JP5225813B2 - Polyisocyanate composition, polyurethane resin and method for producing polyisocyanate composition - Google Patents

Description

  The present invention relates to a polyisocyanate composition and a polyurethane resin, and particularly relates to a polyisocyanate composition and a polyurethane resin used in various industrial fields.

Polyurethane resins are usually produced by the reaction of a polyisocyanate composition and an active hydrogen compound, and are widely used in various industrial fields as, for example, paints, adhesives, and elastomers.
In recent years, from the viewpoint of environmental impact, it has been desired to reduce the use of organic solvents, and low-viscosity polyisocyanate compositions are desired as polyisocyanate compositions capable of suppressing the use of organic solvents. .

As such a polyisocyanate composition, for example, an isocyanurate trimer concentration derived from at least one of an aliphatic / alicyclic diisocyanate and containing no solvent is 60% by mass to 95% by mass. A functional group number ratio of allophanate group / isocyanurate group derived from monoalcohol is 1 to 20%, uretdione dimer concentration is 2 to 25% by mass, and diisocyanate monomer concentration is 1% by mass or less, A polyisocyanate composition excellent in crosslinkability and storage stability having a viscosity at 25 ° C. of 150 to 800 mPa · s and an isocyanate group concentration of 22 to 25% by mass has been proposed (for example, see Patent Document 1). .)
JP 2007-1112936 A

On the other hand, in various industrial fields, even if the amount of the polyisocyanate composition is reduced in the production of polyurethane resin, a polyisocyanate having a higher isocyanate group concentration than that described in Patent Document 1 is required to satisfy sufficient mechanical properties. Isocyanate compositions are also desired.
An object of the present invention is to provide a polyisocyanate composition having a low viscosity and a high isocyanate group concentration, and a polyurethane resin in which the polyisocyanate composition is used.

In order to achieve the above object, the polyisocyanate composition of the present invention is substantially free of a solvent and is obtained by an isocyanuration reaction of pentamethylene diisocyanate. The isocyanate group concentration exceeds 25% by mass, and 28% by mass. % Or less.
Moreover, it is suitable for the polyisocyanate composition of this invention to react a C1-C20 alcohol and pentamethylene diisocyanate in the isocyanuration reaction.

The polyisocyanate composition of the present invention preferably contains 10 to 5000 ppm of a compound containing a sulfonamide group.
The polyurethane resin of the present invention is characterized by being obtained by reacting the polyisocyanate composition with an active hydrogen compound.

The polyisocyanate composition of the present invention has a low viscosity and a high isocyanate group concentration.
Therefore, the polyisocyanate composition of the present invention can satisfy sufficient mechanical properties even if the amount used is reduced. Therefore, the polyurethane resin in which the polyisocyanate composition of the present invention is used can be widely used in various industrial fields.

The polyisocyanate composition of the present invention is a polyisocyanate composition substantially free of a solvent and can be obtained by an isocyanuration reaction of pentamethylene diisocyanate (PDI).
In the present invention, examples of pentamethylene diisocyanate include 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate, or a mixture thereof. From the viewpoint of industrial availability, 1,5-pentamethylene diisocyanate is preferable. 1,5-pentamethylene diisocyanate can be produced from 1,5-diaminopentane by a known method such as a phosgene method or a non-phosgene method. For example, JP-A No. 2003-212835, JP-A No. 2003-25284, It can be produced by the method described in JP-A No. 2004-262892 or International Publication No. 2008/015134.

1,5-diaminopentane is described in, for example, the Chemical Dictionary (Editor: Chemical Dictionary Editorial Committee, Issuer; Kyoritsu Publishing Co., Ltd., February 15, 1987, 30th edition) It is also called cadaverine and is produced from lysine.
Since pentamethylene diisocyanate tends to increase the concentration (HC) of hydrolyzable chlorine, when adopting the phosgene method, if it is necessary to reduce HC, for example, a phosgenation reaction is carried out to remove it. The pentamethylene diisocyanate that has been distilled off after the solvent is distilled, for example, at 150 to 200 ° C., preferably 160 to 190 ° C., for example, for 1 to 8 hours while passing an inert gas such as nitrogen. The heat treatment is preferably performed for 3 to 6 hours. Thereafter, HC of pentamethylene diisocyanate can be remarkably reduced by performing rectification treatment.

In the present invention, the concentration of hydrolyzable chlorine in pentamethylene diisocyanate is, for example, 100 ppm or less, preferably 80 ppm or less, more preferably 60 ppm or less, and still more preferably 50 ppm or less.
The concentration of hydrolyzable chlorine can be measured in accordance with, for example, the test method for hydrolyzable chlorine described in Appendix 3 of JIS K-1556 (2000).

If the concentration of hydrolyzable chlorine exceeds 100 ppm, the reaction rate of isocyanurate formation decreases, and a large amount of isocyanurate formation catalyst (described later) may be required. The polyisocyanate composition obtained may have a high degree of yellowing, a number average molecular weight may increase, and a viscosity may increase.
In the present invention, as a method for obtaining a polyisocyanate composition, for example, pentamethylene diisocyanate and an alcohol are reacted, then isocyanurated in the presence of an isocyanuration catalyst, and then unreacted pentamethylene diisocyanate. For example, there is a method in which only pentamethylene diisocyanate is isocyanurated, then unreacted pentamethylene diisocyanate is removed, and the resulting polyisocyanurate is reacted with an alcohol.

Preferably, a polyisocyanate composition is obtained by a method in which pentamethylene diisocyanate and an alcohol are reacted and then isocyanurated in the presence of an isocyanuration catalyst, and then unreacted pentamethylene diisocyanate is removed.
In the present invention, examples of alcohols include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetrahydric alcohols and the like.

Examples of monohydric alcohols include linear monohydric alcohols and branched monohydric alcohols.
Examples of the linear monohydric alcohol include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, and n. -Undecanol, n-dodecanol (lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n -Nonadecanol, eicosanol and the like.

  Examples of the branched monohydric alcohol include isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol, isononanol, isodecanol, 5-ethyl-2-nonanol, Trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, other branched alkanols (C (carbon number, the same shall apply hereinafter) 5-20 ) And the like.

  Examples of the dihydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-dihydroxy-2-butene, and diethylene glycol. , Triethylene glycol, dipropylene glycol, and other linear dihydric alcohols such as linear alkane (C7-20) diol, such as 1,2-propanediol, 1,3-butylene glycol, 1, 2-butylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, 2,6-dimethyl-1-octene-3, Branches such as 8-diols and other branched alkane (C7-20) diols Dihydric alcohols such as 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A, bisphenol A and the like. It is done.

Examples of the trihydric alcohol include glycerin and trimethylolpropane.
Examples of the tetravalent or higher alcohol include tetramethylolmethane, D-sorbitol, xylitol, and D-mannitol.
In addition, if these alcohols have one or more hydroxy groups in the molecule, the other molecular structures are not particularly limited as long as they do not inhibit the excellent effects of the present invention. Further, it may have an ester group, an ether group, a cyclohexane ring, an aromatic ring, or the like. Examples of such alcohols include addition polymers (random and / or block polymers of two or more types of alkylene oxides) of the above monohydric alcohols and alkylene oxides (eg, ethylene oxide, propylene oxide, etc.). Examples include ether group-containing monohydric alcohols and ester group-containing monohydric alcohols which are addition polymerization products of the above monohydric alcohols and lactones (for example, ε-caprolactone, δ-valerolactone, etc.).

These alcohols can be used alone or in combination of two or more.
The alcohols preferably include monovalent and divalent alcohols, and the monovalent and divalent alcohols are preferably monovalent and divalent alcohols having 1 to 20 carbon atoms, more preferably 1 carbon number. 15 monovalent and dihydric alcohols, more preferably monovalent and dihydric alcohols having 1 to 10 carbon atoms, and particularly preferably monovalent and dihydric alcohols having 2 to 6 carbon atoms. Moreover, as monovalent | monohydric and bivalent alcohol, Preferably, branched monovalent | monohydric and bivalent alcohol is mentioned. In order to further lower the viscosity of the polyisocyanate composition, a monohydric alcohol is most preferable.

Alcohols are used in the resulting polyisocyanate composition so that the average number of functional groups is 2 or more. The blending ratio is, for example, 0.1% of alcohols with respect to 100 parts by weight of pentamethylene diisocyanate. -5 parts by weight, preferably 0.2-3 parts by weight.
In addition, in the isocyanate reaction of pentamethylene diisocyanate, the above alcohols and, for example, thiols, oximes, lactams, phenols, β Active hydrogen compounds such as diketones can be used in combination.

And in this invention, pentamethylene diisocyanate and alcohol are made to react so that the isocyanate group density | concentration will exceed 25 mass% and it may be 28 mass% or less in the polyisocyanate composition obtained.
To react pentamethylene diisocyanate with alcohols so that the isocyanate group concentration is in the above range, after reacting pentamethylene diisocyanate with alcohols, in the presence of an isocyanuration catalyst, predetermined reaction conditions The isocyanurate reaction is carried out with

  The isocyanuration catalyst is not particularly limited as long as it is an effective catalyst for isocyanuration. For example, tetraalkylammonium hydroxide such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium, and the like Weak organic acid salts such as trialkylhydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium and their weak organic acid salts such as acetic acid, caproic acid, octylic acid Alkali metal salts of alkyl carboxylic acids such as myristic acid such as tin, Metal salts such as lead, for example, metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, such as titanium tetrabutyrate, tributylantimony Examples include various organometallic compounds such as oxides, and aminosilyl group-containing compounds such as hexamethylsilazane.

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

These isocyanuration catalysts can be used alone or in combination of two or more.
As the isocyanuration catalyst, N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate is preferably used.
The addition ratio of the isocyanurate-forming catalyst is, for example, 0.001 to 0.1 parts by mass, preferably 0.002 to 0.05 parts by mass with respect to 100 parts by mass of pentamethylene diisocyanate.

In order to control the isocyanuration, for example, an organic phosphite described in JP-A-61-129173 can be used as a co-catalyst.
Examples of organic phosphites include organic phosphite diesters and organic phosphite triesters, and more specifically, for example, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphine. Phyto, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) Monophosphites such as phosphite, diphenyldecyl phosphite, diphenyl (tridecyl) phosphite, such as distearyl pentaerythrityl diphosphite, di-dodecyl pentaerythritol diphosphite, di-tridecyl From polyhydric alcohols such as teraerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, tetraphenyl tetratetradecyl pentaerythrityl tetraphosphite, tetraphenyl dipropylene glycol diphosphite, tripentaerythritol triphosphite Di-, tri- or tetraphosphites derived, for example, dialkyl bisphenol A diphosphite having 1 to 20 carbon atoms, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Diphosphites derived from bisphenol compounds such as phenyl-di-tridecyl) phosphite, polyphosphites such as hydrogenated bisphenol A phosphite polymer (molecular weight 2400-3000), Such as scan (2,3-dichloro-propyl) phosphite.

In this reaction, a hindered phenolic antioxidant such as 2,6-di (tert-butyl) -4-methylphenol, Irganox 1010, Irganox 1076, Irganox 1135, Irganox 245 (or more, Stabilizers such as Ciba Japan, trade name) can also be added.
As the predetermined reaction conditions, for example, the reaction temperature is, for example, 30 to 100 ° C., preferably 40 to 80 ° C. under an atmosphere of an inert gas such as nitrogen gas and normal pressure (atmospheric pressure), and the reaction time. Is, for example, 0.5 to 10 hours, preferably 1 to 5 hours.

In this reaction, pentamethylene diisocyanate and alcohol have an equivalent ratio (NCO / OH) of the isocyanate group of pentamethylene diisocyanate to the hydroxy group of alcohol, for example, 30 or more, preferably 40 or more. Preferably, it is blended at a blending ratio of 60 or more and usually 1000 or less.
After reaching a predetermined isocyanate group concentration, the above-mentioned isocyanurate-forming catalyst is added to cause an isocyanurate-forming reaction.

The conversion rate of the isocyanate group in this reaction is, for example, 5 to 35% by mass, preferably 5 to 20% by mass. When the conversion rate exceeds 35% by mass, the number average molecular weight of the resulting polyisocyanate composition is increased, so that solubility, compatibility, NCO content (isocyanate group concentration) may be decreased, and viscosity may be increased.
The conversion rate of the isocyanate group can be measured by, for example, a method using a high-speed GPC apparatus, an NMR method, or the like.

In this reaction, a known reaction solvent may be blended if necessary, and a known catalyst deactivator (for example, phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, paratoluenesulfonic acid at any timing). Benzoyl chloride, etc.) can also be added.
And after completion | finish of reaction, unreacted pentamethylene diisocyanate is removed by well-known removal methods, such as distillation, as needed.

  Also, as a method for obtaining a polyisocyanate composition, only pentamethylene diisocyanate is isocyanurated, then unreacted pentamethylene diisocyanate is removed, and the resulting polyisocyanate is reacted with an alcohol (the above-mentioned latter). When the method is employed, the reaction between the polyisocyanate and the alcohol is a general urethanization reaction. The reaction conditions for such a urethanization reaction are, for example, room temperature to 100 ° C, preferably 40 to 90 ° C.

Moreover, in the said urethanation reaction, you may add well-known urethanation catalysts, such as amines and an organometallic compound, as needed.
Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, Examples thereof 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, dibutyltin Organic tin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, Examples thereof include 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.
Moreover, the polyisocyanate composition of this invention can also be made to contain the compound containing a sulfonamide group, for example.

In the present invention, examples of the compound containing a sulfonamide group include aromatic sulfonamides and aliphatic sulfonamides.
Examples of aromatic sulfonamides include benzenesulfonamide, dimethylbenzenesulfonamide, sulfanilamide, o- and p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide and the like can be mentioned.

  Examples of the aliphatic sulfonamides include methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N- Examples include dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

These compounds containing a sulfonamide group can be used alone or in combination of two or more.
As the compound containing a sulfonamide group, aromatic sulfonamides are preferable, and o- or p-toluenesulfonamide is more preferable.
When the polyisocyanate composition contains a compound containing a sulfonamide group, the compound containing the sulfonamide group is, for example, 10 to 5000 ppm, preferably 50 to 50%, based on the polyisocyanate composition. The content is 4000 ppm, more preferably 100 to 3000 ppm.

  If the content of the compound containing a sulfonamide group is more than 5000 ppm, the isocyanate group concentration may change in the polyisocyanate composition storage step and the polyurethane resin production step described later. On the other hand, when the content of the compound containing a sulfonamide group is less than 10 ppm, the viscosity and hue may change greatly in the polyisocyanate composition storage step and the polyurethane resin production step described later.

The concentration of the compound containing a sulfonamide group can be determined, for example, by ¹ H-NMR measurement. In addition, although a part of the compound containing a sulfonamide group reacts with an isocyanate group, in the NMR measurement focusing on the proton of the NH bond in the sulfonamide group, the compound containing the sulfonamide group is a sulfonamide group. The total amount of the compound alone containing a group, the compound containing a sulfonamide group, and the reaction product of the polyisocyanate composition can be determined.

  The method for incorporating the compound containing a sulfonamide group into the polyisocyanate composition is not particularly limited. For example, in the isocyanuration reaction of pentamethylene diisocyanate, a sulfonamide group is contained together with pentamethylene diisocyanate and alcohols. And a method of adding a compound containing a sulfonamide group to a polyisocyanate composition obtained by the isocyanuration reaction of pentamethylene diisocyanate.

The polyisocyanate composition thus obtained has an isocyanate group concentration of more than 25% by mass and not more than 28% by mass, preferably more than 25% by mass and not more than 27% by mass, more preferably, It exceeds 25 mass% and is 26.5 mass% or less.
In the polyisocyanate composition thus obtained, the isocyanate monomer concentration (concentration of unreacted pentamethylene diisocyanate) is, for example, 1% by mass or less, preferably 0.7% by mass or less, more preferably 0.5% by mass or less.

Further, the viscosity at 25 ° C. of the polyisocyanate composition thus obtained is, for example, 100 to 5000 mPa · s, preferably 200 to 4000 mPa · s, more preferably 200 to 3000 mPa · s, and still more preferably. 200 to 1000 mPa · s.
The polyisocyanate composition thus obtained can be used for many industrial applications such as paints, adhesives, etc. without being diluted with a solvent. If necessary, it is used by dissolving in various organic solvents. You can also.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate, such as n- Aliphatic hydrocarbons such as hexane, n-heptane, and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, such as 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-methoxy Glycol ether esters such as butyl acetate and ethyl-3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodine Halogenated aliphatic hydrocarbons such as methylene chloride and dichloroethane, for example, polar aprotics such as N-methylpyrrolidone, dimethylformamide, N, N′-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc. .

Furthermore, as an organic solvent, a nonpolar solvent (nonpolar organic solvent) is mentioned, for example, As these nonpolar solvents, the aniline point containing an aliphatic and a naphthene type hydrocarbon organic solvent is 10--10, for example. Examples include non-polar organic solvents having low toxicity and weak dissolving power at 70 ° C., preferably 12 to 65 ° C., vegetable oils represented by terpene oil, and the like.
Such a nonpolar organic solvent is available as a commercial product. Examples of such a commercial product include House (manufactured by Shell Chemical Co., aniline point 15 ° C.), Swazol 310 (manufactured by Maruzen Petroleum Co., Ltd., aniline point 16 ° C.), Essonaphtha No. 6 (manufactured by Exxon Chemical, aniline point 43 ° C.), wax (manufactured by Shell Chemical Co., aniline point 43 ° C.), Essonaphtha No. 5 (exxon, aniline point 55 ° C), pegasol 3040 (mobile oil, aniline point 55 ° C) and other petroleum hydrocarbon organic solvents, methylcyclohexane (aniline point 40 ° C), ethylcyclohexane (aniline point 44 ° C) ), And turpentine oils such as gum turpentine N (manufactured by Anne Crude Oil, aniline point 27 ° C).

The polyisocyanate composition of this invention can be mixed with these organic solvents in arbitrary ratios.
The polyisocyanate composition of the present invention has a low viscosity and a high isocyanate group concentration. Therefore, the polyisocyanate composition of the present invention can satisfy sufficient mechanical strength even if the amount used is reduced. Therefore, the polyurethane resin in which the polyisocyanate composition of the present invention is used can be widely used in various industrial fields.

The polyurethane resin of the present invention can be obtained by reacting the polyisocyanate composition with an active hydrogen compound.
In the present invention, examples of the active hydrogen compound include a polyol component (a component mainly containing a polyol having two or more hydroxyl groups), a polyamine component (a compound mainly containing a polyamine having two or more amino groups), and the like. .

In the present invention, examples of the polyol component include low molecular weight polyols and high molecular weight polyols.
The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of less than 400, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol. 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3 Dimethylol heptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A 1,4-dihydroxy-2-butene, 2,6-dimethyl Dihydric alcohols such as ru-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol and dipropylene glycol, for example, trihydric alcohols such as glycerin and trimethylolpropane, such as tetramethylolmethane (penta Erythritol), tetrahydric alcohols such as diglycerin, for example, pentahydric alcohols such as xylitol, for example, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, for example, perseitol, etc. For example, octavalent alcohols such as sucrose.

  The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, for example, polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, and And vinyl monomer-modified polyol.

Examples of the polyether polyol include polypropylene glycol and polytetramethylene ether glycol.
Examples of the polypropylene glycol include addition polymers of alkylene oxides such as ethylene oxide and propylene oxide (the random and / or two or more types of alkylene oxides) using the above-described low molecular weight polyols or aromatic / aliphatic polyamines as initiators. A block copolymer).

Examples of the polytetramethylene ether glycol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and amorphous polytetramethylene ether glycol obtained by copolymerizing the above-described dihydric alcohol with a polymerization unit of tetrahydrofuran.
Examples of the polyester polyol include polycondensates obtained by reacting the above-described low molecular weight polyol and polybasic acid under known conditions.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other saturated aliphatic dicarboxylic acids (C11-13) such as maleic acid, fumaric acid, itaconic acid, other unsaturated aliphatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid , Toluene dicarboxylic acid, naphthalene dicarboxylic acid, other aromatic dicarboxylic acids such as hexahydrophthalic acid, other alicyclic dicarboxylic acids such as dimer acid, hydrogenated dimer acid, het acid and other carboxylic acids, And acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride , Maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, such as oxalic acid Examples include dichloride, adipic acid dichloride, and sebacic acid dichloride.

  Further, as the polyester polyol, for example, a hydroxyl group-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) using the above low molecular weight polyol as an initiator, etc. Examples thereof include vegetable oil-based polyester polyols obtained by subjecting hydroxycarboxylic acid to a condensation reaction under known conditions.

  Polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, for example, using the above-described low molecular weight polyol (preferably dihydric alcohol) as an initiator, Examples include caprolactone polyol, polyvalerolactone polyol, and lactone polyester polyol obtained by copolymerizing the above-described dihydric alcohol.

  As the polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate using the above-described low molecular weight polyol (preferably a dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5-pentanediol, Examples thereof include amorphous polycarbonate polyols obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

  Further, the polyurethane polyol is a ratio in which the equivalent ratio (OH / NCO) of the hydroxyl group (OH) to the isocyanate group (NCO) of the polyester polyol, polyether polyol and / or polycarbonate polyol obtained as described above exceeds 1, By reacting with polyisocyanate, it can be obtained as polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol.

Examples of the epoxy polyol include an epoxy polyol obtained by a reaction of the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.
Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. For example, castor oil polyol, or ester-modified castor oil polyol obtained by reaction of castor oil fatty acid and polypropylene polyol can be used.

Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.
Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.

  Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, Examples thereof include polyhydroxyalkyl fumarate. Preferably, 2-hydroxyethyl (meth) acrylate etc. are mentioned.

  Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( Alkyls such as (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, etc. (Meth) acrylates (1 to 12 carbon atoms), for example, aromatic vinyl such as styrene, vinyltoluene and α-methylstyrene, for example, vinyl cyanide such as (meth) acrylonitrile, ) Vinyl monomers containing carboxyl groups such as acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof such as ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) ) Acrylates, oligoethylene glycol di (meth) acrylates, alkane polyol poly (meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, such as 3- (2-isocyanate-2- And vinyl monomers containing an isocyanate group such as propyl) -α-methylstyrene.

The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate and copolymerizable vinyl monomer in the presence of a suitable solvent and polymerization initiator.
The acrylic polyol includes, for example, silicone polyol and fluorine polyol.

Examples of the silicone polyol include an acrylic polyol in which a silicone compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane is blended as the copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above. .
As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, as the copolymerizable vinyl monomer, for example, an acrylic polyol in which a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene is blended may be mentioned. .

The vinyl monomer-modified polyol can be obtained by a reaction between the above-described high molecular weight polyol and a vinyl monomer.
The high molecular weight polyol is preferably a high molecular weight polyol selected from polyether polyol, polyester polyol and polycarbonate polyol.

Examples of the vinyl monomer include the above-described alkyl (meth) acrylate, vinyl cyanide, vinylidene cyanide, and the like. These vinyl monomers can be used alone or in combination of two or more. Of these, alkyl (meth) acrylate is preferable.
The vinyl monomer-modified polyol is obtained by reacting these high molecular weight polyol and vinyl monomer in the presence of a radical polymerization initiator (for example, persulfate, organic peroxide, azo compound, etc.), for example. Can be obtained.

These polyol components can be used alone or in combination of two or more.
The polyol component is preferably a high molecular weight polyol, more preferably a polyester polyol or an acrylic polyol.
Examples of the polyamine component include an aromatic polyamine, an araliphatic polyamine, an alicyclic polyamine, an aliphatic polyamine, an amino alcohol, a primary amino group, or an alkoxy having a primary amino group and a secondary amino group. Examples thereof include silyl compounds and polyoxyethylene group-containing polyamines.

Examples of the aromatic polyamine include 4,4′-diphenylmethanediamine and tolylenediamine.
Examples of the araliphatic polyamine include 1,3- or 1,4-xylylenediamine or a mixture thereof.
Examples of the alicyclic polyamine include 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5 (2,6) -bis ( Aminomethyl) bicyclo [2.2.1] heptane, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof Etc.

  Examples of the aliphatic polyamine include ethylenediamine, propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, and hydrazine (including hydrates). ), Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane and the like.

Examples of the amino alcohol include N- (2-aminoethyl) ethanolamine.
Examples of the alkoxysilyl compound having a primary amino group or a primary amino group and a secondary amino group include γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane. Examples include alkoxysilyl group-containing monoamine, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, and the like.

Examples of the polyoxyethylene group-containing polyamine include polyoxyalkylene ether diamines such as polyoxyethylene ether diamine. More specifically, for example, PEG # 1000 diamine manufactured by Nippon Oil & Fats, Jeffamine ED-2003, EDR-148, XTJ-512 manufactured by Huntsman, and the like can be mentioned.
These polyamine components can be used alone or in combination of two or more.

  In the present invention, a known additive, for example, a plasticizer, an anti-blocking agent, a heat stabilizer, a light stabilizer, an antioxidant, a release agent, a catalyst, a pigment, a dye, Lubricants, fillers, hydrolysis inhibitors and the like can be added. These additives may be added at the time of synthesis of each component, or may be added at the time of mixing / dissolving each component, and may be added after the synthesis.

The polyurethane resin of the present invention can be widely used in various industrial fields as, for example, paints, adhesives, elastomers, sealants, foams and the like.
When the polyurethane resin of the present invention is used, for example, as a paint or an adhesive, the polyurethane resin of the present invention is prepared by preparing the polyisocyanate composition and the active hydrogen compound, respectively, and blending them at the time of use. It is prepared as a two-component curable polyurethane resin.

  The two-part curable polyurethane resin is preferably used as a two-part curable paint and / or a two-part curable adhesive. Specifically, the active hydrogen compound is first prepared and separately from the active hydrogen compound. A polyisocyanate composition is prepared, and immediately before use, an active hydrogen compound and a polyisocyanate composition are mixed to prepare a two-part curable polyurethane resin. Or apply to the adherend.

  In the case of producing the polyurethane resin of the present invention as a two-component curable polyurethane resin, if necessary, further known additives, for example, coating compositions include color pigments, dyes, ultraviolet absorbers, Adhesive compositions such as curing accelerators, light stabilizers, matting agents, etc. should contain phosphorus oxygen acid or its derivatives or silane coupling agents, etc. for improving the adhesion of the coating film at an appropriate ratio. Can do.

Examples of color pigments and dyes include inorganic pigments such as carbon black and titanium oxide having good weather resistance, for example, organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, and isoindolinone-based yellow, And dyes.
Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers, and more specifically, tinuvin 213, tinuvin 234, tinuvin 326, tinuvin 571 (and above,・ Products made in Japan and trade names).

Examples of the curing accelerator include dibutyltin dilaurate.
Examples of the light stabilizer include hindered amine light stabilizers (for example, ADK STAB LA62, ADK STAB LA67 (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Tinuvin 765, Tinuvin 144, Tinuvin 770, Tinuvin 622 (above, Ciba For example, Tinuvin B75, Tinuvin PUR866 (above, trade name, manufactured by Ciba Japan Co., Ltd.) and the like.

Examples of the matting agent include ultra fine powder synthetic silica. If a matting agent is blended, an elegant semi-gloss and matte finish film can be formed.
In the oxygen acid of phosphorus or its derivative, examples of the oxygen acid of phosphorus include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, hypophosphoric acid, such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid. Examples thereof include condensed phosphoric acids such as acid and ultraphosphoric acid.

  Examples of phosphorus oxyacid derivatives include, for example, phosphates such as sodium and potassium or condensed phosphates such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, monophosphate orthophosphate. Monoesters such as 2-ethylhexyl, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, For example, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tripropyl orthophosphate, tributyl orthophosphate, tri-2-ethylhexyl orthophosphate, triphenyl orthophosphate, diphosphorous phosphite Chill, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, phosphorous acid Examples thereof include di- and triesters such as tributyl, tri-2-ethylhexyl phosphite and triphenyl phosphite, and mono-, di- and triesters obtained from condensed phosphoric acid and alcohols.

As the oxygen acid of phosphorus or its derivative, the above-mentioned various oxygen acids of phosphorus or their derivatives can be used alone or in combination of two or more kinds.
The silane coupling agent is, for example, structural formula R—Si≡ (X) ₃ or R—Si≡ (R ′) (X) ₂ (wherein R is a vinyl group, an epoxy group, an amino group, an imino group, An organic group having an isocyanate group or a mercapto group, R ′ represents a lower alkyl group having 1 to 4 carbon atoms, and X represents a methoxy group, an ethoxy group, or a chloro atom.

  Specific examples of the silane coupling agent include chlorosilanes such as vinyltrichlorosilane, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxy. Epoxy silanes such as cyclohexyl) ethyltrimethoxysilane, di (γ-glycidoxypropyl) dimethoxysilane, such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Aminosilanes such as N-β- (aminoethyl) -γ-propylmethyldimethoxysilane, n- (dimethoxymethylsilylpropyl) ethylenediamine, n- (triethoxysilylpropyl) ethylenediamine, N-phenyl-γ-aminopropyltrimethoxysilane For example, bi Vinylsilane such as Le triethoxysilane, for example, .gamma.-isocyanatopropyltrimethoxysilane, such as isocyanatosilanes such as .gamma.-isocyanatopropyltriethoxysilane and the like.

As the silane coupling agent, the various silane coupling agents described above can be used singly or in combination.
These functional compounding agents and additives may be blended in advance with the polyisocyanate composition and / or active hydrogen compound, or two-component curable polyurethane resin after blending the polyisocyanate composition and active hydrogen compound. It can also be blended.

When the polyurethane resin of the present invention is produced as a two-part curable polyurethane resin, a two-part curable polyurethane resin is prepared by blending a polyisocyanate composition and an active hydrogen compound at the time of use. Apply to paint or adherend.
The blending ratio of the polyisocyanate composition and the active hydrogen compound is, for example, as an equivalent ratio of the isocyanate group in the polyisocyanate composition to the active hydrogen group in the active hydrogen compound (NCO / active hydrogen group), for example, 0.5 -1.5, preferably 0.8-1.2.

And according to the polyurethane resin of this invention manufactured as a two-component curable polyurethane resin in this way, the coating film which is excellent in a mechanical physical property can be obtained.
Note that the two-component curable polyurethane resin is not particularly limited with respect to the object to be coated or the object to be adhered, for example, any coating such as spray coating, air spray coating, brush coating, dipping method, roll coater, or flow coater. It can be painted by the painting method.

Further, the material to be coated is not particularly limited, and for example, inorganic materials such as concrete, natural stone, and glass, for example, metals such as iron, stainless steel, aluminum, copper, brass, and titanium, such as plastic, rubber, and adhesive And organic materials such as wood.
Further, the adherend is not particularly limited, and examples thereof include various building materials and various laminated films.

More specifically, a packaging material such as a plastic film, a metal foil, and a metal vapor-deposited film, and a civil engineering material such as FRP and steel.
Furthermore, the polyurethane resin of the present invention is produced by a polymerization method such as bulk polymerization or solution polymerization, for example, in applications such as elastomer, in addition to being produced as a two-component curable polyurethane resin.

In bulk polymerization, for example, while stirring the polyisocyanate composition under a nitrogen stream, an active hydrogen compound is added thereto, and the reaction temperature is 50 to 250 ° C., more preferably 50 to 200 ° C., 0.5 to React for about 15 hours.
In solution polymerization, a polyisocyanate composition and an active hydrogen compound are added to the above-described organic solvent and reacted at a reaction temperature of 50 to 120 ° C., more preferably 50 to 100 ° C. for about 0.5 to 15 hours.

Furthermore, in the above polymerization reaction, for example, the above-mentioned known urethanization catalyst such as amines and organometallic compounds may be added as necessary, and (unreacted) polyisocyanate composition may be added. For example, you may remove by well-known removal means, such as distillation and extraction.
In bulk polymerization and solution polymerization, for example, an equivalent ratio of an isocyanate group in a polyisocyanate composition to an active hydrogen group (hydroxyl group, amino group) in an active hydrogen compound (NCO / activity) (Hydrogen group) is, for example, 0.75 to 1.3, preferably 0.9 to 1.1.

Further, when the polymerization reaction is carried out more industrially, the polyurethane resin can be obtained by a known method such as a one-shot method or a prepolymer method, depending on the application. Moreover, a polyurethane resin can also be obtained as an aqueous dispersion (PUD) etc. by another method.
In the one-shot method, for example, the polyisocyanate composition and the active hydrogen compound are converted into an equivalent ratio of the isocyanate group in the polyisocyanate composition to the active hydrogen group (hydroxyl group, amino group) in the active hydrogen compound (NCO / active hydrogen group). ) Is, for example, 0.75 to 1.3, preferably 0.9 to 1.1, and then, for example, room temperature to 250 ° C., preferably room temperature to 200 ° C. For example, the curing reaction is performed for 5 minutes to 72 hours, preferably 4 to 24 hours. The curing temperature may be a constant temperature, or may be raised or cooled stepwise.

  In the prepolymer method, for example, first, an isocyanate composition and a part of an active hydrogen compound (preferably, a high molecular weight polyol) are reacted to synthesize an isocyanate group-terminated prepolymer having an isocyanate group at the molecular terminal. . Next, the obtained isocyanate group-terminated prepolymer and the remainder of the active hydrogen compound (preferably, a low molecular weight polyol and / or polyamine component) are reacted to cause a curing reaction. In the prepolymer method, the remainder of the active hydrogen compound is used as a chain extender.

  To synthesize an isocyanate group-terminated prepolymer, the polyisocyanate composition and a portion of the active hydrogen compound are mixed with an equivalent ratio of isocyanate groups in the polyisocyanate composition to the active hydrogen groups in the portion of the active hydrogen compound (NCO). / Active hydrogen group) is, for example, 1.1-20, preferably 1.3-10, and more preferably 1.3-6, The reaction is carried out at room temperature to 150 ° C., preferably 50 to 120 ° C., for example, for 0.5 to 18 hours, preferably 2 to 10 hours. In this reaction, if necessary, the urethanization catalyst described above may be added, and after completion of the reaction, if necessary, unreacted polyisocyanate composition may be distilled or extracted, for example. It can also be removed by known removal means such as.

  Next, in order to react the obtained isocyanate group-terminated prepolymer with the remainder of the active hydrogen compound, the isocyanate group-terminated prepolymer and the remainder of the active hydrogen compound are reacted with the active hydrogen group in the remainder of the active hydrogen compound. It is formulated (mixed) so that the equivalent ratio of isocyanate groups (NCO / active hydrogen groups) in the isocyanate group-terminated prepolymer is, for example, 0.75 to 1.3, preferably 0.9 to 1.1. For example, the curing reaction is performed at room temperature to 250 ° C., preferably at room temperature to 200 ° C., for example, for 5 minutes to 72 hours, preferably for 1 to 24 hours.

In order to obtain a polyurethane resin as an aqueous dispersion, for example, first, an activity including a polyisocyanate composition and an active hydrogen compound containing a hydrophilic group described below (hereinafter abbreviated as a hydrophilic group-containing active hydrogen compound). By reacting with a hydrogen compound, an isocyanate group-terminated prepolymer is obtained.
Next, the obtained isocyanate group-terminated prepolymer and the chain extender are reacted and dispersed in water. Thus, an aqueous polyurethane resin in which the isocyanate group-terminated prepolymer is chain-extended with a chain extender can be obtained as an internal emulsion type aqueous dispersion.

In order to react the isocyanate group-terminated prepolymer and the chain extender in water, for example, first, the isocyanate group-terminated prepolymer is added to water to disperse the isocyanate group-terminated prepolymer. Next, a chain extender is added thereto to chain extend the isocyanate group-terminated prepolymer.
The hydrophilic group-containing active hydrogen compound is a compound having both a hydrophilic group and an active hydrogen group. Examples of the hydrophilic group include an anionic group (for example, carboxyl group), a cationic group, and a nonionic group (for example, And polyoxyethylene groups). More specifically, examples of the hydrophilic group-containing active hydrogen compound include a carboxylic acid group-containing active hydrogen compound, a polyoxyethylene group-containing active hydrogen compound, and the like.

  Examples of the carboxylic acid group-containing active hydrogen compound include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolbutyric acid. Dihydroxycarboxylic acids such as 2,2-dimethylolvaleric acid, diaminocarboxylic acids such as lysine and arginine, or metal salts and ammonium salts thereof.

The polyoxyethylene group-containing active hydrogen compound is a compound having a polyoxyethylene group in the main chain or side chain and having two or more active hydrogen groups, for example, polyethylene glycol, polyoxyethylene side chain-containing polyol ( And compounds having a polyoxyethylene group in the side chain and having two or more active hydrogen groups).
These hydrophilic group-containing active hydrogen compounds can be used alone or in combination of two or more.

As the chain extender, for example, low molecular weight polyols such as the above-described dihydric alcohols and trivalent alcohols described above, for example, diamines such as alicyclic diamines and aliphatic diamines can be used.
These chain extenders can be used alone or in combination of two or more.
Thus, when using the active hydrogen compound containing a hydrophilic group containing active hydrogen compound, a hydrophilic group is neutralized with a well-known neutralizing agent as needed.

  Further, when a hydrophilic group-containing active hydrogen compound is not used as the active hydrogen compound, it can be obtained as an external emulsion type aqueous dispersion by emulsifying using, for example, a known surfactant.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following description, “part” and “%” are based on mass unless otherwise specified. Moreover, the measuring method used for a manufacture example etc. is shown below.
<Isocyanate group concentration (unit: mass%)>
The isocyanate group concentration of the polyisocyanate composition was measured by an n-dibutylamine method according to JIS K-1556 using a potentiometric titrator.
<Concentration of isocyanate hydrolyzable chlorine (unit: ppm)>
The concentration of hydrolyzable chlorine contained in isocyanate (hereinafter abbreviated as HC) was measured in accordance with the test method for hydrolyzable chlorine described in Annex 3 of JIS K-1556 (2000). did.
<Viscosity measurement (unit: mPa · s)>
It measured at 25 degreeC using the Toki Sangyo Co., Ltd. E type viscometer TV-30.
<Conversion rate of isocyanate group (unit: mass%)>
The conversion rate of the isocyanate group was measured by GPC under the following conditions, and in the obtained chromatogram, the ratio of the peak area of the peak on the high molecular weight side relative to the peak of 1,5-pentamethylene diisocyanate to the total peak area, It was set as the conversion rate of the isocyanate group.

Apparatus; HLC-8020 (manufactured by Tosoh Corporation)
Column; G1000HXL, G2000HXL and G3000HXL (trade name, manufactured by Tosoh Corporation) connected in series Column temperature: 40 ° C
Eluent: Tetrahydrofuran Eluent flow rate: 0.8 mL / min
Detection method: Differential refractive index Standard material: Polyethylene oxide (manufactured by Tosoh, trade name: TSK standard polyethylene oxide)
(Production of 1,5-pentamethylene diisocyanate)
Production Example 1
A cold two-stage phosgenation method was carried out under pressure using 1,5-diaminopentane as a raw material.

  That is, 2000 parts by mass of orthodichlorobenzene was charged into a jacketed pressurized reactor equipped with an electromagnetic induction stirrer, an automatic pressure control valve, a thermometer, a nitrogen introduction line, a phosgene introduction line, a condenser, and a raw material feed pump. Subsequently, 2300 mass parts of phosgene was added from the phosgene introduction line, and stirring was started. Cold water was passed through the reactor jacket to maintain the internal temperature at about 10 ° C. A solution prepared by dissolving 400 parts by mass of 1,5-diaminopentane in 2600 parts by mass of orthodichlorobenzene was fed with a feed pump over 60 minutes, and cold phosgenation was started at 30 ° C. or lower and normal pressure. After the feed was completed, the inside of the pressurized reactor became a pale brown white slurry.

  Next, the internal liquid of the reactor was pressurized to 0.25 MPa while gradually raising the temperature to 160 ° C., and further subjected to thermal phosgenation at a pressure of 0.25 MPa and a reaction temperature of 160 ° C. for 90 minutes. During the thermal phosgenation, 1100 parts by mass of phosgene was further added. During the thermal phosgenation, the liquid in the pressurized reactor became a light brown clear solution. After the completion of the thermal phosgenation, nitrogen gas was aerated at 100 to 140 ° C. and degassed.

Then, after the solvent orthodichlorobenzene was distilled off under reduced pressure, 1,5-pentamethylene diisocyanate (hereinafter abbreviated as 1,5-PDI) was also distilled off under reduced pressure. At this time, the HC of 1,5-PDI was 2400 ppm.
Then, 1,5-PDI distilled off was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, and at 190 ° C. under normal pressure while introducing nitrogen. Heat treatment was performed for 3 hours. At this time, the HC of 1,5-PDI was 950 ppm.

  Next, 1,5-PDI after the heat treatment was charged into a glass flask, and a distillation tube filled with 4 elements of a packing (manufactured by Sumitomo Heavy Industries, Ltd., trade name: Sumitomo / Sulzer Lab Packing EX type). Using a distillation tower equipped with a reflux ratio adjustment timer (manufactured by Shibata Kagaku Co., Ltd., trade name: distillation head K type), and a rectifier equipped with a cooler, conditions of 127 to 132 ° C. and 2.7 KPa Then, rectification was conducted while further refluxing to obtain 480 parts by mass of 1,5-PDI.

The purity of the obtained 1,5-PDI as measured by gas chromatography was 99.9%, the hue as measured by APHA was 5, and HC was 21 ppm.
(Production of polyisocyanate composition)
Example 1
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 500 parts by mass of 1,5-PDI of Production Example, 4.90 parts by mass of isobutyl alcohol, 2,6-di ( tert-butyl) -4-methylphenol and 0.25 part by mass of tris (tridecyl) phosphite were charged and reacted at 80 ° C. for 3 hours. The isocyanate group concentration was 53.3% by mass. A solution was obtained. After the temperature of this solution was lowered to 65 ° C., 0.1 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added as an isocyanuration catalyst. After reacting for 1 hour, 0.25 part by mass of o-toluenesulfonamide was added (conversion rate of isocyanate group: 15% by mass). The obtained reaction liquid was passed through a thin film distillation apparatus (vacuum degree: 0.093 KPa, temperature: 150 ° C.) to remove unreacted 1,5-PDI, thereby obtaining a transparent polyisocyanate composition.

This polyisocyanate composition had an isocyanate group concentration of 25.6% by mass, a viscosity of 410 mPa · s, and an isocyanate monomer concentration of 0.42% by mass. Moreover, the compound concentration containing the sulfonamide group calculated | required from < ¹ > H-NMR measurement was 520 ppm.
Comparative Example 1
The same conditions and operation as in the examples except that instead of 1,5-PDI, 500 parts by mass of hexamethylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., trade name: Takenate 700, hereinafter abbreviated as HDI) was used. A transparent polyisocyanate composition was obtained.

This polyisocyanate composition had an isocyanate group concentration of 23.2% by mass, a viscosity of 600 mPa · s, and an isocyanate monomer concentration of 0.46% by mass. Moreover, the compound concentration containing the sulfonamide group calculated | required from < ¹ > H-NMR measurement was 560 ppm.
(Manufacture of polyurethane resin)
Preparation Example 1
The polyisocyanate composition obtained in Example 1 and acrylic polyol (trade name: Takelac UA-702, hereinafter abbreviated as UA-702, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) with respect to the hydroxyl group in the acrylic polyol. An isocyanate group equivalent ratio (NCO / OH) in the polyisocyanate composition was blended at a ratio of 1.0 and stirred at 23 ° C. for 90 seconds to obtain a reaction mixture. Next, this reaction mixture was applied to a standard test plate (type: electroplating tinplate, hereinafter abbreviated as test plate) in accordance with JIS G 3303, and then at 80 ° C. for 30 minutes and further at 110 ° C. It was cured for 1 hour to obtain a polyurethane resin having a thickness of about 45 μm.

The obtained polyurethane resin was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.
Preparation Example 2
The same conditions and operations as in Preparation Example 1 except that polyester polyol (Mitsui Chemicals Polyurethane Co., Ltd., trade name: Takelac U-27, hereinafter abbreviated as U-27) was used instead of UA-702. A polyurethane resin having a thickness of about 30 μm was obtained.

The obtained polyurethane resin was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.
Preparation Comparative Example 1
Instead of the polyisocyanate composition obtained in Example 1, a polyurethane resin was obtained under the same conditions and operation as in Preparation Example 1, except that the polyisocyanate composition obtained in Comparative Example 1 was used.

The obtained polyurethane resin was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.
Preparation Comparative Example 2
Instead of the polyisocyanate composition obtained in Example 1, a polyurethane resin was obtained under the same conditions and operations as in Preparation Example 2, except that the polyisocyanate composition obtained in Comparative Example 1 was used.

The obtained polyurethane resin was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.
Evaluation of physical properties The Martens hardness, breaking strength, solvent resistance, and scratch hardness of the polyurethane resins (hereinafter abbreviated as “coating films”) obtained in each of the preparation examples and the comparative preparation examples were measured by the following methods. The results are shown in Table 1.
<Martens hardness (unit: N / mm ² )>
Using an ultra-micro hardness tester (Shimadzu Corporation, DUH-211), the indentation type: Triangular 115, test mode: load-unloading test, test force: 10.00 mN The Martens hardness (HMT115) was measured under the conditions of a load speed of 3.0 mN / sec and a load holding time of 10 sec.
<Breaking strength (TS) (unit: MPa)>
The coating film was punched with a dumbbell into a size of 1 cm width and 10 cm length. Next, this test sample was subjected to a tensile test using a tensile / compression tester (Model 205N, manufactured by Intesco) under the conditions of 23 ° C., a tensile speed of 10 mm / min, and a distance between chucks of 50 mm. Thereby, the breaking strength (TS) was measured.
<Solvent resistance (unit: times)>
A cotton swab sufficiently impregnated with the test solution was placed on the coating film in intimate contact with the test plate, and reciprocated a distance of about 1 cm so that a constant load was applied. This operation was repeated, and when the coating film was observed to be damaged, the test was terminated. The outward path and the return path were each performed once, and the number of times until damage was observed in the coating film was defined as solvent resistance. The test solutions were ethyl acetate, toluene, and methyl ethyl ketone (hereinafter abbreviated as MEK).
<Scratch hardness>
The coating film in close contact with the test plate was tested in accordance with JIS K 5600-5-4 using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., model: No. 553-M1).

Details of the abbreviations in Table 1 are shown below.
UA-702: Acrylic polyol, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name: Takelac UA-702
U-27: Polyester polyol, Mitsui Chemicals Polyurethane Co., Ltd., trade name: Takelac U-27
MEK: Methyl ethyl ketone

Claims (6)

Substantially free of solvent,
Obtained by the isocyanuration reaction of pentamethylene diisocyanate,
Isocyanate group concentration exceeds 25% by mass and is 28% by mass or less ,
A polyisocyanate composition, wherein the concentration of hydrolyzable chlorine in pentamethylene diisocyanate is 100 ppm or less .   2. The polyisocyanate composition according to claim 1, wherein in the isocyanuration reaction, an alcohol having 1 to 20 carbon atoms is reacted with pentamethylene diisocyanate.   The polyisocyanate composition according to claim 1 or 2, comprising 10 to 5000 ppm of a compound containing a sulfonamide group.   A polyurethane resin obtained by reacting the polyisocyanate composition according to any one of claims 1 to 3 with an active hydrogen compound.   A hydrolyzable chlorine concentration reducing step for reducing the hydrolyzable chlorine concentration of pentamethylene diisocyanate to 100 ppm or less;
  An isocyanurate conversion step in which pentamethylene diisocyanate having a hydrolyzable chlorine concentration of 100 ppm or less is reacted with an isocyanurate in the presence of an isocyanurate conversion catalyst;
A process for producing a polyisocyanate composition, comprising:   6. The method for producing a polyisocyanate composition according to claim 5, wherein, in the hydrolyzable chlorine concentration reducing step, pentamethylene diisocyanate is heat-treated in the presence of an inert gas and then distilled.