 μm was coated on a glass plate and dried in an atmosphere of 23 ° C./50% RH. The coated film was tested based on JIS K 5600-5-4 scratch hardness (pencil method).
The judging method was as follows.
○: F or more ×: Less than F

[Production Example 13 (Preparation of coating main agent)]
92 parts by mass of water-based acrylic polyol (trade name “Macrynal VSM6299w / 42WA” manufactured by Allnex Co., Ltd.) Name “SCT275”) 0.5 parts by mass, thickener (manufactured by Dow Chemical, trade name “RM5000”) 0.5 parts by mass and 7 parts by mass of deionized water are stirred and mixed to obtain a coating base (2). It was.

[Examples 31 to 40, Comparative Examples 25 to 32]
Using the compositions containing the modified polyisocyanates obtained in Examples 1 to 10 and Comparative Examples 1 to 8, coating compositions were prepared as follows according to the correspondence in Table 4.

[Preparation of coating composition]
40 g of the coating main agent (2) produced in Production Example 13 was weighed into a container, and the molar ratio of the isocyanate group in the composition containing each modified polyisocyanate to the hydroxyl group in the polyol aqueous dispersion was NCO / OH = 1. The composition containing the modified polyisocyanate was added so as to obtain a mixture of 3 to obtain a mixture. Deionized water was added to the resulting mixture so that the solid content of the coating composition was 45% by mass, and the mixture was stirred at 600 rpm for 5 minutes using a disper feather to prepare a coating composition. The following coating film evaluation was performed using the produced coating composition. The evaluation results are shown in Table 4.

(Evaluation 11) Drying property of coating film Using the above coating composition, a coating film having a thickness of 40 μm was coated on a glass plate, dried in an atmosphere of 23 ° C./50% RH, and after 4 hours, A cylindrical cotton having a diameter of 2.5 cm and a height of 2.0 cm was placed on the obtained coating film, and 100 g of a weight was placed thereon for 60 seconds. Thereafter, the weight and cotton were removed, and the cotton marks remaining on the coating film were observed.
The judging method was as follows.
○: Slight or no cotton marks △: Slightly cotton marks ×: Many cotton marks

(Evaluation 12) Pencil Hardness of Coating Film Using the above coating composition, a coating film having a thickness of 40 μm was applied on a glass plate and dried in an atmosphere of 23 ° C./50% RH. The coated film was tested based on JIS K 5600-5-4 scratch hardness (pencil method).
The judging method was as follows.
○: F or more ×: Less than F

  This application is based on a Japanese patent application (Japanese Patent Application No. 2014-231676) filed with the Japan Patent Office on November 14, 2014, the contents of which are incorporated herein by reference.

Claims (8)

A polyisocyanate composition containing a modified polyisocyanate obtained from a polyisocyanate and a polyalkylene glycol alkyl ether represented by the following general formula (1):
The portion derived from the polyalkylene glycol alkyl ether is 1.0% by mass or more and less than 13% by mass with respect to 100% by mass of the polyisocyanate composition.
The average isocyanate functional group number is 2.3 or more and 3.3 or less,
The polyisocyanate composition whose viscosity in 23 degreeC is 330 mPa * s or more and 1000 mPa * s or less.

(In Formula (1), R ₁ is an alkylene group having 1 to 4 carbon atoms, and R ₂ is an alkyl group having 1 to 4 carbon atoms. The average number of n is 5.0 or more and 20 or less. ) 2. The polyisocyanate composition according to claim 1, wherein in general formula (1), R ₁ is an ethylene group, and the average number of n is 5.0 or more and 11 or less.   The polyisocyanate composition according to claim 1 or 2, wherein the average number of isocyanate functional groups is 2.5 or more and 3.2 or less.   The area ratio of the diisocyanate trimer to the total peak area of the polyisocyanate and the modified polyisocyanate determined by differential refractometer detection with gel permeation chromatography is 45% or more with respect to the total area of 100%. The polyisocyanate composition according to any one of claims 1 to 3, which is 65% or less.   The area ratio of the diisocyanate trimer to the total peak area of the polyisocyanate and the modified polyisocyanate obtained by differential refractometer detection with gel permeation chromatography is 47% or more with respect to the total area of 100%. The polyisocyanate composition according to any one of claims 1 to 4, which is 60% or less.   The coating composition containing the polyisocyanate composition as described in any one of Claims 1-5.   An aqueous coating composition comprising the coating composition according to claim 6 and water.   A coated substrate coated with the coating composition according to claim 6 or the aqueous coating composition according to claim 7.