JP2020007450A - Isocyanate composition and polyurethane composition - Google Patents

Abstract

To provide an isocyanate composition that is excellent in dispersibility in water and when mixing a polyisocyanate component with a polyol component, has a long usable life (pot life), is excellent in dispersibility in the polyol component and can estimate the usable life (pot life) by a viscosity rise rate after mixing and to provide a polyurethane composition including the isocyanate composition.SOLUTION: The isocyanate composition is a reaction product of an isocyanurate of pentamethylene diisocyanate with a one end-blocked polyoxyalkylene glycol. The isocyanurate of pentamethylene diisocyanate is modified with alcohols. The modified amount of alcohols based on the isocyanurate of pentamethylene diisocyanate is 0.5 mass% to 20 mass%. The content of a polyoxyalkylene unit is 5 mass% to 30 mass%.SELECTED DRAWING: None

Description

  The present invention relates to an isocyanate composition and a polyurethane composition, and more particularly to an isocyanate composition and a polyurethane composition containing the isocyanate composition.

  The polyurethane composition contains a polyisocyanate component (curing agent) and a polyol component (main component), and is used as a paint or an adhesive by reacting and curing them.

  In recent years, as such a polyisocyanate component, pentamethylene diisocyanate may be used instead of hexamethylene diisocyanate.

  As a polyisocyanate component using pentamethylene diisocyanate, for example, a polyisocyanate composition obtained by reacting pentamethylene diisocyanate with methoxypolyethylene glycol in the presence of a trimerization catalyst has been proposed (for example, see Patent Document 1). .).

  In addition, a polyisocyanate composition obtained by reacting isocyanurate of 1,5-pentamethylene diisocyanate with polyethylene oxide polyether has been proposed (for example, see Patent Document 2).

International Publication No. 2012/121291 WO 2016/146579

  However, the polyisocyanate component using pentamethylene diisocyanate disclosed in Patent Document 1 has a problem that the pot life is short because the content of the polyoxyethylene unit is 47.15% by mass.

  Further, in the polyisocyanate component using pentamethylene diisocyanate of Patent Document 2, there is a problem that the isocyanurate of 1,5-pentamethylene diisocyanate is not modified with alcohols, and thus the dispersibility in the polyol component is reduced. .

  Furthermore, in the polyisocyanate component using hexamethylene diisocyanate, after mixing the polyisocyanate component and the polyol component, the viscosity of the mixture gradually increases. For this reason, there is a problem that it is difficult to estimate the pot life (pot life) especially at the work site.

  The present invention has excellent dispersibility in water, and when the polyisocyanate component and the polyol component are mixed, the pot life is long, the dispersibility in the polyol component is excellent, and the viscosity after mixing is high. It is an object of the present invention to provide an isocyanate composition whose pot life (pot life) can be estimated from the rate of increase, and a polyurethane composition containing the isocyanate composition.

  The present invention [1] is a reaction product of an isocyanurate of pentamethylene diisocyanate and a polyoxyalkylene glycol having one end capped, wherein the isocyanurate of pentamethylene diisocyanate is modified with an alcohol, and pentamethylene diisocyanate is used. Is an isocyanurate, wherein the alcohol is modified in an amount of 0.5% by mass or more and 20% by mass or less and a polyoxyalkylene unit content is 5% by mass or more and 30% by mass or less. .

  The present invention [2] includes the isocyanate composition according to the above [1], wherein the alcohol is a monohydric alcohol.

  The present invention [3] includes the isocyanate composition according to the above [1] or [2], wherein the content of the polyoxyalkylene unit is 7% by mass or more and 25% by mass or less.

  The present invention [4] includes a polyurethane composition containing a polyisocyanate component containing the isocyanate composition according to any one of the above [1] to [3], and a polyol component.

  The isocyanate composition of the present invention is a reaction product of an isocyanurate of pentamethylene diisocyanate and a polyoxyalkylene glycol having one end blocked. Therefore, when this isocyanate composition is mixed with a polyol component, the pot life (pot life) can be estimated from the viscosity increase rate after mixing.

  Further, isocyanurate of pentamethylene diisocyanate is modified with alcohols. Therefore, when this isocyanate composition is mixed with a polyol component, it is excellent in dispersibility.

  Further, the amount of modification of the alcohol with respect to the isocyanurate of pentamethylene diisocyanate is 0.5% by mass or more and 20% by mass or less. Therefore, when this isocyanate composition is mixed with a polyol component, it is excellent in dispersibility, the pot life (pot life) is long, and the pot life (pot life) is estimated from the viscosity increase rate after mixing. Can be.

  The isocyanate composition of the present invention has a polyoxyalkylene unit content of 5% by mass or more and 30% by mass or less. Therefore, when this isocyanate composition is mixed with a polyol component, the pot life is long and the dispersibility in water is excellent.

FIG. 1 is a graph showing the results of measuring the viscosity of Ford cup (No. 2) of the isocyanate compositions of Examples 1 to 6 and Comparative Example 2. FIG. 2 is a graph showing the results of measuring the viscosity of Ford cup (No. 2) of the isocyanate compositions of Examples 4, 5 and 7. FIG. 3 is a graph showing the results of measuring the viscosity of Ford cup (No. 2) of the isocyanate compositions of Example 3, Examples 8 to 10 and Comparative Example 6. FIG. 4 is a graph showing the results of measuring the viscosity of Ford cup (No. 2) of the isocyanate compositions of Example 3 and Comparative Example 7. FIG. 5 is a graph showing the results of measuring the viscosity of Ford cup (No. 2) of the isocyanate compositions of Example 3 and Example 11. FIG. 6 is a chromatogram of the isocyanate composition of Example 3 when measured by gel permeation chromatography.

  The isocyanate composition of the present invention is a reaction product of an isocyanurate of pentamethylene diisocyanate and a polyoxyalkylene glycol having one end blocked.

  The isocyanurate of pentamethylene diisocyanate includes a trimer of pentamethylene diisocyanate (monomer) (mononuclear isocyanurate) and a multimer having a plurality of trimer skeletons (polynuclear isocyanurate).

  Specifically, pentamethylene diisocyanate is 1,5-pentamethylene diisocyanate. In the present invention, pentamethylene diisocyanate also includes structural isomers such as 1,4-pentamethylene diisocyanate (1,4-pentane diisocyanate) and 1,3-pentamethylene diisocyanate (1,3-pentane diisocyanate). It is.

  These pentamethylene diisocyanate monomers can be used alone or in combination of two or more.

  As the monomer of pentamethylene diisocyanate, preferably, 1,5-pentamethylene diisocyanate is used.

  In addition, pentamethylene diisocyanate is not particularly limited, and can be produced, for example, according to Example 1 in the specification of WO 2012/121291 pamphlet.

  Further, such isocyanurate of pentamethylene diisocyanate is modified with alcohols by a method described later.

  Specifically, such an isocyanurate of pentamethylene diisocyanate is obtained by subjecting pentamethylene diisocyanate to an urethanation reaction with an alcohol, and then adding an isocyanuration catalyst to the urethane reaction liquid to form a urethane reaction liquid ( Specifically, after pentamethylene diisocyanate and a reaction product of pentamethylene diisocyanate and alcohols, the same applies hereinafter)), an unreacted pentamethylene diisocyanate is removed, if necessary. can get.

  In this method, the allophanate reaction proceeds along with the isocyanurate reaction. Thus, isocyanurates of pentamethylene diisocyanate include allophanates of pentamethylene diisocyanate. That is, the isocyanurate of pentamethylene diisocyanate includes mononuclear isocyanurate of pentamethylene diisocyanate, polynuclear isocyanurate of pentamethylene diisocyanate, and allophanate of pentamethylene diisocyanate.

  More specifically, first, pentamethylene diisocyanate and alcohols are mixed and urethanized.

  Examples of the alcohols include monohydric alcohols and polyhydric alcohols.

  The monohydric alcohol is an organic compound having one hydroxyl group in one molecule, and is methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-octanol. -Nonanol, n-decanol, n-undecanol, n-dodecanol (lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octa Linear monohydric alcohols such as decanol (stearyl alcohol), n-nonadecanol and eicosanol, for example, isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol , 2- Tylhexan-1-ol, isononanol, isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyl Examples include branched monohydric alcohols such as dodecanol and other branched alkanols (5 to 20 carbon atoms).

  Polyhydric alcohols are organic compounds having two or more hydroxyl groups in one molecule, and include, for example, ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or a mixture thereof), butylene glycol (1,2). 2- or 1,3- or 1,4-butanediol or a mixture thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2, Alkanediols such as 2,2-trimethylpentanediol and 3,3-dimethylolheptane, for example, dihydric alcohols such as ether diols such as diethylene glycol, triethylene glycol and dipropylene glycol, for example, glycerin, trimethylolpropane, Isopropanolamine Trihydric alcohols such as tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, and pentahydric alcohols such as xylitol, for example, sorbitol, mannitol, allitol, iditol, darcitol, altitol, inositol, Hexahydric alcohols such as dipentaerythritol, for example, 7-hydric alcohols such as perseitol, aliphatic polyhydric alcohols such as octahydric alcohols such as sucrose, and the like are preferable, and dihydric alcohols are more preferable. , 3-butanediol.

  Preferably, the alcohols include monohydric alcohols, more preferably, branched monohydric alcohols, and more preferably, isobutanol.

  When the alcohol is a monohydric alcohol, when this isocyanate composition is mixed with a polyol component, the dispersibility is excellent and the pot life (pot life) can be extended.

  The mixing ratio of the alcohol is, for example, 0.1 part by mass or more, preferably 1 part by mass or more, and for example, 10 parts by mass or less, preferably 3 parts by mass with respect to 100 parts by mass of pentamethylene diisocyanate. Parts by weight, more preferably 2 parts by weight or less.

  The equivalent ratio (NCO / OH) of the isocyanate group of pentamethylene diisocyanate to the hydroxy group of the alcohol is, for example, 5 or more, preferably 20 or more, more preferably 50 or more, and for example, 1000 or more. Or less, preferably 500 or less.

  The urethane reaction between pentamethylene diisocyanate and alcohols is performed, for example, in an atmosphere of an inert gas such as a nitrogen gas under normal pressure (atmospheric pressure). As reaction conditions, the reaction temperature is, for example, room temperature (for example, 25 ° C.) or higher, preferably 40 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and the reaction time is, for example, 3 minutes or longer. Preferably, it is 12 minutes or more, for example, 10 hours or less, preferably 6 hours or less.

  In addition, the above urethane reaction can be carried out without a solvent, but if necessary, a known organic solvent can be blended.

  As the organic solvent, for example, aliphatic hydrocarbon organic solvents such as n-hexane and octane, for example, alicyclic hydrocarbon organic solvents such as cyclohexane and methylcyclohexane, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Ketone-based organic solvents such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; and alkyl ester-based organic solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, and 3-methyl-3-methoxybutyl. Glycol ether ester organic solvents such as acetate and ethyl-3-ethoxypropionate, for example, ether organic solvents such as diethyl ether, tetrahydrofuran and dioxane, for example, methyl chloride Halogenated aliphatic organic solvents such as methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, and dichloroethane, for example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphospho And polar aprotic organic solvents such as nilamide.

  These organic solvents can be used alone or in combination of two or more.

  By such a urethane-forming reaction, a urethane reaction liquid is obtained. The urethane reaction liquid contains a reaction product of pentamethylene diisocyanate and alcohols, unreacted pentamethylene diisocyanate, and an organic solvent blended if necessary.

  Next, an isocyanuration catalyst is added to the obtained urethane reaction liquid, and the urethane reaction liquid is subjected to an isocyanuration reaction.

  The isocyanuration catalyst is not particularly limited as long as it is a catalyst effective for isocyanuration.For example, tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium, and organic compounds thereof can be used. Weak acid salts, for example, trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, trialkylhydroxyalkylammonium hydroxides and organic weak acid salts thereof such as triethylhydroxyethylammonium, for example, acetic acid, caproic acid, octylic acid, Alkali metal salts of alkyl carboxylic acids such as myristic acid, for example, tin, zinc and lead of the above alkyl carboxylic acids Any metal salt, for example, a metal chelate compound of β-diketone such as aluminum acetylacetone and lithium acetylacetone, for example, Friedel-Crafts catalyst such as aluminum chloride, boron trifluoride and the like, for example, titanium tetrabutylate, tributylantimony oxide and the like And various organic metal compounds, for example, an aminosilyl group-containing compound such as hexamethylsilazane.

  Specific examples include, for example, Zwitterion-type hydroxyalkyl quaternary ammonium compounds, and more specifically, for example, N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2 -Ethylhexanoate, N, N-dimethyl-N-hydroxyethyl-N-2-hydroxypropylammonium hexanoate, triethyl-N-2-hydroxypropylammonium hexadecanoate, trimethyl-N-2-hydroxypropyl Ammonium phenyl carbonate, trimethyl-N-2-hydroxypropylammonium formate, and the like.

  These isocyanuration catalysts can be used alone or in combination of two or more.

  Preferred examples of the isocyanuration catalyst include Zwitterion type hydroxyalkyl quaternary ammonium compounds, and more preferably N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexa. Noate.

  The addition ratio of the isocyanuration catalyst is, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, for example, 0.1 part by mass or less, based on 100 parts by mass of the urethane reaction liquid, preferably It is 0.05 parts by mass or less.

  This isocyanuration reaction is carried out, for example, in an atmosphere of an inert gas such as nitrogen gas under normal pressure (atmospheric pressure). As the reaction conditions for the isocyanuration reaction, the reaction temperature is, for example, room temperature (eg, 25 ° C.) or higher, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower. And the reaction time is, for example, 30 minutes or more, preferably 1 hour or more, more preferably 2 hours or more, for example, 12 hours or less, preferably 10 hours or less, more preferably 8 hours or less. is there.

  In the above isocyanurate conversion reaction, the isocyanurate conversion of pentamethylene diisocyanate is, for example, 1% by mass or more, preferably 5% by mass or more, and for example, 20% by mass or less, preferably 12% by mass. It is as follows.

  The isocyanurate conversion can be measured, for example, based on gel permeation chromatography (GPC), NMR, isocyanate group concentration, refractive index, density, infrared spectrum, and the like.

  The above isocyanurate-forming reaction can be carried out without solvent, but if necessary, a known organic solvent can be blended. When an organic solvent is used in the urethanization reaction, the organic solvent can be used as it is in the isocyanuration reaction.

  In the above-mentioned isocyanurate-forming reaction, known additives such as an antioxidant and a co-catalyst can be added as necessary.

  Examples of the antioxidant include a phenolic antioxidant and a hindered phenolic antioxidant, and from the viewpoint of hygiene, preferably a hindered phenolic antioxidant. Specific examples of the hindered phenol-based antioxidant include, for example, 2,6-di (tert-butyl) -4-methylphenol (alias: dibutylhydroxytoluene, sometimes abbreviated as BHT hereinafter), [3- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyloxy] -2,2-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propanoyloxymethyl] propyl] 3- (3,5-ditert-butyl-4-hydroxyphenyl) propanoate (Irganox 1010, Ciba Japan, trade name), octadecyl 3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Japan, trade name), 3- (4-hid Roxy-3,5-diisopropylphenyl) propionic acid octyl ester (Irganox 1135, manufactured by Ciba Japan, trade name), bis [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propionic acid And ethylenebisoxybisethylene (Irganox 245, manufactured by Ciba Japan, trade name).

  These antioxidants can be used alone or in combination of two or more.

  As the antioxidant, preferably, 2,6-di (tert-butyl) -4-methylphenol is used.

  Examples of the co-catalyst include organic phosphites.

  Examples of the organic phosphite include organic phosphite diesters and organic phosphite triesters, and more specifically, for example, triethyl phosphite, tributyl phosphite, tridecyl phosphite, tris ( Monophosphites such as tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and diphenyl (tridecyl) phosphite; Examples thereof include di, tri, and tetraphosphites derived from polyhydric alcohols such as stearyl pentaerythrityl diphosphite, tripentaerythritol triphosphite, and tetraphenyl dipropylene glycol diphosphite.

  These organic phosphites can be used alone or in combination of two or more.

  Preferred examples of the organic phosphite include monophosphites, and more preferred are tridecyl phosphite and tris (tridecyl) phosphite.

  The timing of adding the additive is not particularly limited, and may be added to the pentamethylene diisocyanate or urethane reaction solution before the isocyanuration reaction, or may be added to the isocyanurate reaction solution during the isocyanuration reaction. And further may be added to the isocyanurate reaction solution after the isocyanurate-forming reaction. Preferably, it is added to pentamethylene diisocyanate.

  The addition ratio of the additive is appropriately set according to the purpose and use.

  In the above-mentioned reaction, the isocyanurate-forming reaction is stopped by adding the catalyst deactivator after the isocyanurate conversion reaches the above-mentioned range.

  Examples of the catalyst deactivator include a phosphoric acid compound, a sulfonic acid compound, and a sulfonamide compound.

  Examples of the phosphoric acid compound include phosphoric acid and phosphoric acid ester. Examples of the phosphate ester include methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, dipropyl phosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, and phosphoric acid (C12-18) alkyl, isotridecyl phosphate, oleyl phosphate, tetracosyl phosphate, ethylene glycol phosphate, 2-hydroxyethyl methacrylate phosphate, dibutyl phosphate and the like.

  Examples of the sulfonic acid compound include sulfonic acid and sulfonic acid ester. Examples of the sulfonic acid include dodecylbenzenesulfonic acid, paratoluenesulfonic acid, and the like. Examples of the sulfonic acid ester include alkyl dodecylbenzenesulfonic acid such as methyl dodecylbenzenesulfonate, ethyl dodecylbenzenesulfonate, propyl dodecylbenzenesulfonate, and butyl dodecylbenzenesulfonate, for example, methyl paratoluenesulfonate, paratoluene Examples thereof include p-toluenesulfonic acid alkyl esters such as ethyl sulfonate, propyl paratoluenesulfonate, and butyl paratoluenesulfonate.

  Examples of the sulfonamide compound include aromatic sulfonamides (eg, benzenesulfonamide, dimethylbenzenesulfonamide, sulfanylamide, o- and p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene -2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, etc.), aliphatic sulfonamides (for example, methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide Donado), and the like.

  In addition, examples of the catalyst deactivator include, in addition to the above, monochloroacetic acid, benzoyl chloride, and the like.

  These catalyst deactivators can be used alone or in combination of two or more.

  As the catalyst deactivator, preferably, a sulfonamide compound, preferably, o-toluenesulfonamide is used.

  Further, the addition ratio of the catalyst deactivator (in terms of the active ingredient) is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more with respect to the total amount of the isocyanurate reaction solution (described later), Also, for example, it is 0.5 parts by mass or less.

  By such an isocyanurate-forming reaction, an isocyanurate reaction liquid is obtained.

  The isocyanurate reaction liquid contains pentamethylene diisocyanate isocyanurate containing pentamethylene diisocyanate allophanate, unreacted pentamethylene diisocyanate, and optionally an organic solvent.

  Then, unreacted pentamethylene diisocyanate and the organic solvent are removed by a known removal method such as distillation, if necessary.

  The content of the allophanate of pentamethylene diisocyanate in the isocyanurate of pentamethylene diisocyanate is, for example, 0.2% by mass or more, preferably 10% by mass or more, and for example, 40% by mass or less, preferably 37% by mass. %, More preferably 30% by mass or less, further preferably 20% by mass or less.

  When the content is at least the lower limit, when the isocyanate composition is mixed with the polyol component, the dispersibility in the polyol component is excellent.

  When the content is equal to or less than the upper limit, when the isocyanate composition is mixed with the polyol component, the pot life (pot life) is long, and the pot life (pot life) depends on the viscosity increase rate after mixing. Pot life) can be estimated.

  The content of the allophanate can be determined by measuring the isocyanurate of pentamethylene diisocyanate by gel permeation chromatography (GPC).

  Specifically, for example, the molecular weight distribution of isocyanurate of pentamethylene diisocyanate is measured by a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), and the obtained chromatogram (chart) is obtained. From the total area of the peaks corresponding to the isocyanurate of pentamethylene diisocyanate (mononuclear isocyanurate of pentamethylene diisocyanate, polynuclear isocyanurate of pentamethylene diisocyanate, and allophanate of pentamethylene diisocyanate) with respect to the total area of peaks corresponding to pentamethylene diisocyanate. Can be calculated by determining the area ratio of the peak corresponding to

  More specifically, when the alcohol is a monohydric alcohol, a peak corresponding to the isocyanurate of pentamethylene diisocyanate (mononuclear isocyanurate of pentamethylene diisocyanate, polynuclear isocyanurate of pentamethylene diisocyanate, and The total area of pentamethylene diisocyanate) can be calculated by determining the area ratio of the peak corresponding to the allophanate of pentamethylene diisocyanate (specifically, the following general formula (1)).

(In the formula, R1 represents a residue of an alcohol.)
When the alcohol is a dihydric alcohol, the isocyanurate of pentamethylene diisocyanate (mononuclear isocyanurate of pentamethylene diisocyanate, polynuclear isocyanurate of pentamethylene diisocyanate, and allophanate of pentamethylene diisocyanate) It can be calculated by obtaining the area ratio of the peak corresponding to the allophanate of pentamethylene diisocyanate (specifically, the following general formula (2)) to the total area of the corresponding peak.

(In the formula, R1 represents a residue of an alcohol.)
Specifically, in the chromatogram measured by GPC, the peaks other than the peak corresponding to the allophanate of pentamethylene diisocyanate are determined by using isocyanurate of pentamethylene diisocyanate (mononuclear body of isocyanurate of pentamethylene diisocyanate and pentamethylene diisocyanate). (If the unreacted pentamethylene diisocyanate remains, the peak corresponding to the unreacted pentamethylene diisocyanate is excluded), and pentamethylene for all peaks The area ratio of the peak corresponding to the allophanate of the diisocyanate is calculated as the content of the allophanate.

  The isocyanurate of pentamethylene diisocyanate is modified with alcohols.

  Since the isocyanurate of pentamethylene diisocyanate has been modified with alcohols, when this isocyanate composition is mixed with a polyol component, it is excellent in dispersibility.

  The modification amount of alcohols with respect to isocyanurate of pentamethylene diisocyanate (alcohol modification rate of isocyanurate) is, for example, 0.5% by mass or more, preferably 5% by mass or more, and for example, 20% by mass or less, Preferably it is 15% by mass or less, more preferably 8% by mass or less.

  When the amount of modification is not less than the lower limit, when the isocyanate composition is mixed with the polyol component, the dispersibility in the polyol component is excellent.

  Further, when the above-mentioned modification amount is equal to or less than the above-mentioned upper limit, when the isocyanate composition is mixed with the polyol component, the pot life is long, and the viscosity rise rate after mixing increases the pot life. Time (pot life) can be estimated.

  The above modification amount can be calculated by the following equation.

Denaturation amount of alcohols with respect to isocyanurate of pentamethylene diisocyanate (% by mass) = (Modification amount of alcohols in isocyanurate reaction solution (% by mass) / distillation yield) × 100
In the above formula, the modified amount of alcohol in the isocyanurate reaction liquid means the content of alcohol relative to the charged amount of pentamethylene diisocyanate and alcohol.

  In the above formula, the distillation yield means the yield of isocyanurate of pentamethylene diisocyanate obtained by the above distillation.

  The isocyanurate content of pentamethylene diisocyanate (NCO%) is, for example, 10% by mass or more, preferably 18% by mass or more, and for example, 28% by mass or less.

  In addition, the said isocyanate group content (NCO%) can be measured by the n-dibutylamine method based on JISK-1556 (2006) using a potentiometric titrator.

  As the one-end-blocked polyoxyalkylene glycol, for example, one-end-blocked polyoxyalkylene (C2-3) glycol is exemplified.

  Examples of the polyoxyalkylene (C2-3) glycol having one end sealed include polyoxyethylene glycol having one end sealed, polyoxypropylene glycol having one end sealed, and polyoxyethylene polyoxypropylene glycol having one end sealed. Preferably, one end-blocked polyoxyethylene glycol, one end-blocked polyoxyethylene polyoxypropylene glycol, and more preferably, one end-blocked polyoxyethylene glycol.

  One-end-blocked polyoxyethylene glycol is a polyoxyethylene ether monoalkyl alcohol in which one terminal hydroxyl group of polyoxyethylene glycol is substituted with an oxyalkylene group.

  The polyoxyethylene ether monoalkyl alcohol is represented, for example, by the following formula (3).

(In the formula, R2 represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 3 to 100.)
In the formula, examples of the alkyl group having 1 to 4 carbon atoms represented by R2 include methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl and the like. Preferably, methyl and ethyl are used. In the formula, m is the degree of polymerization of polyoxyethylene, and is 3 or more, preferably 5 or more, more preferably more than 8, and, for example, 100 or less, preferably 50 or less, more preferably , 25 or less.

  Specifically, methoxypolyoxyethylene alcohol (methoxy PEG), ethoxypolyoxyethylene alcohol (ethoxy PEG) and the like can be mentioned, and their number average molecular weight is 200 or more, preferably 390 or more, Preferably it is 500 or more, for example, 5000 or less, preferably 2000 or less.

  One end-blocked polyoxyethylene glycol can be used alone or in combination of two or more.

  As one end-blocked polyoxyethylene glycol, preferably, methoxy polyoxyethylene alcohol is used.

  Then, the isocyanate composition can be obtained by a reaction between the isocyanurate of pentamethylene diisocyanate and the polyoxyalkylene glycol having one end blocked.

  In this reaction, the blending ratio of the isocyanurate of pentamethylene diisocyanate and the polyoxyalkylene glycol having one end capped is the equivalent ratio of the isocyanate group of isocyanurate of pentamethylene diisocyanate to the hydroxyl group of the polyoxyalkylene glycol having one end capped. (NCO / OH) is an NCO excess ratio, for example, 2 or more, preferably 3 or more, and for example, 50 or less, preferably 30 or less. The reaction temperature is, for example, 40 ° C. or more and 100 ° C. or less, and the reaction time is, for example, 0.5 hour or more and 20 hours or less. This reaction is preferably performed under an inert gas atmosphere.

  Thereby, an isocyanate composition is obtained.

  And in the isocyanate composition thus obtained, the isocyanate group content (NCO%) is, for example, 10% by mass or more, preferably 18% by mass or more, and for example, 28% by mass or less. .

  In addition, the isocyanate group content (NCO%) can be measured by an n-dibutylamine method based on JIS K-1556 (2006) using a potentiometric titrator.

  The polyoxyalkylene unit content is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, further preferably 8% by mass or more, and 30% by mass or less. It is preferably at most 28% by mass, more preferably at most 25% by mass, still more preferably at most 20% by mass, particularly preferably at most 15% by mass.

  When the polyoxyalkylene unit content is equal to or less than the upper limit, when the isocyanate composition is mixed with the polyol component, the pot life (pot life) can be extended.

  On the other hand, when the polyoxyalkylene unit content exceeds the upper limit, when the isocyanate composition is mixed with the polyol component, the pot life (pot life) becomes short.

  When the content of the polyoxyalkylene unit is at least the above lower limit, the dispersibility in water is excellent.

  On the other hand, when the polyoxyalkylene unit content is less than the above lower limit, the dispersibility in water is reduced.

The polyoxyalkylene unit content can be calculated by the following equation.
((One-end-blocked polyoxyalkylene glycol molecular weight-molecular weight of oxyalkylene group) / one-end-blocked polyoxyalkylene glycol molecular weight) × (single-end-blocked polyoxyalkylene glycol charge / isocyanate composition) × 100
Further, when the polyoxyalkylene glycol having one end capped is polyoxyethylene glycol having one end capped, the polyoxyethylene unit content is, for example, 5% by mass or more, preferably 6% by mass or more, It is preferably at least 7 mass%, more preferably at least 8 mass%, and for example, at most 30 mass%, preferably at most 28 mass%, more preferably at most 25 mass%, even more preferably at most 20 mass%. % By mass, particularly preferably 15% by mass or less.

  When the polyoxyethylene unit content is equal to or less than the above upper limit, when the isocyanate composition is mixed with the polyol component, the pot life (pot life) can be extended.

  When the polyoxyethylene unit content is at least the above lower limit, the dispersibility in water will be excellent.

The polyoxyethylene unit content can be calculated by the following equation.
((One-end-blocked polyoxyethylene glycol molecular weight−molecular weight of oxyalkylene group) / one-end-blocked polyoxyethylene glycol molecular weight) × (one-end-blocked polyoxyethylene glycol charge / isocyanate composition) × 100
Further, the content of the allophanate of pentamethylene diisocyanate in the isocyanate composition is, for example, 0.2% by mass or more, preferably 10% by mass or more, and, for example, 35% by mass or less, preferably 30% by mass. Or less, more preferably 20% by mass or less.

  The content of the allophanate can be determined by measuring the isocyanate composition by GPC using the method described above.

  When the content is at least the lower limit, when the isocyanate composition is mixed with the polyol component, the dispersibility in the polyol component is excellent.

  When the content is equal to or less than the upper limit, when the isocyanate composition is mixed with the polyol component, the pot life (pot life) is long, and the pot life (pot life) depends on the viscosity increase rate after mixing. Pot life) can be estimated.

  The content of the allophanate can be determined by measuring the isocyanate composition by gel permeation chromatography (GPC).

  The modification amount of alcohols in the isocyanate composition (alcohol modification ratio of isocyanurate) is 0.5% by mass or more, preferably 3% by mass or more, and 20% by mass or less, preferably 13% by mass. %, More preferably 9% by mass or less.

  When the amount of modification is not less than the lower limit, when the isocyanate composition is mixed with the polyol component, the dispersibility in the polyol component is excellent.

  On the other hand, when the modification amount is less than the lower limit, when the isocyanate composition is mixed with the polyol component, dispersibility in the polyol component is reduced.

  If the above-mentioned modification amount is equal to or less than the above-mentioned upper limit, when the isocyanate composition is mixed with the polyol component, the pot life (pot life) is long, and the pot life is increased depending on the viscosity increase rate after mixing. Time (pot life) can be estimated.

  On the other hand, if the amount of modification exceeds the upper limit, when the isocyanate composition is mixed with the polyol component, the rate of increase in viscosity becomes excessively high, and the pot life (pot life) cannot be estimated.

  The above modification amount can be calculated by the following equation.

Modification amount of alcohols in isocyanate composition (% by mass) = (Modification amount of alcohols to isocyanurate of pentamethylene diisocyanate / isocyanate composition) × 100
And, such an isocyanate composition is a reaction product of an isocyanurate of pentamethylene diisocyanate and a polyoxyalkylene glycol having one end blocked. Therefore, when this isocyanate composition is mixed with a polyol component, the pot life (pot life) can be estimated from the viscosity increase rate after mixing.

  The viscosity of the isocyanate composition at 25 ° C. is, for example, 300 mPa · s or more, preferably 800 mPa · s or more, and for example, 2000 mPa · s or less.

  Such an isocyanate composition can be used as an aqueous isocyanate composition dispersed or dissolved in water.

  Further, in such an isocyanate composition, in order to further improve water dispersibility and solubility, a compound having both a free isocyanate group and a hydrophilic group and an active hydrogen group of the isocyanate composition (hereinafter referred to as a hydrophilic group-containing activity). (A hydrogen compound).

  The hydrophilic group-containing active hydrogen compound is a compound having at least one hydrophilic group and at least one active hydrogen group. Examples of the hydrophilic group include an ionic group (anionic group and a cationic group). And a hydroxyl group. The active hydrogen group is a group that reacts with an isocyanate group, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, and an epoxy group.

  More specifically, examples of the active hydrogen compound having a hydrophilic group include an active hydrogen compound having a carboxylic acid group, an active hydrogen compound having a sulfonic acid group, and an active hydrogen compound having a hydroxyl group.

  Examples of the carboxylic acid group-containing active hydrogen compound include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid (DMBA), Examples thereof include dihydroxycarboxylic acids such as 2,2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid, for example, diaminocarboxylic acids such as lysine and arginine, and metal salts and ammonium salts thereof.

  Examples of the sulfonic acid group-containing active hydrogen compound include dihydroxybutanesulfonic acid and dihydroxypropanesulfonic acid obtained from a synthesis reaction between an epoxy group-containing compound and an acidic sulfite. Further, for example, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, N, N-bis (2-hydroxyethyl) -2-aminobutanesulfonic acid, 1,3-phenylenediamine-4 , 6-Disulfonic acid, diaminobutanesulfonic acid, diaminopropanesulfonic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid, 2-aminoethanesulfonic acid, N- (2-aminoethyl) -2- Aminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,4-diamino-5-toluenesulfonic acid, 2- (cyclohexylamino) -ethanesulfonic acid, 3- (cyclohexylamino) propanesulfonic acid Or metal salts or ammonium salts of these sulfonic acids.

  Examples of the sulfonic acid group-containing active hydrogen compound include, for example, sulfonic acid-containing polybasic acids, more specifically, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (p-sulfophthalic acid). Phenoxy) isophthalic acid, 5- (sulfopropoxy) isophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfopropylmalonic acid, sulfosuccinic acid, 2-sulfobenzoic acid, 2,3-sulfobenzoic acid, 5- Examples include sulfosalicylic acid, alkyl esters of these carboxylic acids, and polybasic acids containing hydrophilic groups such as metal salts and ammonium salts of sulfonic acids.

  Examples of the hydroxyl group-containing active hydrogen compound include N- (2-aminoethyl) ethanolamine.

  Then, the hydrophilic group-containing active hydrogen compound is blended with the active hydrogen groups of the hydrophilic group-containing active hydrogen compound in such a ratio that the free isocyanate groups of the above isocyanate composition become excessive, and reacted under known conditions. Can be obtained.

  Particularly, when the active hydrogen compound having a hydrophilic group is 2- (cyclohexylamino) -ethanesulfonic acid or 3- (cyclohexylamino) propanesulfonic acid, the above reaction is carried out in the presence of a neutralizing amine. I do.

  The neutralizing amine is blended to neutralize the sulfonic acid group of aminosulfonic acid, and includes, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, Tertiary monoamines such as -methylpiperidine and N-ethylpiperidine, such as 1,3-bis- (dimethylamino) -propane, 1,4-bis- (dimethylamino) -butane or N, N'-dimethylpiperazine; Tertiary diamine and the like.

  In the above description, the isocyanate composition is reacted with the hydrophilic group-containing active hydrogen compound, that is, first, the isocyanurate of pentamethylene diisocyanate is reacted with the polyoxyalkylene glycol having one end blocked to obtain an isocyanate composition. The isocyanate composition was reacted with the hydrophilic group-containing active hydrogen compound, but the order of these reactions is not particularly limited.

  Specifically, first, the isocyanurate of pentamethylene diisocyanate is reacted with a hydrophilic group-containing active hydrogen compound to obtain a reaction product, and the reaction product is reacted with a polyoxyalkylene glycol having one end-blocked end. Alternatively, an isocyanurate of pentamethylene diisocyanate, a polyoxyalkylene glycol having one end-blocked end, and an active hydrogen compound having a hydrophilic group may be simultaneously mixed and reacted.

  Further, in the above isocyanate composition, a blocked isocyanate composition can be prepared by blocking a free isocyanate group with a blocking agent.

  Examples of the blocking agent include oxime, phenol, alcohol, imine, amine, carbamic acid, urea, imidazole, imide, mercaptan, active methylene, acid amide (lactam), Blocking agents such as bisulfites are included.

  Examples of the oxime-based blocking agent include, for example, formaldoxime, acetoaldoxime, methylethylketoxime, cyclohexanone oxime, acetoxime, diacetylmonooxime, benzophenoxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropylketone oxime , Methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethylheptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone Oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4′-dimethoxybenzophenone oxime, Such as cycloheptanone oxime, and the like.

  Examples of the phenol-based blocking agent include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-sec-butylphenol, di-tert-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di- n-nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol Nol, methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] nonylphenol, Bis (4-hydroxyphenyl) acetic acid, pyridinol, 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, pyridine-2-thiol and the like can be mentioned.

  Examples of the alcohol-based blocking agent include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2, 2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2- Ethoxyethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-ethylhexyloxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N, N-dibu 2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholineethanol, 2,2-dimethyl-1,3-dioxolan-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12- Examples include hydroxystearic acid, triphenylsilanol, 2-hydroxyethyl methacrylate, and the like.

  Examples of the imine-based blocking agent include ethylene imine, polyethylene imine, 1,4,5,6-tetrahydropyrimidine, guanidine and the like.

  Examples of the amine-based blocking agent include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di-n-propylamine, and diisopropylamine. Isopropylethylamine, 2,2,4- or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3,5,5-trimethylcyclohexyl) amine, piperidine, 2, 6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino) -2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6 -Methyl-2-piperidine, 6-aminocaproic acid and the like. It is.

  Examples of the carbamic acid-based blocking agent include phenyl N-phenylcarbamate and the like.

  Examples of the urea-based blocking agent include urea, thiourea, and ethylene urea.

  Examples of the imidazole blocking agent include, for example, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-methyl -2-phenylimidazole, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 1,2,4-triazole, benzotriazole and the like.

  Examples of the imide-based blocking agent include succinimide, maleic imide, and phthalimide.

  Examples of the mercaptan-based blocking agent include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan and the like.

  Examples of the active methylene-based blocking agent include Meldrum's acid, dimethyl malonate, methyl acetoacetate, ethyl acetoacetate, di-tert-butyl malonate, 1-tert-butyl 3-methyl malonate, diethyl malonate, acetoacetic acid Examples include tert-butyl, 2-acetoacetoxyethyl methacrylate, acetylacetone, ethyl cyanoacetate and the like.

  Examples of the acid amide (lactam) blocking agent include acetanilide, N-methylacetamide, acetate amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, laurolactam and the like. No.

  Further, the blocking agent is not limited to the above, and examples thereof include other blocking agents such as benzoxazolone, isatoic anhydride, and tetrabutylphosphonium acetate.

  These blocking agents can be used alone or in combination of two or more.

  As the blocking agent, preferably, a blocking agent that dissociates at a temperature of 200 ° C. or lower, preferably 100 to 180 ° C., and more specifically, for example, active methylene compounds such as ethyl acetoacetate, for example, methyl ethyl ketoxime Oximes and the like.

  Then, the blocked isocyanate composition can be obtained by blending the blocking agent in an excess ratio with respect to the isocyanate group of the isocyanate composition and reacting the mixture under known conditions.

  Such a blocked isocyanate composition is also one embodiment of the isocyanate composition, and is included in the isocyanate composition.

  The polyurethane composition of the present invention contains, as a curing agent, a polyisocyanate component containing the above isocyanate composition (or a blocked isocyanate composition, the same applies hereinafter), and a polyol component as a main component.

  The polyisocyanate component contains the above-mentioned isocyanate composition, and preferably consists of the above-mentioned isocyanate composition.

  Examples of the polyol component include a high molecular weight polyol (macropolyol).

  The high molecular weight polyol is an organic compound having a number average molecular weight of 300 or more having two or more hydroxyl groups, preferably 400 or more, more preferably 500 or more, and 10,000 or less, preferably 5000 or less. Ether polyols (eg, polyoxyalkylene (C2-3) polyols, polytetramethylene ether polyols, etc.), polyester polyols (eg, adipic acid-based polyester polyols, phthalic acid-based polyester polyols, lactone-based polyester polyols, etc.), polycarbonate polyols, Acrylic polyols, epoxy polyols, natural oil polyols, silicone polyols, fluorine polyols, polyolefin polyols and the like can be mentioned.

  As the polyol component, preferably, acrylic polyl is used.

  The high molecular weight polyol may be an aqueous resin. In such a case, the high molecular weight polyol preferably includes a water-dispersed acrylic polyol and a water-dispersed polyurethane polyol.

  These high molecular weight polyols can be used alone or in combination of two or more.

  Then, the polyurethane composition is prepared as a two-pack polyurethane composition in which a polyisocyanate component and a polyol component are separately prepared and blended and mixed at the time of use.

  The mixing ratio of the polyisocyanate component (curing agent) and the polyol component (main component) is such that the equivalent ratio (OH / NCO) of the hydroxyl group in the polyol component (main component) to the isocyanate group in the polyisocyanate component (curing agent) is For example, it is adjusted to be 0.5 or more, preferably 0.75 or more, for example, 2 or less, preferably 1.5 or less.

  The polyisocyanate component and the polyol component may have, if necessary, one or both of them, such as an epoxy resin, a catalyst, a coating improver, a leveling agent, an antifoaming agent, an antioxidant, and an ultraviolet absorber. An additive such as a stabilizer such as an agent, a plasticizer, a surfactant, a pigment (for example, titanium oxide, etc.), a filler, organic or inorganic fine particles, a fungicide, and a silane coupling agent may be blended. The amounts of these additives are appropriately determined depending on the purpose and use.

  And since such a two-pack type polyurethane composition contains the isocyanate composition of the present invention, the pot life (pot life) is long, and the pot life (pot life) is estimated by the viscosity increase rate. Can be.

  As will be described in detail in Examples below, the viscosity increase rate is calculated from Ford cup (No. 2) viscosity measurement at each time from the following formula, and the maximum value is defined as the maximum viscosity increase rate.

Maximum viscosity increase rate (second / hour) = (flowing time (X) after X hour)-(flowing time (second) after (X-1) hour) / 1 (hour)
However, in the above formula, X is 2 or more.

  The maximum rate of increase in viscosity is, for example, 200 seconds / hour or more, preferably 300 seconds / hour or more, more preferably 450 seconds / hour or more, and even more preferably 550 seconds / hour or more. The rate is not more than seconds / hour, preferably not more than 1300 seconds / hour, more preferably not more than 1180 seconds / hour, still more preferably not more than 1100 seconds / hour, particularly preferably not more than 800 seconds / hour.

  When the maximum viscosity increase rate is equal to or more than the lower limit, it is possible to suppress the viscosity increase rate from becoming excessively high. Therefore, the pot life can be estimated from the viscosity increase rate.

  When the maximum viscosity increase rate is equal to or less than the above upper limit, it is possible to suppress a gradual increase in the viscosity increase rate. Therefore, the pot life can be estimated from the viscosity increase rate.

  Such two-component polyurethane compositions are suitably used in various fields such as coating materials, adhesive materials (adhesives), adhesive materials (adhesives), inks, sealants, molding materials, foams and optical materials. .

  When used as a coating material, for example, paints for plastics, paints for car exteriors, paints for car interiors, paints for electric and electronic materials, paints for optical materials (such as lenses), paints for building materials, glass coat paints, woodwork Paints, film coating paints, ink paints, artificial leather paints (coating agents), can coatings (coating agents), precoat metal (PCM) coatings (coating agents), paper coatings, and the like.

  Examples of the plastic paint include paints for housings (mobile phones, smartphones, personal computers, tablets, etc.), paints for automobile parts (automobile interior materials, headlamps, etc.), paints for household electrical appliances, paints for robot materials. Paints for furniture, paints for stationery, paints for flexible materials such as rubber, elastomers and gels, paints for eyewear materials (such as lenses), paints for optical lenses of electronic equipment (surface coating agents), and the like.

  Examples of the paint for automobile exteriors include paints for new cars (intermediate coating, base, top, etc.), coatings for automobile repair (intermediate coating, base, top, etc.), and coatings for exterior parts (aluminum wheels, bumpers, etc.). And the like.

  Examples of the film coating paints include paints for optical members (optical films, optical sheets, etc.), coating materials for optical materials, paints for textiles, paints for electronic / electrical materials, paints for food packages, paints for medical films, Examples include paints for cosmetic packages, paints for decorative films, paints for release films, and the like.

  Examples of the adhesive include an adhesive for a packaging material, an adhesive for an electric device, an adhesive for a liquid crystal display (LCD), an adhesive for an organic EL display, an adhesive for an organic EL lighting, and a display device (an electronic paper or a plasma display). , Adhesives for automobiles, adhesives for home appliances, adhesives for solar cell back sheets, adhesives for various batteries (such as lithium ion batteries), and the like.

  Examples of the resin for ink include vehicles of various inks (plate ink, screen ink, flexo ink, gravure ink, jet ink, etc.).

  Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are those corresponding to the mixing ratios (content ratio) described in the above-mentioned “Embodiments for Carrying Out the Invention”. ), Physical property values, parameters, etc., may be replaced with the upper limit (the value defined as “less than” or “less than”) or the lower limit (the value defined as “greater than” or “exceeding”) it can. In the following description, “parts” and “%” are based on mass unless otherwise specified.

  The abbreviations of the active ingredients used in the following Examples and Comparative Examples are shown below.

UNIOX M-550: methoxypolyoxyethylene alcohol, number average molecular weight 550, manufactured by NOF Methoxy PEG-400: methoxypolyoxyethylene alcohol, number average molecular weight 400, manufactured by Toho Chemical Co., Ltd. IBA: isobutanol 1,3-BG: 1 , 3-Butanediol Almatex RE4788: acrylic resin emulsion, solids concentration 44.3 mass%, hydroxyl value 86 mgKOH / g, manufactured by Mitsui Chemicals, Inc. Preparation of Isocyanurate of Pentamethylene Diisocyanate Preparation Example 1 (Preparation of Nurate A)
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 500.0 mass of pentamethylene diisocyanate produced in the same manner as in Example 1 in the specification of WO 2012/121291 pamphlet. Parts, 6.6 parts by mass of isobutanol (equivalent ratio of isocyanate groups of pentamethylene diisocyanate to hydroxyl groups of isobutanol (NCO / OH) 73) and 2,6-di (tert-butyl) -4-methylphenol in 0. 3 parts by mass and 0.3 parts by mass of tris (tridecyl) phosphite were charged and charged, followed by a urethanization reaction at 80 ° C. for 2 hours.

  Next, 0.05 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate as an isocyanuration catalyst was added to the obtained urethane reaction solution. Then, the refractive index and the purity of the isocyanate were measured, and the reaction was continued until a predetermined isocyanate group conversion was reached. After 50 minutes, the conversion of the isocyanate group reached a predetermined value (10% by mass), so 0.12 parts by mass of o-toluenesulfonamide was added. The obtained isocyanurate reaction liquid is passed through a thin film distillation apparatus (degree of vacuum: 0.093 KPa, temperature: 150 ° C.) to remove unreacted pentamethylene diisocyanate. Further, 100 parts by mass of the obtained isocyanurate reaction liquid is added. On the other hand, 0.02 parts by mass of o-toluenesulfonamide was added. Thus, isocyanurate of pentamethylene diisocyanate (nurate A) containing allophanate of pentamethylene diisocyanate was obtained.

Preparation Example 2 to Preparation Example 8 (Preparation of Nurate B to Nurate H)
The same treatment as in Preparation Example 1 was carried out, except that the formulation was changed as described in Table 1, to obtain an isocyanurate of pentamethylene diisocyanate.
2) Preparation of isocyanate composition Example 1
946.9 parts by mass of Nurate A and 53.1 parts by mass of methoxypolyoxyethylene alcohol having a number average molecular weight of 550 (Uniox M550, manufactured by Nippon Oil & Fats Co., Ltd.) are mixed, and the mixture is heated at 85 ° C. for 15 hours under an inert gas atmosphere. The reaction was performed to obtain an isocyanate composition.

Examples 2 to 12, Comparative Examples 1 to 7
An isocyanate composition was obtained by treating in the same manner as in Example 1 except that the formulation was changed as described in Tables 2 to 5.
3. Evaluation The isocyanurate of pentamethylene diisocyanate and the isocyanate composition obtained in each of Examples and Comparative Examples were evaluated by the following methods. Tables 2 to 5 show the results.

  Table 2 shows Examples 1 to 6 and Comparative Examples 1 to 3 in which the content of the polyoxyalkylene unit is different using UNIOX M-550 as the polyoxyalkylene glycol having one end blocked.

  Further, Table 3 shows Example 7 and Comparative Example 4 in which methoxy PEG-400 was used as the polyoxyalkylene glycol having one end blocked and the content of the polyoxyalkylene unit was different.

  Table 4 shows Examples 3, 8 to 10 and Comparative Examples 5 and 6 in which the amounts of alcohol modification are different.

  Table 5 shows Comparative Example 7 using an IBA-modified isocyanurate of 1,6-hexamethylene diisocyanate and Example 3 using an IBA-modified isocyanurate of 1,5-pentamethylene diisocyanate. Is shown.

  Table 6 shows Example 11 using 1,3-BG as the alcohol.

  The results of Ford cup (No. 2) viscosity measurement are shown in FIGS.

(Content of allophanate)
The molecular weight distribution of the isocyanurate of pentamethylene diisocyanate and the isocyanate composition of each example and each comparative example was measured with a GPC apparatus shown below, and the area ratio of the peak corresponding to allophanate to all peaks was determined as the content of allophanate. It was calculated as The results are shown in Tables 2 to 6.
GPC device:
Equipment used: HLC-8020 (Tosoh)
Injection volume: 100 μL
Column used: G1000HXL, G2000HXL and G3000HXL (all trade names made by Tosoh) connected in series Eluent: Flow rate of tetrahydrofuran eluent: 0.8 ml / min
Column temperature: 40 ° C
Detection method: Differential refractive index standard substance: Polyethylene oxide (manufactured by Tosoh, trade name: TSK standard polyethylene oxide)
FIG. 6 shows a chromatogram of the isocyanate composition of Example 3 when measured by gel permeation chromatography.

  Then, the area ratio of peak A (peak attributed to allophanate) to all peaks was calculated as the content of allophanate in the isocyanate composition.

(Content (% by mass) of polyoxyalkylene unit (polyoxyethylene unit))
It was calculated from the following equation.
((Methoxypolyoxyethylene glycol molecular weight-32) / methoxypolyoxyethylene glycol molecular weight) × (methoxypolyoxyethylene glycol charge / isocyanate composition) × 100
The results are shown in Tables 2 to 6.

(Isocyanate group content (% by mass))
It measured by the n-dibutylamine method based on JISK-1556 (2006) using the potentiometric titrator.

  The results are shown in Tables 2 to 6.

(Viscosity (mPa · s (25 ° C))
It measured at 25 degreeC using the E-type viscometer TV-30 by Toki Sangyo Co., Ltd. The results are shown in Tables 2 to 6.

(Evaluation when dispersed in water)
1) Dispersibility 95 g of water was weighed into a sample bottle, stirred at 750 rpm with a stirrer, 5 g of the isocyanate composition of each example and each comparative example was added thereto, and the average particle diameter after 15 minutes was measured. did.
2) Stability 95 g of water was weighed into a sample bottle, stirred at 750 rpm with a stirrer, 5 g of the isocyanate composition of each example and each comparative example was added thereto, stirred for 15 minutes, and then stirred. Stopped and allowed to stand for 15 minutes. After standing, the presence or absence of deposits on the wall of the sample bottle and sediment on the bottom was visually checked.

The stability was evaluated based on the following criteria.
：: No deposit or sediment could be confirmed.
Δ: Deposits and sediments could be slightly confirmed.
X: Deposits and sediments could be confirmed.

(Evaluation at the time of dispersion in the polyol component (base agent))
1) Dispersibility The solid content concentration of each of the isocyanate compositions of Examples and Comparative Examples was adjusted to 70% by mass with propylene glycol methyl ether acetate (PMA).

  Next, this isocyanate composition was weighed with respect to the polyol component (main component) so that NCO / OH = 1.0. Then, half of the mass of the isocyanate composition was added to water and mixed well with a spatula. Thereafter, the polyol component was added, and the mixture was stirred 60 times with a spatula, filtered through a 100-mesh filter cloth, and the amount of the residue was evaluated for dispersibility in the polyol component.

As a polyol component, a mixture of Almatex RE4788 / dipropylene glycol monobutyl ether = 100 / 12.5 (mass ratio) was used.
2) Measurement of viscosity of Ford cup (No. 2) A predetermined amount of the filtrate obtained by the above-described measurement of dispersibility was charged into a Ford cup, and the flow time was measured with time.

  Each time was calculated from the following formula, and the maximum value was calculated as the maximum viscosity rise rate, and it was judged whether pot life determination was possible (whether pot life (pot life) could be estimated or not).

Maximum viscosity increase rate (second / hour) = (flowing time (X) after X hour)-(flowing time (second) after (X-1) hour) / 1 (hour)
However, in the above formula, X is 2 or more.

The following criteria were used to determine whether pot life was judged.
：: Since the maximum viscosity increase rate is 300 seconds / hour or more and 1500 seconds / hour or less, the pot life and the pot life (pot life) can be easily estimated.
Δ: Since the maximum viscosity increase rate is 200 seconds / hour or more and less than 300 seconds / hour, pot life and pot life (pot life) can be estimated.
X: Since the maximum rate of increase in viscosity is less than 200 seconds / hour or exceeds 1500 seconds / hour, the pot life of the pot life cannot be estimated.

  When the pot life judgment was “O” or “Δ”, the pot life was measured.

Claims (4)

A reaction product of an isocyanurate of pentamethylene diisocyanate and a polyoxyalkylene glycol having one end capped,
Isocyanurate of pentamethylene diisocyanate is modified with alcohols,
The amount of modification of the alcohol with respect to the isocyanurate of pentamethylene diisocyanate is 0.5% by mass or more and 20% by mass or less;
The isocyanate composition, wherein the content of the polyoxyalkylene unit is 5% by mass or more and 30% by mass or less.   The isocyanate composition according to claim 1, wherein the alcohol is a monohydric alcohol.   The isocyanate composition according to claim 1, wherein the content of the polyoxyalkylene unit is 7% by mass or more and 25% by mass or less. A polyisocyanate component containing the isocyanate composition according to any one of claims 1 to 3,
A polyurethane composition comprising a polyol component.

Images