JP2015010182A - Polyisocyanate composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyisocyanate composition excellent in resistance to yellowing of a coated film in high-temperature seizure.SOLUTION: There is provided a polyisocyanate composition obtained by using at least one 1,6-diisocyanato-hexane of a purity of 97.0 mass% or higher containing 1-200 mass ppm of 1-isocyanato-6-chlorohexane. Also there are provided the polyisocyanate composition containing an imino-oxadiazine-dione structure and an isocyanurate structure, and the polyisocyanate composition containing an uretdione structure and an isocyanurate structure.

Description

  The present invention relates to a polyisocyanate composition.

  Polyisocyanate compositions obtained from 1,6-diisocyanatohexane (HDI; also referred to as hexamethylene diisocyanate) and containing an isocyanurate structure are known (for example, Patent Documents 1 to 3). Polyisocyanate compositions having such an isocyanurate structure are widely used.

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

  Since the polyisocyanate composition obtained from 1,6-diisocyanatohexane described above generally has a low degree of yellowing, it is widely used as a curing agent for paints for automobiles and building outer walls. However, such a polyisocyanate composition has a problem of yellowing when baked to form a coating film. Such a problem becomes prominent when baked at a high temperature of about 160 ° C. Thus, the present condition is that the polyisocyanate composition which can suppress yellowing of the coating film at the time of high temperature baking has not been developed yet (coating yellowing resistance).

  This invention is made | formed in view of the said situation, and can provide the polyisocyanate composition which is excellent in the coating-film yellowing resistance at the time of high temperature baking.

  As a result of intensive studies by the present inventors, 1,6-isocyanato-6-chlorohexane (hereinafter sometimes referred to as ICH) containing 1 to 200 ppm by mass and having a purity of 97.0% by mass or more 1,6 -It discovered that the polyisocyanate composition obtained by using at least diisocyanatohexane can achieve the said subject, and came to make this invention.

That is, the present invention is as follows.
[1]
A polyisocyanate composition obtained by using at least 1,6-diisocyanatohexane having a purity of 97.0 mass% or more and containing 1-200 massppm of 1-isocyanato-6-chlorohexane.
[2]
The polyisocyanate composition contains an iminooxadiazinedione structure and an isocyanurate structure,
^The polyisocyanate composition according to [1], wherein a molar ratio of the iminooxadiazinedione structure / the isocyanurate structure measured by ¹³ C-NMR is 6.0 / 100 to 20/100.
[3]
The polyisocyanate composition contains a uretdione structure and an isocyanurate structure,
^The polyisocyanate composition according to [1] or [2], wherein the molar ratio of the uretdione structure / the isocyanurate structure measured by ¹³ C-NMR is 0.1 / 100 to 5.0 / 100. .

  ADVANTAGE OF THE INVENTION According to this invention, the polyisocyanate composition which is excellent in the anti-coating yellowing resistance at the time of high temperature baking 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 polyisocyanate composition of this embodiment is obtained by using at least 1,6-diisocyanatohexane having a purity of 97.0% by mass or more and containing 1-200 mass ppm of 1-isocyanato-6-chlorohexane. A polyisocyanate composition. The polyisocyanate composition of this embodiment uses 1,6-diisocyanatohexane as a raw material. This 1,6-diisocyanatohexane has a purity of 97.0% by mass or more and contains 1-200 mass ppm of 1-isocyanato-6-chlorohexane. Such a polyisocyanate composition is excellent in coating film yellowing resistance during high-temperature baking. And good curability can also be maintained.

  The purity of 1,6-diisocyanatohexane, which is a raw material of the polyisocyanate composition of the present embodiment, is 97.0% by mass or more, preferably 98.0% by mass or more, more preferably 98.5% by mass. % Or more, more preferably 99.0% by mass or more. When the purity of 1,6-diisocyanatohexane is less than 97.0% by mass, the yield of the polyisocyanate composition obtained by polymerization or the like is lowered, which is not preferable. Further, the purity of 1,6-diisocyanatohexane referred to here is the purity of the monomer used at the time of production, and the component (for example, solvent component) used accompanying the polymerization reaction is the monomer. exclude. For example, a solvent component used for diluting the monomer is not included when considering the purity of the above 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 polyisocyanate composition of this 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 (1).

By containing an iminooxadiazinedione structure having an asymmetric structure, the smoothness (coating smoothness) of a coating film prepared using a polyisocyanate composition can be improved. The iminooxadiazinedione structure is a structure represented by the formula (2).

  The molar ratio of iminooxadiazinedione structure / isocyanurate structure in the polyisocyanate 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 value, the coating film smoothness is improved.

  It is preferable that the polyisocyanate composition of this embodiment 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 (3). 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 preferably 5.0 / 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 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 and heat resistance of the polyisocyanate composition are further improved. When the molar ratio of the uretdione structure / isocyanurate structure is not less than the above lower limit, the coating film smoothness is further improved.

The polyisocyanate composition of the present embodiment preferably has an allophanate structure from the viewpoint of viscosity and the like. The allophanate structure is a structure represented by the following formula (4). 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 compatibility with a resin such as polyol 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.

  1,6-diisocyanatohexane, which is a raw material of the polyisocyanate composition of this embodiment, contains 1-200 mass ppm of 1-isocyanato-6-chlorohexane. When the content of 1-isocyanato-6-chlorohexane is less than 1 ppm by mass, the suppression of yellowing resistance of the coating film during high-temperature baking is not sufficient. When the content of 1-isocyanato-6-chlorohexane exceeds 200 ppm by mass, the suppression of coating film yellowing resistance during high-temperature baking is not sufficient.

  The lower limit of the content of 1-isocyanato-6-chlorohexane in 1,6-diisocyanatohexane is preferably 3 ppm by mass or more, more preferably from the viewpoint of anti-coating yellowing resistance at high temperature baking. Is 5 ppm by mass or more, more preferably 10 ppm by mass or more, and still more preferably 20 ppm by mass or more. The upper limit of the content of 1-isocyanato-6-chlorohexane is preferably 150 ppm by mass or less, more preferably 125 ppm by mass or less, still more preferably 100 ppm by mass or less, and even more preferably 75. The mass is ppm or less.

  For example, 1-isocyanato-6-chlorohexane contained in 1,6-diisocyanatohexane reacts with an isocyanato group in 1-isocyanato-6-chlorohexane by a subsequent polymerization reaction or the like. Incorporated into the polyisocyanate skeleton. For example, in an isocyanurate trimer in which 1-isocyanato-6-chlorohexane is incorporated into an isocyanurate compound, one of three isocyanato groups is converted to a chloro group. Here, a trimer compound in which none of the three isocyanato groups is converted to a chloro group is a compound α, and a trimer in which one of the above three isocyanato groups is converted to a chloro group When the compound is the compound β, the mass ratio of the compound β to the compound α in the polyisocyanate composition of the present embodiment is preferably 5 to 100 ppm by mass. The upper limit of this mass ratio (β / α) is preferably 80 ppm by mass or less, more preferably 60 ppm by mass or less, and still more preferably 40 ppm by mass or less. The lower limit of this mass ratio (β / α) is preferably 6 ppm by mass or more, more preferably 10 ppm by mass or more, and more preferably 15 ppm by mass or more. By controlling the content ratio of the compound α and the compound β in the polyisocyanate composition obtained by a polymerization reaction or the like within the above range, the effect of this embodiment is further improved. One specific example of such a compound α is an isocyanurate trimer obtained by polymerizing three 1,6-isocyanatohexanes as described above. One specific example of such compound β is an isocyanurate trimer obtained by polymerizing two 1,6-isocyanatohexanes and one ICH. The compound α and the compound β (polyisocyanate compound in which 1-isocyanato-6-chlorohexane is incorporated (ICH introduction compound)) can be quantified by liquid chromatography-mass spectrum (LC / MS). Specifically, it can measure according to the method as described in an Example.

  The amount of chlorine component in the polyisocyanate composition of the present embodiment is preferably 1 to 100 ppm by mass. The upper limit value of the chlorine component amount is more preferably 75 mass ppm or less, further preferably 50 mass ppm or less, and further preferably 30 mass ppm or less. The lower limit value of the chlorine component amount is more preferably 5 ppm by mass or more, further preferably 10 ppm by mass or more, and further preferably 15 ppm by mass or more.

  Examples of a method for controlling the content of 1-isocyanato-6-chlorohexane in 1,6-diisocyanatohexane within the above range include, for example, 1,6-diisocyanatohexane and 1-isocyanato-6-chlorohexane. And the like.

  In addition, it does not specifically limit as a method to prepare 1, 6- diisocyanato hexane used by this embodiment, You may employ | adopt a well-known method. For example, a non-phosgene method such as described in Japanese Patent No. 4859255 can be employed. Specifically, 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. By thermally decomposing an aryl compound, 1,6-diisocyanatohexane can also be obtained.

  The 1,6-diisocyanatohexane (HDI) monomer mass concentration (HDI monomer concentration) in the polyisocyanate composition of the present embodiment is preferably 2.0% by mass or less, more preferably 1.0% by mass or less. More preferably, it is 0.5 mass% or less. When the concentration of the HDI monomer in the polyisocyanate composition is not more than the above upper limit, the danger during handling can be further reduced, and the curability of the coating composition can be further improved.

The content of isocyanate groups (NCO content) in the polyisocyanate composition of the present embodiment is preferably 19.0 to 24.0% by mass, with a nonvolatile content of 98.0% 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. When the NCO content is less than or equal to the above upper limit, the HDI monomer concentration of the polyisocyanate composition can be reduced, and the danger can be further reduced. By setting the NCO content to the above lower limit or more, the crosslinkability of the polyisocyanate composition can be further improved. 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 upper limit of the number average molecular weight is more preferably 750 or less, and still more preferably 700 or less. The lower limit of the number average molecular weight is more preferably 600 or more, and still more preferably 630 or more. When the number average molecular weight is not more than the above upper limit, the gloss of the resulting coating film is further improved. When the number average molecular weight is not less than the above lower limit, the yield of the resulting polyisocyanate composition 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 of this embodiment is demonstrated.
At least 1,6-diisocyanatohexane is used as a raw material for the polyisocyanate composition of the present embodiment. Furthermore, alcohol compounds such as alkyl monoalcohols and alkyl diols can be used in combination as auxiliary materials. When using an alcohol compound, it is preferable to control the molar ratio of the allophanate structure / isocyanurate structure in the polyisocyanate composition 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. That is, an example of a polyisocyanate composition obtained by a suitable method is a polyisocyanate obtained by polymerizing at least the above-mentioned 1,6-diisocyanatohexane in the presence of an auxiliary material (alcohol compound or the like). A composition.

  A polymerization catalyst is added to the raw material 1,6-diisocyanatohexane and the above-mentioned auxiliary materials, and the reaction is allowed to proceed until a predetermined degree of polymerization is reached. A polyisocyanate composition can be obtained by removing isocyanatohexane. An example of a polyisocyanate composition obtained by a suitable method in this case is a polyisocyanate composition obtained by polymerizing at least the above-mentioned 1,6-diisocyanatohexane in the presence of the above-mentioned auxiliary materials and a polymerization catalyst. An isocyanate composition is mentioned.

  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. Preferable specific examples of such a polymerization catalyst include a mixture containing the following A component and B component in a ratio of 5/100 to 100/5 as a mass ratio (A / B) of the A component to the B component. It is done. 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 ₁ = CR′—C (O) O— (a)

R ₂ —CR ′ ₂ —C (O) O— (b)

(In the formula, R ₁ and R ₂ 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 ₁ , R ₂ and R ′ may contain a hetero atom.)
R ₁ and R ₂ 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 viewpoints of product coloring and discoloration suppression 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 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. 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. As an example of the polyisocyanate composition obtained by a suitable method in this case, at least the 1,6-disilane described above in the presence of the above-mentioned auxiliary materials (for example, the above-mentioned alcohol compound and other components) and the polymerization catalyst. A polyisocyanate composition obtained by polymerization reaction of isocyanatohexane within the above-described range of the polymerization reaction temperature may be mentioned.

  When the polymerization reaction reaches a desired degree of polymerization, the polymerization reaction is stopped. The polymerization reaction is 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, thermally decompose, or chemically decompose the polymerization reaction catalyst. 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 1.0% 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 of the present embodiment can also be suitably used as a curing agent for coating compositions. That is, it can be set as the coating composition containing the polyisocyanate composition of this embodiment. 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 of this 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.

  The polyester polyol can be modified by using any of aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, and polyisocyanate 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 (ii) such as 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) ) For example, disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, (v), for example, raffinose, gentianose, meleti Trisaccharides such as over scan, (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.

  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 of the present embodiment as a curing agent can be used as a coating such as roll coating, curtain flow coating, spray coating, bell coating, and electrostatic coating. 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.

<Purity analysis of HDI monomer>
The purity analysis of the HDI monomer was calculated by area ratio by gas chromatography (GC) using GC-2014 (manufactured by SIMADZU).
The sample was weighed, diluted with acetone to a 10% by mass solution, and measured under the following GC conditions.
Carrier gas: helium gas Column: DB-5 (inner diameter 0.25 mm, length 30 m, film thickness 1.0 μm)
Oven conditions: The temperature was raised from 50 ° C. to 320 ° C. at a temperature raising rate of 10 ° C./min, and held at 320 ° C. for 3 minutes.
Inlet temperature: 320 ° C, interface temperature: 320 ° C
Injection amount: 1.0 μm, split ratio: 1/10
The retention time of 1,6-isocyanatohexane under the above measurement conditions was 15.0 minutes.
In the above measurement conditions, the component before the retention time of 10.0 minutes was determined as a solvent component, and when calculating the purity, the component was excluded from the calculation.

<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 it is 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 98.0 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 determined by performing ¹³ C-NMR measurement of the 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>
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 concentration in polyisocyanate composition>
The chlorine concentration and bromine concentration (mass basis) in 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. Thereafter, the sample board was moved to the combustion section and burned with an automatic combustion apparatus, and the gasified component was absorbed into 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

<Method for quantifying ICH-introduced compound in polyisocyanate composition>
In the polyisocyanate composition, two 1,6-isocyanatohexanes and one ICH were polymerized with respect to an isocyanurate trimer (compound α) obtained by polymerizing three 1,6-isocyanatohexanes. The abundance ratio of isocyanurate trimer (referred to as compound β) was determined according to the following method (quantification of ICH-introduced compound in polyisocyanate composition).
Specifically, the terminal isocyanate groups of the compound α and the compound β in the polyisocyanate composition were replaced with methanol, and analyzed by liquid chromatography-mass spectrum (LC / MS).
The sample preparation method and measurement method are described below.
(1) Preparation method of sample 100 mg of polyisocyanate compositions were weighed, and methanol was added so that it might become 10 mg / mL. Thereafter, the mixture was allowed to stand for 3 days, and the existing isocyanato group was completely reacted with methanol to prepare a methanol solution.
(2) Measuring method About the methanol solution obtained above, it measured using the following apparatuses.
・ LC
Equipment: Agilent 1100 series
Column: Phenomenex, Kinetex 2.6μ XB-C18 100A
(Inner diameter 2.1mm, length 50mm)
Column temperature: 40 ° C
Detection: 205nm
Flow rate: 0.35 mL / min Mobile phase: A, B liquid gradient A = water (0.05% formic acid), B = methanol Injection volume: 2 μL
・ MS
Equipment: ThermoElectron, LCQ
Ionization: APCI
Mode: Positive
Scan range: m / z 250-2000

Two 1,6-isocyanurate trimers (compound α) obtained by polymerization of three 1,6-isocyanatohexanes with respect to a methanol adduct (methanol adduct of compound α; see formula (5) below) It was calculated by a quantitative ratio (β / α) of a methanol adduct of isocyanurate trimer (compound β) polymerized with isocyanatohexane and one ICH (methanol adduct of compound β; see formula (6) below). .
The methanol adduct of compound α was detected with a detection ion (m / z) 601 at a retention time of 10.1 minutes.
The methanol adduct of compound β was detected with a detection ion (m / z) 562 at a retention time of 9.7 minutes.

<Evaluation of yellowing resistance of paint film during baking>
A solvent-based two-component urethane paint (polyol: acrylic polyol-based urethane; trade name “Mighty rack (white)”, manufactured by Nippon Paint Co., Ltd.) was spray-coated with an aluminum plate so as to have a thickness of 50 μm. Then, after leaving still at 23 degreeC and 50% humidity conditions for 2 weeks, the surface was grind | polished with the 1000th sandpaper, and the white board was produced.
Next, the acrylic polyol Ac-1 and the polyisocyanate compositions P-1 to P-6, C-1 to C-6 obtained in Synthesis Example 2 below are mixed into the polyisocyanate composition with respect to the OH group of the acrylic polyol. The NCO group molar ratio (NCO / OH) is mixed at a ratio of 1.0, and the solid content is 55% by mass using “Solvesso # 100” (trade name, aromatic solvent manufactured by Exxon). Thus, a coating composition was prepared. Using a spray, the coating composition was applied to the white plate prepared above so that the dry film thickness was 40 μm. After baking this at 160 ° C. for 30 minutes, the yellow index (YI) was measured according to ASTM D1925 using a chromaticity system “SM-T45” (manufactured by Suga Test Instruments Co., Ltd.). The smaller the YI of the paint film after baking, the better the yellowing resistance of the paint film.

<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 coating film smoothness>
The acrylic polyol Ac-1 obtained in Synthesis Example 2 below and the polyisocyanate compositions P-1 to P-6, C-1 to C-2 are mixed with the NCO group of the polyisocyanate composition relative to the OH group of the acrylic polyol. Mix at a ratio of molar ratio (NCO / OH) of 1.0 and adjust to a solids content of 55% by weight using “Sorvesso # 100” (trade name, aromatic solvent manufactured by Exxon). Thus, a coating 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 it was judged that 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 condenser tube was charged with 120.0 g of “Solvesso # 150” (an aromatic solvent manufactured by Exxon Chemical Co.) and 60.0 g of xylene, and the interior was purged with nitrogen. Thereafter, the temperature was raised to 120 ° C. Thereafter, (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 peroxide 8.0 g Was added dropwise over 2 hours to cause a stirring reaction. 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
To 1000 g of HDI having a purity of 98.8% by mass, 0.01 g (corresponding to 10 ppm by mass with respect to HDI) of 1-isocyanato-6-chlorohexane (ICH) was added, and these were heated at 80 ° C. Ammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd., CAS No. 665-46-3) 10 mass% n-butanol solution 1.5 g (0.77 mmol) and tetramethylammonium decanoate prepared in Synthesis Example 1 When 0.5 g (corresponding to 0.20 mmol) of a 10% by mass n-butanol solution was added and the NCO content in the reaction solution reached 39.3% by mass, 0.73 g of di-n-butyl phosphate was added. (3.5 mmol) was added to stop the reaction. Next, it was purified twice using a thin film evaporator under the conditions of 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 A polyisocyanate composition P-1 having an average molecular weight of 656 and 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. Moreover, it was 1 mass ppm when the amount of chlorine components of the polyisocyanate composition P-1 was measured. Further, the quantitative value (β / α) of the compound β with respect to the compound α was 6 mass ppm. The production conditions and physical properties of the polyisocyanate composition P-1 are shown in Table 1.

(Example 2)
To 1000 g of HDI having a purity of 98.8% by mass, 0.06 g (corresponding to 60 mass ppm with respect to HDI) of 1-isocyanato-6-chlorohexane (ICH) was added, and these were heated at 80 ° C. 0.20 g (0.51 mmol) of 50% by mass n-butanol solution of ammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50% by mass n-butanol solution of tetramethylammonium decanoate prepared in Synthesis Example 1 .10 g (equivalent to 0.20 mmol) was added, and 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 and reacted. Was stopped. Next, it was purified twice using a thin film evaporator under the conditions of 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 A polyisocyanate composition P-2 having an average molecular weight of 660 and 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. It was 7 mass ppm when the chlorine component amount of polyisocyanate composition P-1 was measured. Further, the quantitative value (β / α) of the compound β with respect to the compound α was 35 ppm by mass. The production conditions and physical properties of the polyisocyanate composition P-2 are shown in Table 1.

Example 3
To 1000 g of HDI having a purity of 98.8% by mass, 0.03 g (corresponding to 30 mass ppm with respect to HDI) of 1-isocyanato-6-chlorohexane (ICH) was added, and these were heated at 60 ° C. 0.30 g (corresponding to 0.77 mmol) of 50% by mass n-butanol solution of ammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50% by mass n-butanol solution of tetramethylammonium decanoate prepared in Synthesis Example 1 (Catalyst concentration 50% by mass) 0.15 g (corresponding to 0.31 mmol) was added, and when the NCO content of the reaction solution reached 39.2% by mass, 1.25 g (10. 8 mmol) was added to stop the reaction. Subsequently, it heated up at 90 degreeC and stirred for 1 hour. Then, after cooling to 40 ° C., the generated catalyst residue was filtered under reduced pressure with a membrane filter having a pore diameter 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. Moreover, it was 3 mass ppm when the chlorine component amount of polyisocyanate composition P-3 was measured. Further, the quantitative value (β / α) of the compound β with respect to the compound α was 17 mass ppm. The production conditions and physical properties of the polyisocyanate composition P-3 are shown in Table 1.

Example 4
Except that the amount of 1-isocyanato-6-chlorohexane (ICH) initially added to 1000 g of HDI having a purity of 99.3% by mass was changed to 0.16 g (corresponding to 160 mass ppm with respect to HDI). In the same manner as in Example 1, polyisocyanate composition P-4 was obtained. The production conditions and physical properties of the resulting polyisocyanate composition P-4 are shown in Table 1.

(Example 5)
Except that the amount of 1-isocyanato-6-chlorohexane (ICH) initially added to 1000 g of HDI having a purity of 98.8% by mass was changed to 0.09 g (corresponding to 90 mass ppm with respect to HDI). In the same manner as in Example 1, polyisocyanate composition P-5 was obtained. The production conditions and physical properties of the obtained polyisocyanate composition P-5 are shown in Table 1.

(Example 6)
To 1000 g of HDI having a purity of 98.8% by mass, 0.06 g (corresponding to 60 mass ppm with respect to HDI) of 1-isocyanato-6-chlorohexane (ICH) was added, and these were 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. 2.0 g (corresponding to 0.32 mmol) of this was added, and when the NCO content of the reaction solution reached 39.3% by mass, 0.73 g (3.5 mmol) of di-n-butyl phosphate was added. The reaction was stopped. 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-6 having an HDI monomer mass concentration of 0.12% by mass was obtained.
When structural analysis of the resulting polyisocyanate composition P-6 was performed, 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. Moreover, it was 7 mass ppm when the chlorine component amount of polyisocyanate composition P-6 was measured. Further, the quantitative value (β / α) of the compound β with respect to the compound α was 35 ppm by mass. The production conditions and physical properties of the polyisocyanate composition P-6 are shown in Table 1.

(Example 7)
To 1000 g of HDI having a purity of 98.8% by mass, 0.06 g (corresponding to 60 mass ppm with respect to HDI) of 1-isocyanato-6-chlorohexane (ICH) was added, and these were heated at 80 ° C. When 1.9 g (corresponding to 1.0 mmol) of a 10% by mass n-butanol solution of ammonium fluoride hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and the NCO content of the reaction solution reached 39.2% by mass, The reaction was stopped by adding 1.05 g (5.0 mmol) of di-n-butyl phosphate. Next, it was purified twice using a thin film evaporator under the conditions of 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 A polyisocyanate composition P-7 having an average molecular weight of 660 and an HDI monomer mass concentration of 0.18% by mass was obtained.
When structural analysis of the obtained polyisocyanate composition P-7 was performed, the molar ratio of isocyanurate structure / iminooxadiazinedione structure / uretodione structure / allophanate structure was 100/30 / 1.0 / 2.7. Met. 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. Moreover, it was 7 mass ppm when the chlorine component amount of polyisocyanate composition P-7 was measured. In addition, the quantitative value (β / α) of compound β with respect to compound α was 36 mass ppm. Table 1 shows the production conditions and physical properties of the polyisocyanate composition P-7.

(Comparative Example 1)
Polyisocyanate composition C-1 was obtained in the same manner as in Example 1 except that 1-isocyanato-6-chlorohexane (ICH) was not added to 1000 g of HDI having a purity of 98.8% by mass. Table 2 shows the production conditions and physical properties of the resulting polyisocyanate composition C-1.

(Comparative Example 2)
Except for changing the amount of 1-isocyanato-6-chlorohexane (ICH) initially added to 1000 g of HDI having a purity of 98.8% by mass to 0.25 g (corresponding to 250 mass ppm with respect to HDI), In the same manner as in Example 1, polyisocyanate composition C-2 was obtained. The production conditions and physical properties of the resulting polyisocyanate composition C-2 are shown in Table 2.

(Comparative Example 3)
Instead of ICH initially added to 1000 g of HDI having a purity of 98.8% by mass, 0.10 g of 1,6-dichlorohexane (DCH) (corresponding to 100 ppm by mass with respect to HDI) was added. In the same manner as in Example 1, polyisocyanate composition C-3 was obtained. The production conditions and physical properties of the resulting polyisocyanate composition C-3 are shown in Table 2.

(Comparative Example 4)
1-isocyanato-6-chlorohexane (ICH) was further added to the polyisocyanate composition C-1 obtained in Comparative Example 1 to obtain a polyisocyanate composition C-4. The addition amount of ICH was 50 mass ppm with respect to HDI. The production conditions and physical properties of the resulting polyisocyanate composition C-4 are shown in Table 2.

(Comparative Example 5)
Example 1 except that 0.01 g (corresponding to 10 mass ppm with respect to HDI) of hydrogen chloride (HCl) was added to 1000 g of HDI having a purity of 98.8 mass% instead of ICH added initially. Similarly, polyisocyanate composition C-5 was obtained. The production conditions and physical properties of the resulting polyisocyanate composition C-5 are shown in Table 2.

(Comparative Example 6)
Hydrogen chloride (HCl) was further added to the polyisocyanate composition C-1 obtained in Comparative Example 1 to obtain a polyisocyanate composition C-6. The amount of ICH added was 0.01 g with respect to 1000 g of HDI (corresponding to 10 mass ppm with respect to HDI). The production conditions and physical properties of the resulting polyisocyanate composition C-6 are shown in Table 2.

  The polyisocyanate composition and paint composition of the present invention can be used as paints for roll coating, curtain flow coating, spray coating, bell coating, electrostatic coating and the like. 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)

  A polyisocyanate composition obtained by using at least 1,6-diisocyanatohexane having a purity of 97.0 mass% or more and containing 1-200 massppm of 1-isocyanato-6-chlorohexane. The polyisocyanate composition contains an iminooxadiazinedione structure and an isocyanurate structure,
^The polyisocyanate composition according to claim 1, wherein a molar ratio of the iminooxadiazinedione structure / the isocyanurate structure measured by ¹³ C-NMR is 6.0 / 100 to 20/100. The polyisocyanate composition contains a uretdione structure and an isocyanurate structure,
^The polyisocyanate composition according to claim 1 or 2, wherein a molar ratio of the uretdione structure / the isocyanurate structure measured by ¹³ C-NMR is 0.1 / 100 to 5.0 / 100.