JP7399003B2 - polyisocyanate composition - Google Patents

Description

The present invention relates to polyisocyanate compositions.

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

Examples of the polyisocyanate used in the production of polyurethane resin include polyisocyanate having an isocyanurate ring, which is obtained by reacting a diisocyanate compound and a monoalcohol having 10 to 50 carbon atoms in the presence of an isocyanurate catalyst. is proposed. More specifically, a polyisocyanate has been proposed in which 1,6-hexamethylene diisocyanate and 5-ethyl-2-nonal are reacted in the presence of an isocyanurate catalyst. It is also known that such polyisocyanates have excellent solubility in low polar solvents (weak solvents) (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 does not have sufficient solubility in weak solvents, and in recent years, further improvement in solubility has been required from the viewpoint of environmental friendliness.

On the other hand, it is also being considered to improve the solubility in weak solvents by selecting the type of monoalcohol that reacts with hexamethylene diisocyanate.

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

The present invention is a polyisocyanate composition that has excellent solubility in weak solvents and provides a coating film with excellent physical properties.

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

In the present invention [2], the polyisocyanate composition includes a monourethane compound consisting of one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol, and the content ratio of the monourethane compound is in the polyisocyanate composition. The polyisocyanate composition described in [1] above is contained in an amount of 10% by mass or less based on the total amount of the product.

The present invention [3] provides that the polyisocyanate composition contains 5 molecules of pentamethylene diisocyanate, an isocyanurate binuclear body containing two isocyanurate groups, and 7 or more molecules of pentamethylene diisocyanate, The polyisocyanurate composition contains an isocyanurate trinucleate or more containing three isocyanurate groups, and the total content of the isocyanurate dinuclear and the isocyanurate trinuclear or more is the total amount of the polyisocyanurate composition. The polyisocyanate composition according to [1] or [2] above, 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 monoallophanate containing one allophanate group, and three molecules of pentamethylene diisocyanate. methylene diisocyanate and dialophanate containing two allophanate groups; The ratio of the isocyanurate mononucleate content to the total amount of the polyisocyanate composition (isocyanurate mononuclear content) to the total amount (allophanate content) The polyisocyanate composition according to any one of [1] to [3] above, wherein the ratio (nurate mononuclear content/allophanate content) is 0.40 or more and 0.60 or less.

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

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

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

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

Isocyanurate is a modified product containing one or more (one nucleus) symmetrical isocyanurate group and/or asymmetrical isocyanurate group (iminooxadiazinedione group) consisting of three isocyanate groups in the molecule.

Note that the modified product containing a symmetrical isocyanurate group (symmetrical isocyanurate modified product) and the modified product containing an asymmetrical isocyanurate group (iminooxadiazinedione modified product) are structural isomers. Therefore, when producing a symmetric isocyanurate modified product, an iminooxadiazinedione modified product may be produced as a by-product, and when producing an iminooxadiazinedione modified product, a symmetric isocyanurate modified product may be produced as a by-product. may occur.

In the following, a modified product containing only one symmetrical isocyanurate group or asymmetrical isocyanurate group (iminooxadiazinedione group) in the molecule is referred to as an "isocyanurate mononuclear product."

Note that the isocyanurate mononuclear body is an isocyanate trimolecular body (a modified body consisting of three molecules of isocyanate).

Furthermore, a modified product containing two or more (binary) symmetrical isocyanurate groups or asymmetrical isocyanurate groups (iminooxadiazinedione groups) in the molecule is referred to as an "isocyanurate polynuclear product."

Examples of isocyanurate polynuclear bodies include isocyanurate n-nuclear bodies (n: an integer of 2 or more), specifically, isocyanurate dinuclear bodies (isocyanurate pentamolecular bodies (modified products consisting of 5 molecules of isocyanate)). , isocyanurate trinuclear body (isocyanate heptamolecular body (modified product consisting of seven molecules of isocyanate)), and the like.

The polyisocyanate composition contains an isocyanurate mononucleate of pentamethylene diisocyanate in a predetermined ratio described below.

Further, the polyisocyanate composition preferably contains an allophanate of pentamethylene diisocyanate in addition to the above-mentioned isocyanurate.

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 will be referred to as a "monoallophanate". Furthermore, 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 and a long-chain monoalcohol by the method described below.

Examples of 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-pentamethylene diisocyanate). Examples include pentamethylene diisocyanate monomers such as 1,5-pentane diisocyanate (1,5-pentane diisocyanate) and 1,5-pentane diisocyanate (1,5-pentane diisocyanate).

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

Preferably, pentamethylene diisocyanate is 1,5-pentamethylene diisocyanate (1,5-pentanediisocyanate).

Examples of the long-chain monoalcohol include long-chain monoalcohols having 8 or more and less than 20 carbon atoms. That is, examples of long-chain monoalcohols include long-chain monoalcohols having 8 or more and 19 or less carbon atoms. Note that, hereinafter, 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 long-chain monoalcohols include linear monoalcohols having 8 or more and less than 20 carbon atoms, branched monoalcohols having 8 or more 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 branched monoalcohols having 8 or more carbon atoms and less than 20 carbon atoms include 2-ethylhexanol, 5-ethyl-2-nonanol, trimethylnonanol, 2-hexyldecanol, 2-ethylhexyldecanol, 3,9-diethyl-6 -tridecanol, 2-isoheptyl isoundecanol, 2-octyldodecanol, and the like. 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.

From the viewpoint of solubility in weak solvents, the carbon number of the long chain monoalcohol (when two or more types of long chain monoalcohols are used together, the average carbon number) is 8 or more, preferably 9 or more, as described above. More preferably, it is 10 or more, still more 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, 14 or less.

Further, as the long-chain monoalcohol, preferably a straight-chain monoalcohol is mentioned.

As the long chain monoalcohol, more preferably a linear monoalcohol having 8 or more and 18 or less carbon atoms is mentioned, more preferably a linear monoalcohol having 10 or more and 16 or less carbon atoms is mentioned, and even more preferably, Examples include linear monoalcohols having 11 to 14 carbon atoms, particularly preferably linear monoalcohols having 12 carbon atoms (namely, lauryl alcohol).

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

More specifically, in the reaction between pentamethylene diisocyanate and a long-chain monoalcohol, preferably, the pentamethylene diisocyanate and the long-chain monoalcohol are first subjected to a urethanization reaction, and then the resulting urethanization reaction solution is subjected to an isocyanation reaction. The isocyanurate reaction is carried out in the presence of a nurate 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, per 100 parts by mass of pentamethylene diisocyanate. It is.

Further, the equivalent ratio (NCO/OH) of the isocyanate group of 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, and still more preferably , 10 or more, for example, 100 or less, preferably 50 or less, more preferably 35 or less, still more preferably 25 or less.Reaction conditions for the urethanization reaction include, for example, inert gas such as nitrogen gas Under normal pressure (atmospheric pressure), the temperature is, 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 duration is preferably 2 hours or more, for example 10 hours or less, and preferably 6 hours or less.

Furthermore, in the above urethanization reaction, a known urethanization catalyst such as amines or organometallic compounds may be added in an appropriate ratio, if necessary.

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

Examples of organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dilauric acid) Organotin compounds such as dibutyltin (IV), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride; organolead compounds such as lead octoate and lead naphthenate, e.g. Examples include organic nickel compounds such as nickel naphthenate, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

Furthermore, 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.

Thereby, a urethanization reaction liquid 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 into the urethane-forming reaction solution, and the isocyanate groups derived from pentamethylene diisocyanate are subjected to an isocyanurate-forming reaction.

The isocyanurate-forming catalyst is not particularly limited as long as it is a catalyst that activates isocyanurate-formation, and examples thereof include triethylamine, tributylamine, triethylenediamine, secondary amine copolymers (for example, secondary amines such as dialkylamine, , and tertiary amines such as 2-dimethylaminomethylphenol, 2,4,6-tris( Mannich bases such as (dimethylaminomethyl)phenol, hydroxides of tetraalkyl ammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and their weak organic acid salts, trialkylaryls such as trimethylbenzylammonium, tributylbenzylammonium, etc. Ammonium hydroxide and its weak organic acid salts, such as trimethylhydroxypropylammonium (also known as N-(2-hydroxypropyl)-N,N,N-trimethylammonium), trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxy Hydroxides of trialkylhydroxyalkylammonium such as ethyl ammonium and their organic weak acid salts; for example, metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylic acid, myristic acid, naphthenic acid (e.g. alkali metal salts, magnesium salts) , tin salts, zinc salts, lead salts, etc.), metal chelate compounds of β-diketones such as, e.g., aluminum acetylacetone, lithium acetylacetone, etc., Friedel-Crafts catalysts, e.g., aluminum chloride, boron trifluoride, etc. Examples include various organometallic compounds such as titanium tetrabutyrate and tributylantimony oxide, aminosilyl group-containing compounds such as hexamethylsilazane, and halogen-substituted organic phosphorus compounds such as tetrabutylphosphonium hydrogen difluoride.

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

From the viewpoint of production efficiency, the isocyanuration catalyst is preferably a tetraalkylammonium hydroxide or a trialkylhydroxyalkylammonium hydroxide, more preferably a tetraalkylammonium hydroxide, and even more preferably a tetraalkylammonium hydroxide. Examples include tetrabutylammonium hydroxide.

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

Preferably, the isocyanuration catalyst is used as a catalyst solution.

In the catalyst solution, examples of organic solvents include alcohols (e.g., methanol, ethanol, propanol, butanol, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (e.g., acetonitrile, etc.). ), alkyl esters (e.g. methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.), glycol ether esters (e.g. 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 (e.g. diethyl ether, tetrahydrofuran, dioxane, etc.), polar aprotons (e.g. , N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc.). The organic solvents can be used alone or in combination of two or more.

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

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

The addition ratio of the isocyanurating catalyst (in terms of solid content) is, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, for example, 0.1 part by mass or more, based on 100 parts by mass of pentamethylene diisocyanate. It is not more than 0.05 parts by mass, preferably not more than 0.05 parts by mass.

The isocyanurate catalyst may be added all at once or in portions.

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

Further, 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.

Further, the reaction completion temperature (achieved 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 less, more preferably 130°C or less.

Further, the conversion rate of isocyanate groups (NCO conversion rate) 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 is 25% by mass or less, more preferably 15% by mass or less.

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

In the above-mentioned isocyanurate 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 isocyanate groups reaches a target value (eg, 10% or more, preferably 20% or more, and, for example, 40% or less).

Examples of the catalyst deactivator include phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, orthotoluenesulfonic acid, benzoyl chloride, p-toluenesulfonamide, o-toluenesulfonamide, and the like. The catalyst deactivators can be used alone or in combination of two or more types. Further, the blending ratio of the catalyst deactivator is not particularly limited, and is appropriately set depending on the purpose and use.

Further, in the above-mentioned isocyanurate reaction, known additives can be added as necessary.

Examples of additives include antioxidants, cocatalysts (eg, organic phosphites, etc.), and the like.

Examples of the antioxidant include phenolic antioxidants and hindered phenolic antioxidants, and from the viewpoint of hygiene, hindered phenolic antioxidants are preferred. Specifically, examples of hindered phenolic antioxidants include 2,6-di(tert-butyl)-4-methylphenol, [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, Ciba Japan Co., Ltd., trade name), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, Ciba Japan Co., Ltd.) Japan Co., Ltd., trade name), 3-(4-hydroxy-3,5-diisopropylphenyl)propionic acid octyl ester (Irganox 1135, Ciba Japan Co., Ltd., trade name), bis[3-(3-methyl- Examples include 4-hydroxy-5-tert-butylphenyl)propionic acid] ethylenebisoxybisethylene (Irganox 245, manufactured by Ciba Japan, trade name).

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).

Note that the addition ratio of the additive is appropriately set depending on the purpose and use.

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

In this method, after the completion of the isocyanurate reaction, unreacted pentamethylene diisocyanate monomer and reaction solvent (further, if necessary, catalysts, additives, etc.) are extracted from the resulting reaction mixture. ) 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.

Moreover, the above-mentioned isocyanurate-forming catalyst is also used as an allophanate-forming catalyst.

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

Therefore, by the above reactions (isocyanurate reaction and allophanate reaction), isocyanurate of pentamethylene diisocyanate and allophanate of pentamethylene diisocyanate are obtained.

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

In addition to the method described above, the polyisocyanate composition can also be prepared by, for example, first subjecting only pentamethylene diisocyanate to an isocyanurate reaction, and then subjecting the isocyanurate reaction product and a long-chain monoalcohol (described below) to a urethane reaction. It can also be obtained by letting

In such cases, the reaction conditions for isocyanurating pentamethylene diisocyanate are the same as above. After the reaction is completed, unreacted pentamethylene diisocyanate is removed, if necessary, by a known removal method such as distillation. Thereafter, the obtained reaction product (isocyanurate reaction product) and a long-chain monoalcohol are subjected to a urethanization reaction under the same conditions as above.

Such a method also provides a polyisocyanate composition containing an isocyanurate of pentamethylene diisocyanate and an allophanate of pentamethylene diisocyanate.

The polyisocyanate composition preferably does not contain a 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.

In addition, in the polyisocyanate composition (solid content (the same applies hereinafter)), 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.

As described above, the obtained polyisocyanate composition contains an isocyanurate mononucleate of pentamethylene diisocyanate.

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

The content ratio of isocyanurate mononucleus (isocyanurate mononuclear 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 physical properties of the coating film. Preferably, the content is 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 weak solvents, 35% by mass or less, preferably 33% by mass or less, More preferably, it is 30% by mass or less, and still more preferably 28% by mass or less.

The isocyanurate mononuclear content is calculated based on a chromatogram obtained by measuring a polyisocyanate composition using a gel permeation chromatograph (GPC measurement), as shown in FIG.

In the GPC measurement, the GPC measurement device and GPC measurement method are not particularly limited, and any device and method having a resolution capable of calculating each area ratio of each peak, which will be described later, may be employed as appropriate.

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

Then, in the chromatogram obtained by GPC measurement of the polyisocyanate composition, a peak derived from the isocyanurate mononucleus is identified, and the area ratio of the peak is taken as the isocyanurate mononuclear content.

In this case, the peak derived from the isocyanurate mononucleate is identified, for example, based on the polystyrene equivalent molecular weight (average molecular weight). In this case, the polystyrene equivalent molecular weight (average molecular weight) varies depending on the number of carbon atoms in 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) range of 450 or more and less than 500 is identified as a peak derived from isocyanurate mononuclear body. .

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) range of 400 or more and less than 500 is considered to be a peak derived from an isocyanurate mononuclear body. identify

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) range of 450 or more and less than 550 is considered to be a peak derived from an isocyanurate mononuclear body. 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 determined by measuring the polyisocyanate composition with a differential refractometer. In a chromatogram measured by gel permeation chromatography (GPC), the area ratio of the area of a peak having a peak top in the polystyrene equivalent molecular weight (number average molecular weight) range of 400 to less than 500 to the area of all peaks ( (Hereinafter, it may be referred to as the Mn400-500 area ratio or the isocyanurate mononuclear body area ratio.)

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

From the viewpoint of coating physical properties, the isocyanurate mononuclear area ratio (for example, Mn400-500 area ratio) is 5% or more, preferably 10% or more, more preferably 15% or more, and even more preferably 20%. Above, it is particularly preferably 23% or more, and from the viewpoint of solubility in weak solvents, it is 35% or less, preferably 33% or less, more preferably 30% or less, and still more preferably 28% or less.

Note that there is usually one peak indicating the isocyanurate mononuclear content in the above chromatogram.

In FIG. 1, a peak indicating the isocyanurate mononuclear content is shown as peak 6.

In addition, the polyisocyanate composition is obtained by a urethanization reaction between one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol as a by-product, and is a compound (monourethane compound) having a free isocyanate group at the end. can include.

In other words, the monourethane compound is a modified product 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 determined based on the solubility in a weak solvent and the physical properties of the coating film, based on the total amount of the polyisocyanate composition. From this point of view, it is, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less, for example, 0 It is at least 0.1% by mass, more preferably at least 0.5% by mass.

The monourethane content is calculated based on a chromatogram obtained by measuring the polyisocyanate composition using gel permeation chromatography (GPC measurement) in the same manner as described above.

In this case as well, the polystyrene equivalent molecular weight (average molecular weight) varies depending on the number of carbon atoms in 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 a polystyrene equivalent molecular weight (number average molecular weight) range of 200 or more and less than 300 is identified as a peak derived from a monourethane compound.

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) 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 range of polystyrene equivalent molecular weight (number average molecular weight) 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 measured using a gel permeation chromatograph equipped with a differential refractometer. In the chromatogram at the time of measurement, the area ratio of the area of a peak having a peak top in the range of polystyrene equivalent molecular weight (number average molecular weight) 300 to less than 400 to the area of all peaks (hereinafter referred to as Mn300-400 area ratio, or, (Sometimes referred to as monourethane area ratio.)

Preferably, the monourethane content in the polyisocyanate composition is determined by the area of all peaks having peak tops in the range of polystyrene equivalent molecular weight (number average molecular weight) from 320 to 350 in a chromatogram measured by GPC. It can be determined as the area ratio 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 weak solvents and coating film properties. , more preferably 3% or less, particularly preferably 2% or less, for example, 0% or more, preferably 0.1% or more, more preferably 0.5% or more.

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

Note that there is usually one peak indicating the monourethane content in the above chromatogram.

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

Additionally, the polyisocyanate composition preferably includes an allophanate of pentamethylene diisocyanate.

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

Preferably, the allophanate of pentamethylene diisocyanate preferably includes a monoallophanate and a diallophanate.

Monoallophanate contains two molecules of pentamethylene diisocyanate and contains one allophanate group.

When the polyisocyanate composition contains a monoallophanate, the content ratio of the monoallophanate (monoallophanate content) is determined based on the total amount of the polyisocyanate composition from the viewpoint of solubility in a weak solvent and physical properties of the coating film. , for example, 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 monoallophanate content is calculated based on a chromatogram obtained by measuring the polyisocyanate composition using gel permeation chromatography (GPC measurement) in the same manner as described above.

In this case as well, the polystyrene equivalent molecular weight (average molecular weight) varies depending on the number of carbon atoms in 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 a polystyrene equivalent molecular weight (number average molecular weight) range of 300 or more and less than 450 is identified as a peak derived from monoallophanate.

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

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

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the monoallophanate content of pentamethylene diisocyanate in the polyisocyanate composition can be measured by gel permeation with a differential refractometer. In a chromatogram measured by chromatography, the area ratio of the area of a peak having a peak top in the polystyrene equivalent molecular weight (number average molecular weight) range of 500 to less than 700 to the area of all peaks (hereinafter referred to as Mn500-700 area) (also sometimes referred to as monoallophanate area ratio).

Preferably, the monoallophanate content in the polyisocyanate composition is determined by the area of all peaks having peak tops in the polystyrene equivalent molecular weight (number average molecular weight) range of 550 to 650 in a chromatogram measured by GPC. It can be determined as the area ratio to the area of .

The monoallophanate 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.

Note that there is usually one peak indicating the monoallophanate content in the above chromatogram.

In FIG. 1, the peak indicating the monoallophanate content is shown as peak 5.

Diallophanate contains two molecules of pentamethylene diisocyanate and contains two allophanate groups.

When the polyisocyanate composition contains diallophanate, the content ratio of diallophanate (dialophanate content) is determined based on the total amount of the polyisocyanate composition from the viewpoint of solubility in a weak solvent and physical properties of the coating film. , for example, 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 diallophanate content is calculated based on a chromatogram obtained by measuring the polyisocyanate composition using gel permeation chromatography (GPC measurement) in the same manner as described above.

In this case as well, the polystyrene equivalent molecular weight (average molecular weight) varies depending on the number of carbon atoms in 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 a polystyrene equivalent molecular weight (number average molecular weight) range of 500 or more and less than 750 is identified as a peak derived from diallophanate.

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

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

More specifically, for example, when the long-chain monoalcohol has 12 carbon atoms, the diallophanate content of pentamethylene diisocyanate in the polyisocyanate composition can be measured by gel permeation with a differential refractometer. In a chromatogram measured by chromatography, the area ratio of the area of a peak having a peak top in the range of polystyrene equivalent molecular weight (number average molecular weight) 830 to less than 1000 to the area of all peaks (hereinafter referred to as Mn830-1000 area) (also referred to as dialophanate area ratio).

Preferably, the diallophanate content in the polyisocyanate composition is determined by the area of all peaks having peak tops in the polystyrene equivalent molecular weight (number average molecular weight) range of 840 to 980 in a chromatogram measured by GPC. It can be determined as the area ratio to the area of .

The diallophanate 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.

Note that there is usually one peak indicating the diallophanate content in the above chromatogram.

In FIG. 1, the peak indicating the diallophanate content is shown as peak 3.

The total amount (allophanate content) of the content ratio of monoallophanate to the total amount of the polyisocyanate composition (monoallophanate content rate) and the content ratio of diallophanate to the total amount of the polyisocyanate composition (dialophanate content rate) is: For example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less, more preferably 60% by mass or less. be.

In addition, in the polyisocyanate composition, the content ratio (content rate) of allophanate is the above-mentioned monoallophanate area ratio (for example, Mn 500-700 area ratio) and the above-mentioned diallophanate area ratio (for example, Mn 830-1000 area ratio). It is calculated as the total area ratio (hereinafter sometimes referred to as allophanate area ratio).

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

In addition, the polyisocyanate composition can contain not only the mononuclear isocyanurate described above but also a polynuclear isocyanurate as the isocyanurate of pentamethylene diisocyanate.

As described above, isocyanurate polynuclear bodies are isocyanurate n-nuclear bodies (n: an integer of 2 or more), and are, for example, isocyanurate dinuclear bodies (isocyanate pentamolecular bodies), isocyanurate trinuclear bodies (isocyanate 7 molecules body), body), etc.

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

The isocyanurate dinuclear substance is a modified product of pentamethylene diisocyanate, contains five molecules of pentamethylene diisocyanate, and contains two isocyanurate groups.

When the polyisocyanate composition contains isocyanurate binuclear bodies, the content ratio of isocyanurate binuclear bodies (isocyanurate binuclear body content rate) is determined based on the solubility in a weak solvent with respect to the total amount of the polyisocyanate composition. and, from the viewpoint of the physical properties of the coating film, for example, 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 content is calculated based on a chromatogram obtained by measuring the polyisocyanate composition using gel permeation chromatography (GPC measurement) using the same method as described above.

In this case as well, the polystyrene equivalent molecular weight (average molecular weight) varies depending on the number of carbon atoms in 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) range of 750 or more and less than 800 is identified as a peak derived from isocyanurate dinuclear bodies. .

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) range of 730 or more and less than 830 is considered to be a peak derived from isocyanurate dinuclear bodies. identify

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) range of 730 or more and less than 830 is considered to be a peak derived from isocyanurate dinuclear bodies. 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 determined by measuring the polyisocyanate composition with a differential refractometer. In a chromatogram measured by gel permeation chromatography, the area ratio of the area of a peak having a peak top in the polystyrene equivalent molecular weight (number average molecular weight) range of 730 or more and less than 830 to the area of all peaks (hereinafter referred to as Mn730 -830 area ratio or isocyanurate binuclear body area ratio).

Preferably, the isocyanurate binuclear content in the polyisocyanate composition is determined by the area of a peak having a peak top in a polystyrene equivalent molecular weight (number average molecular weight) range of 740 to 820 in a chromatogram measured by GPC. , can be determined 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, and, for example, 15% or less, preferably 10% or less.

In FIG. 1, the peak indicating the isocyanurate dinuclear content is shown as peak 4.

Preferably, the polyisocyanate composition contains three or more isocyanurate nuclei of pentamethylene diisocyanate.

Trinuclear isocyanurate is a modified form of pentamethylene diisocyanate, contains 7 or more molecules of pentamethylene diisocyanate, and contains 3 or more isocyanurate groups.

When the polyisocyanate composition contains 3 or more isocyanurates, the content ratio of 3 or more isocyanurates (content rate of 3 or more isocyanurates) is the weak solvent based on the total amount of the polyisocyanate composition. From the viewpoints of solubility in water and physical properties of the coating film, the content is, for example, 0% by mass or more, preferably 1% by mass or more, and is, for example, 20% by mass or less, preferably 15% by mass or less.

Incidentally, the isocyanurate trinuclear content is calculated based on a chromatogram obtained by measuring the polyisocyanate composition using a gel permeation chromatograph (GPC measurement) in the same manner as described above.

In this case as well, the polystyrene equivalent molecular weight (average molecular weight) varies depending on the number of carbon atoms in 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 a polystyrene equivalent molecular weight (number average molecular weight) of 800 or more is identified as a peak derived from isocyanurate trinucleate or more.

For example, if the long-chain monoalcohol has 12 carbon atoms, a peak with 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 isocyanurate with 3 or more nuclei. do.

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) 1050 or more is identified as a peak derived from isocyanurate trinucleate 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 can be determined by measuring the polyisocyanate composition using a differential refractometer. In a chromatogram measured using a gel permeation chromatograph, the area ratio of the area of a peak having a peak top in the polystyrene equivalent molecular weight (number average molecular weight) range of 1000 or more to the area of all peaks (hereinafter referred to as Mn1000- It can be determined as the area ratio (sometimes referred to as the area ratio of three or more isocyanurate nuclei).

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

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

In FIG. 1, peaks indicating the isocyanurate trinuclear or more isocyanurate content are shown as peak 1 and peak 2.

The total amount of the isocyanurate dinuclear content and the isocyanurate trinuclear content (that is, the isocyanurate polynuclear content (isocyanurate polynuclear content)) is determined by the solubility in weak solvents and the isocyanurate polynuclear content. , from the viewpoint of coating physical properties, 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, Preferably it is 2% by mass or more, more preferably 5% by mass or more.

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

In addition, in the polyisocyanate composition, the content ratio of isocyanurate polynuclear bodies is the above-mentioned isocyanurate binuclear body area ratio (for example, Mn730-830 area ratio) and the above-mentioned isocyanurate 3 or more nuclear body area ratio (for example, It is calculated as the total area ratio (hereinafter sometimes referred to as isocyanurate multi-area ratio) including Mn1000-area ratio).

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

In the above polyisocyanate composition, the ratio of isocyanurate mononuclear content (isocyanurate mononuclear content / allophanate content) to allophanate content (total amount of monoallophanate content and diallophanate 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, particularly preferably 0.40, from the viewpoint of coating physical properties. From the viewpoint of solubility in weak solvents, 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.

In addition, the said ratio is also shown as the ratio of the area ratio in the chromatogram when the polyisocyanate composition is measured with a gel permeation chromatograph equipped with a differential refractometer.

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

In addition, in the above polyisocyanate composition, the ratio of isocyanurate polynuclear content (isocyanurate polynuclear content / allophanate content) to allophanate content (total amount of monoallophanate content and diallophanate content) is , from the viewpoint of physical properties of the coating film, 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 weak solvents, for example, 0.70 or less, preferably 0.60 or less, more preferably 0.50 or less, still more preferably 0.40 or less, particularly preferably 0. 30 or less.

In addition, the said ratio is also shown as the ratio of the area ratio in the chromatogram when the polyisocyanate composition is measured with a gel permeation chromatograph equipped with a differential refractometer.

That is, in the above polyisocyanate composition, the ratio of the isocyanurate polynuclear body area rate to the allophanate area rate (isocyanurate polynuclear body area rate/allophanate area rate) is, for example, 0.03 or more from the viewpoint of the physical properties of the coating film. , 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 weak solvents, for example, 0. .70 or less, preferably 0.60 or less, more preferably 0.50 or less, even more preferably 0.40 or less, particularly preferably 0.30 or less.

In addition, in the above polyisocyanate composition, the ratio of the monourethane content (monourethane content/allophanate content) to the allophanate content (total amount of monoallophanate content and diallophanate content) is determined by the physical properties of the coating film. and, 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 .05 or less.

In addition, the said ratio is also shown as the ratio of the area ratio in the chromatogram when the polyisocyanate composition is measured with 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 determined from the viewpoint of coating film physical 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, even more preferably 0.10 or less, particularly preferably 0.05 or less.

Such polyisocyanate compositions have excellent solubility in weak solvents and are environmentally friendly because the isocyanurate mononuclear area ratio is within the above range in the reaction product of pentamethylene diisocyanate and long-chain monoalcohol. Excellent.

A weak solvent is defined as a particularly low polar solvent and a solvent with an aniline point of 20° C. or higher. Examples of such weak solvents include Mineral Spirits A (manufactured by JXTG Energy Corporation, aniline point: 44.5°C), Ipsol TP (manufactured by Idemitsu Showa Shell, aniline point: 43°C), and T-SOL3040FLUID (manufactured by JXTG Energy Corporation, aniline point: 43°C). For example, petroleum hydrocarbons such as gum turpentine N (manufactured by Yasuhara Chemical, aniline point 27°C) and turpentine oils such as methylcyclohexane (aniline point 40°C) can be mentioned. These weak solvents can be used alone or in combination of two or more.

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

In addition, the polyisocyanate composition has an isocyanurate mononuclear content in the above range in the reaction product of the pentamethylene diisocyanate and the long-chain monoalcohol, and therefore can form a coating film with excellent physical properties. .

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

Therefore, the above polyisocyanate composition is suitably used as a raw material for producing polyurethane resins, for example, in the field of coating polyurethane resins such as paints, adhesives, and coating agents.

The form of the polyurethane resin is not particularly limited, but preferably includes a two-component curing type polyurethane. A two-component curable polyurethane is a resin composition in which a curing agent and a base agent are prepared as separate packages, and when they are mixed together at the time of use, a polyurethane resin (cured coating film, etc.) is formed.

As the curing agent (polyisocyanate component) in such a two-part 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, to prepare 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, the above polyisocyanate composition has excellent solubility in weak solvents and is therefore suitably used as a curing agent for fluoropolyols.

Examples of acrylic polyols include copolymers obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups and another monomer copolymerizable therewith.

Examples of polymerizable monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxy Examples include alkyl maleate and polyhydroxyalkyl fumarate.

In addition, other monomers copolymerizable with them include, for example, (meth)acrylic acid, alkyl (meth)acrylate (1 to 12 carbon atoms), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth)acrylonitrile, 3-(2-isocyanate-2-propyl)-α-methylstyrene, trimethylolpropane tri(meth)acrylate, Examples include pentaerythritol tetra(meth)acrylate.

Acrylic polyols can be obtained by copolymerizing these monomers in the presence of a suitable solvent and polymerization initiator.

As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, a copolymer obtained by using a vinyl group-containing fluorine compound such as tetrafluoroethylene, chlorotrifluoroethylene, etc. as another copolymerizable monomer is used. Examples include polymers.

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

In addition, the polyol component is dissolved in the above-mentioned organic solvent, etc., if necessary, and prepared as a main ingredient.

Two-component curing polyurethane can be suitably used as paint (two-component curing paint), adhesive (two-component curing adhesive), etc. by mixing and stirring the curing agent and main agent at the time of use. .

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

The blending ratio of the base 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 base agent (polyol component). .5, preferably 0.8 to 1.2.

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

The adherend is not particularly limited, and includes, for example, various building materials and various laminated films. More specifically, examples thereof include packaging materials such as plastic films, metal foils, and metallized films, and civil engineering materials such as FRP and steel materials.

Then, by drying and curing the mixture of the base resin and the curing agent, a polyurethane resin (cured coating film, adhesive layer, etc.) is obtained.

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

Next, the present invention will be explained based on production examples, working examples, and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are based on mass unless otherwise specified. In addition, the specific numerical values of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description are the corresponding blending ratios ( Substitute with the upper limit value (value defined as "less than" or "less than") or lower limit value (value defined as "more than" or "exceeding") of the relevant description, such as content percentage), physical property value, parameter, etc. be able to.

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

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

Table 1 shows the type of polyisocyanate, the number of carbon atoms in the monoalcohol, the molecular weight of the peak top in terms of polystyrene, and the assignment of each component.

<GPC measurement>
In the GPC measurement, about 0.03 g of sample was taken and 10 mL of tetrahydrofuran was added to dissolve it. Then, the obtained solution was subjected to GPC measurement under the following conditions.
(1) Analyzer: Alliance (Waters)
(2) Pump: Alliance 2695 (Waters)
(3) Detector: 2414 type differential refraction detector (Waters)
(4) Eluent: Tetrahydrofuran
(5) Separation column: Plgel GUARD + Plgel 5μm Mixed-C x 3 (50 x 7.5 mm, 300 x 7.5 mm)
Manufacturer: Polymer Laboratories
Product number: PL1110-6500
(6) Measurement temperature: 40℃
(7) Flow rate: 1mL/min
(8) Sample injection volume: 100μL
(9) Analysis device: EMPOWER data processing device (Waters)
・System correction (1) Standard material name: Polystyrene
(2) Calibration curve creation method: Create a graph of retention time and molecular weight using TOSOH's TSK standard Polystyrene with different molecular weights.
(3) Injection volume, injection concentration: 100μL, 1mg/mL
Note that a gel permeation chromatogram of the polyisocyanate composition of Example 1 is shown in FIG.

Examples 1 to 7, Reference Examples 8 to 10 , and Comparative Examples 1 to 10
Polyisocyanate compositions were obtained using the raw materials and conditions shown in Tables 2 to 4.

That is, 100 parts by mass of the polyisocyanate listed in the table and octadecyl 3-(3,5-di-tert-butyl 0.05 parts by mass of -4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Japan Co., Ltd., trade name) and 0.05 parts by mass of tridecyl phosphite (JP-310, manufactured by Johoku Kagaku Co., Ltd., trade name). The mixture was charged and the temperature was raised to 80°C.

Next, the monoalcohol listed in the table was added to the above mixture so that the equivalent ratio of isocyanate groups to hydroxyl groups (R(NCO/OH)) became the value shown in the table, and urethane was added to the mixture at 80°C for 3 hours. chemical reaction.

Next, the temperature was raised to the reaction initiation temperature listed in the table, and 0.01 part by mass of N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate was added as an isocyanurate catalyst. A mixed solution with 0.03 parts by mass of propylene glycol methyl ether acetate as a solvent was added to the urethanation reaction product to cause isocyanurate and allophanate reactions.

Next, by utilizing the heat of reaction, after reaching the reaction completion temperature listed in the table, 0.01 part by mass of o-toluenesulfonamide was added so as to reach the isocyanate group conversion rate listed in the table. The reaction was stopped.

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

Thereby, a polyisocyanate composition was obtained.

Evaluation (1) Solubility in weak solvents Take 1 g of the polyisocyanate composition in a test tube, add 1 g of turpentine oil (Gum Turpentine N, manufactured by Yasuhara Chemical, trade name, aniline point: 27°C) as a weak solvent, and stir for 30 seconds with a shaker. The presence or absence of turbidity was confirmed.

Furthermore, 1 g of turpentine oil (Gum Turpentine N, manufactured by Yasuhara Chemical Co., Ltd., trade name, aniline point: 27°C) was added as a weak solvent, stirring was repeated, and the maximum concentration at which a cloudy state could be maintained was measured.

Then, the maximum concentration of the weak solvent ([mass of weak solvent/mass of polyisocyanate composition] x 100) that can maintain a non-turbid state was evaluated based on the following criteria.

◎: 2000% or more ○: 500% or more and less than 2000% △: 100% or more and less than 500% ×: less than 100% (2) Coating film physical properties - Creation of cured coating Polyisocyanate composition and acrylic polyol (Orestar Q -166 manufactured by Mitsui Chemicals, Inc.) at an equivalent ratio of 1.0 (NCO/OH = 1.0), and thinner (ethyl acetate: butyl acetate: propylene glycol methyl ether acetate) to give a solid content concentration of 50%. = 1:1:1 mixture), mixed at 23° C. for 5 minutes, and then subjected to ultrasonication for 10 minutes to defoam to obtain a coating agent.

The obtained coating agent was applied to a steel plate (SPCC steel plate, PBN-144 treated product) using a 4 mil applicator, heated in an oven at 80°C for 30 minutes, and cured in an oven at 30°C for 5 days to form a cured film. I got it.

・Solvent resistance evaluation (rubbing test)
The cured film was set in a rubbing tester (model IMC-0717, manufactured by Imoto Seisakusho Co., Ltd.), and rubbing was performed by placing absorbent cotton moistened with methyl ethyl ketone on the tip of a 0.5 kg weight. Evaluation was made based on the number of times the coating film was torn and the base material was exposed by the number of times the rubbing was repeated.

Then, the physical properties of the coating film (solvent resistance) were evaluated based on the following criteria.

◎: 100 times or more ○: 80 times or more and less than 100 △: 20 times or more and less than 80 ×: less than 20 times

Claims (3)

A polyisocyanate composition containing an isocyanurate group, comprising a reaction product of pentamethylene diisocyanate and a long-chain monoalcohol having 8 or more and less than 20 carbon atoms,
The polyisocyanate composition contains three molecules of pentamethylene diisocyanate and contains an isocyanurate mononuclear body containing one isocyanurate group,
The content ratio of the isocyanurate mononucleate 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 includes a monourethane compound consisting of one molecule of pentamethylene diisocyanate and one molecule of long-chain monoalcohol,
The content ratio of the monourethane compound is 10% by mass or less based on the total amount of the polyisocyanate composition.
A polyisocyanate composition characterized by: The polyisocyanate composition includes:
an isocyanurate dinuclear body containing five molecules of pentamethylene diisocyanate and two isocyanurate groups;
Containing 7 or more molecules of pentamethylene diisocyanate and containing 3 or more isocyanurate groups containing 3 isocyanurate groups,
The total amount of the content of the isocyanurate di-nucleate and the content of the isocyanurate trinuclear or more is 20% by mass or less based on the total amount of the polyisocyanate composition. Item 1. The polyisocyanate composition according to item 1 . The polyisocyanate composition includes an allophanate of pentamethylene diisocyanate,
The allophanate includes a monoallophanate containing two molecules of pentamethylene diisocyanate and one allophanate group, and a diallophanate containing three molecules of pentamethylene diisocyanate and containing two allophanate groups,
The total amount of the content ratio of the monoallophanate to the total amount of the polyisocyanate composition (monoallophanate content) and the content ratio of the diallophanate to the total amount of the polyisocyanate composition (dialophanate content) (allophanate content) against,
Content ratio of the isocyanurate mononucleate to the total amount of the polyisocyanate composition (isocyanurate mononuclear content)
The ratio (isocyanurate mononuclear content rate/allophanate content rate) is
The polyisocyanate composition according to claim 1 or 2 , wherein the polyisocyanate composition is 0.40 or more and 0.60 or less.