JP2021155533A - Polyisocyanate composition - Google Patents

Abstract

To provide a polyisocyanate composition that has excellent solubility in weak solvent and can yield a coating film having excellent physical property.SOLUTION: In a polyisocyanate composition that contains a reaction product of pentamethylene diisocyanate and a long-chain monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms, and contains an isocyanurate group, the polyisocyanate composition contains an isocyanurate 1 nucleus containing 3 molecule pentamethylene diisocyanate, and the content ratio of the isocyanurate 1 nucleus is 5 mass% or more and 35 mass% or less for the total amount of the polyisocyanate composition.SELECTED DRAWING: None

Description

The present invention relates to polyisocyanate compositions.

Polyurethane resins are usually produced by the reaction of polyisocyanates with active hydrogen group-containing compounds, and are widely used in various industrial fields as, for example, coating materials, adhesive materials, adhesive materials, elastomers, and the like.

As the polyisocyanate used for producing a polyurethane resin, for example, a polyisocyanate having an isocyanurate ring obtained by reacting a diisocyanate compound with a monoalcohol having 10 to 50 carbon atoms in the presence of an isocyanurate-forming catalyst. However, it has been proposed. More specifically, a polyisocyanate obtained by reacting 1,6-hexamethylene diisocyanate and 5-ethyl-2-nonal in the presence of an isocyanurate-forming catalyst has been proposed. It is also known that such a polyisocyanate has excellent solubility in a low-polarity solvent (weak solvent) (see, for example, Patent Document 1 (Example 1)).

Japanese Unexamined Patent Publication No. 2-250872

On the other hand, the polyisocyanate described in Patent Document 1 is not sufficiently soluble in a weak solvent, and in recent years, further improvement in solubility is required from the viewpoint of environmental friendliness.

On the other hand, it is also considered to select the type of monoalcohol that reacts with hexamethylene diisocyanate to improve the solubility in a weak solvent.

However, in that case, there is a problem that sufficient physical characteristics (durability, etc.) of the coating film cannot be obtained.

The present invention is a polyisocyanate composition capable of obtaining a coating film having excellent solubility in a weak solvent and excellent physical properties.

The present invention [1] is a polyisocyanate composition containing a reaction product of pentamethylene diisocyanate and a long-chain monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms and containing an isocyanurate group. 3, Isocyanurate mononuclear body containing 3 molecules of pentamethylene diisocyanate and 1 isocyanurate group, and the content ratio of the isocyanurate mononuclear body is 5 with respect to the total amount of the polyisocyanate composition. It contains a polyisocyanate composition having a mass% or more and 35% by mass or less.

In the present invention [2], the polyisocyanate composition contains a monourethane compound composed of one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol, and the content ratio of the monourethane compound is the polyisocyanate composition. The polyisocyanate composition according to the above [1], which is 10% by mass or less based on the total amount of the compound, is contained.

In the present invention [3], the polyisocyanate composition contains 5 molecules of pentamethylene diisocyanate, isocyanurate dinuclear body containing 2 isocyanurate groups, and 7 or more molecules of pentamethylene diisocyanate. The polyisocyanate composition contains three or more isocyanurates containing three isocyanurate groups, and the total amount of the content ratio of the isocyanurate binuclear body and the content ratio of the isocyanurate trinuclear body is the polyisocyanate composition. The polyisocyanate composition according to the above [1] or [2], which is 20% by mass or less based on the total amount.

In the present invention [4], the polyisocyanate composition contains an allophanate of pentamethylene diisocyanate, and the allophanate contains two molecules of pentamethylene diisocyanate, a monoalofanate containing one allophanate group, and three molecules of penta. The polyisocyanate composition containing the methylene diisocyanate and containing two allophanate groups, the content ratio of the monoalofanate to the total amount of the polyisocyanate composition (monoalofanate content), and the polyisocyanate composition of the dialofanate. The ratio of the content ratio of the isocyanurate mononuclear to the total amount of the polyisocyanate composition (isocyanurate mononuclear content) to the total amount (alofanate content) with the content ratio to the total amount (dialophanate content) (isocyanate mononuclear content). The polyisocyanate composition according to any one of the above [1] to [3], wherein the nurate mononuclear body content / allophanate content) is 0.40 or more and 0.60 or less.

The polyisocyanate composition of the present invention is excellent in solubility in a weak solvent and can form a coating film having excellent physical properties.

FIG. 1 is an example of a chromatogram when the polyisocyanate composition of the present invention is measured by a gel permeation chromatograph. FIG. 2 is a chromatogram when the polyisocyanate composition of Example 1 was measured by a gel permeation chromatograph.

The polyisocyanate composition of the present invention contains a reaction product of pentamethylene diisocyanate (described later) and a long-chain monoalcohol (described later) having 8 or more and less than 20 carbon atoms, and contains an isocyanurate group.

That is, the polyisocyanate composition of the present invention contains isocyanurate of pentamethylene diisocyanate (described later).

Isocyanurate is a modified product containing at least one (one nucleus) of a symmetric isocyanurate group consisting of three isocyanate groups and / or an asymmetric isocyanurate group (iminooxadiazinedione group) in the molecule.

The modified product containing a symmetric isocyanurate group (symmetrical isocyanurate modified product) and the modified product containing an asymmetrical isocyanurate group (iminooxadiazinedione modified product) are structural isomers. Therefore, an iminooxadiazine dione modified product may be produced as a by-product during the production of the symmetrical isocyanurate modified product, and a symmetrical isocyanurate modified product may be produced as a by-product during the production of the iminooxadiazine dione modified product. May occur.

Hereinafter, a modified product containing only one symmetric isocyanurate group or an asymmetric isocyanurate group (iminooxadiazidinedione group) in the molecule is referred to as an "isocyanurate mononuclear body".

The isocyanurate mononuclear body is a trimolecular body of isocyanate (a modified product composed of 3 molecules of isocyanate).

Further, a modified product containing two or more (two nuclei) of a symmetric isocyanurate group or an asymmetric isocyanurate group (iminooxadiazinedione group) in a molecule is referred to as an "isocyanurate polynuclear body".

Examples of the isocyanurate polynuclear body include isocyanurate n nuclei (n: an integer of 2 or more), and specifically, isocyanurate dinuclear bodies (isocyanurate 5 molecules (modified product consisting of 5 molecules of isocyanate)). , Isocyanurate trinuclear (isocyanate 7 molecule (modified product consisting of 7 molecules of isocyanate)) and the like.

The polyisocyanate composition contains an isocyanurate mononuclear body of pentamethylene diisocyanate in a predetermined ratio described later.

In addition, the polyisocyanate composition preferably contains an allophanate of pentamethylene diisocyanate together with the above-mentioned isocyanurate.

An allophanate is a modified product containing one or more allophanate groups in the molecule.

Hereinafter, a modified product containing only one allophanate group in the molecule is referred to as "monoalofanate". Further, a modified product containing two allophanate groups in the molecule is referred to as "dialophanate".

Such a polyisocyanate composition can be obtained by reacting pentamethylene diisocyanate with a long-chain monoalcohol by the method described below.

Examples of the pentamethylene diisocyanate include 1,2-pentamethylene diisocyanate (1,2-pentane diisocyanate), 1,3-pentamethylene diisocyanate (1,3-pentane diisocyanate), and 1,4-pentamethylene diisocyanate (1,4-). Examples thereof include pentamethylene diisocyanate monomers such as (pentane diisocyanate) and 1,5-pentamethylene diisocyanate (1,5-pentane diisocyanate).

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

The pentamethylene diisocyanate is preferably 1,5-pentamethylene diisocyanate (1,5-pentane diisocyanate).

Examples of the long-chain monoalcohol include long-chain monoalcohols having 8 or more carbon atoms and less than 20 carbon atoms. That is, examples of the long-chain monoalcohol include long-chain monoalcohols having 8 to 19 carbon atoms. In the following, a long-chain monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms may be simply referred to as a long-chain monoalcohol.

Examples of the long-chain monoalcohol include a linear monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms, a branched chain monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms, and the like.

Examples of linear monoalcohols having 8 or more carbon atoms and less than 20 carbon atoms include n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol (lauryl alcohol), n-tridecanol, and n-tetradecanol. , N-pentadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol and the like. These can be used alone or in combination of two or more.

Examples of the branched chain monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms include 2-ethylhexanol, 5-ethyl-2-nonanol, trimethylnonanol, 2-hexyldecanol, 2-ethylhexyldecanol, and 3,9-diethyl-6. -Tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol and the like can be mentioned. These can be used alone or in combination of two or more.

These long-chain monoalcohols can be used alone or in combination of two or more.

The carbon number of the long-chain monoalcohol (when two or more types of long-chain monoalcohols are used in combination, the average carbon number) is 8 or more, preferably 9 or more, as described above, from the viewpoint of solubility in a weak solvent. More preferably, it is 10 or more, further preferably 11 or more, and from the viewpoint of the physical properties of the coating film, it is less than 20, preferably 19 or less, more preferably 18 or less, still more preferably 16 or less, and particularly preferably 16 or less. It is 14 or less.

Further, as the long-chain monoalcohol, a linear monoalcohol is preferably used.

The long-chain monoalcohol is more preferably a linear monoalcohol having 8 or more and 18 or less carbon atoms, and more preferably a linear monoalcohol having 10 or more and 16 or less carbon atoms. Linear monoalcohols having 11 or more and 14 or less carbon atoms can be mentioned, and particularly preferably, linear monoalcohols having 12 or more carbon atoms (that is, lauryl alcohol) can be mentioned.

In the polyisocyanate composition of the present invention, the reaction of pentamethylene diisocyanate with a long-chain monoalcohol includes, for example, a urethanization reaction and an isocyanurate-forming reaction.

More specifically, in the reaction between pentamethylene diisocyanate and long-chain monoalcohol, preferably, first, pentamethylene diisocyanate and long-chain monoalcohol are urethanized, and then the obtained urethanization reaction solution is used as isocia. The isocyanurate-forming reaction is carried out in the presence of a nucleating catalyst.

The blending ratio of the long-chain monoalcohol is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 50 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of pentamethylene diisocyanate. Is.

The equivalent ratio (NCO / OH) of the isocyanate group of the pentamethylene diisocyanate to the hydroxy group of the long-chain monoalcohol is, for example, 1.5 or more, preferably 2 or more, more preferably 5 or more, still more preferably. The reaction conditions for the urethanization reaction are, for example, 10 or more, preferably 100 or less, preferably 50 or less, more preferably 35 or less, and even more preferably 25 or less, as an inert gas such as nitrogen gas. Under an atmosphere and normal pressure (atmospheric pressure), for example, room temperature (25 ° C.) or higher, preferably 40 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and the mixing time is, for example, 30 minutes. The above is preferably 2 hours or more, for example, 10 hours or less, preferably 6 hours or less.

Further, in the urethanization reaction, for example, a known urethanization catalyst such as amines or an organometallic compound may be added at an appropriate ratio, if necessary.

Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

Examples of the organic metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, and dibutyltin dilaurate (dilauric acid). Organic tin compounds such as dibutyltin (IV)), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, eg organic lead compounds such as lead octanoate, lead naphthenate, eg Examples thereof include organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octeneate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.

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

As a result, a urethanization reaction solution containing a urethanization reaction product of pentamethylene diisocyanate and a long-chain monoalcohol is obtained.

Next, in this method, an isocyanurate-forming catalyst is blended with a urethanization reaction solution, and an isocyanate group derived from pentamethylene diisocyanate is subjected to an isocyanurate-forming reaction.

The isocyanurate-forming catalyst is not particularly limited as long as it is a catalyst that activates isocyanurate-forming, and is, for example, a secondary amine such as triethylamine, tributylamine, triethylenediamine, or a secondary amine copolymer (for example, dialkylamine). , And tertiary amines such as polycondensates of monomers copolymerizable with secondary amines (eg, phenol, formaldehyde, etc.), such as 2-dimethylaminomethylphenol, 2,4,6-tris (eg, phenol, formaldehyde, etc.). Mannig bases such as dimethylaminomethyl) phenol, eg tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium and organic weakened salts thereof, eg trialkylaryl such as trimethylbenzylammonium, tributylbenzylammonium. Ammonium hydrooxide and its organic weakened salts, such as trimethylhydroxypropylammonium (also known as N- (2-hydroxypropyl) -N, N, N-trimethylammonium), trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxy Hydroxides of trialkylhydroxyalkylammoniums such as ethylammonium and their organic weakened salts, such as metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylic acid, myristic acid, naphthenic acid (eg alkali metal salts, magnesium salts). , Tin salt, zinc salt, lead salt, etc.), eg, metal chelate compounds of β-diketone, such as aluminum acetylacetone, lithium acetylacetone, etc., Friedel Crafts catalysts such as aluminum chloride, boron trifluoride, eg. Various organic metal compounds such as titanium tetrabutyrate and tributylantimon oxide, for example, aminosilyl group-containing compounds such as hexamethylsilazane, halogen-substituted organic phosphorus compounds such as tetrabutylphosphonium hydrogen difluoride, and the like can be mentioned.

These isocyanurate-forming catalysts can be used alone or in combination of two or more.

From the viewpoint of production efficiency, the isocyanurate-forming catalyst preferably includes a tetraalkylammonium hydroxide and a trialkylhydroxyalkylammonium hydroxide, and more preferably a tetraalkylammonium hydroxide. Is a tetrabutylammonium hydrooxide.

Further, the isocyanurate-forming catalyst may be used as a solid content of 100%, or a catalyst solution in which the isocyanurate-forming catalyst is dissolved in an organic solvent may be used.

Preferably, the isocyanurate-forming catalyst is used as a catalytic solution.

In the catalyst solution, examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, butanol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (eg, acetonitrile, etc.). ), Alkyl esters (eg, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.), glycol ether esters (eg, methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl Ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc.), ethers (eg, diethyl ether, tetrahydrofuran, dioxane, etc.), polar aprotons (eg, diethyl ether, tetrahydrofuran, dioxane, etc.) , N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc.) and the like. The organic solvent can be used alone or in combination of two or more.

Among the organic solvents, glycol ether esters are preferable, and propylene glycol methyl ether acetate is more preferable.

The solid content concentration of the catalyst solution (content ratio of the isocyanurate-forming catalyst) is, for example, 60.0% by mass or less, preferably 50.0% by mass or less.

The addition ratio of the isocyanurate-forming catalyst (in terms of solid content) is, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, and for example, 0.1 part by mass with respect to 100 parts by mass of pentamethylene diisocyanate. It is less than or equal to parts by mass, preferably not more than 0.05 parts by mass.

The method for adding the isocyanurate-forming catalyst may be batch addition or divided addition.

The reaction conditions for the isocyanurate-forming reaction of pentamethylene diisocyanate include, for example, an atmosphere of an inert gas such as nitrogen gas, under normal pressure (atmospheric pressure), and a reaction starting temperature of, for example, room temperature (25) ° C. or higher, preferably. It is 50 ° C. or higher, more preferably 70 ° C. or higher, and for example, 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 100 ° C. or lower.

The reaction time is, for example, 5 minutes or more, preferably 10 minutes or more, and for example, 1 hour or less, preferably 30 minutes or less.

The reaction end temperature (reached temperature) is, for example, 60 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and for example, 250 ° C. or lower, preferably 200 ° C. or lower, more preferably. , 150 ° C. or lower, more preferably 130 ° C. or lower.

The conversion rate (NCO conversion rate) of the isocyanate group is, for example, 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and for example, 30% by mass or less, preferably 30% by mass or less. Is 25% by mass or less, more preferably 15% by mass or less.

Further, in the above reaction, if necessary, a known reaction solvent may be blended in an appropriate ratio.

Then, in the above-mentioned isocyanurate-forming reaction, preferably, a catalyst deactivator is added at an arbitrary timing to stop the reaction. The timing of adding the catalyst deactivator is, for example, when the conversion rate of the isocyanate group reaches a target value (for example, 10% or more, preferably 20% or more, for example, 40% or less).

Examples of the catalytic deactivator include phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, paratoluenesulfonic acid, orthotoluenesulfonic acid, benzoylchloride, p-toluenesulfonamide, o-toluenesulfonamide and the like. The catalyst deactivator can be used alone or in combination of two or more. The blending ratio of the catalyst deactivator is not particularly limited, and is appropriately set according to the purpose and application.

Further, in the above-mentioned isocyanurate-forming reaction, a known additive can be added, if necessary.

Examples of the additive include an antioxidant, a co-catalyst (for example, an organic phosphite ester, etc.) and the like.

Examples of the antioxidant include a phenol-based antioxidant and a hindered phenol-based antioxidant, and from the viewpoint of hygiene, a hindered phenol-based antioxidant is preferable. Specific examples of the hindered phenolic antioxidant include 2,6-di (tert-butyl) -4-methylphenol and [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, manufactured by Ciba Japan, trade name), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, Ciba- Japan, trade name), 3- (4-hydroxy-3,5-diisopropylphenyl) propionic acid octyl ester (Irganox 1135, Ciba Japan, trade name), bis [3- (3-methyl-) 4-Hydroxy-5-tert-butylphenyl) propionic acid] ethylene bisoxybisethylene (Irganox 245, manufactured by Ciba Japan, trade name) and the like can be mentioned.

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

From the viewpoint of hygiene, the antioxidant is preferably a hindered phenolic antioxidant other than BHT, and more preferably octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate (Irganox 1076, manufactured by Ciba Japan, trade name) can be mentioned.

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

The timing of adding the additive is not particularly limited, and the additive may be added to pentamethylene diisocyanate or long-chain monoalcohol before the isocyanurate-forming reaction, or added to the isocyanurate reaction solution during the isocyanurate-forming reaction. Alternatively, it may be added to the isocyanurate reaction solution after the isocyanurate conversion reaction. Preferably, it is added to pentamethylene diisocyanate before the isocyanurate-forming reaction.

Then, in this method, after the completion of the isocyanurate-forming reaction, if necessary, from the obtained reaction mixture, an unreacted pentamethylene diisocyanate monomer and a reaction solvent (further, if necessary, a catalyst, an additive, etc., etc. ) Is removed by a known method such as distillation such as thin film distillation (Smith distillation) or extraction.

Thereby, isocyanurate of pentamethylene diisocyanate can be obtained.

The isocyanurate-forming catalyst is also used as an allophanate-forming catalyst.

That is, by performing the above-mentioned isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst, an allophanate of pentamethylene diisocyanate is produced together with the above-mentioned isocyanurate of pentamethylene diisocyanate.

Therefore, isocyanurate of pentamethylene diisocyanate and allophanate of pentamethylene diisocyanate can be obtained by the above reactions (isocyanurate-forming reaction and allophanate-forming reaction).

As a result, a polyisocyanate composition containing isocyanurate of pentamethylene diisocyanate and allophanate of pentamethylene diisocyanate is obtained.

In addition to the above methods, for the polyisocyanate composition, for example, first, only pentamethylene diisocyanate is subjected to an isocyanurate-forming reaction, and then the isocyanurate-forming reaction product and a long-chain monoalcohol (described later) are urethanized. It can also be obtained by letting it.

In such a case, the reaction conditions for isocyanurate formation of pentamethylene diisocyanate are the same as described above. Then, after the reaction is completed, the unreacted pentamethylene diisocyanate is removed by a known removal method such as distillation, if necessary. Then, the obtained reaction product (isocyanurate-forming reaction product) and the long-chain monoalcohol are subjected to a urethanization reaction under the same conditions as described above.

Even in such a method, a polyisocyanate composition containing isocyanurate of pentamethylene diisocyanate and allophanate of pentamethylene diisocyanate can be obtained.

The polyisocyanate composition preferably contains no solvent, and the solid content concentration is, for example, 95% by mass or more, preferably 99% by mass or more, and for example, 100% by mass or less.

Further, in the polyisocyanate composition (solid content (hereinafter the same)), the isocyanate monomer concentration (concentration of unreacted pentamethylene diisocyanate) is, for example, 5% by mass or less, preferably 2% by mass or less, more preferably. It is 1% by mass or less.

Further, in the polyisocyanate composition, the isocyanate group concentration (based on solid content) is, for example, 10% by mass or more, preferably 15% by mass or more, and for example, 30% by mass or less, preferably 25% by mass or less. be.

Then, as described above, the obtained polyisocyanate composition contains an isocyanurate mononuclear body of pentamethylene diisocyanate.

The isocyanurate mononuclear body is a modified version of pentamethylene diisocyanate, and more specifically, it contains three molecules of pentamethylene diisocyanate and one isocyanurate group. The isocyanurate mononuclear preferably consists of three molecules of pentamethylene diisocyanate.

The content ratio of isocyanurate mononuclear body (isocyanurate mononuclear body content) is 5% by mass or more, preferably 10% by mass or more, based on the total amount of the polyisocyanate composition, from the viewpoint of the physical properties of the coating film. It is preferably 15% by mass or more, more preferably 20% by mass or more, particularly preferably 23% by mass or more, and from the viewpoint of solubility in a weak solvent, 35% by mass or less, preferably 33% by mass or less. More preferably, it is 30% by mass or less, and further preferably 28% by mass or less.

The isocyanurate mononuclear content is calculated based on a chromatogram when the polyisocyanate composition is measured by gel permeation chromatography (GPC measurement), as shown in FIG.

In the GPC measurement, the GPC measuring device and the GPC measuring method are not particularly limited, and a device and a method having a resolution capable of calculating each area ratio of each peak, which will be described later, are appropriately adopted.

The method for calculating the area ratio of each peak is not particularly limited, but usually, each peak of the chromatogram obtained by GPC measurement is vertically divided, and the ratio of the area of each vertically divided peak is calculated by the area percentage method. Calculated by.

Then, in the chromatogram obtained by GPC measurement of the polyisocyanate composition, by identifying the peak derived from the isocyanurate mononuclear body, the area ratio of the peak is defined as the isocyanurate mononuclear body content.

In this case, the peak derived from the isocyanate mononuclear body is identified based on, for example, the polystyrene-equivalent molecular weight (average molecular weight). In this case, the polystyrene-equivalent molecular weight (average molecular weight) differs depending on the carbon number of the long-chain monoalcohol used in the above reaction.

For example, when the long-chain monoalcohol has 8 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 450 or more and less than 500 is identified as a peak derived from an isocyanate mononuclear body. ..

Further, for example, when the long-chain monoalcohol has 12 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 400 or more and less than 500 is considered to be a peak derived from an isocyanurate mononuclear body. To identify.

Further, for example, when the carbon number of the long-chain monoalcohol is 18, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 450 or more and less than 550 is considered to be a peak derived from an isocyanurate mononuclear body. To identify.

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the isocyanurate mononuclear content of pentamethylene diisocyanate in the polyisocyanate composition is such that the polyisocyanate composition is equipped with a differential refractometer. In the chromatogram measured by the gel permeation chromatograph (GPC), the area ratio of the area of the peak having the peak top in the range of the polystyrene-equivalent molecular weight (number average molecular weight) of 400 or more and less than 500 to the total peak area ( Hereinafter, it may be referred to as Mn400-500 area ratio or isocyanurate mononuclear body area ratio).

Preferably, the isocyanurate mononuclear content in the polyisocyanate composition is the area of the peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 430 or more and 470 or less in the chromatogram measured by GPC. , Can be obtained as the area ratio to the area of all peaks.

The isocyanurate mononuclear area ratio (for example, Mn400-500 area ratio) is 5% or more, preferably 10% or more, more preferably 15% or more, still more preferably 20%, from the viewpoint of coating film physical characteristics. The above is particularly preferably 23% or more, and from the viewpoint of solubility in a weak solvent, it is 35% or less, preferably 33% or less, more preferably 30% or less, and further preferably 28% or less.

The number of peaks indicating the isocyanurate mononuclear content is usually one in the above chromatogram.

In FIG. 1, the peak showing the isocyanate mononuclear content is shown as peak 6.

The polyisocyanate composition is obtained as a by-product by a urethanization reaction of one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol, and has a free isocyanate group at the end (monourethane compound). Can be included.

In other words, the monourethane compound is a modified version of pentamethylene diisocyanate and consists of one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol.

When the polyisocyanate composition contains a monourethane compound, the content ratio of the monourethane compound (monourethane content) is based on the solubility in a weak solvent and the physical properties of the coating film with respect to the total amount of the polyisocyanate composition. From the viewpoint, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 2% by mass or less, for example, 0. By mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

The monourethane content is calculated based on a chromatogram when the polyisocyanate composition is measured by a gel permeation chromatograph (GPC measurement) by the same method as described above.

In this case as well, the polystyrene-equivalent molecular weight (average molecular weight) differs depending on the carbon number of the long-chain monoalcohol used in the above reaction.

For example, when the long-chain monoalcohol has 8 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 200 or more and less than 300 is identified as a peak derived from a monourethane compound.

Further, for example, when the long-chain monoalcohol has 12 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 300 or more and less than 400 is identified as a peak derived from a monourethane compound. ..

Further, for example, when the long-chain monoalcohol has 18 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 400 or more and less than 450 is identified as a peak derived from a monourethane compound. ..

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the monourethane content in the polyisocyanate composition can be determined by using a gel permeation chromatograph equipped with a differential refractometer. In the chromatogram when measured, the area ratio of the area of the peak having the peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 300 or more and less than 400 to the area of all peaks (hereinafter, Mn300-400 area ratio, or Mn300-400 area ratio, or It may be referred to as a monourethane area ratio.).

Preferably, the monourethane content in the polyisocyanate composition is the total peak area of the peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 320 or more and 350 or less in the chromatogram measured by GPC. It can be obtained as the area ratio with respect to the area of.

The monourethane area ratio (for example, Mn300-400 area ratio) is, for example, 15% or less, preferably 10% or less, more preferably 5% or less, from the viewpoint of solubility in a weak solvent and physical characteristics of the coating film. More preferably, it is 3% or less, particularly preferably 2% or less, for example, 0% or more, preferably 0.1% or more, and more preferably 0.5% or more.

That is, the polyisocyanate composition does not have to contain the monourethane compound, but preferably contains the monourethane compound in a proportion equal to or higher than the above lower limit.

The number of peaks indicating the monourethane content is usually one in the above chromatogram.

In FIG. 1, the peak showing the monourethane content is shown as peak 7.

In addition, the polyisocyanate composition preferably contains an allophanate of pentamethylene diisocyanate.

The allophanate of pentamethylene diisocyanate is a modified form of pentamethylene diisocyanate and contains two or more molecules of pentamethylene diisocyanate and one or more allophanate groups.

Preferably, the allophanate of pentamethylene diisocyanate preferably contains monoalofanate and dialofanate.

The monoalofanate contains two molecules of pentamethylene diisocyanate and contains one allophanate group.

When the polyisocyanate composition contains monoalofanate, the content ratio of monoalofanate (monoalofanate content) is determined from the viewpoint of solubility in a weak solvent and physical properties of the coating film with respect to the total amount of the polyisocyanate composition. For example, it is 20% by mass or more, preferably 40% by mass or more, and for example, 80% by mass or less, preferably 60% by mass or less.

The monoalofanate content is calculated based on a chromatogram when the polyisocyanate composition is measured by a gel permeation chromatograph (GPC measurement) by the same method as described above.

In this case as well, the polystyrene-equivalent molecular weight (average molecular weight) differs depending on the carbon number of the long-chain monoalcohol used in the above reaction.

For example, when the long-chain monoalcohol has 8 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 300 or more and less than 450 is identified as a peak derived from monoalofanate.

Further, for example, when the long-chain monoalcohol has 12 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 500 or more and less than 730 is identified as a peak derived from monoalofanate.

Further, for example, when the long-chain monoalcohol has 18 carbon atoms, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 550 or more and less than 730 is identified as a peak derived from monoalofanate.

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the monoalofanate content of pentamethylene diisocyanate in the polyisocyanate composition is a gel permeation of the polyisocyanate composition equipped with a differential refractometer. In the chromatogram measured by a chromatograph, the area ratio of the peak area having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 500 or more and less than 700 to the total peak area (hereinafter, Mn500-700 area). It can be obtained as a rate or a monoalofanate area rate).

Preferably, the monoalofanate content in the polyisocyanate composition is the total peak area of the peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 550 or more and 650 or less in the chromatogram measured by GPC. It can be obtained as the area ratio with respect to the area of.

The monoalofanate area ratio (for example, Mn500-700 area ratio) is, for example, 20% or more, preferably 40% or more, and for example, 80% or less, preferably 60% or less.

The number of peaks indicating the monoalofanate content is usually one in the above chromatogram.

In FIG. 1, the peak showing the monoalofanate content is shown as peak 5.

The dialofanate contains two molecules of pentamethylene diisocyanate and contains two allophanate groups.

When the polyisocyanate composition contains dialofanate, the content ratio of dialofanate (dialofanate content) is determined from the viewpoint of solubility in a weak solvent and physical properties of the coating film with respect to the total amount of the polyisocyanate composition. For example, it is 2% by mass or more, preferably 5% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less.

The dialofanate content is calculated based on a chromatogram when the polyisocyanate composition is measured by a gel permeation chromatograph (GPC measurement) by the same method as described above.

In this case as well, the polystyrene-equivalent molecular weight (average molecular weight) differs depending on the carbon number of the long-chain monoalcohol used in the above reaction.

For example, when the long-chain monoalcohol has 8 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 500 or more and less than 750 is identified as a peak derived from dialofanate.

Further, for example, when the long-chain monoalcohol has 12 carbon atoms, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 830 or more and less than 1000 is identified as a peak derived from dialofanate.

Further, for example, when the long-chain monoalcohol has 18 carbon atoms, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 830 or more and less than 1050 is identified as a peak derived from dialofanate.

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the dialofanate content of pentamethylene diisocyanate in the polyisocyanate composition is a gel permeation of the polyisocyanate composition equipped with a differential refractometer. In the chromatogram measured by a chromatograph, the area ratio of the peak area having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 830 or more and less than 1000 to the total peak area (hereinafter, Mn830-1000 area). It can be determined as a rate or a dialofanate area rate).

Preferably, the dialofanate content in the polyisocyanate composition is the total peak area of the peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 840 or more and 980 or less in the chromatogram measured by GPC. It can be obtained as the area ratio with respect to the area of.

The dialofanate area ratio (for example, Mn830-1000 area ratio) is, for example, 2% or more, preferably 5% or more, and for example, 20% or less, preferably 15% or less.

The peak showing the dialofanate content is usually one in the above chromatogram.

In FIG. 1, the peak showing the dialofanate content is shown as peak 3.

The total amount (alofanate content) of the content ratio of monoalofanate to the total amount of the polyisocyanate composition (monoalofanate content) and the content ratio of dialofanate to the total amount of the polyisocyanate composition (diarophanate content) is For example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 60% by mass or less. be.

In the polyisocyanate composition, the content ratio (content rate) of allophanate is the above-mentioned monoalofanate area ratio (for example, Mn500-700 area ratio) and the above-mentioned dialofanate area ratio (for example, Mn830-1000 area ratio). It is calculated as the total area ratio with and (hereinafter, may be referred to as an allophanate area ratio).

The allophanate area ratio is, for example, 30% or more, preferably 40% or more, more preferably 50% or more, and for example, 90% or less, preferably 80% or less, more preferably 60% or less. ..

Further, the polyisocyanate composition may contain not only the above-mentioned isocyanurate mononuclear body but also an isocyanurate polynuclear body as the isocyanurate of pentamethylene diisocyanate.

As described above, the isocyanurate polynuclear body is an isocyanurate n-nucleus (n: an integer of 2 or more), for example, an isocyanurate dinuclear body (isocyanate 5 molecule) and an isocyanurate trinuclear body (isocyanate 7 molecule). Body) and so on.

Preferably, the polyisocyanate composition comprises an isocyanurate dinuclear of pentamethylene diisocyanate.

The isocyanurate dinuclear compound is a modified version of pentamethylene diisocyanate, contains 5 molecules of pentamethylene diisocyanate, and contains two isocyanurate groups.

When the polyisocyanate composition contains an isocyanurate binuclear body, the content ratio of the isocyanurate binuclear body (isocyanurate dinuclear body content) is soluble in a weak solvent with respect to the total amount of the polyisocyanate composition. From the viewpoint of the physical properties of the coating film, for example, it is 0% by mass or more, preferably 1% by mass or more, and for example, 15% by mass or less, preferably 10% by mass or less.

The isocyanurate binuclear body content is calculated based on the chromatogram when the polyisocyanate composition is measured by gel permeation chromatography (GPC measurement) by the same method as described above.

In this case as well, the polystyrene-equivalent molecular weight (average molecular weight) differs depending on the carbon number of the long-chain monoalcohol used in the above reaction.

For example, when the long-chain monoalcohol has 8 carbon atoms, a peak having a peak top in the polystyrene-equivalent molecular weight (number average molecular weight) of 750 or more and less than 800 is identified as a peak derived from an isocyanurate dinuclear body. ..

Further, for example, when the long-chain monoalcohol has 12 carbon atoms, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 730 or more and less than 830 is considered to be a peak derived from an isocyanurate dinuclear body. To identify.

Further, for example, when the carbon number of the long-chain monoalcohol is 18, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 730 or more and less than 830 is considered to be a peak derived from an isocyanurate dinuclear body. To identify.

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the isocyanurate binuclear content of pentamethylene diisocyanate in the polyisocyanate composition is such that the polyisocyanate composition is equipped with a differential refractometer. In the chromatogram measured by the gel permeation chromatograph, the area ratio of the peak area having the peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 730 or more and less than 830 with respect to the total peak area (hereinafter, Mn730). It can be determined as −830 area ratio or isocyanurate dinuclear body area ratio).

Preferably, the isocyanurate binuclear content in the polyisocyanate composition is the area of the peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 740 or more and 820 or less in the chromatogram measured by GPC. , Can be obtained as the area ratio to the area of all peaks.

The isocyanurate binuclear body area ratio (for example, Mn730-830 area ratio) is, for example, 1% or more, preferably 2% or more, for example, 15% or less, preferably 10% or less.

In FIG. 1, the peak showing the isocyanate dinuclear content is shown as peak 4.

Also, preferably, the polyisocyanate composition contains three or more isocyanurates of pentamethylene diisocyanate.

The isocyanurate trinuclear or higher is a modified version of pentamethylene diisocyanate, contains 7 or more molecules of pentamethylene diisocyanate, and contains 3 or more isocyanurate groups.

When the polyisocyanate composition contains isocyanurate trinuclear or higher, the content ratio of isocyanurate trinuclear or higher (isocyanurate trinuclear or higher content) is a weak solvent with respect to the total amount of the polyisocyanate composition. From the viewpoint of solubility in water and physical properties of the coating film, for example, it is 0% by mass or more, preferably 1% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less.

The isocyanurate trinuclear or higher body content is calculated based on a chromatogram when the polyisocyanate composition is measured by gel permeation chromatography (GPC measurement) by the same method as described above.

In this case as well, the polystyrene-equivalent molecular weight (average molecular weight) differs depending on the carbon number of the long-chain monoalcohol used in the above reaction.

For example, when the long-chain monoalcohol has 8 carbon atoms, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 800 or more is identified as a peak derived from an isocyanurate trinuclear body or more.

Further, for example, when the long-chain monoalcohol has 12 carbon atoms, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 1000 or more is identified as a peak derived from an isocyanurate trinuclear body or more. do.

Further, for example, when the carbon number of the long-chain monoalcohol is 18, a peak having a peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 1050 or more is identified as a peak derived from an isocyanurate trinuclear body or more. do.

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the isocyanurate trinuclear content of pentamethylene diisocyanate in the polyisocyanate composition is such that the polyisocyanate composition is equipped with a differential refractometer. In the chromatogram measured by the gel permeation chromatograph, the area ratio of the peak area having the peak top in the range of the polystyrene-equivalent molecular weight (number average molecular weight) of 1000 or more to the total peak area (hereinafter, Mn1000-). It can be determined as the area ratio or the body area ratio of three or more isocyanurate nuclei).

Preferably, the content of isocyanurate trinuclear or more in the polyisocyanate composition is the area of the peak having the peak top in the range of polystyrene-equivalent molecular weight (number average molecular weight) of 1050 or more in the chromatogram measured by GPC. It can be obtained as the area ratio to the area of all peaks.

The body area ratio of isocyanurate 3 or more nuclei (for example, Mn1000-area ratio) is, for example, 1% or more, preferably 5% or more, for example, 20% or less, preferably 15% or less.

In FIG. 1, peaks showing the content of three or more isocyanurate nuclei are shown as peak 1 and peak 2.

The total amount of the isocyanurate binuclear body content and the isocyanurate trinuclear body content (that is, the content ratio of the isocyanurate polynuclear body (isocyanurate polynuclear body content)) is the solubility in a weak solvent and the solubility in a weak solvent. From the viewpoint of the physical properties of the coating film, for example, 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, for example, 0% by mass or more. It is preferably 2% by mass or more, more preferably 5% by mass or more.

That is, the polyisocyanate composition does not have to contain the isocyanurate polynuclear body, but preferably contains the isocyanurate polynuclear body in a ratio of the above lower limit or more.

In the polyisocyanate composition, the content ratio of the isocyanurate polynuclear body is the above-mentioned isocyanurate binuclear body area ratio (for example, Mn730-830 area ratio) and the above-mentioned isocyanurate trinuclear body area ratio (for example, Mn730-830 area ratio). It is calculated as the total area ratio (hereinafter, may be referred to as isocyanurate multi-area ratio) with Mn1000-area ratio).

The isocyanurate polynuclear area ratio is, for example, 30% or less, preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, for example, 0% or more, preferably 2%. Above, more preferably, it is 5% or more.

Then, in the above polyisocyanate composition, the ratio of the isocyanurate mononuclear content to the allophanate content (total amount of the monoalofanate content and the dialofanate content) (isocyanurate mononuclear content / allophanate content). ) Is, for example, 0.20 or more, preferably 0.25 or more, more preferably 0.30 or more, still more preferably 0.35 or more, and particularly preferably 0.40, from the viewpoint of the physical properties of the coating film. From the viewpoint of solubility in a weak solvent, for example, 0.80 or less, preferably 0.70 or less, more preferably 0.60 or less, still more preferably 0.50 or less, particularly preferably. It is 0.45 or less.

The above ratio is also shown as the ratio of the area ratio in the chromatogram when the polyisocyanate composition is measured by a gel permeation chromatograph equipped with a differential refractometer.

That is, in the above polyisocyanate composition, the ratio of the isocyanurate 1 nuclei area ratio to the allophanate area ratio (isocyanurate 1 nuclei area ratio / allophanate area ratio) is, for example, 0. It is 20 or more, preferably 0.25 or more, more preferably 0.30 or more, still more preferably 0.35 or more, particularly preferably 0.40 or more, and from the viewpoint of solubility in a weak solvent, for example. , 0.80 or less, preferably 0.70 or less, more preferably 0.60 or less, still more preferably 0.50 or less, and particularly preferably 0.45 or less.

Further, in the above polyisocyanate composition, the ratio of the isocyanurate polynuclear body content (isocyanurate polynuclear content / allophanate content) to the allophanate content (total amount of monoalofanate content and dialofanate content) is From the viewpoint of coating material properties, for example, 0.03 or more, preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.15 or more, particularly preferably 0.20 or more. From the viewpoint of solubility in a weak solvent, for example, 0.70 or less, preferably 0.60 or less, more preferably 0.50 or less, still more preferably 0.40 or less, and particularly preferably 0. It is 30 or less.

The above ratio is also shown as the ratio of the area ratio in the chromatogram when the polyisocyanate composition is measured by a gel permeation chromatograph equipped with a differential refractometer.

That is, in the above polyisocyanate composition, the ratio of the isocyanurate polynuclear body area ratio (isocyanurate polynuclear body area ratio / allophanate area ratio) to the allophanate area ratio is, for example, 0.03 or more from the viewpoint of coating material properties. It is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.15 or more, particularly preferably 0.20 or more, and from the viewpoint of solubility in a weak solvent, for example, 0. It is .70 or less, preferably 0.60 or less, more preferably 0.50 or less, still more preferably 0.40 or less, and particularly preferably 0.30 or less.

Further, in the above polyisocyanate composition, the ratio of the monourethane content (monourethane content / allophanate content) to the allophanate content (total amount of monoalofanate content and dialofanate content) is the property of the coating film. From the viewpoint of solubility in weak solvents, for example, 0.30 or less, preferably 0.25 or less, more preferably 0.20 or less, still more preferably 0.10 or less, particularly preferably 0. It is 0.05 or less.

The above ratio is also shown as the ratio of the area ratio in the chromatogram when the polyisocyanate composition is measured by a gel permeation chromatograph equipped with a differential refractometer.

That is, in the above polyisocyanate composition, the ratio of the monourethane area ratio to the allophanate area ratio (monourethane area ratio / allophanate area ratio) is, for example, from the viewpoint of coating material properties and solubility in a weak solvent, for example. It is 0.30 or less, preferably 0.25 or less, more preferably 0.20 or less, still more preferably 0.10 or less, and particularly preferably 0.05 or less.

Since such a polyisocyanate composition has an isocyanurate mononuclear area ratio in the above range in the reaction product of the pentamethylene diisocyanate and the long-chain monoalcohol, it has excellent solubility in a weak solvent and is environmentally friendly. Excellent.

A weak solvent is a solvent having a particularly low polarity and is defined as a solvent having an aniline point of 20 ° C. or higher. Examples of such weak solvents include Mineral Spirits A (aniline point 44.5 ° C. manufactured by JXTG Energy Co., Ltd.), Ipsol TP (aniline point 43 ° C. manufactured by Idemitsu Showa Shell Co., Ltd.), and T-SOL3040FLUID (aniline point manufactured by JXTG Energy Co., Ltd.). Examples thereof include petroleum hydrocarbons such as 52 ° C.), and tarpen oils such as gum terepine N (aniline point 27 ° C. manufactured by Yasuhara Chemical Co., Ltd.) and methylcyclohexane (aniline point 40 ° C.). These weak solvents can be used alone or in combination of two or more.

The above-mentioned polyisocyanate composition is excellent in solubility in a weak solvent. For example, the amount of the weak solvent that can be dissolved with respect to 100 parts by mass of the polyisocyanate composition is, for example, 100 parts by mass or more, preferably 100 parts by mass or more. It is 500 parts by mass or more, and usually less than 10,000 parts by mass.

Further, in the above-mentioned polyisocyanate composition, in the reaction product of the above-mentioned pentamethylene diisocyanate and the long-chain monoalcohol, the isocyanurate mononuclear content is in the above range, so that a coating film having excellent physical properties can be formed. ..

Examples of the physical properties of the coating film include mechanical strength and durability (chemical resistance, light resistance, etc.).

Therefore, the polyisocyanate composition is suitably used as a raw material for producing a polyurethane resin in the field of applying a polyurethane resin, such as a paint, an adhesive, and a coating agent.

The form of the polyurethane resin is not particularly limited, but a two-component curable polyurethane is preferable. The two-component curable polyurethane is a resin composition in which a curing agent and a main agent are prepared as independent packages, and they are blended at the time of use to form a polyurethane resin (cured coating film or the like).

As the curing agent (polyisocyanate component) in such a two-component curable polyurethane, the above-mentioned polyisocyanate composition is preferably used.

Then, the polyisocyanate composition is dissolved in the above-mentioned weak solvent or the like, if necessary, and prepared as a curing agent.

The main ingredient of the two-component curable polyurethane contains, for example, a polyol component.

Examples of the polyol component include acrylic polyols and fluorine polyols, and preferably fluorine polyols. That is, since the above polyisocyanate composition has excellent solubility in a weak solvent, it is preferably used as a curing agent for a fluorine polyol.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups with another monomer copolymerizable therewith.

Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, and polyhydroxy. Alkyl maleate, polyhydroxyalkyl fumarate and the like can be mentioned.

Examples of other monomers copolymerizable with them include (meth) acrylic acid, alkyl (meth) acrylate (1 to 12 carbon atoms), maleic acid, alkyl maleate, fumaric acid, and fumaric acid. Alkyl, itaconic acid, alkyl itaconic acid, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanate-2-propyl) -α-methylstyrene, trimethylpropanetri (meth) acrylate, Examples thereof include pentaerythritol tetra (meth) acrylate.

Then, the acrylic polyol can be obtained by copolymerizing these monomers in the presence of a suitable solvent and a polymerization initiator.

As the fluorine polyol, for example, in the above-mentioned copolymerization of the acrylic polyol, a co-polymer obtained by using a vinyl group-containing fluorine compound, for example, tetrafluoroethylene, chlorotrifluoroethylene, or the like as another copolymerizable monomer. Examples include polymers.

Further, as the fluorine polyol, for example, the fluorine-containing copolymer for paints described in JP-A-2004-277716 can also be used.

If necessary, the polyol component is dissolved in the above-mentioned organic solvent or the like and prepared as a main agent.

The two-component curable polyurethane is suitably used as a paint (two-component curable paint), an adhesive (two-component curable adhesive), etc. by blending a curing agent and a main agent at the time of use and mixing and stirring. ..

More specifically, first, the above-mentioned main agent and the above-mentioned curing agent are prepared, and immediately before use, the main agent and the curing agent are mixed to prepare a two-component curable polyurethane resin (paint, adhesive). A two-component curable polyurethane resin is applied to an object to be coated or an adherend.

The blending ratio of the main agent and the curing agent is, for example, 0.5 to 1 as the equivalent ratio (NCO / OH) of the isocyanate groups in the curing agent (polyisocyanate composition) to the hydroxyl groups in the main agent (polyoxide component). The ratio is 5.5, preferably 0.8 to 1.2.

The mixture of the main agent and the curing agent can be obtained by any method such as spray coating, air spray coating, brush coating, dipping method, roll coating method, flow coating method, dry laminating method, wet laminating method, direct coating method and the like. Is applied to the adherend.

The adherend is not particularly limited, and examples thereof include various building materials and various laminated films. More specifically, packaging materials such as plastic films, metal foils, and metal-deposited films, civil engineering materials such as FRP and steel materials, and the like can be mentioned.

Then, the mixture of the main agent and the curing agent is dried and cured to obtain a polyurethane resin (cured coating film, adhesive layer, etc.).

Therefore, the above-mentioned polyurethane resin and polyisocyanate composition are preferably used in various industrial fields such as paints and adhesives.

Next, the present invention will be described based on Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned "Form for carrying out the invention", and the compounding ratios corresponding to them ( Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, parameter, etc. be able to.

1. 1. GPC
The sample was measured by gel permeation chromatography (GPC), and the area ratio of the area of each peak in the obtained chromatogram (chart) to the area of all peaks was determined.

Then, each peak was identified according to the polystyrene-equivalent molecular weight of the peak top, and the content rate of each component was calculated from the area ratio of each peak.

Table 1 shows the types of polyisocyanates, the carbon number of monoalcohols, the polystyrene-equivalent molecular weight of peak top, and the attribution of each component.

<GPC measurement>
In GPC measurement, about 0.03 g of a sample was collected, and 10 mL of tetrahydrofuran was added and dissolved. Then, the obtained solution was GPC-measured under the following conditions.
(1) Analyzer: Alliance (Waters)
(2) Pump: Alliance 2695 (Waters)
(3) Detector: 2414 type differential refractometer (Waters)
(4) Eluent: Tetrahydrofuran
(5) Separation column: Plgel GUARD + Plgel 5 μm Mixed-C x 3 (50 x 7.5 mm, 300 x 7.5 mm)
Manufacturer; Polymer Laboratories
Part number; PL1110-6500
(6) Measurement temperature: 40 ° C
(7) Flow velocity: 1 mL / min
(8) Sample injection amount: 100 μL
(9) Analytical device: EMPOWER data processing device (Waters)
・ System correction (1) Standard substance name: Polystyrene
(2) Calibration curve creation method: Create a graph of retention time and molecular weight using TSK standard Polystyrene manufactured by TOSOH with different molecular weights.
(3) Injection amount, injection concentration: 100 μL, 1 mg / mL
The gel permeation chromatogram of the polyisocyanate composition of Example 1 is shown in FIG.

Examples 1-10 and Comparative Examples 1-10
A polyisocyanate composition was obtained under the raw materials and conditions shown in Tables 2 to 4.

That is, in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100 parts by mass of the polyisocyanate shown in the table and octadecyl 3- (3,5-di-tert-butyl) -4-Hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Japan, trade name) 0.05 parts by mass and tridecylphosphite (JP-310, manufactured by Johoku Kagaku Co., Ltd.) 0.05 parts by mass. It was charged and the temperature was raised to 80 ° C.

Next, the monoalcohol described in the table was added to the above mixture so that the equivalent ratio (R (NCO / OH)) of the isocyanate group to the hydroxyl group was the value in the table, and urethane was charged at 80 ° C. for 3 hours. It was made to react.

Then, the temperature was raised to the reaction start temperature shown in the table, and 0.01 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was used as an isocyanurate-forming catalyst. Solvent A mixed solution with 0.03 parts by mass of propylene glycol methyl ether acetate was added to the urethanization reaction product for isocyanurate and allophanate reactions.

Then, using the heat generated by the heat of reaction, after reaching the reaction termination temperature shown in the table, 0.01 part by mass of o-toluenesulfonamide was added so as to reach the isocyanate group conversion rate shown in the table. And stopped the reaction.

Then, the obtained reaction solution was passed through a thin film distillation apparatus (vacuum degree 50 Pa, temperature 150 ° C.) to remove unreacted isocyanate (polyisocyanate described in the table).

As a result, a polyisocyanate composition was obtained.

Evaluation (1) Solubility in a weak solvent Take 1 g of a polyisocyanate composition in a test tube, add 1 g of tarpen oil (Gum Telepin N Yasuhara Chemical Co., Ltd., trade name aniline point 27 ° C.) as a weak solvent, and stir with a shaker for 30 seconds. Then, the presence or absence of turbidity was confirmed.

Further, 1 g of tarpen oil (Gum Telepin N Yasuhara Chemical Co., Ltd., trade name: aniline point 27 ° C.) as a weak solvent was added, and stirring was repeated to measure the maximum concentration capable of maintaining a non-turbid state.

Then, the maximum concentration of the weak solvent ([mass of the weak solvent / mass of the polyisocyanate composition] × 100) capable of maintaining the non-turbid state was evaluated according to the following criteria.

⊚: 2000% or more 〇: 500% or more and less than 2000% Δ: 100% or more and less than 500% ×: less than 100% (2) Physical characteristics of coating film ・ Preparation of cured coating film Polyisocyanate composition and acrylic polyol (Olestar Q) -166 (manufactured by Mitsui Chemicals, Inc.) is mixed with an equivalent ratio of 1.0 (NCO / OH = 1.0), and thinner (ethyl acetate: butyl acetate: propylene glycol methyl ether acetate) is used so that the solid content concentration is 50%. (Mixed at 1: 1: 1) was added, mixed at 23 ° C. for 5 minutes, and then subjected to ultrasonic treatment for 10 minutes to defoam to obtain a coating agent.

The obtained coating agent is applied to a steel sheet (SPCC steel sheet, PBN-144 treated product) with a 4 mil applicator, heated in an oven at 80 ° C. for 30 minutes, cured in an oven at 30 ° C. for 5 days, and cured film. Got

・ Solvent resistance evaluation (rubbing test)
The above cured film was set in a rubbing tester (IMC-0717 type manufactured by Imoto Seisakusho Co., Ltd.), and absorbent cotton moistened with methyl ethyl ketone was placed on the tip of a weight having a load of 0.5 kg to perform rubbing. The number of times the coating film was torn and the base material was exposed was evaluated by the number of rubbing round trips.

Then, the physical characteristics (solvent resistance) of the coating film were evaluated according to the following criteria.

⊚: 100 times or more 〇: 80 times or more and less than 100 Δ: 20 times or more and less than 80 ×: less than 20 times

Claims (4)

A polyisocyanate composition containing a reaction product of pentamethylene diisocyanate and a long-chain monoalcohol having 8 or more carbon atoms and less than 20 carbon atoms and containing an isocyanurate group.
The polyisocyanate composition contains three molecules of pentamethylene diisocyanate and contains an isocyanurate mononuclear body containing one isocyanurate group.
A polyisocyanate composition, wherein the content ratio of the isocyanurate mononuclear body is 5% by mass or more and 35% by mass or less with respect to the total amount of the polyisocyanate composition. The polyisocyanate composition contains a monourethane compound composed of one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol.
The polyisocyanate composition according to claim 1, wherein the content ratio of the monourethane compound is 10% by mass or less with respect to the total amount of the polyisocyanate composition. The polyisocyanate composition is
An isocyanurate binuclear body containing 5 molecules of pentamethylene diisocyanate and containing 2 isocyanurate groups,
It contains 7 or more molecules of pentamethylene diisocyanate and contains 3 or more isocyanurate groups containing 3 or more isocyanurate groups.
Claimed that the total amount of the content ratio of the isocyanurate dinuclear body and the content ratio of the isocyanurate trinuclear body or more is 20% by mass or less with respect to the total amount of the polyisocyanate composition. Item 2. The polyisocyanate composition according to Item 1 or 2. The polyisocyanate composition contains an allophanate of pentamethylene diisocyanate and contains.
The allophanate contains a monoalofanate containing two molecules of pentamethylene diisocyanate and containing one allophanate group, and a dialofanate containing three molecules of pentamethylene diisocyanate and containing two allophanate groups.
The total amount (alofanate content) of the content ratio of the monoalofanate to the total amount of the polyisocyanate composition (monoalofanate content) and the content ratio of the dialofanate to the total amount of the polyisocyanate composition (dialophanate content). Against
Content ratio of the isocyanurate mononuclear to the total amount of the polyisocyanate composition (isocyanurate mononuclear content)
(Isocyanurate mononuclear content / allophanate content)
The polyisocyanate composition according to any one of claims 1 to 3, which is 0.40 or more and 0.60 or less.

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