JP2015010183A - Diisocyanate composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a diisocyanate composition which enables synthesis of a polyisocyanate composition suppressed in coloring.SOLUTION: The diisocyanate composition comprises 1,6-diisocyanato-hexane and 1-100 mass ppm of a chlorine-containing compound relative to 1,6-diisocyanato-hexane and as a chlorine ingredient.

Description

  The present invention relates to a diisocyanate composition.

  An aliphatic diisocyanate composition typified by 1,6-diisocyanatohexane (HDI; also referred to as hexamethylene diisocyanate) is made into a polyisocyanate composition by oligomerization using various synthetic techniques, and various uses. Widely used in Among them, polyisocyanate compositions containing an isocyanurate structure are widely used because various physical property improvements are expected compared to other structures (for example, Patent Documents 1 to 3).

Japanese Examined Patent Publication No. 45-027982 JP-A-55-038380 Japanese Patent Laid-Open No. 57-150677

  However, a polyisocyanate composition prepared using an aliphatic diisocyanate composition such as HDI has a problem that it is difficult to suppress coloring.

  This invention is made | formed in view of the said situation, and it aims at providing the diisocyanate composition which can synthesize | combine the polyisocyanate composition by which coloring was suppressed.

  As a result of intensive studies by the inventor, 1,6-diisocyanatohexane and 1-6-mass ppm as a chlorine component are contained as a chlorine component with respect to 1,6-diisocyanatohexane. The present inventors have found that a diisocyanate composition can achieve the above-described problems and have come to achieve the present invention.

That is, the present invention is as follows.
[1]
1,6-diisocyanatohexane,
With respect to the 1,6-diisocyanatohexane, a chlorine-containing compound as a chlorine component, 1 to 100 ppm by mass,
A diisocyanate composition.
[2]
The diisocyanate composition according to [1], containing 1 to 100 mass ppm of a bromine-containing compound as a bromine component with respect to the 1,6-diisocyanatohexane.
[3]
The diisocyanate composition according to [1] or [2], wherein a content of the 1,6-diisocyanatohexane is 97.0% by mass or more.

  ADVANTAGE OF THE INVENTION According to this invention, the diisocyanate composition which can synthesize | combine the polyisocyanate composition by which coloring was suppressed can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof. Unless otherwise specified, “(meth) acryl” includes methacryl and acryl, and “(meth) acrylate” includes methacrylate and acrylate.

  The diisocyanate composition of this embodiment contains 1 to 100 mass ppm of a chlorine-containing compound as a chlorine component with respect to 1,6-diisocyanatohexane and 1,6-diisocyanatohexane, It is a diisocyanate composition. Such a diisocyanate composition can synthesize a polyisocyanate composition in which coloring is suppressed.

  That is, the diisocyanate composition of the present embodiment is preferably a diisocyanate composition containing 1,6-diisocyanatohexane as a main component. By including 1,6-diisocyanatohexane as a main component, various durability such as weather resistance can be obtained as compared with aromatic diisocyanate monomers such as diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDI). It will be excellent. From this viewpoint, the content of 1,6-diisocyanatohexane in the diisocyanate composition is preferably 97.0% by mass or more, more preferably 98.0% by mass or more, and still more preferably 98.% by mass. It is 5 mass% or more, More preferably, it is 99.0 mass% or more. By making content of 1, 6- diisocyanato hexane more than the said lower limit, the improvement of the yield of the polyisocyanate composition obtained by superposition | polymerization and suppression of high viscosity are attained. The content of 1,6-diisocyanatohexane referred to here is the purity of the monomer used in the so-called production, and the component (for example, solvent component) used accompanying the polymerization reaction or the like is included in this. exclude. For example, the solvent component used for diluting the monomer is not included when considering the content of 1,6-diisocyanatohexane. The purity of 1,6-diisocyanatohexane can be determined by gas chromatography measurement. Specifically, it can measure according to the method as described in an Example.

  The diisocyanate composition of this embodiment is any one selected from the group consisting of other diisocyanate monomers; polyisocyanates such as uretdione dimers, isocyanurate trimers, and iminooxadiazine dione trimers of diisocyanate monomers. You may further contain a seed | species or more.

  Examples of other diisocyanate monomers include aliphatic groups such as 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 2,2,4-trimethyl-1,6-diisocyanatohexane, and lysine diisocyanate. Diisocyanate monomers; isophorone diisocyanate (hereinafter sometimes referred to as IPDI), 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, etc. And alicyclic diisocyanate monomers; aromatic diisocyanate monomers such as MDI, TDI, naphthalene diisocyanate, and xylylene diisocyanate.

  Polyisocyanates such as uretdione dimer, isocyanurate trimer, and iminooxadiazine dione trimer are taken out from the low-boiling components produced when the polyisocyanate composition is synthesized from the diisocyanate composition of this embodiment. Can also be used. Specifically, a polymerization reaction is performed using a diisocyanate composition as a raw material, and the reaction is stopped at a predetermined conversion rate. And while isolating a polyisocyanate composition by refinement | purification, reusing the low boiling fraction collect | recovered as a diisocyanate composition etc. are mentioned.

  The total content of other diisocyanate monomers and polyisocyanates is preferably less than 3.0% by mass, more preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less, More preferably, it is 1.0 mass% or less.

  The diisocyanate composition of the present embodiment contains a chlorine-containing compound and 1 to 100 mass ppm as a chlorine component with respect to 1,6-diisocyanatohexane. As a result of intensive studies by the present inventors, surprisingly, by controlling the content of the chlorine-containing compound in the diisocyanate composition that is the raw material of the polyisocyanate composition to 1 to 100 mass ppm as the chlorine component, at least, It has been found that coloring of the polyisocyanate composition can be sufficiently suppressed. Content of a chlorine containing compound can be measured by the method as described in an Example.

  The upper limit of the content of the chlorine-containing compound is preferably 80 ppm by mass or less, more preferably 70 ppm by mass or less, still more preferably 60 ppm by mass or less, and still more preferably 50 ppm by mass as the chlorine component. ppm or less. If the chlorine component exceeds 100 mass ppm, the effect of suppressing coloration of the polyisocyanate composition may not be sufficiently obtained, or depending on the additive used, it may cause turbidity due to the interaction with the additive. is there.

  The lower limit of the content of the chlorine-containing compound is preferably 3 ppm by mass or more, more preferably 6 ppm by mass or more, still more preferably 10 ppm by mass or more, and even more preferably 15 masses as the chlorine component. ppm or more. If the content of the chlorine component is less than 1 ppm by mass, the effect of suppressing coloration of the polyisocyanate composition cannot be obtained sufficiently.

  As a method for controlling the content of the chlorine-containing compound within the above range, for example, a method of adding 1-isocyanato-6-chlorohexane to 1,6-diisocyanatohexane obtained by a non-phosgene process, a phosgene method Examples include controlling the distillation conditions of 1,6-diisocyanatohexane, which is the final step of the process, and controlling the amount of chlorine component derived from phosgene as a raw material. Among these, a method of adding a chlorine-containing compound to 1,6-diisocyanatohexane obtained by a non-phosgene process is preferable from the viewpoint of ease of controlling the chlorine component amount.

  Examples of the method for producing 1,6-diisocyanatohexane used in the present embodiment include a method not using a phosgene compound (non-phosgene process) as shown in Japanese Patent No. 4859255 and the like. . As one specific example, hexamethylene diamine and bis (3-methylbutyl) carbonate are reacted and then transesterified with 2,4-di-tert-amylphenol to give N, N′-hexanediyl-bis. -Carbamic acid di (2,4-di-tert-amylphenyl) ester is obtained. And the method of obtaining 1, 6- diisocyanato hexane by thermally decomposing this carbamate aryl compound, etc. are mentioned.

  The chlorine-containing compound contained in the diisocyanate composition of the present embodiment is not particularly limited as long as it contains 1 to 100 ppm by mass of the chlorine component, but the effect of suppressing the coloration of the polyisocyanate composition and other components From the viewpoint of compatibility and the like, a compound having a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. The lower limit value of the carbon number of the alkyl group is more preferably 2 or more, and further preferably 3 or more. The upper limit of the carbon number of the alkyl group is more preferably 16 or less, and still more preferably 12 or less. When the number of carbon atoms of the alkyl group is not more than the above upper limit, compatibility with other components when the diisocyanate composition is obtained may be reduced.

（式中、Ｒ_１及びＲ_２は、それぞれ独立して、水素、炭素数１〜２０の直鎖若しくは分岐のアルキル基、フェニル基、又はアルキルフェニル基を表し、これらには官能基が結合していてもよい。） Specific examples of the chlorine-containing compound include carbamyl chloride group-containing compounds, carbonyl chloride group-containing compounds, alkyl chloride group-containing compounds, silyl chloride group-containing compounds, and the like. Among these, a carbamyl chloride group-containing compound is preferable. The carbamyl chloride group-containing compound has a structure represented by the following formula (1).

(Wherein R ₁ and R ₂ each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkylphenyl group, and a functional group is bonded to these groups. May be.)

  The carbamyl chloride group-containing compound can be obtained by a method of reacting a primary amine compound or a secondary amine compound with phosgene or a method of reacting an isocyanate group-containing compound with hydrogen chloride. From this point of view, a method of reacting an isocyanate group-containing compound with hydrogen chloride is preferable.

R ₁ and R ₂ in the above formula (1) each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkylphenyl group. R ₁ and R ₂ may each independently have a functional group bonded to a terminal or linear structure. Examples of the functional group include a halogen group (chloro group, bromo group, iodine group, etc.), carbonyl chloride group, carbonyl bromide group, carbamyl chloride group, carbamyl bromide group, isocyanate group, nitrile group, ester group, keto group. , Ketoester groups, hydroxyl groups, ether groups and the like.

  Specific examples of the carbamyl chloride group-containing compound include, for example, 1-isocyanato-6-carbamyl chloride hexane, 1,6-dicarbamyl chloride hexane, 1-carbamyl chloride hexane, 1,6-diisocyanatohexane. Examples include compounds in which at least one of the isocyanate groups of the isocyanurate compound is converted to a carbamyl chloride group.

  Examples of the compound not containing a carbamyl chloride group include a compound containing any structure selected from the group consisting of a carbonyl chloride group, an alkyl chloride group, and a silyl chloride group, and not containing a carbamyl chloride group. Can be mentioned. The compound not containing a carbamyl chloride group preferably has a linear or branched alkyl group having 1 to 20 carbon atoms. Functional groups such as halogen groups (chloro groups, bromo groups, iodine groups, etc.), carbonyl chloride groups, carbonyl bromide groups, carbamyl bromide groups, isocyanate groups, nitrile groups, ester groups, keto groups, keto ester groups, hydroxyl groups, ether groups, etc. May be combined.

  Specific examples of carbonyl chloride group-containing compounds include chloride salts of saturated monocarboxylic acids such as ethanoic chloride, propanoic chloride, butanoic chloride, pentanoic chloride, hexanoic chloride, heptanoic chloride, octanoic chloride; olein Chloride salt compounds of unsaturated carboxylic acids such as acid chloride, linoleic acid chloride, linolenic acid chloride; oxalic acid monochloride, oxalic acid dichloride, malonic acid monochloride, malonic acid dichloride, succinic acid monochloride, succinic acid dichloride, adipic acid Examples thereof include chloride salts of dicarboxylic acids such as monochloride and adipic acid dichloride. Among these, a chloride salt compound of a saturated monocarboxylic acid is preferable from the viewpoint of coloring suppression effect during storage and compatibility.

  Specific examples of the alkyl chloride group-containing compound include chloroethane, dichloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloropentane, 2-chloropentane, 3-chloropentane, 1-chlorohexane, 2-chlorohexane, 3-chlorohexane, 1-chloroheptane, 2-chloroheptane, 3-chloroheptane, 4-chloroheptane, 1-chlorooctane, Examples thereof include monochloride compounds and dichloride compounds such as 2-chlorooctane, 1-chlorononane, 2-chlorononane, and 1-isocyanato-6-chlorohexane. Among these, 1-chloropentane, 2-chloropentane, 1-chlorohexane, 2-chlorohexane, 3-chlorohexane, 1-chloroheptane, 3-chloroheptane, 4-chloroheptane, 1-chlorooctane, 2 Monochloroide compounds such as -chlorooctane and 1-isocyanato-6-chlorohexane are preferred, and 1,6-dichlorohexane and 1-isocyanato-6-chlorohexane are more preferred.

  Specific examples of the silyl chloride group-containing compound include triethylsilyl chloride, tripropylsilyl chloride, tert-butyldimethylsilyl chloride, trimethylchloromethylsilane and the like.

  The diisocyanate composition of the present embodiment may contain either one or both of the above-mentioned carbamyl chloride group-containing compound and carbamyl chloride group-free compound.

  The diisocyanate composition of this embodiment preferably further contains a bromine-containing compound. The polyisocyanate composition of this embodiment can suppress coloring more effectively by containing not only a chlorine-containing compound but also a bromine-containing compound. From this viewpoint, the bromine-containing compound content relative to 1,6-diisocyanatohexane is preferably 1 to 100 ppm by mass as the bromine component. Content of a bromine containing compound can be measured by the method as described in an Example. The lower limit of the content of the bromine-containing compound is preferably 2 ppm by mass or more, more preferably 3 ppm by mass or more, as the bromine component. The upper limit of the bromine-containing compound content is preferably 75 ppm by mass or less, more preferably 50 ppm by mass or less, still more preferably 30 ppm by mass or less, and still more preferably 20 masses as a bromine component. ppm or less. By containing not only the chlorine-containing compound but also the bromine-containing compound in the above proportion, it is considered that turbidity due to interaction with the additive and the like can be more effectively prevented (however, the action of the present embodiment is these) Not limited to.)

  Examples of a method for controlling the content of the bromine-containing compound within the above range include a method of adding a predetermined amount of a bromine-containing compound to 1,6-diisocyanatohexane.

  The bromine-containing compound contained in the diisocyanate composition of the present embodiment is not particularly limited as long as it contains a bromine component, but the effect of suppressing coloration of the polyisocyanate composition, compatibility with other components, etc. From the viewpoint, a compound having a linear or branched alkyl group having 2 to 20 carbon atoms is preferable. The upper limit of the carbon number of the alkyl group is more preferably 16 or less, and still more preferably 12 or less. When the carbon number of the alkyl group is not more than the above upper limit value, it is expected that the compatibility in the polyisocyanate composition is further improved. The lower limit of the carbon number of the alkyl group is more preferably 3 or more, and further preferably 4 or more.

（式中、Ｒ_３及びＲ_４は、それぞれ独立して、水素、炭素数１〜２０の直鎖若しくは分岐のアルキル基、フェニル基、又はアルキルフェニル基を表し、これらには官能基が結合していてもよい。） Specific examples of the bromine-containing compounds include carbamyl bromide group-containing compounds, carbonyl bromide group-containing compounds, alkyl bromide group-containing compounds, silyl bromide group-containing compounds, and the like. The carbamyl bromide group-containing compound has a structure represented by the following formula (2).

(In the formula, R ₃ and R ₄ each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkylphenyl group, and a functional group is bonded thereto. May be.)

  The carbamyl bromide group-containing compound can be obtained by a method of reacting a primary amine compound or a secondary amine compound with carbonyl bromide or a method of reacting an isocyanate group-containing compound with hydrogen bromide. From the viewpoint of easiness, it is preferable to react the isocyanate group-containing compound with hydrogen bromide.

R ₃ and R ₄ in the above formula (2) each independently represent hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group, or an alkylphenyl group. R ₃ and R ₄ may each independently have a functional group bonded to a terminal or linear structure. Examples of the functional group include a halogen group (chloro group, bromo group, iodine group, etc.), carbonyl chloride group, carbonyl bromide group, carbamyl chloride group, carbamyl bromide group, isocyanate group, nitrile group, ester group, keto group. , Ketoester groups, hydroxyl groups, ether groups and the like.

  Specific examples of the carbamyl bromide group-containing compound include, for example, 1-isocyanato-6-carbamyl bromide hexane, 1,6-dicarbamyl bromide hexane, 1-carbamyl bromide hexane, 1,6-diisocyanatohexane. And the like in which at least one isocyanate group of the isocyanurate compound is converted to a carbamyl bromide group.

  Examples of the compound that does not contain a carbamyl bromide group include compounds that have any structure selected from the group consisting of a carbonyl bromide group, an alkyl bromide group, and a silyl bromide group, and that do not contain a carbamyl bromide group. . The compound not containing a carbamyl bromide group preferably has a linear or branched alkyl group having 1 to 20 carbon atoms, and the compound not containing a carbamyl bromide group includes a halogen group (chloro group, bromo group, iodine group). Etc.), functional groups such as carbonyl chloride group, carbonyl bromide group, carbamyl chloride group, isocyanate group, nitrile group, ester group, keto group, keto ester group, hydroxyl group and ether group may be bonded.

  Specific examples of the carbonyl bromide group-containing compound include, for example, ethane acid bromide, propanoic acid bromide, butanoic acid bromide, pentanoic acid bromide, hexanoic acid bromide, heptanoic acid bromide, octanoic acid bromide bromide salt compound, etc. ; Brominated salt compounds of unsaturated carboxylic acids such as oleic acid bromide, linoleic acid bromide, linolenic acid bromide; oxalic acid monobromide, oxalic acid dibromide, malonic acid monobromide, malonic acid dibromide, succinic acid monobromide, succinic acid dibromide, adipic acid monobromide And bromide salt compounds of dicarboxylic acids such as adipic acid dibromide. Among these, a bromide salt compound of a saturated monocarboxylic acid is preferable from the viewpoint of coloring suppression effect and compatibility.

  Specific examples of the alkyl bromide group-containing compound include bromoethane, dibromoethane, 1-bromopropane, 2-bromopropane, 1,2-dibromopropane, 1,3-dibromopropane, 1-bromobutane, 2-bromobutane, 1-bromobutane, Bromopentane, 2-bromopentane, 3-bromopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromoheptane, 2-bromoheptane, 3-bromoheptane, 4-bromoheptane, 1- Examples thereof include monobromide compounds and dibromide compounds such as bromooctane, 2-bromooctane, 1-bromononane, 2-bromononane, and 1-isocyanato-6-bromohexane. Among these, 1-bromopentane, 2-bromopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromoheptane, 3-bromoheptane, 4-bromoheptane, 1-bromooctane, 2 Monobromide compounds such as -bromooctane and 1-isocyanato-6-bromohexane are preferred, and 1,6-dibromohexane and 1-isocyanato-6-bromohexane are more preferred.

  Specific examples of the silyl bromide group-containing compound include triethylsilyl bromide, tolpropylsilyl bromide, tert-butyldimethylsilyl bromide, trimethylbromomethylsilane and the like.

  Specific examples of the compound not containing a carbamyl bromide group include 1,6-dibromohexane and 1-isocyanato-6-bromohexane.

  The polyisocyanate composition of this embodiment may contain either one of the above-mentioned carbamyl bromide group-containing compound or a compound not containing a carbamyl bromide group, or may contain both of them.

The diisocyanate composition of this embodiment is used as a raw material for various polyisocyanate compositions. The polyisocyanate composition obtained from the diisocyanate composition of the present embodiment preferably contains an isocyanurate structure and an iminooxadiazinedione structure. By containing the isocyanurate structure, the weather resistance and heat resistance of the polyisocyanate composition can be improved. The isocyanurate structure is a structure represented by the formula (3).

By containing an iminooxadiazinedione structure having an asymmetric structure, the smoothness of a coating film produced using a diisocyanate composition or a polyisocyanate composition can be improved. The iminooxadiazinedione structure is a structure represented by the formula (4).

  The molar ratio of iminooxadiazinedione structure / isocyanurate structure in the polyisocyanate composition obtained from the diisocyanate composition of the present embodiment is not particularly limited, but is preferably 6.0 / 100 to 25/100. . The upper limit of the molar ratio is preferably 25/100 or less, more preferably 20/100 or less, still more preferably 17/100 or less, and still more preferably 15/100 or less. The lower limit of the molar ratio is preferably 6.0 / 100 or more, more preferably 7.0 / 100 or more, still more preferably 8.5 / 100 or more, and even more preferably 10/100. That's it. When the molar ratio of iminooxadiazinedione structure / isocyanurate structure is not more than the above upper limit, the heat resistance of the polyisocyanate composition is improved. When the molar ratio of iminooxadiazinedione structure / isocyanurate structure is not less than the above lower limit, the smoothness of the coating film is improved.

  The polyisocyanate composition obtained from the diisocyanate composition of this embodiment preferably contains a uretdione structure. Furthermore, it preferably contains an isocyanurate structure and a uretdione structure, and more preferably contains an iminooxadiazine dione structure, an isocyanurate structure and a uretdione structure.

The uretdione structure is a structure represented by the following formula (5). When not only the uretdione structure but also the isocyanurate structure is contained, the molar ratio of the uretdione structure / isocyanurate structure is not particularly limited, but is preferably 0.1 / 100 to 5.0 / 100. The upper limit of the molar ratio of the uretdione structure / isocyanurate structure is not particularly limited, but is preferably 5.0 / 100 or less, more preferably 3.0 / 100 or less, and still more preferably 2.0 / 100. It is as follows. The lower limit of the molar ratio of the uretdione structure / isocyanurate structure is preferably 0.1 / 100 or more, more preferably 0.2 / 100 or more, and further preferably 0.5 / 100 or more. When the molar ratio of the uretdione structure / isocyanurate structure is not more than the above upper limit, the curability of the polyisocyanate composition can be further improved, the amount of increase in the HDI monomer after storage can be reduced, and the heat resistance of the polyisocyanate composition can be reduced. Further improvement. When the molar ratio of the uretdione structure / isocyanurate structure is not less than the above lower limit, the smoothness of the coating film is further improved.

The polyisocyanate composition using the diisocyanate composition of this embodiment as a raw material preferably has an allophanate structure from the viewpoint of viscosity. The allophanate structure is a structure represented by the following formula (6). When not only the allophanate structure but also the isocyanurate structure, the molar ratio of the allophanate structure / isocyanurate structure is not particularly limited, but is preferably 0.1 / 100 to 4.0 / 100. The upper limit of the molar ratio of the allophanate structure / isocyanurate structure is preferably 4.0 / 100 or less, more preferably 3.0 / 100 or less, and still more preferably 2.0 / 100 or less. The lower limit of the molar ratio of allophanate structure / isocyanurate structure is preferably 0.1 / 100 or more, more preferably 0.2 / 100 or more, and further preferably 0.5 / 100 or more. When the allophanate structure / isocyanurate structure molar ratio is not more than the above upper limit value, the curability is further improved. When the molar ratio of the allophanate structure / isocyanurate structure is not less than the above lower limit, the smoothness of the coating film is further improved.

Each ratio regarding the above-described iminooxadiazinedione structure, isocyanurate structure, uretdione structure, and allophanate structure can be determined by ¹³ C-NMR measurement. Specifically, it can measure according to the method as described in an Example.

  The 1,6-diisocyanatohexane (HDI) monomer mass concentration (HDI monomer concentration) in the polyisocyanate composition of the present embodiment is preferably 2% by mass or less, more preferably 1% by mass or less, and further Preferably it is 0.5 mass% or less. When the HDI monomer concentration is 2% by mass or less, the danger during handling can be further reduced, and the curability of the coating composition can be further improved.

The isocyanate group content (NCO content) of the polyisocyanate composition of the present embodiment is preferably 19.0 to 24.0% by mass under a condition of a nonvolatile content of 98% by mass or more. The lower limit value of the NCO content is more preferably 20.0% by mass or more, and further preferably 21.0% by mass or more. The upper limit of the NCO content is more preferably 23.0% by mass or less, and further preferably 22.5% by mass or less. By setting the NCO content to 19.0% by mass or more, the crosslinkability of the polyisocyanate composition can be further improved. When the NCO content is 24.0% by mass or less, the HDI monomer concentration of the polyisocyanate composition can be reduced, and the danger can be further reduced. The NCO content can be determined by back titration with 1N hydrochloric acid after neutralizing the isocyanate group of the polyisocyanate composition with an excess of 2N amine. The nonvolatile content can be determined from the remaining amount when the polyisocyanate composition is heated at 105 ° C. for 3 hours.

Nonvolatile content (mass%) = (mass of polyisocyanate composition after heating at 105 ° C. for 3 hours) / (mass of polyisocyanate composition before heating) × 100

  The viscosity of the solid content in the polyisocyanate composition of the present embodiment at 25 ° C. is preferably 1000 to 4000 mPa · s under the condition of a nonvolatile content of 98% by mass or more. The upper limit of the viscosity is more preferably 3500 mPa · s or less, and still more preferably 3000 mPa · s or less. The lower limit of the viscosity is more preferably 1500 mPa · s or more, and still more preferably 2000 mPa · s. s or more. When the viscosity of the polyisocyanate composition is not more than the above upper limit, the gloss of the resulting coating film is further improved. The yield of a polyisocyanate composition improves further as the viscosity of a polyisocyanate composition is more than the said lower limit. The viscosity can be measured using an E-type viscometer (manufactured by Tokimec).

  The number average molecular weight of the solid content in the polyisocyanate composition of the present embodiment is 550 to 800 under the condition of a nonvolatile content of 98% by mass or more. The lower limit of the number average molecular weight is more preferably 600 or more, and still more preferably 630 or more. The upper limit of the number average molecular weight is more preferably 750 or less, and still more preferably 700 or less. When the number average molecular weight is 550 or more, the yield of the resulting polyisocyanate composition is further improved. When the number average molecular weight is 800 or less, the gloss of the resulting coating film is further improved. The number average molecular weight can be determined by gel permeation chromatography (GPC). Specifically, it can measure according to the method as described in an Example.

Hereinafter, an example of the manufacturing method of the polyisocyanate composition which uses the diisocyanate composition of this embodiment as a raw material is demonstrated.
Alcohol compounds such as alkyl monoalcohols and alkyl diols can be used as auxiliary materials for the polyisocyanate composition using the diisocyanate composition of the present embodiment as a raw material, but when using an alcohol compound, the polyisocyanate composition It is preferable to control the molar ratio of the allophanate structure / isocyanurate structure in the product to be in the range of 0.1 / 100 / to 4.0 / 100. By controlling the molar ratio of alphanate structure / isocyanurate structure within the above range, compatibility with resins such as polyols and curability can be achieved at a higher level.

  After adding a polymerization catalyst to the diisocyanate composition of the present embodiment and the above-mentioned auxiliary materials and allowing the reaction to proceed until a predetermined degree of polymerization is reached, unreacted 1,6-diisocyanatohexane is necessary. A polyisocyanate composition can be obtained by removing.

  Although it does not specifically limit as a polymerization catalyst, The thing which can control structures, such as an iminooxadiazine dione structure of a polyisocyanate composition, an isocyanurate structure, and a uretdione structure, is preferable. As a specific example of such a polymerization catalyst, a mixture containing the following A component and B component as a mass ratio (A / B) of the A component to the B component in a ratio of 5/100 to 100/5 is preferable. The mass ratio (A / B) of the A component to the B component is preferably 15/100 to 100/15, and more preferably 30/100 to 100/30.

Component A: A component containing at least one of the following (1) to (5).
(1) Tetraalkylammonium (eg, tetramethylammonium, tetraethylammonium, etc.) hydroxides and organic acid salts thereof (eg, salts of acetic acid, butyric acid, decanoic acid, etc.),
(2) Hydroxyalkylammonium hydroxide (for example, tetramethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium, etc.) and organic acid salts thereof (for example, acetic acid, butyric acid, decanoic acid, etc.) Salt),
(3) metal salts of alkyl carboxylic acids such as acetic acid, capric acid, octylic acid, myristic acid (for example, tin, zinc, lead, sodium, potassium, etc.),
(4) Metal alcoholates such as sodium and potassium,
(5) Aminosilyl group-containing compound (for example, hexamethyldillasan etc.).

Component B: A component containing at least one of the following (6) to (7).
(6) Fluorine compound or polyhydrofluoride compound (for example, tetraalkylammonium fluoride such as tetramethylammonium fluoride hydrate and tetraethylammonium fluoride)
(7) A compound having a structure represented by the following general formula (a) or general formula (b) (for example, 3,3,3-trifluorocarboxylic acid; 4,4,4,3,3-pentafluorobutane Acid; 5,5,5,4,4,3,3-heptafluoropentanoic acid; 3,3-difluoroprop-2-enoic acid and the like) and a quaternary ammonium cation or a quaternary phosphonium cation. Compound.

R ₅ = CR′−C (O) O− (a)

R ₆ —CR ′ ₂ —C (O) O— (b)

(Wherein R ₅ and R ₆ each independently represent a perfluoroalkyl group having 1 to 30 carbon atoms. R ′ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, And any one selected from the group consisting of aryl groups and R ₅ , R ₆ , and R ′ may contain a hetero atom.)
R ₅ and R ₆ may be linear, branched or cyclic. R ¹ and R ² may be a saturated perfluoroalkyl group or an unsaturated perfluoroalkyl group.

  Among the above components A, (1) and (2) are preferable from the viewpoint of catalyst efficiency. Among the above-described components B, (6) is preferable from the viewpoint of availability, and (7) is preferable from the viewpoint of safety.

  Although the usage-amount of the polymerization catalyst with respect to 1, 6- diisocyanato hexane is not specifically limited, Preferably it is 5-5000 mass ppm. The upper limit of the amount of the polymerization catalyst used is more preferably 2000 ppm by mass or less, and even more preferably 500 ppm by mass or less, from the viewpoint of suppressing coloration / discoloration of the product and reaction control. From the viewpoint of reactivity, the lower limit of the amount of the polymerization catalyst used is more preferably 10 mass ppm or more, and still more preferably 20 mass ppm or more.

  The polymerization reaction temperature is not particularly limited, but is preferably 40 to 150 ° C. The upper limit of the polymerization reaction temperature is more preferably 120 ° C. or less, and still more preferably 110 ° C. or less, from the viewpoint of suppression of product coloring and discoloration. The lower limit of the polymerization reaction temperature is more preferably 50 ° C. or more, and further preferably 60 ° C. or more, from the viewpoint of the reaction rate.

  When the polymerization reaction reaches a desired degree of polymerization, the polymerization reaction is stopped. The polymerization reaction can be stopped, for example, by adding an acidic compound such as phosphoric acid, acidic phosphate ester, sulfuric acid, hydrochloric acid, sulfonic acid compound, etc. to the reaction solution to neutralize the polymerization reaction catalyst, thermal decomposition, chemical decomposition, etc. This can be achieved by inactivation. After the reaction is stopped, filtration may be performed as necessary.

  Since the reaction liquid immediately after stopping the reaction usually contains unreacted HDI monomer, it is preferably removed by a thin film evaporator or extraction. It is preferable to control the concentration of the HDI monomer contained in the polyisocyanate composition to 1% by mass or less by performing such post-treatment. The upper limit value of the HDI monomer concentration is more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and still more preferably 0.8%. 1% by mass or less. By setting the HDI monomer concentration to be not more than the above upper limit, the toxicity of the polyisocyanate composition can be further reduced and the safety can be improved.

  The polyisocyanate composition using the diisocyanate composition of the present embodiment as a raw material can also be suitably used as a curing agent for the coating composition. That is, the polyisocyanate composition obtained by using at least the diisocyanate monomer of the present embodiment can be used as a coating composition containing it. The resin component of the coating composition is preferably a compound having two or more active hydrogens having reactivity with isocyanate groups in the molecule. Examples of the compound having two or more active hydrogens in the molecule include polyols, polyamines, polythiols and the like. Among these, a polyol is preferable. Specific examples of the polyol include polyester polyol, polyether polyol, acrylic polyol, polyolefin polyol, and fluorine polyol.

  The coating composition using the polyisocyanate composition made from the diisocyanate composition of the present embodiment can be applied to both so-called solvent-based coating compositions and water-based coating compositions.

  In the case of a solvent-based coating composition, a resin containing a compound having two or more active hydrogens in the molecule, or a solvent dilution thereof, if necessary, other resins, catalysts, pigments, leveling agents, The polyisocyanate composition of the present embodiment is added as a curing agent to an additive such as an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, and a surfactant, and if necessary, a solvent is further added. The solvent-based coating composition can be obtained by adjusting the viscosity and adding the mixture by hand stirring or stirring using a stirring device such as Mazelar.

  In the case of a water-based coating composition, an aqueous dispersion of a resin containing a compound having two or more active hydrogen atoms in the molecule, or an aqueous solution, if necessary, other resins, catalysts, pigments, leveling In addition to additives such as an agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, and a surfactant, the polyisocyanate composition of the present embodiment is added as a curing agent, and if necessary, After further adding water or a solvent, a water-based coating composition can be obtained by forcibly stirring with a stirring device.

  Polyester polyols include, for example, dibasic acids (succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, carboxylic acids such as 1,4-cyclohexanedicarboxylic acid, etc.) and polyvalent acids. Alcohol (ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, Ethoxylated trimethylolpropane and the like) can be obtained by a condensation reaction. About each of a dibasic acid and a polyhydric alcohol, you may use individually by 1 type and may use 2 or more types together.

  For example, the polyester polyol can be obtained by mixing the above components and heating at about 160 to 220 ° C. to cause a condensation reaction. Examples of such polyester polyols include polycaprolactones obtained by ring-opening polymerization of lactones such as ε-caprolactone with polyhydric alcohols.

  Polyester polyols can also be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom. As such a modified polyisocyanate, a modified polyisocyanate obtained from an aliphatic diisocyanate or an alicyclic diisocyanate is preferable from the viewpoint of weather resistance, yellowing resistance and the like.

  When used as an aqueous base paint, a water-soluble or water-dispersible resin can be obtained by neutralizing a carboxylic acid residue such as a dibasic acid with a base such as an amine or ammonia.

  As the polyether polyol, for example, a polyhydric hydroxy compound alone or in a mixture, for example, hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), strong basic catalyst (alcolate, alkylamine, etc.), Using a complex metal cyanide complex (metal porphyrin, hexacyanocobaltate zinc complex, etc.) or the like, an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, etc.) alone or as a mixture, a polyvalent hydroxy compound Polyether polyols obtained by random or block addition to the above; polyether polyols obtained by reacting a polyamine compound (ethylenediamine, etc.) with an alkylene oxide; using these polyether polyols as a medium Obtained by polymerizing acrylamide or the like, so-called polymer polyols, and the like.

  Examples of the polyvalent hydroxy compound include (i) polyvalent hydroxy compounds such as diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and (ii) e.g. erythritol, D-threitol, L-arabinitol, ribitol. Sugar alcohol compounds such as xylitol, sorbitol, mannitol, galactitol, rhamnitol, (iii) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesource iv) disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, etc. (v) e.g. raffinose, gentianose, mele Trisaccharides such as toast, (vi) e.g., tetrasaccharides such as stachyose, and the like.

  The acrylic polyol can be obtained, for example, by copolymerizing a polymerizable monomer having one or more active hydrogens in one molecule and another monomer copolymerizable with the polymerizable monomer.

  Acrylic polyols are, for example, acrylic acid esters having active hydrogen (acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, acrylic acid-2-hydroxybutyl, etc.) or methacrylic acid esters having active hydrogen. (Methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-2-hydroxybutyl, methacrylic acid-3-hydroxypropyl, methacrylic acid-4-hydroxybutyl, etc.), glycerin, trimethylolpropane, etc. (Meth) acrylic acid esters having polyvalent active hydrogen such as (meth) acrylic acid monoester of triol; polyether polyols (polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and the above active hydrogen Monoethers with (meth) acrylic acid esters; adducts of glycidyl (meth) acrylate and monobasic acids (acetic acid, propionic acid, p-tert-butylbenzoic acid, etc.); having the above active hydrogen (meth) As an essential component, one or more selected from the group consisting of adducts obtained by ring-opening polymerization of lactones (ε-caprolactam, γ-valerolactone, etc.) to active hydrogen of acrylic acid esters, as necessary (Meth) acrylic acid esters (methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid-n -Butyl, isobutyl methacrylate, methacrylic acid-n-hexyl, methacrylate Cyclohexyl acid, lauryl methacrylate, glycidyl methacrylate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.), unsaturated amides (acrylamide, N-methylolacrylamide, diacetone acrylamide, etc.), Or vinyl monomers having a hydrolyzable silyl group (vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acrylopropyltrimethoxysilane, etc.) and other polymerizable monomers (styrene, vinyltoluene, vinyl acetate) , Acrylonitrile, dibutyl fumarate, etc.) can be obtained by copolymerizing by a conventional method.

  The polyester polyol is, for example, a dibasic acid such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid or the like alone or in a mixture. And ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, It can be obtained by subjecting a polyhydric alcohol such as ethoxylated trimethylolpropane alone or a mixture to a condensation reaction. For example, the condensation reaction can be carried out by combining the above components and heating at about 160-220 ° C. Furthermore, for example, polycaprolactones obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol can also be used as the polyester polyol. These polyester polyols can be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom. In this case, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained from these are particularly preferred from the viewpoints of weather resistance, yellowing resistance, and the like. When used as a water-based base paint, a part of the remaining carboxylic acid such as dibasic acid is left and neutralized with a base such as amine or ammonia, so that it is water-soluble or water-dispersible. It can be a resin.

  As the polyether polyol, for example, a polyhydric hydroxy compound alone or in a mixture, for example, hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), strong basic catalyst (alcolate, alkylamine, etc.), Using a complex metal cyanide complex (metal porphyrin, hexacyanocobaltate zinc complex, etc.) or the like, an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, etc.) alone or as a mixture, a polyvalent hydroxy compound Polyether polyols obtained by random or block addition to the above; polyether polyols obtained by reacting a polyamine compound (ethylenediamine, etc.) with an alkylene oxide; and these polyether polyols as a medium Obtained by polymerizing acrylamide Te, so-called polymer polyols, and the like.

  Examples of the polyvalent hydroxy compound include (i), for example, diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc. (ii), for example, erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, Sugar alcohol compounds such as mannitol, galactitol, rhamnitol, (iii) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesource, (iv) eg trehalose Disaccharides such as sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, (v) for example, trisaccharides such as raffinose, gentianose, meretitol, ( i) For example, tetrasaccharides such as stachyose, and the like.

  The acrylic polyol can be obtained, for example, by copolymerizing a polymerizable monomer having one or more active hydrogens in one molecule and another monomer copolymerizable with the polymerizable monomer.

  Acrylic polyols are, for example, acrylic acid esters having active hydrogen (acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, acrylic acid-2-hydroxybutyl, etc.) or methacrylic acid esters having active hydrogen. (Methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-2-hydroxybutyl, methacrylic acid-3-hydroxypropyl, methacrylic acid-4-hydroxybutyl, etc.), glycerin, trimethylolpropane, etc. (Meth) acrylic acid esters having polyvalent active hydrogen such as (meth) acrylic acid monoester of triol; polyether polyols (polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and the above active hydrogen Monoethers with (meth) acrylic acid esters; adducts of glycidyl (meth) acrylate and monobasic acids such as acetic acid, propionic acid, p-tert-butylbenzoic acid; (meth) acrylic having the above active hydrogen As an essential component, one or more selected from the group consisting of adducts obtained by ring-opening polymerization of lactones (ε-caprolactam, γ-valerolactone, etc.) to active hydrogen of acid esters, as necessary ( (Meth) acrylic acid esters (methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid -n- Butyl, isobutyl methacrylate, methacrylic acid-n-hexyl, methacryl Cyclohexyl, lauryl methacrylate, glycidyl methacrylate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.), unsaturated amides (acrylamide, N-methylolacrylamide, diacetone acrylamide, etc.), or Vinyl monomers having a hydrolyzable silyl group (vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acrylopropyltrimethoxysilane, etc.) and other polymerizable monomers (styrene, vinyltoluene, vinyl acetate, One or more selected from the group consisting of (acrylonitrile, dibutyl fumarate, etc.) can be obtained by copolymerization by a conventional method.

  For example, an acrylic polyol can be obtained by solution polymerization of the above monomer components in the presence of a radical polymerization initiator such as a known peroxide or azo compound, and diluting with an organic solvent as necessary. Can do. In the case of obtaining an aqueous base acrylic polyol, it can be produced by a known method such as a method in which an olefinically unsaturated compound is subjected to solution polymerization and converted into an aqueous layer, or emulsion polymerization. In that case, water solubility or water dispersibility can be imparted by neutralizing an acidic moiety such as a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer with an amine or ammonia.

  Fluorine polyol is a polyol containing fluorine in the molecule. For example, fluoroolefin, cyclovinyl ether, hydroxyalkyl vinyl ether disclosed in JP-A-57-341075, JP-A-61-215311, etc. Examples thereof include copolymers such as monocarboxylic acid vinyl esters.

  Although the hydroxyl value of the said polyol is not specifically limited, Usually, it is 30-200 mgKOH / g, and an acid value is 0-30 mgKOH / g. The hydroxyl value can be measured according to JIS K1557.

  Among the above, as the polyol, an acrylic polyol is preferable from the viewpoint of weather resistance, chemical resistance, and hardness, and a polyester polyol is preferable from the viewpoint of mechanical strength and oil resistance.

  The equivalent ratio (NCO / OH ratio) of the isocyanate group of the polyisocyanate composition of the present embodiment to the hydroxyl group of the compound having two or more active hydrogens in the molecule is preferably 0.2 to 5.0. More preferably, it is 0.4-3.0, More preferably, it is 0.5-2.0. When the equivalent ratio is 0.2 or more, a tougher coating film can be obtained. When the equivalent ratio is 5.0 or less, the smoothness of the coating film can be further improved.

  A melamine curing agent such as a complete alkyl type, a methylol type alkyl, or an iminoxy type alkyl can be added to the coating composition as necessary.

  Any of the compound having two or more active hydrogens in the molecule, the polyisocyanate composition and the coating composition of the present embodiment can be used by mixing with an organic solvent. The organic solvent preferably has no functional group that reacts with a hydroxyl group and an isocyanate group. Moreover, it is preferable to be compatible with the polyisocyanate composition. Examples of such organic solvents include ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylate compounds, hydrocarbon solvents generally used as paint solvents. And aromatic solvents.

  The compound having two or more active hydrogens in the molecule, the polyisocyanate composition and the coating composition of the present embodiment are all catalysts, depending on the purpose and application, within a range not impairing the effects of the present embodiment. Various additives used in the technical field such as pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, and surfactants can also be mixed and used.

  Specific examples of the catalyst for accelerating the curing include metal salts such as dibutyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt salt; triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N -Tertiary amines such as dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N'-endoethylenepiperazine, N, N'-dimethylpiperazine and the like.

  The coating composition using the polyisocyanate composition made from the diisocyanate composition of the present embodiment as a curing agent can be used as a coating for roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating, and the like. . For example, it is useful as a primer or a top intermediate coating material for materials such as metal (steel plate, surface-treated steel plate, etc.), plastic, wood, film, inorganic material and the like. Further, it is also useful as a paint for imparting cosmetic properties, weather resistance, acid resistance, rust resistance, chipping resistance, etc. to pre-coated metals including rust-proof steel plates and automobile coatings. It is also useful as a urethane raw material for adhesives, pressure-sensitive adhesives, elastomers, foams, surface treatment agents and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example and a comparative example, this invention is not limited at all by the following examples.

<Viscosity>
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 (when less than 128 mPa · s)
50 rpm (when it is 128 mPa · s or more and less than 256 mPa · s)
20 rpm (when it is 256 mPa · s or more and less than 640 mPa · s)
10 rpm (when it is 640 mPa · s or more and less than 1280 mPa · s)
5 rpm (when it is 1280 mPa · s or more and less than 2560 mPa · s)

In addition, the non volatile matter of the polyisocyanate composition produced by each Example and each comparative example which are mentioned later was investigated by the method of the following, The thing whose value was 98 mass% or more was measured as it was. For those that were not, the measurement was performed using a thin film evaporator with a nonvolatile content concentration of 98% by mass or more.

<Nonvolatile content>
The nonvolatile content was determined based on the following formula after heating the polyisocyanate composition at 105 ° C. for 3 hours.

Nonvolatile content (mass%) = (mass of polyisocyanate composition after heating at 105 ° C. for 3 hours) / (mass of polyisocyanate composition before heating) × 100

<NCO content (NCO%)>
The NCO content (mass%) was determined by back titration with 1N hydrochloric acid after neutralizing the isocyanate group in the measurement sample with excess 2N amine. In addition, the non-volatile content of the polyisocyanate composition produced by the Example and comparative example which are mentioned later was investigated by the method mentioned above, and the thing whose value was 98 mass% or more was measured as it was. For those that were not, the measurement was performed using a thin film evaporator with a nonvolatile content concentration of 98% by mass or more.

<Number average molecular weight>
The number average molecular weight of the measurement sample was measured by gel permeation chromatography (GPC). The GPC measurement method was as follows.
Equipment used: HLC-8120 (manufactured by Tosoh Corporation),
Columns used: TSK GEL SuperH1000, TSK GEL SuperH2000, TSK GEL SuperH3000 (all manufactured by Tosoh Corporation),
Sample concentration: 5 wt / vol% (50 mg of sample was dissolved in 1 mL of tetrahydrofuran (THF)),
Carrier: THF,
Detection method: parallax refractometer,
(Flow rate 0.6 mL / min, column temperature 30 ° C.).
For the preparation of the calibration curve, polystyrene having a molecular weight of 1000 to 20000 and an isocyanurate of 1,6-diisocyanatohexane (trimer, pentamer, and heptamer) were used. In addition, the non-volatile content of the polyisocyanate composition produced by each Example and each comparative example which are mentioned later was investigated by the method mentioned above, and the thing whose value was 98 mass% or more was measured as it was. For those that were not, the measurement was performed using a thin film evaporator with a nonvolatile content concentration of 98% by mass or more.

<Molar ratio of isocyanurate structure, iminoxadiazinedione structure, uretdione structure, and allophanate structure>
The ratio regarding the iminooxadiazinedione structure, isocyanurate structure, uretdione structure, and allophanate structure was calculated | required by performing the ¹³ C-NMR measurement of a measurement sample. Specific measurement conditions were as follows.
¹³ C-NMR apparatus: AVANCE 600 (manufactured by Bruker)
Cryoprobe (Bruker)
Cryo Probe
CPDUUL
600S3-C / HD-05Z
Resonance frequency: 150 MHz
Concentration: 60 wt / vol%
Shift standard: CDCl ₃ (77 mass ppm)
Integration count: 10,000 times Pulse program: zgpg30 (proton complete decoupling method, waiting time 2 sec)
The integral values of the following signals were divided by the number of carbons being measured, and each molar ratio was determined from the value.
Iminooxadiazinedione structure: around 145 ppm: integral value / 1
Isocyanurate structure: around 149 ppm: integral value / 3
Uretodione structure: around 157.5 ppm: integral value / 2
Allophanate structure: around 154 ppm: integral value ÷ 1

<Measurement of HDI monomer mass concentration in polyisocyanate composition>
First, a 20 mL sample bottle was placed on a digital balance, and 1 g of the sample was precisely weighed and added. Next, 0.03-0.04 g of nitrobenzene (internal standard solution) was precisely weighed and added to the sample bottle. Finally, 9 mL of ethyl acetate was added to the sample bottle and the lid was closed. And it was made to stir well and it was set as the measurement sample. The measurement sample was subjected to gas chromatography analysis under the following conditions to quantify the amount of HDI monomer.
Equipment: “GC-8A” manufactured by SHIMADZU
Column: “Silicon OV-17” manufactured by Shinwa Kako Co., Ltd.
Column oven temperature: 120 ° C
Injection / detector temperature: 160 ° C

<Measurement of chlorine and bromine concentrations in diisocyanate monomer composition and polyisocyanate composition>
The chlorine concentration and bromine concentration (mass basis) in the diisocyanate monomer composition and the polyisocyanate composition were measured by the following methods. First, about 0.01 to 0.06 g of the sample weighed was placed on the sample board of the combustion pretreatment apparatus. Then, the sample board was moved to the combustion part, it burned with the automatic combustion apparatus, and the gasified component was absorbed in the absorption liquid. Further, the absorption liquid was injected into an ion chromatograph apparatus to quantify the target component. Details of the used combustion pretreatment apparatus and ion chromatograph are described below.
Combustion pretreatment equipment: Automatic combustion equipment manufactured by Mitsubishi Analytical
Model: AQF-100 GA-100
Furnace temperature: Inlet 900 ° C Outlet 1000 ° C
Gas flow rate: Ar / O ₂ : 400 mL / min
O ₂ : 200 mL / min
Measuring device: Ion chromatograph made by DIONEX
Model: ICS-1500
Guard column: AG12A
Separation column: AS12A
Suppressor: ASRS-300
Flow rate: 1.5mL / min
Suppressor current: 50 mA
Eluent: 2.7 mM Na ₂ CO ₃
0.3 mM NaHCO ₃

<Evaluation of coloring degree of polyisocyanate obtained>
The degree of coloring (Hazen color number) of the obtained polyisocyanate composition was measured and evaluated according to the following criteria. The Hazen color number was measured according to JIS K0071-1. A smaller Hazen color number indicates that coloring can be suppressed.

<Weight reduction rate evaluation>
Using a differential thermothermal gravimetric simultaneous measurement apparatus “TG / DTA6200” (manufactured by Seiko Instruments Inc.), the weight reduction rate was measured when the polyisocyanate composition was held at 205 ° C. for 6 hours. It shows that it is excellent in heat resistance, so that a weight decreasing rate is small.

<Evaluation of smoothness of coating film>
Acrylic polyol Ac-1 obtained in Synthesis Example 2 below and the polyisocyanate composition obtained in each Example and each Comparative Example were mixed with a molar ratio of NCO groups of the polyisocyanate composition to OH groups of the acrylic polyol (NCO). / OH) is mixed at a ratio of 1.0, and adjusted to a solid content of 55% by mass using “Solvesso # 100” (trade name, aromatic solvent manufactured by Exxon). A composition was prepared. The coating composition was applied to an ABS plate (acrylonitrile-butadiene-styrene resin; black, 150 mm × 75 mm) using a spray so that the dry film thickness was 50 μm. This was baked at 60 ° C. for 30 minutes and then allowed to stand for 1 week at 23 ° C. and 50% humidity to form a coating film on the ABS plate.
The appearance (sharpness and surface smoothness) of the coating film was measured using a digital oscilloscope “Wave Scan DOI” (BYK Gardner) along the long side direction of the ABS plate. “Wave Scan DOI” is an arrangement in which a laser point light source emits a laser beam at an angle of 60 ° with respect to a normal to the film surface, and a detector receives reflected light of the same angle opposite to the normal. This apparatus moves the laser point light source over the film surface and scans it, thereby measuring the brightness of the reflected light point by point at a predetermined interval and detecting the optical profile of the film surface. The detected optical profile can be spectrally analyzed through a frequency filter to analyze the surface structure. In that, the value of the Wc area (wavelength 1.0-3.0 mm) of a coating film was used and evaluated. The measured value was an arithmetic average value of three measured values. Wc is an index of the smoothness of the coating film, and the smaller the value, the better the smoothness.

(Synthesis Example 1; synthesis of catalyst)
In a 500 mL eggplant-shaped flask purged with nitrogen, 200 g (0.116 mol) of tetramethylammonium hydroxide (10% by mass methanol solution) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature. 0.1 g was added dropwise (tetramethylammonium hydroxide / decanoic acid = 1 / 1.1 (molar ratio)) and stirred at room temperature for 30 minutes. Thereafter, methanol was distilled off under conditions of 10 Torr, 50 ° C. and 30 minutes. To this, 32 g of n-butanol was added to obtain a 50 mass% butanol solution of tetramethylammonium decanoate. Then, 40 g of n-butanol was further added to 10 g of a 50 mass% butanol solution of tetramethylammonium decanoate to obtain a 10 mass% butanol solution of tetramethylammonium decanoate. Furthermore, 15 g of n-butanol was further added to 10 g of a 10% by weight butanol solution of tetramethylammonium decanoate to obtain a 4% by weight butanol solution of tetramethylammonium decanoate.

(Synthesis Example 2: Synthesis of acrylic polyol)
A four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was charged with 120.0 g of “Solvesso # 150” (an aromatic solvent manufactured by Exxon Chemical) and 60.0 g of xylene, and the inside was replaced with nitrogen. Then, the temperature was raised to 120 ° C. Then, (meth) acrylic monomer (methyl methacrylate: 128.8 g, n-butyl acrylate: 84.8 g, cyclohexane methacrylate: 80.0 g, 2-hydroxyethyl methacrylate: 74.4 g, styrene: 32.0 g) and benzoyl The peroxide 8.0g was dripped over 2 hours, and was made to stir-react. After completion of the dropwise addition, the reaction was further continued at 120 ° C. for 4 hours to obtain acrylic polyol Ac-1.
The obtained acrylic polyol Ac-1 had a nonvolatile content of 70% by mass, a hydroxyl value of 80 mgKOH / g (calculated from the charging ratio, JIS K1557 with respect to the resin content), a glass transition temperature (Tg) of 40 ° C., and a number average. The molecular weight was 1700. The glass transition temperature was measured according to JIS K7121.

Example 1
While stirring 10,000 g of a diisocyanate composition having an HDI content of 98.8% by mass, 0.20 g of hydrogen chloride (HCl) (corresponding to 20 mass ppm with respect to HDI) and hydrogen bromide (HBr) 0 .45 g (corresponding to 45 mass ppm with respect to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain diisocyanate monomer composition M-1. When the amount of chlorine components and the amount of bromine components of the obtained diisocyanate monomer composition M-1 were measured, the amount of chlorine components was 18 ppm by mass, and the amount of bromine components was 44 ppm by mass. The production conditions and physical properties of the polyisocyanate monomer composition M-1 are shown in Table 1.

(Example 2)
While stirring 10,000 g of a diisocyanate composition having an HDI content of 98.8% by mass, 0.20 g of hydrogen chloride (HCl) (corresponding to 20 ppm by mass with respect to HDI), 1-isocyanato-6-chloro 1.10 g of hexane (ICH) (corresponding to 110 mass ppm with respect to HDI) and 0.05 g of hydrogen bromide (HBr) (corresponding to 5 mass ppm with respect to HDI) were added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a diisocyanate monomer composition M-2. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition M-2 were measured, the chlorine component amount was 45 ppm by mass and the bromine component amount was 5 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition M-2 are shown in Table 1.

Example 3
While stirring 10,000 g of a diisocyanate composition having an HDI content of 98.8% by mass, 0.83 g of hydrogen chloride (HCl) (corresponding to 83 ppm by mass with respect to HDI) and hydrogen bromide (HBr) 0 0.08 g (corresponding to 8 mass ppm with respect to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain diisocyanate monomer composition M-3. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition M-3 were measured, the chlorine component amount was 80 mass ppm and the bromine component amount was 8 mass ppm. The production conditions and physical properties of the diisocyanate monomer composition M-3 are shown in Table 1.

Example 4
While stirring 10,000 g of a diisocyanate composition having an HDI content of 99.3% by mass, 0.42 g of hydrogen chloride (HCl) (corresponding to 42 ppm by mass with respect to HDI) and hydrogen bromide (HBr) 0 0.06 g (corresponding to 6 mass ppm relative to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain diisocyanate monomer composition M-4. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition M-4 were measured, the chlorine component amount was 40 ppm by mass and the bromine component amount was 6 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition M-4 are shown in Table 1.

(Example 5)
While stirring 10,000 g of a diisocyanate composition having an HDI content of 98.6% by mass, 0.04 g of hydrogen chloride (HCl) (corresponding to 4 ppm by mass with respect to HDI) and hydrogen bromide (HBr) 0 0.02 g (corresponding to 2 mass ppm relative to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a diisocyanate monomer composition M-5. When the amount of chlorine components and the amount of bromine components of the obtained diisocyanate monomer composition M-5 were measured, the amount of chlorine components was 4 ppm by mass, and the amount of bromine components was 2 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition M-5 are shown in Table 1.

(Example 6)
While stirring 10,000 g of a diisocyanate composition having an HDI content of 99.3% by mass, 0.20 g of hydrogen chloride (HCl) (corresponding to 20 mass ppm with respect to HDI) and 1,6-dichlorohexane ( DCH) 0.50 g (corresponding to 50 mass ppm with respect to HDI) and 0.05 g of hydrogen bromide (HBr) (corresponding to 5 mass ppm with respect to HDI) were added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a diisocyanate monomer composition M-6. When the amount of chlorine components and the amount of bromine components of the obtained diisocyanate monomer composition M-6 were measured, the amount of chlorine components was 43 ppm by mass, and the amount of bromine components was 5 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition M-6 are shown in Table 1.

(Example 7)
While stirring 10,000 g of a diisocyanate composition having an HDI content of 99.3% by mass, 0.42 g of hydrogen chloride (HCl) (corresponding to 42 mass ppm with respect to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a diisocyanate monomer composition M-7. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition M-7 were measured, the chlorine component amount was 40 ppm by mass and the bromine component amount was less than 1 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition M-7 are shown in Table 1.

(Comparative Example 1)
The diisocyanate composition 10,000g whose HDI content rate is 98.8 mass% was stirred for 30 minutes, and the diisocyanate monomer composition C-1 was obtained. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition C-1 were measured, the chlorine component amount was less than 1 ppm by mass, and the bromine component amount was less than 1 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition C-1 are shown in Table 1.

(Comparative Example 2)
While stirring 10,000 g of a diisocyanate composition having an HDI content of 98.8% by mass, 1.24 g of hydrogen chloride (HCl) (corresponding to 124 ppm by mass with respect to HDI) and hydrogen bromide (HBr) 0 .21 g (corresponding to 21 mass ppm with respect to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain diisocyanate monomer composition C-2. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition C-2 were measured, the chlorine component amount was 120 mass ppm and the bromine component amount was 20 mass ppm. The production conditions and physical properties of the diisocyanate monomer composition C-2 are shown in Table 1.

(Comparative Example 3)
While stirring 10,000 g of a diisocyanate composition having an HDI content of 98.8% by mass, 0.43 g of hydrogen bromide (HBr) (corresponding to 43 ppm by mass with respect to HDI) was added dropwise. After completion of dropping, the mixture was further stirred for 30 minutes to obtain diisocyanate monomer composition C-3. When the chlorine component amount and bromine component amount of the obtained diisocyanate monomer composition C-3 were measured, the chlorine component amount was less than 1 ppm by mass and the bromine component amount was 42 ppm by mass. The production conditions and physical properties of the diisocyanate monomer composition C-3 are shown in Table 1.

(Example 8)
1,000 g of diisocyanate monomer composition M-1 prepared in Example 1 was heated at 80 ° C., and 10 mass% n− of tetraethylammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd., CAS No. 665-46-3). 1.5 g (0.77 mmol) of butanol solution and 0.5 g (corresponding to 0.20 mmol) of a 10% by mass n-butanol solution of tetramethylammonium decanoate prepared in Synthesis Example 1 were added. When the NCO content in the reaction solution reached 39.3% by mass, 0.73 g (3.5 mmol) of phosphoric acid di-n-butyl ester was added to stop the reaction. Using a thin film evaporator, purification was performed twice at 160 ° C. and 0.2 Torr, non-volatile content 99.3% by mass, viscosity 2700 mPa · s (23 ° C.), NCO content 22.0% by mass, number average molecular weight 656, a polyisocyanate composition P-1 having an HDI monomer mass concentration of 0.16% by mass was obtained.
When structural analysis of the obtained polyisocyanate composition P-1 was performed, the molar ratio of isocyanurate structure / iminooxadiazinedione structure / uretodione structure / allophanate structure was 100/14 / 1.0 / 2.8. Met. That is, the molar ratio of iminooxadiazinedione structure / isocyanurate structure is 14/100, the molar ratio of uretdione structure / isocyanurate structure is 1.0 / 100, and the mole ratio of allophanate structure / isocyanurate structure. The ratio was 2.8 / 100. As a result of measuring the chlorine component amount and bromine component amount of the obtained polyisocyanate composition P-1, the chlorine component amount was 11 ppm by mass and the bromine component amount was 27 ppm by mass. The production conditions and physical properties of the polyisocyanate composition P-1 are shown in Table 2.

Example 9
1,000 g of the diisocyanate monomer composition M-2 prepared in Example 2 was heated at 80 ° C., and 0.20 g (0. 0 g) of a 50 mass% n-butanol solution of tetraethylammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.). 51 mmol) and 0.10 g (corresponding to 0.20 mmol) of a 50 mass% n-butanol solution of tetramethylammonium decanoate prepared in Synthesis Example 1 was added. When the NCO content of the reaction solution reached 39.3 mass%, 0.46 g (2.2 mmol) of phosphoric acid di-n-butyl ester was added to stop the reaction. Using a thin film evaporator, it was purified twice at 160 ° C. and 0.2 Torr, non-volatile content 99.4% by mass, viscosity 2700 mPa · s (23 ° C.), NCO content 22.0% by mass, number average molecular weight 660, a polyisocyanate composition P-2 having an HDI monomer mass concentration of 0.15% by mass was obtained.
When structural analysis of the resulting polyisocyanate composition P-2 was performed, the molar ratio of isocyanurate structure / iminooxadiazinedione structure / uretodione structure / allophanate structure was 100/11 / 0.9 / 0.2. Met. That is, the molar ratio of iminooxadiazinedione structure / isocyanurate structure is 11/100, the molar ratio of uretdione structure / isocyanurate structure is 0.9 / 100, and the mole ratio of allophanate structure / isocyanurate structure. The ratio was 0.2 / 100. As a result of measuring the chlorine component amount and bromine component amount of the obtained polyisocyanate composition P-2, the chlorine component amount was 18 ppm by mass and the bromine component amount was 3 ppm by mass. Table 2 shows the production conditions and physical property results of the polyisocyanate composition P-2.

(Example 10)
1,000 g of diisocyanate monomer composition M-3 prepared in Example 3 was heated at 60 ° C., and 0.30 g (0. 77 mmol) and 0.15 g (corresponding to 0.31 mmol) of a 50% by mass n-butanol solution (catalyst concentration of 50% by mass) of tetramethylammonium decanoate prepared in Synthesis Example 1 was added. When the NCO content of the reaction solution reached 39.2 mass%, 1.25 g (10.8 mmol) of 85 mass% phosphoric acid aqueous solution was added to stop the reaction. Subsequently, it heated up at 90 degreeC and stirred for 1 hour. Thereafter, the resulting catalyst residue was cooled to 40 ° C. and filtered under reduced pressure through a membrane filter having a pore size of 1 μm. Using a thin film evaporator, it was purified twice under the conditions of 160 ° C. and 0.2 Torr, non-volatile content 99.4% by mass, viscosity 2800 mPa · s (23 ° C.), NCO content 22.0% by mass, number average molecular weight 664, a polyisocyanate composition P-3 having an HDI monomer mass concentration of 0.14% by mass was obtained.
When structural analysis of the obtained polyisocyanate composition P-3 was performed, the molar ratio of isocyanurate structure / iminooxadiazinedione structure / uretodione structure / allophanate structure was 100 / 7.0 / 0.4 / 0. .7. That is, the molar ratio of iminooxadiazinedione structure / isocyanurate structure is 7.0 / 100, the molar ratio of uretdione structure / isocyanurate structure is 0.4 / 100, and allophanate structure / isocyanurate structure. The molar ratio of was 0.7 / 100. As a result of measuring the chlorine component amount and bromine component amount of the obtained polyisocyanate composition P-3, the chlorine component amount was 47 mass ppm and the bromine component amount was 5 mass ppm. The production conditions and physical properties of the polyisocyanate composition P-3 are shown in Table 2.

(Example 11)
Polyisocyanate composition P-4 was obtained in the same manner as in Example 8, except that diisocyanate monomer composition M-4 prepared in Example 4 was used instead of diisocyanate monomer M-1. The production conditions and physical properties of the resulting polyisocyanate composition P-4 are shown in Table 2.

(Example 12)
1,000 g of diisocyanate monomer composition M-5 prepared in Example 5 was heated at 80 ° C. The 10% by mass n-butanol solution of tetramethylammonium decanoate prepared in Synthesis Example 1 was further diluted with n-butanol to obtain a 4.0% by mass n-butanol solution. To the diisocyanate monomer composition M-5, 2.0 g (corresponding to 0.32 mmol) of a 4.0 mass% n-butanol solution of tetramethylammonium decanoate was added. When the NCO content of the reaction solution reached 39.3% by mass, 0.73 g (3.5 mmol) of phosphoric acid di-n-butyl ester was added to stop the reaction. Using a thin film evaporator, it was purified twice under the conditions of 160 ° C. and 0.2 Torr, non-volatile content 99.5% by mass, viscosity 2700 mPa · s (23 ° C.), NCO content 22.0% by mass, number average molecular weight 655, a polyisocyanate composition P-5 having an HDI monomer mass concentration of 0.12% by mass was obtained.
When structural analysis of the obtained polyisocyanate composition P-5 was conducted, the molar ratio of isocyanurate structure / iminooxadiazinedione structure / uretodione structure / allophanate structure was 100 / 3.0 / 1.0 / 2. .8. That is, the molar ratio of iminooxadiazinedione structure / isocyanurate structure is 3.0 / 100, the molar ratio of uretdione structure / isocyanurate structure is 1.0 / 100, and allophanate structure / isocyanurate structure. The molar ratio of was 2.8 / 100. As a result of measuring the amount of chlorine components and the amount of bromine components of the resulting polyisocyanate composition P-5, the amount of chlorine components was 3 ppm by mass, and the amount of bromine components was 1 ppm by mass. The production conditions and physical properties of the polyisocyanate composition P-5 are shown in Table 2.

(Example 13)
1,000 g of diisocyanate monomer composition M-6 prepared in Example 6 was heated at 80 ° C., and 1.9 g of a 10 mass% n-butanol solution of tetraethylammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 mmol equivalent) was added. When the NCO content of the reaction solution reached 39.2% by mass, 1.05 g (5.0 mmol) of phosphoric acid di-n-butyl ester was added to stop the reaction. Using a thin film evaporator, it was purified twice at 160 ° C. and 0.2 Torr, non-volatile content 99.3% by mass, viscosity 2500 mPa · s (23 ° C.), NCO content 22.0% by mass, number average molecular weight 660, a polyisocyanate composition P-6 having an HDI monomer mass concentration of 0.18% by mass was obtained.
When structural analysis of the polyisocyanate composition P-6 was performed, the molar ratio of isocyanurate structure / iminooxadiazinedione structure / uretodione structure / allophanate structure was 100/30 / 1.0 / 2.7. . That is, the molar ratio of iminooxadiazinedione structure / isocyanurate structure is 30/100, the molar ratio of uretdione structure / isocyanurate structure is 1.0 / 100, and the mole ratio of allophanate structure / isocyanurate structure. The ratio was 2.7 / 100. As a result of measuring the amount of chlorine components and the amount of bromine components of the resulting polyisocyanate composition P-6, the amount of chlorine components was 12 ppm by mass, and the amount of bromine components was 3 ppm by mass. Table 2 shows the production conditions and physical properties of the polyisocyanate composition P-6.

(Example 14)
A polyisocyanate composition P-7 was obtained in the same manner as in Example 8, except that the diisocyanate monomer composition M-7 prepared in Example 7 was used instead of the diisocyanate monomer M-1. Table 2 shows the production conditions and physical properties of the resulting polyisocyanate composition P-7.

(Comparative Example 4)
A polyisocyanate composition C-4 was obtained in the same manner as in Example 8 except that the diisocyanate monomer composition C-1 prepared in Comparative Example 1 was used instead of the diisocyanate monomer composition M-1. The production conditions and physical properties of the resulting polyisocyanate composition C-4 are shown in Table 2.

(Comparative Example 5)
A polyisocyanate composition C-5 was obtained in the same manner as in Example 8, except that the diisocyanate monomer composition C-2 prepared in Comparative Example 2 was used instead of the diisocyanate monomer composition M-1. The production conditions and physical properties of the resulting polyisocyanate composition C-5 are shown in Table 2.

(Comparative Example 6)
A polyisocyanate composition C-6 was obtained in the same manner as in Example 8 except that the diisocyanate monomer composition C-3 prepared in Comparative Example 3 was used instead of the diisocyanate monomer composition M-1. The production conditions and physical properties of the resulting polyisocyanate composition C-6 are shown in Table 2.

  The diisocyanate monomer composition of the present invention can be used as a raw material for various polyisocyanate compositions, and the obtained polyisocyanate composition and coating composition can be used for roll coating, curtain flow coating, spray coating, bell coating, static coating. It can be used as a paint for electropainting. Moreover, it can be used as a primer or top intermediate coating material for metals such as steel plates and surface-treated steel plates, and materials such as plastics, wood, films, and inorganic materials. Furthermore, it is also useful as a paint for imparting heat resistance, cosmetic properties (surface smoothness, sharpness), etc. to pre-coated metal including rust-proof steel plates, automobile coating, and the like. Furthermore, it is also useful as a urethane raw material for adhesives, pressure-sensitive adhesives, elastomers, foams, surface treatment agents and the like. Furthermore, when used as a curing agent for water-based paints, the VOC component (volatile organic compound) can be reduced, so that it can be used in a wide range of fields such as water-based plastic paints and water-based automobile paint raw materials.

Claims (3)

1,6-diisocyanatohexane,
With respect to the 1,6-diisocyanatohexane, a chlorine-containing compound as a chlorine component, 1 to 100 ppm by mass,
A diisocyanate composition.   The diisocyanate composition of Claim 1 which contains a bromine containing compound 1-100 mass ppm as a bromine component with respect to the said 1, 6- diisocyanato hexane.   The diisocyanate composition of Claim 1 or 2 whose content rate of the said 1, 6- diisocyanato hexane is 97.0 mass% or more.