JP7199855B2 - Isocyanate composition and polyurethane composition - Google Patents

Description

The present invention relates to isocyanate compositions and polyurethane compositions, and more particularly to isocyanate compositions and polyurethane compositions containing the isocyanate compositions.

Polyurethane compositions contain a polyisocyanate component (curing agent) and a polyol component (main agent), and are used as paints and adhesives by reacting and curing them.

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

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

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

WO2012/121291 WO2016/146579

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

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

Furthermore, with the polyisocyanate component using hexamethylene diisocyanate, the viscosity of the mixture gradually increases after the polyisocyanate component and the polyol component are mixed. Therefore, there is a problem that it is difficult to estimate the usable time (pot life) especially at the work site.

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

The present invention [1] provides a reaction product of an isocyanurate of pentamethylene diisocyanate and a one-end-blocked polyoxyalkylene glycol, wherein the isocyanurate of pentamethylene diisocyanate is modified with an alcohol, and pentamethylene diisocyanate is obtained. The amount of modification of the alcohol with respect to the isocyanurate of is 0.5% by mass or more and 20% by mass or less, and the content of the polyoxyalkylene unit is 5% by mass or more and 30% by mass or less. .

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

The present invention [3] includes the isocyanate composition according to [1] or [2] above, 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 comprising a polyisocyanate component containing the isocyanate composition according to any one of [1] to [3] above, and a polyol component.

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

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

Further, the amount of alcohol modified 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 has excellent dispersibility, has a long pot life, and can be estimated from the viscosity increase rate after mixing. can be done.

In addition, 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 usable time (pot life) is long and the dispersibility in water is excellent.

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

The isocyanate composition of the present invention is the reaction product of the isocyanurate of pentamethylene diisocyanate and a single end-capped polyoxyalkylene glycol.

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

Pentamethylene diisocyanate is specifically 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). be

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

Pentamethylene diisocyanate monomers preferably include 1,5-pentamethylene diisocyanate.

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

In addition, such an isocyanurate of pentamethylene diisocyanate is modified with alcohols by the method described later.

Specifically, such an isocyanurate of pentamethylene diisocyanate is obtained by subjecting pentamethylene diisocyanate and an alcohol to a urethanization reaction, then adding an isocyanurate catalyst to the urethane reaction liquid to obtain the urethane reaction liquid ( Specifically, pentamethylene diisocyanate and reaction products of pentamethylene diisocyanate and alcohols, hereinafter the same) are subjected to an isocyanurate reaction, and if necessary, unreacted pentamethylene diisocyanate is removed. can get.

In addition, in this method, an allophanatization reaction also proceeds together with the isocyanurate reaction. Isocyanurates of pentamethylene diisocyanate thus 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 alcohols include monohydric alcohols and polyhydric alcohols.

Monohydric alcohols are organic compounds having one hydroxyl group in one molecule, and include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n -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, eicosanol, e.g. isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol , 2-ethylhexan-1-ol, isononanol, isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, Branched monohydric alcohols such as 2-octyldodecanol and other branched alkanols (having 5 to 20 carbon atoms) can be mentioned.

Polyhydric alcohols are organic compounds having two or more hydroxyl groups in one molecule, and examples thereof include ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or mixtures thereof), butylene glycol (1, 2- or 1,3- or 1,4-butanediol or mixtures thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2, alkane diols such as 2,2-trimethylpentanediol and 3,3-dimethylolheptane; dihydric alcohols such as ether diols such as diethylene glycol, triethylene glycol and dipropylene glycol; trihydric alcohols such as isopropanolamine; tetramethylolmethane (pentaerythritol); tetrahydric alcohols such as diglycerin; pentahydric alcohols such as xylitol; Hexavalent alcohols such as inositol and dipentaerythritol, heptahydric alcohols such as perseitol, and aliphatic polyhydric alcohols such as octahydric alcohols such as sucrose, preferably dihydric alcohols, more preferably , 1,3-butanediol.

Alcohols include preferably monohydric alcohols, more preferably branched monohydric alcohols, and more preferably isobutanol.

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

The blending ratio of the alcohol is, for example, 0.1 parts 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 or less, more preferably 2 parts by mass or less.

Further, the equivalent ratio (NCO/OH) of the isocyanate group of pentamethylene diisocyanate to the hydroxyl group of the alcohol is, for example, 5 or more, preferably 20 or more, more preferably 50 or more. Below, preferably 500 or less.

Such a urethane reaction between pentamethylene diisocyanate and alcohols is carried out, for example, in an inert gas atmosphere such as nitrogen gas under normal pressure (atmospheric pressure). As the reaction conditions, the reaction temperature is, for example, room temperature (e.g., 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 12 minutes or more, for example, 10 hours or less, preferably 6 hours or less.

The above urethane reaction can be carried out without solvent, but if necessary, a known organic solvent can be added.

Examples of organic solvents include aliphatic hydrocarbon organic solvents such as n-hexane and octane; alicyclic hydrocarbon organic solvents such as cyclohexane and methylcyclohexane; and acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. ketone organic solvents such as methyl acetate, ethyl acetate, butyl acetate, alkyl ester organic solvents such as isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl Glycol ether ester organic solvents such as acetate and ethyl-3-ethoxypropionate, ether organic solvents such as diethyl ether, tetrahydrofuran, and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, bromide halogenated aliphatic hydrocarbon organic solvents such as methyl, methylene iodide and dichloroethane; polar aprotic organic solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide; mentioned.

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

A urethane reaction liquid is obtained by such a urethanization reaction. The urethane reaction liquid contains a reaction product of pentamethylene diisocyanate and alcohols, unreacted pentamethylene diisocyanate, and an organic solvent blended as necessary.

Next, an isocyanurate-forming catalyst is added to the obtained urethane reaction liquid, and the urethane reaction liquid is subjected to an isocyanurate-forming reaction.

The isocyanurate-forming catalyst is not particularly limited as long as it is an effective catalyst for isocyanurate-forming. Weak acid salts such as trialkylhydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium and triethylhydroxyethylammonium, and organic weak acid salts thereof such as acetic acid, caproic acid, octylic acid, Alkali metal salts of alkylcarboxylic acids such as myristic acid, metal salts of the above alkylcarboxylic acids such as tin, zinc and lead, metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone, such as aluminum chloride , Friedel-Crafts catalysts such as boron trifluoride, various organometallic compounds such as titanium tetrabutylate and tributylantimony oxide, and aminosilyl group-containing compounds such as hexamethylsilazane.

Specific examples include Zwitter ion type hydroxyalkyl quaternary ammonium compounds, and more specific examples include 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 isocyanurate-forming catalysts can be used alone or in combination of two or more.

The isocyanuration catalyst preferably includes a Zwitter ion type hydroxyalkyl quaternary ammonium compound, more preferably N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexa Noate is mentioned.

The addition ratio of the isocyanurate catalyst is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, for example, 0.1 parts by mass or less, with respect to 100 parts by mass of the urethane reaction liquid. It is 0.05 parts by mass or less.

This isocyanurate-forming reaction is carried out, for example, in an inert gas atmosphere such as nitrogen gas under normal pressure (atmospheric pressure). As reaction conditions for the isocyanurate reaction, the reaction temperature is, for example, room temperature (e.g., 25°C) or higher, preferably 40°C or higher, more preferably 60°C or higher, for example, 100°C or lower, preferably 90°C. and the reaction time is, for example, 30 minutes or longer, preferably 1 hour or longer, more preferably 2 hours or longer, for example 12 hours or shorter, preferably 10 hours or shorter, more preferably 8 hours or shorter. be.

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

The isocyanurate conversion rate can be measured based on, for example, 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 a solvent, but if necessary, a known organic solvent can be added. Moreover, when an organic solvent is used in the above urethanization reaction, the organic solvent can be used as it is in the above isocyanurate formation reaction.

In the above isocyanurate-forming reaction, known additives such as antioxidants and co-catalysts can be added as necessary.

Antioxidants include, for example, phenolic antioxidants and hindered phenolic antioxidants. From the viewpoint of hygiene, hindered phenolic antioxidants are preferred. Specific examples of hindered phenol-based antioxidants include, for example, 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, hereinafter sometimes abbreviated as BHT), [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-di-tert-butyl-4-hydroxyphenyl)propanoate (Irganox 1010, manufactured by Ciba Japan, trade name), octadecyl 3-(3,5-di -tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Japan, trade name), 3-(4-hydroxy-3,5-diisopropylphenyl) propionic acid octyl ester (Irganox 1135, Ciba Japan Co., Ltd., trade name), bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid] ethylene bisoxybisethylene (Irganox 245, Ciba Japan Co., trade name) ) and the like.

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

Antioxidants preferably include 2,6-di(tert-butyl)-4-methylphenol.

Examples of promoters include organic phosphites.

Examples of organic phosphites include organic phosphite diesters and organic phosphite triesters. More specifically, for example, triethylphosphite, tributylphosphite, tridecylphosphite, tris ( monophosphites such as tridecyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, diphenyl(tridecyl)phosphite; Di-, tri- or 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.

The organic phosphites are preferably monophosphites, more preferably tridecylphosphite and tris(tridecyl)phosphite.

The timing of adding the additive is not particularly limited, and it may be added to the pentamethylene diisocyanate or the urethane reaction liquid before the isocyanurate-forming reaction, or added to the isocyanurate reaction liquid during the isocyanurate-forming reaction. Further, it 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 application.

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

Examples of catalyst deactivators include phosphoric acid compounds, sulfonic acid compounds, and sulfonamide compounds.

Examples of phosphoric acid compounds include phosphoric acid and phosphoric acid esters. Phosphate esters include, for example, methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, dipropyl phosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, 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 sulfonic acid compounds include sulfonic acid and sulfonic acid esters. Sulfonic acids include, for example, dodecylbenzenesulfonic acid and p-toluenesulfonic acid. Sulfonic acid esters include, for example, dodecylbenzenesulfonic acid alkyl esters such as methyl dodecylbenzenesulfonate, ethyl dodecylbenzenesulfonate, propyl dodecylbenzenesulfonate, and butyl dodecylbenzenesulfonate; p-toluenesulfonic acid alkyl esters such as ethyl sulfonate, propyl p-toluenesulfonate, and butyl p-toluenesulfonate;

Examples of sulfonamide compounds include aromatic sulfonamides (e.g., benzenesulfonamide, dimethylbenzenesulfonamide, sulfanilamide, o- and p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene -2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, etc.), aliphatic sulfonamides (e.g., methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.).

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

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

Catalyst deactivators preferably include sulfonamide compounds, preferably o-toluenesulfonamide.

Further, the addition ratio (effective ingredient conversion) of the catalyst deactivator 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), Moreover, it is 0.5 mass part or less, for example.

An isocyanurate reaction solution is obtained by such an isocyanurate-forming reaction.

The isocyanurate reaction liquid contains an isocyanurate of pentamethylene diisocyanate containing allophanate of pentamethylene diisocyanate, unreacted pentamethylene diisocyanate, and an organic solvent blended as necessary.

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

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

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

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

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

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

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

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

The isocyanurate of pentamethylene diisocyanate is modified with alcohols.

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

The alcohol modification amount of the isocyanurate of pentamethylene diisocyanate (alcohol modification rate of the isocyanurate) is, for example, 0.5% by mass or more, preferably 5% by mass or more, and is, for example, 20% by mass or less, It is preferably 15% by mass or less, more preferably 8% by mass or less.

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

Further, if the amount of modification is equal to or less than the above upper limit, when the isocyanate composition is mixed with the polyol component, the usable time (pot life) is long, and the viscosity increase rate after mixing reduces the usable time. Time (pot life) can be estimated.

In addition, said modification|denaturation amount can be calculated by the following formula.

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

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

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

The isocyanate group content (NCO%) can be measured by the n-dibutylamine method according to JIS K-1556 (2006) using a potentiometric titrator.

Examples of the one-end-capped polyoxyalkylene glycol include one-end-capped polyoxyalkylene (C2-3) glycol.

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

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

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

(Wherein, 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 alkyl groups having 1 to 4 carbon atoms represented by R2 include methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl and tert-butyl. Methyl and ethyl are preferred. In the formula, m is the degree of polymerization of polyoxyethylene, which is 3 or more, preferably 5 or more, more preferably exceeds 8, and is, for example, 100 or less, preferably 50 or less, more preferably , 25 or less.

Specific examples include methoxypolyoxyethylene alcohol (methoxy PEG), ethoxypolyoxyethylene alcohol (ethoxy PEG), etc., and their number average molecular weights are 200 or more, preferably 390 or more, and more. It is preferably 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.

Methoxypolyoxyethylene alcohol is preferably used as the single end-capped polyoxyethylene glycol.

Then, the isocyanate composition can be obtained by reacting the isocyanurate of pentamethylene diisocyanate with the one-end-blocked polyoxyalkylene glycol.

In this reaction, the mixing ratio of the isocyanurate of pentamethylene diisocyanate and the one-end-blocked polyoxyalkylene glycol is the equivalent ratio of the isocyanate group of the isocyanurate of pentamethylene diisocyanate to the hydroxyl group of the one-end-blocked polyoxyalkylene glycol. (NCO/OH) is a ratio of excess NCO, 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 higher and 100° C. or lower, and the reaction time is, for example, 0.5 hours or longer and 20 hours or shorter. Also, this reaction is preferably carried out under an inert gas atmosphere.

This gives an isocyanate composition.

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. .

The isocyanate group content (NCO %) can be measured by the n-dibutylamine method in accordance with JIS K-1556 (2006) using a potentiometric titrator.

In addition, the polyoxyalkylene unit content is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, still more preferably 8% by mass or more, and 30% by mass or less, It is preferably 28% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

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

On the other hand, if the polyoxyalkylene unit content exceeds the above upper limit, pot life will be shortened when this isocyanate composition is mixed with the polyol component.

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

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

In addition, polyoxyalkylene unit content can be calculated by the following formula.
((Molecular weight of one-end-capped polyoxyalkylene glycol-Molecular weight of oxyalkylene group)/Molecular weight of one-end-capped polyoxyalkylene glycol)×(Feed amount of one-end-capped polyoxyalkylene glycol/Isocyanate composition)×100
Further, when the single-end-capped polyoxyalkylene glycol is a single-end-capped polyoxyethylene glycol, the polyoxyethylene unit content is, for example, 5% by mass or more, preferably 6% by mass or more, and more Preferably, it is 7% by mass or more, more preferably 8% by mass or more. % by mass or less, particularly preferably 15% by mass or less.

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

Moreover, when the polyoxyethylene unit content is at least the above lower limit, excellent dispersibility in water is obtained.

In addition, polyoxyethylene unit content can be calculated by the following formula.
((Molecular weight of one-end-capped polyoxyethylene glycol-Molecular weight of oxyalkylene group)/Molecular weight of one-end-capped polyoxyethylene glycol)×(Feed amount of one-end-capped polyoxyethylene glycol/Isocyanate composition)×100
The content of allophanate of pentamethylene diisocyanate in the isocyanate composition is, for example, 0.2% by mass or more, preferably 10% by mass or more, and is, for example, 35% by mass or less, preferably 30% by mass. Below, more preferably, it is 20 mass % or less.

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

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

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

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

In addition, the alcohol modification amount (alcohol modification rate of isocyanurate) in the isocyanate composition is 0.5% by mass or more, preferably 3% by mass or more, and 20% by mass or less, preferably 13% by mass. % or less, more preferably 9 mass % or less.

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

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

Further, if the amount of modification is equal to or less than the above upper limit, when the isocyanate composition is mixed with the polyol component, the usable time (pot life) is long, and the viscosity increase rate after mixing reduces the usable time. Time (pot life) can be estimated.

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

In addition, said modification|denaturation amount can be calculated by the following formula.

Amount of modification of alcohol in the isocyanate composition (% by mass)=(Amount of modification of alcohol relative to isocyanurate of pentamethylene diisocyanate/isocyanate composition)×100
And such an isocyanate composition is a reaction product of the isocyanurate of pentamethylene diisocyanate and a single end-capped polyoxyalkylene glycol. Therefore, when this isocyanate composition is mixed with a polyol component, the usable time (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 is, for example, 2000 mPa·s or less.

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

In such an isocyanate composition, in order to further improve water dispersibility and solubility, a compound having both a free isocyanate group of the isocyanate composition and a hydrophilic group and an active hydrogen group (hereinafter referred to as a hydrophilic group-containing active hydrogen compounds) can also be reacted.

The hydrophilic group-containing active hydrogen compound is a compound having both at least one hydrophilic group and at least one active hydrogen group, and the hydrophilic group includes, for example, an ionic group (anionic group, cationic group). , a hydroxyl group, and the like. 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.

Specific examples of hydrophilic group-containing active hydrogen compounds include carboxylic acid group-containing active hydrogen compounds, sulfonic acid group-containing active hydrogen compounds, and hydroxyl group-containing active hydrogen compounds.

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

Examples of sulfonic acid group-containing active hydrogen compounds include dihydroxybutanesulfonic acid and dihydroxypropanesulfonic acid obtained from a synthetic reaction between an epoxy group-containing compound and an acid sulfite. Also, 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 and ammonium salts of these sulfonic acids.

Examples of sulfonic acid group-containing active hydrogen compounds include polybasic acids containing sulfonic acid, more specifically 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5-(p-sulfo 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 thereof include sulfosalicylic acid, alkyl esters of these carboxylic acids, and hydrophilic group-containing polybasic acids such as metal salts and ammonium salts of these sulfonic acids.

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

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

Further, especially when the hydrophilic group-containing active hydrogen compound is 2-(cyclohexylamino)-ethanesulfonic acid or 3-(cyclohexylamino)propanesulfonic acid, the above reaction is carried out in the presence of a neutralized amine. do.

Neutralizing amines are blended to neutralize the sulfonic acid group of aminosulfonic acid. -tertiary monoamines such as methylpiperidine, N-ethylpiperidine, such as 1,3-bis-(dimethylamino)-propane, 1,4-bis-(dimethylamino)-butane or N,N'-dimethylpiperazine, etc. and tertiary diamines of.

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

Specifically, first, an isocyanurate of pentamethylene diisocyanate and a hydrophilic group-containing active hydrogen compound are reacted to obtain a reaction product, and the reaction product is reacted with one-end-capped polyoxyalkylene glycol. Alternatively, the isocyanurate of pentamethylene diisocyanate, one end-capped polyoxyalkylene glycol, and the hydrophilic group-containing active hydrogen compound may be blended at the same time and reacted.

A blocked isocyanate composition can also be prepared by blocking free isocyanate groups in the above isocyanate composition with a blocking agent.

Examples of blocking agents 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 oxime-based blocking agents include formaldoxime, acetaldoxime, methylethylketoxime, cyclohexanone oxime, acetoxime, diacetylmonoxime, benzophenoxime, 2,2,6,6-tetramethylcyclohexanone oxime, and 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 monoxime, 4,4'-dimethoxybenzophenone oxime, 2-heptanone oxime and the like.

Examples of phenolic blocking agents 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, 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.

Examples of alcohol-based blocking agents 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-dibutyl-2-hydroxyacetamide, N-hydroxysuccinimide, N- Morpholine ethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidine ethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, triphenylsilanol, 2-hydroxyethyl methacrylate etc.

Examples of imine blocking agents include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine and guanidine.

Amine blocking agents include, for example, 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.

Carbamic acid-based blocking agents include, for example, phenyl N-phenylcarbamate.

Urea-based blocking agents include, for example, urea, thiourea, and ethyleneurea.

Examples of imidazole blocking agents include 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 imide-based blocking agents include succinimide, maleimide, and phthalimide.

Mercaptan-based blocking agents include, for example, butyl mercaptan, dodecyl mercaptan, and hexyl mercaptan.

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

Examples of acid amide-based (lactam-based) blocking agents include acetanilide, N-methylacetamide, acetic amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, laurolactam, and the like. mentioned.

Moreover, the blocking agent is not limited to the above, and other blocking agents such as benzoxazolone, isatoic anhydride, and tetrabutylphosphonium acetate can also be used.

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

The blocking agent preferably includes a blocking agent that dissociates at 200° C. or lower, preferably 100 to 180° C. More specifically, for example, active methylene compounds such as ethyl acetoacetate, such as methyl ethyl ketoxime, etc. and oximes of

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

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

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

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

Polyol components include, for example, high-molecular-weight polyols (macropolyols).

The high-molecular-weight polyol is an organic compound having a number average molecular weight of 300 or more, preferably 400 or more, more preferably 500 or more, and 10000 or less, preferably 5000 or less, having two or more hydroxyl groups. Ether polyols (e.g., polyoxyalkylene (C2-3) polyols, polytetramethylene ether polyols, etc.), polyester polyols (e.g., 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.

The polyol component preferably includes acrylic polyol.

Moreover, the high molecular weight polyol may be an aqueous resin, and 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.

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

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

In addition, one or both of the polyisocyanate component and the polyol component may optionally contain, for example, an epoxy resin, a catalyst, a coating modifier, a leveling agent, an antifoaming agent, an antioxidant or an ultraviolet absorbing agent. Additives such as stabilizers such as agents, plasticizers, surfactants, pigments (eg, titanium oxide), fillers, organic or inorganic fine particles, antifungal agents, and silane coupling agents may be added. The amount of these additives to be added is appropriately determined depending on the purpose and application.

And since such a two-component polyurethane composition contains the isocyanate composition of the present invention, it has a long usable life (pot life), and the usable time (pot life) can be estimated from the viscosity increase rate. can be done.

The rate of increase in viscosity is calculated from Ford Cup (No. 2) viscosity measurement by the following formula for each time, as will be described in detail in the examples below, and the maximum value is taken as the maximum rate of increase in viscosity.

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

The maximum viscosity increase rate is, for example, 200 seconds/hour or more, preferably 300 seconds/hour or more, more preferably 450 seconds/hour or more, still more preferably 550 seconds/hour or more. seconds/hour or less, preferably 1300 seconds/hour or less, more preferably 1180 seconds/hour or less, even more preferably 1100 seconds/hour or less, and particularly preferably 800 seconds/hour or less.

When the maximum viscosity increase rate is equal to or higher than the above lower limit, it is possible to prevent the viscosity increase rate from becoming excessively high. Therefore, the usable time (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 moderate increase in the viscosity increase rate. Therefore, the usable time (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, plastic paints, automotive exterior paints, automotive interior paints, electrical and electronic material paints, optical material (lenses, etc.) paints, building material paints, glass coat paints, woodworking Paints, film coating paints, ink paints, artificial leather paints (coating agents), can paints (coating agents), pre-coated metal (PCM) paints (coating agents), paper coat paints, and the like.

Examples of the above plastic paints 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. , furniture paints, stationery paints, paints for flexible materials such as rubber, elastomers and gels, paints for eyewear materials (such as lenses), and paints for optical lenses of electronic equipment (surface coating agents).

Examples of the above automotive exterior paints include paints for new cars (intermediate coating, base, top, etc.), automotive repair paints (intermediate coating, base, top, etc.), and paints for exterior parts (aluminum wheels, bumpers, etc.). etc.

Examples of the film coating paint include optical member (optical films, optical sheets, etc.) paints, optical coating materials, fiber paints, electronic and electrical material paints, food packaging paints, medical film paints, Examples include paints for cosmetic packaging, paints for decorative films, and paints for release films.

Examples of adhesives include packaging adhesives, electrical equipment adhesives, liquid crystal display (LCD) adhesives, organic EL display adhesives, organic EL lighting adhesives, display devices (electronic paper and plasma display etc.), adhesives for automobiles, adhesives for home appliances, adhesives for solar battery back sheets, adhesives for various batteries (lithium ion batteries, etc.), and the like.

Examples of the ink resin include vehicles for 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 described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical properties, parameters, etc. can. In the description below, "parts" and "%" are based on mass unless otherwise specified.

Abbreviations of active ingredients used in the following examples and comparative examples are shown below.

Uniox M-550: Methoxypolyoxyethylene alcohol, number average molecular weight 550, NOF Methoxy PEG-400: Methoxypolyoxyethylene alcohol, number average molecular weight 400, Toho Chemical IBA: Isobutanol 1,3-BG: 1 , 3-butanediol Almatex RE4788: acrylic resin emulsion, solid content concentration 44.3% by mass, hydroxyl value 86 mgKOH/g, manufactured by Mitsui Chemicals, Inc. 1. Preparation of Isocyanurate of Pentamethylene Diisocyanate Preparation Example 1 (Preparation of Nurate A)
500.0 mass of pentamethylene diisocyanate produced in the same manner as in Example 1 in the specification of WO 2012/121291 pamphlet was placed in a four-necked flask equipped with a stirrer, thermometer, reflux tube and nitrogen inlet tube. 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 0.5 parts of 2,6-di(tert-butyl)-4-methylphenol. 3 parts by mass and 0.3 parts by mass of tris(tridecyl)phosphite were charged and urethanized at 80° C. for 2 hours.

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

Preparation Examples 2 to 8 (Preparation of Nurate B to Nurate H)
An isocyanurate of pentamethylene diisocyanate was obtained in the same manner as in Preparation Example 1, except that the formulation was changed according to Table 1.
2) Preparation of isocyanate composition Example 1
946.9 parts by mass of Nurate A and 53.1 parts by mass of methoxypolyoxyethylene alcohol (Uniox M550, manufactured by NOF) with a number average molecular weight of 550 are blended and heated at 85 ° C. for 15 hours in an inert gas atmosphere. It was made to react and the isocyanate composition was obtained.

Examples 2 to 7, Examples 9 to 12, Comparative Examples 1 to 8
Treated in the same manner as in Example 1, except that the formulation was changed according to the descriptions in Tables 2 to 5,
An isocyanate composition was obtained.
3. Evaluation The isocyanurate of pentamethylene diisocyanate and the isocyanate composition obtained in each example and each comparative example were evaluated by the following methods. The results are shown in Tables 2-5.

Table 2 shows Examples 1 to 6 and Comparative Examples 1 to 3 in which Uniox M-550 was used as the one-end-capped polyoxyalkylene glycol and the polyoxyalkylene unit content was different.

Table 3 also shows Example 7 and Comparative Example 4 in which methoxy PEG-400 was used as the polyoxyalkylene glycol with one end capped and the content of the polyoxyalkylene unit was different.

Table 4 shows Example 3, Comparative Example 8, Example 9, Example 10 and Comparative Example 5 and Comparative Example 6, which differ in the amount of alcohol modification.

Table 5 also 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. indicate.

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

1 to 5 show the results of Ford Cup (No. 2) viscosity measurements.

(Allophanate content)
The isocyanurate of pentamethylene diisocyanate and the isocyanate composition of each example and each comparative example were subjected to molecular weight distribution measurement with the GPC apparatus shown below, and the area ratio of the peak corresponding to allophanate to all peaks was calculated as the content of allophanate. calculated as The results are shown in Tables 2-6.
GPC device:
Equipment used: HLC-8020 (manufactured by Tosoh)
Injection volume: 100 μL
Columns used: G1000HXL, G2000HXL and G3000HXL (trade names of Tosoh Corporation) connected in series Eluent: Tetrahydrofuran Eluent flow rate: 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 measured by gel permeation chromatography.

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

(Content (% by mass) of polyoxyalkylene unit (polyoxyethylene unit))
It was calculated from the following formula.
((Methoxypolyoxyethylene glycol molecular weight -32)/Methoxypolyoxyethylene glycol molecular weight) x (Methoxypolyoxyethylene glycol charging amount/isocyanate composition) x 100
The results are shown in Tables 2-6.

(Isocyanate group content (mass%))
It was measured by the n-dibutylamine method according to JIS K-1556 (2006) using a potentiometric titrator.

The results are shown in Tables 2-6.

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

(Evaluation when dispersing 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 size was measured after 15 minutes. bottom.
2) Stability Weigh 95 g of water in a sample bottle, stir with a stirrer at 750 rpm, add 5 g of the isocyanate composition of each example and each comparative example, stir for 15 minutes, and then stir. It was stopped and allowed to stand for 15 minutes. After standing still, the presence or absence of deposits on the wall of the sample bottle and sediment on the bottom was visually confirmed.

The stability was evaluated according to the following criteria.
○: Deposits and sediments could not be confirmed.
Δ: Adhesion and sediment were slightly observed.
x: Attachment and sediment could be confirmed.

(Evaluation when dispersed in polyol component (main agent))
1) Dispersibility The isocyanate compositions of each example and each comparative example were prepared with propylene glycol methyl ether acetate (PMA) to a solid concentration of 70% by mass.

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

As the polyol component, a mixture of Almatex RE4788/dipropylene glycol monobutyl ether=100/12.5 (mass ratio) was used.
2) Ford Cup (No. 2) Viscosity Measurement A predetermined amount of the filtrate obtained by the above dispersibility measurement was placed in a Ford cup, and the flowing time was measured over time.

It was calculated for each time from the following formula, the maximum value was calculated as the maximum viscosity increase rate, and it was determined whether pot life can be judged (whether or not the usable time (pot life) can be estimated).

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

The pot life determination was evaluated according to the following criteria.
○: Since the maximum viscosity increase rate is 300 seconds/hour or more and 1500 seconds/hour or less, the pot life can be easily estimated.
Δ: The maximum viscosity increase rate is 200 seconds/hour or more and less than 300 seconds/hour, so the pot life can be estimated.
x: The maximum viscosity increase rate is less than 200 seconds/hour or exceeds 1500 seconds/hour, so the pot life cannot be estimated.

In addition, when the pot life determination was "○" or "Δ", the pot life was measured.

Claims (4)

A reaction product of an isocyanurate of pentamethylene diisocyanate and a one-end-capped polyoxyalkylene glycol,
The isocyanurate of pentamethylene diisocyanate is an isocyanurate of pentamethylene diisocyanate modified with an alcohol (excluding polyether polyol),
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 content of the polyoxyalkylene unit is 5% by mass or more and 30% by mass or less,
Isocyanurates of pentamethylene diisocyanate include allophanates of pentamethylene diisocyanate,
The content of the allophanate of pentamethylene diisocyanate in the isocyanurate of pentamethylene diisocyanate is 5.8% by mass or more and 40% by mass or less ,
The alcohols are linear alkanemonools having 1 to 20 carbon atoms, branched alkanemonools having 3 to 20 carbon atoms, and/or alkanediols having 2 to 9 carbon atoms. An isocyanate composition characterized by: The isocyanate composition according to claim 1, wherein the alcohol is a linear alkanemonool having 1 to 20 carbon atoms or a branched alkanemonool having 3 to 20 carbon atoms . . 3. 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,
and a polyol component.

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