JP2011201863A - Pentamethylene diisocyanate, polyisocyanate composition, method for preparing the pentamethylene diisocyanate and polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide pentamethylene diisocyanate enabling efficient preparation of a modified isocyanate and a polyurethane resin having excellent characteristics, a polyisocyanate resin obtained using the pentamethylene diisocyanate, a method for preparing the pentamethylene diisocyanate capable of preparing the pentamethylene diisocyanate, and a polyurethane resin obtained by using the pentamethylene diisocyanate or the polyisocyanate resin.SOLUTION: The pentamethylene diisocyanate is synthesized from pentamethylene diamine or a salt thereof, provided that the pentamethylene diamine contains ≤2 mass% nitrogen-containing 6-membered ring compound having a C=N bond.

Description

  The present invention relates to a pentamethylene diisocyanate, a polyisocyanate composition, a method for producing pentamethylene diisocyanate, and a polyurethane resin. It relates to a process and to polyurethane resins obtained from these pentamethylene diisocyanate or polyisocyanate compositions.

  Polyurethane resins are usually produced by the reaction of polyisocyanates and active hydrogen compounds, and are widely used in various industrial fields as, for example, paints, adhesives, elastomers and the like.

  As a polyisocyanate used for producing a polyurethane resin, for example, 1,5-pentamethylene diisocyanate is known. As a method for producing such 1,5-pentamethylene diisocyanate, for example, 1,5-diaminopentane is obtained from lysine (also known as lysine), and then 1,5-diaminopentane is converted to 1,5-pentane. Conversion to methylene diisocyanate has been proposed (see, for example, Patent Document 1).

  In Patent Document 1, 1,5-pentamethylene diisocyanate thus obtained is an isocyanate-modified product, more specifically, for example, a polyisocyanate having an isocyanurate group, an iminooxadiazinedione group, or the like. It is described that it is used for the production of (trimer body), polyisocyanate having an allophanate group (allophanate body) and the like.

  On the other hand, as a method of obtaining 1,5-diaminopentane from lysine, for example, lysine decarboxylase is allowed to act on lysine hydrochloride aqueous solution to convert lysine into 1,5-diaminopentane, and then the reaction obtained A method of adding chloroform to the liquid and extracting 1,5-diaminopentane to the chloroform phase has been proposed (see, for example, Patent Document 2).

Special table 2009-545553 JP 2003-292612 A

  However, in the method described in Patent Document 2, impurities such as 2,3,4,5-tetrahydropyridine are contained in the obtained 1,5-diaminopentane (see Patent Document 2 and Reference Example 2). ).

  Using 1,5-diaminopentane containing impurities, as described in Patent Document 1, 1,5-pentamethylene diisocyanate is produced, and the 1,5-pentamethylene diisocyanate is further reacted to modify the isocyanate. In the case of producing a product, the reaction rate of 1,5-pentamethylene diisocyanate is not sufficient, and a large amount of catalyst may be required. For example, storage stability may not be sufficiently ensured.

  Further, 1,5-pentamethylene diisocyanate obtained by the method described in Patent Documents 1 and 2 or an isocyanate-modified product obtained from 1,5-pentamethylene diisocyanate and an active hydrogen compound are reacted to produce polyurethane. Even in the case of producing a resin, the physical properties (for example, mechanical strength, chemical resistance, etc.) of the resulting polyurethane resin may not be sufficiently ensured.

  An object of the present invention is to provide a pentamethylene diisocyanate capable of efficiently producing an isocyanate-modified product and a polyurethane resin having excellent properties, a polyisocyanate composition obtained using the pentamethylene diisocyanate, and such a pentamethylene. Another object of the present invention is to provide a process for producing pentamethylene diisocyanate capable of producing diisocyanate, and further to provide a polyurethane resin obtained using the pentamethylene diisocyanate or polyisocyanate composition.

  In order to achieve the above object, the pentamethylene diisocyanate of the present invention is a pentamethylene diisocyanate synthesized from pentamethylenediamine or a salt thereof, and contains a C═N bond with respect to the total amount of pentamethylenediamine or a salt thereof. The content of the nitrogen six-membered ring compound is 2% by mass or less.

  In the pentamethylene diisocyanate of the present invention, the content of the nitrogen-containing six-membered ring compound having an amino group and a C═N bond with respect to the total amount of pentamethylenediamine or a salt thereof is 1.5% by mass or less. Is preferred.

  In the pentamethylene diisocyanate of the present invention, the nitrogen-containing six-membered ring compound having an amino group and a C═N bond is preferably 2- (aminomethyl) -3,4,5,6-tetrahydropyridine. It is.

  The pentamethylene diisocyanate of the present invention is preferably obtained by phosgenating pentamethylenediamine or a salt thereof.

  In addition, the pentamethylene diisocyanate of the present invention is obtained by carbamation and thermal decomposition of pentamethylenediamine or a salt thereof, and contains an antioxidant and an acidic compound and / or a compound having a sulfonamide group. Is preferred.

The polyisocyanate composition of the present invention is obtained by modifying the above pentamethylene diisocyanate, and is characterized by containing at least one of the following functional groups (a) to (e).
(A) isocyanurate group (b) allophanate group (c) biuret group (d) urethane group (e) urea group Moreover, the manufacturing method of the pentamethylene diisocyanate of this invention is manufacturing method of said pentamethylene diisocyanate, Further, pentamethylenediamine or a salt thereof is extracted with a non-halogen aliphatic organic solvent and then isisocyanated.

  In the method for producing pentamethylene diisocyanate according to the present invention, the non-halogen aliphatic organic solvent is preferably a linear monohydric alcohol having 4 to 7 carbon atoms.

  In the method for producing pentamethylene diisocyanate of the present invention, it is preferable to extract pentamethylenediamine or a salt thereof from an aqueous solution containing pentamethylenediamine or a salt thereof.

  In the method for producing pentamethylene diisocyanate of the present invention, it is preferable to obtain an aqueous solution containing pentamethylenediamine or a salt thereof by decarboxylase reaction of lysine or a salt thereof.

  The polyurethane resin of the present invention is obtained by reacting the above pentamethylene diisocyanate with an active hydrogen compound.

  The polyurethane resin of the present invention is characterized by being obtained by reacting the above polyisocyanate composition with an active hydrogen compound.

  The pentamethylene diisocyanate of the present invention does not contain a nitrogen-containing six-membered ring compound having a C═N bond, or is synthesized from pentamethylenediamine or a salt thereof whose content is reduced.

  Therefore, according to the pentamethylene diisocyanate of the present invention, an isocyanate-modified product having excellent properties can be produced efficiently.

  Moreover, according to the pentamethylene diisocyanate of this invention, the polyurethane resin provided with the outstanding property can also be manufactured.

  The polyisocyanate composition of the present invention can be obtained by trimming the above pentamethylene diisocyanate. Therefore, the polyisocyanate composition of the present invention can be produced efficiently and can have excellent storage stability.

  In the method for producing pentamethylene diisocyanate of the present invention, pentamethylenediamine or a salt thereof is extracted with a non-halogen aliphatic organic solvent.

  Therefore, according to the method for producing pentamethylene diisocyanate of the present invention, the content ratio of the nitrogen-containing six-membered ring compound having a C═N bond in pentamethylenediamine or a salt thereof can be reduced.

  As a result, according to the method for producing pentamethylene diisocyanate of the present invention, it is possible to produce pentamethylene diisocyanate capable of efficiently producing an isocyanate-modified product having excellent properties and a polyurethane resin having excellent properties. it can.

  Moreover, since the polyurethane resin of this invention is manufactured using the pentamethylene diisocyanate of this invention, or the polyisocyanate composition of this invention, it can be equipped with the outstanding property.

The chromatogram of GC-MS analysis 1 in the structural analysis of an unknown substance is shown. The spectrum of GC-MS analysis 1 in the structural analysis of an unknown substance is shown. The chromatogram of GC-MS analysis 2 in the structural analysis of an unknown substance is shown. The result of ¹ H-NMR in the structural analysis of the unknown substance is shown. The result of ¹³ C-NMR in the structural analysis of the unknown substance is shown. The result of COSY in the structural analysis of an unknown substance is shown. The result of HMQC in the structural analysis of an unknown substance is shown. The result of HMBC in the structural analysis of an unknown substance is shown. The result (enlarged view) of HMBC in the structural analysis of an unknown substance is shown.

  The pentamethylene diisocyanate (PDI) of the present invention is synthesized from pentamethylenediamine (PDA) or a salt thereof, and is produced, for example, by the following method for producing pentamethylene diisocyanate.

  That is, in this method, first, pentamethylenediamine or a salt thereof is produced.

  Examples of pentamethylenediamine include 1,5-pentamethylenediamine (also known as cadaverine, 1,5-diaminopentane), 1,4-pentamethylenediamine, 1,3-pentamethylenediamine, and 2,5-pentamethylene. Examples thereof include diamines and mixtures thereof.

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

  As the pentamethylenediamine, 1,5-pentamethylenediamine is preferable.

  Examples of the salt of pentamethylenediamine include, for example, carboxylate (eg, acetate, oxalate, 2-ethylhexanoate, stearate), sulfonate, etc. Organic acid salts, for example, inorganic acid salts such as nitrates, sulfates, hydrochlorides, phosphates, carbonates, bicarbonates, and the like.

  As the salt of pentamethylenediamine, preferably, the hydrochloride of pentamethylenediamine is used.

  Such pentamethylenediamine or a salt thereof is extracted from, for example, an aqueous solution containing pentamethylenediamine or a salt thereof (hereinafter referred to as a pentamethylenediamine aqueous solution).

  As such pentamethylenediamine or a salt thereof, preferably, pentamethylenediamine is used.

  The pentamethylenediamine aqueous solution is not particularly limited, and can be obtained, for example, by decarboxylase reaction of lysine in water.

  Hereinafter, the decarboxylase reaction of lysine will be described in detail.

In lysine decarboxylase reaction, lysine decarboxylase is allowed to act on lysine (chemical formula: NH ₂ (CH ₂ ) ₄ CH (NH ₂ ) COOH, also known as: 1,5-pentamethylenediamine-1-carboxylic acid). .

  Examples of lysine include L-lysine.

  As lysine, a salt of lysine can also be used.

  Examples of lysine salts include carboxylate (for example, acetate, oxalate, 2-ethylhexanoate, stearate, etc.), organic acid salt such as sulfonate, for example, nitrate, sulfate, Examples thereof include inorganic acid salts such as hydrochloride, phosphate, carbonate, and bicarbonate.

  As a salt of lysine, lysine hydrochloride is preferable.

  Examples of such lysine hydrochloride include L-lysine monohydrochloride.

  The concentration of lysine (or a salt thereof) is not particularly limited, but is, for example, 10 to 700 g / L, preferably 20 to 500 g / L.

  The lysine decarboxylase is an enzyme that converts lysine (or a salt thereof) to pentamethylenediamine (or a salt thereof), and is not particularly limited, and examples thereof include those derived from known organisms. More specific examples of lysine decarboxylase include, for example, Bacillus halodurans, Bacillus subtilis, Escherichia coli, Selenomonas luminobis, and Selenomonas luminobia. (Vibrio cholerae), Vibrio parahaemolyticus, Streptomyces coelicolor, Streptomyces pirosus (St), and Streptomyces pirosus (St). Cuterium acididaminofilm, Salmonella typhimurium, Hafnia albei, Neisseria meningitide Examples include those derived from microorganisms such as Pyrococcus abyssi) or Corynebacterium glutamicum. From the viewpoint of safety, preferably, those derived from Escherichia coli are used.

  Lysine decarboxylase can be produced by a known method, for example, according to the description in JP-A No. 2004-114 (for example, paragraph numbers [0015] to [0042], etc.).

  More specifically, as a method for producing lysine decarboxylase, for example, recombinant cells in which lysine decarboxylase is highly expressed in cells (hereinafter referred to as internal expression cells) are cultured in a known medium, and then proliferated. A method of recovering and disrupting the internally expressed cells, for example, a recombinant cell in which lysine decarboxylase is localized on the cell surface (hereinafter referred to as a surface-expressing cell) is cultured in a known medium, and then proliferated surface expression Examples include a method of recovering cells and crushing them if necessary.

  In such a method, the recombinant cell is not particularly limited, and examples include those derived from microorganisms, animals, plants, or insects. More specifically, for example, when animals are used, examples include mice, rats and cultured cells thereof, and when plants are used, examples include Arabidopsis, tobacco and cultured cells thereof. In addition, in the case of using insects, for example, silkworms and cultured cells thereof can be mentioned, and in the case of using microorganisms, for example, Escherichia coli and the like can be mentioned.

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

  The method for localizing lysine decarboxylase on the surface of a recombinant cell is not particularly limited. For example, a part of a secretory signal sequence, a gene sequence encoding a part of a cell surface localized protein, and lysine A known method such as a method of introducing DNA having a decarboxylase structural gene sequence in this order into E. coli can be employed.

  The secretory signal sequence is not particularly limited as long as it is a sequence necessary for secreting the protein in the host. For example, in Escherichia coli, for example, a part of the lipoprotein sequence, more specifically, Examples of the amino acid sequence include a gene sequence translated as MKATKLVLGAVILGSTLLAGCSSSNAKIDQ (single letter code of amino acid).

  The gene sequence encoding a part of the cell surface localized protein is not particularly limited. In E. coli, for example, a part of the sequence of the outer membrane-bound protein can be mentioned, and more specifically, for example, OmpA ( And a part of the sequence from the 46th amino acid to the 159th amino acid of the outer membrane binding protein).

  The method for cloning the lysine decarboxylase gene, lipoprotein gene, and OmpA gene is not particularly limited. For example, based on known gene information, a necessary genetic region is amplified and obtained using the PCR (polymerase chain reaction) method. For example, based on known gene information, a method of cloning from a genomic library or cDNA library using homology or enzyme activity as an index may be mentioned.

  These genes also include mutated genes due to genetic polymorphism (those in which the base sequence of the gene is partially changed due to natural mutation on the gene).

  More specifically, for example, the cadA gene or the ldc gene, which is a gene encoding lysine decarboxylase, is cloned from the chromosomal DNA of Escherichia coli K12 using the PCR method. In addition, the chromosome DNA employ | adopted at this time will not be restrict | limited if it is Escherichia coli origin, The thing derived from arbitrary strains can be employ | adopted.

  In addition, lysine decarboxylase is localized on the surface of the surface-expressing cells obtained in this way, for example, after surface-expressing cells are immunoreacted with an antibody prepared using lysine decarboxylase as an antigen. It can be confirmed by embedding and slicing, for example, by observing with an electron microscope (immunoelectron microscopy).

  In the surface-expressing cells, lysine decarboxylase may be localized on the cell surface. For example, lysine decarboxylase may be localized on the cell surface and expressed inside the cell.

  Examples of the lysine decarboxylase include those prepared from recombinant cells in which the activity of lysine decarboxylase in the cells and / or on the cell surface is increased.

  The method for increasing the activity of lysine decarboxylase in the cell and / or on the cell surface is not particularly limited, and for example, a method for increasing the amount of lysine decarboxylase, for example, intracellular of lysine decarboxylase and And / or a method for increasing the activity on the cell surface.

  Examples of means for increasing the amount of enzyme in the cell or on the cell surface include improvement of the transcriptional regulatory region of the gene, increase in the copy number of the gene, and efficient translation into the protein.

  Improving the transcriptional regulatory region means adding a modification that increases the transcription amount of the gene. For example, the promoter is strengthened by introducing a mutation into the promoter, and the transcription amount of the downstream gene is increased. it can. In addition to introducing a mutation into the promoter, a promoter that is strongly expressed in the host can also be introduced. More specifically, examples of the promoter include lac, tac, trp and the like in E. coli. In addition, the amount of gene transcription can be increased by newly introducing an enhancer. The introduction of a gene such as a chromosomal DNA promoter can be based on, for example, the description of JP-A-1-215280.

  Specifically, the increase in the copy number of a gene can be achieved by connecting the gene to a multi-copy vector to produce a recombinant DNA and allowing the host cell to hold the recombinant DNA. Vectors include those widely used, such as plasmids and phages, but besides these, for example, transposon (Berg, DE and Berg. CM, Bio / Technol., Vol. 1, P.417 (1983)) and Mu phage (Japanese Patent Laid-Open No. 2-109985). Furthermore, the number of copies can be increased by incorporating the gene into the chromosome by a method using a plasmid for homologous recombination.

  As a method for increasing the translation efficiency of a protein, for example, in prokaryotes, an SD sequence (Shine, J. and Dalgarno, L., Proc. Natl. Acad. Sci. USA, 71, 1342-1346 (1974)) In eukaryotes, Kozak consensus sequences (Kozak, M., Nuc. Acids Res., Vol. 15, p. 8125-8148 (1987)) are introduced and modified, and codon optimization (special No. 59-125895).

  As a method for increasing the intracellular and / or cell surface activity of lysine decarboxylase, a mutation may be introduced into the structural gene itself of lysine decarboxylase to increase the activity of lysine decarboxylase itself. It is done.

  Examples of methods for causing mutations in genes include site-specific mutagenesis (Kramer, W. and frita, HJ, Methods in Enzymology, vol. 154, P. 350 (1987)), recombinant PCR method ( PCR Technology, Stockton Press (1989), a method of chemically synthesizing a specific portion of DNA, a method of treating a gene with a hydroxylamine, a strain carrying the gene with ultraviolet irradiation, or a chemical agent such as nitrosoguanidine or nitrous acid The method of processing is mentioned.

  In addition, the method for culturing such recombinant cells (internally expressed cells, surface-expressing cells, etc.) is not particularly limited, and known methods can be employed. More specifically, for example, when culturing a microorganism, a medium containing, for example, a carbon source, a nitrogen source, and inorganic ions is used as the medium.

  Examples of the carbon source include sugars such as glucose, lactose, galactose, fructose, arabinose, maltose, xylose, trehalose, ribose and starch hydrolysate, for example, alcohols such as glycerol, mannitol and sorbitol, for example, gluconic acid , Organic acids such as fumaric acid, citric acid and succinic acid.

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

  Examples of the nitrogen source include inorganic ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium phosphate, and organic nitrogen such as soybean hydrolysate, such as ammonia gas and aqueous ammonia.

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

  Examples of the inorganic ions include sodium ions, magnesium ions, potassium ions, calcium ions, chlorine ions, manganese ions, iron ions, phosphate ions, and sulfate ions.

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

Moreover, the medium, if necessary, can also be added other organic components (organic trace nutrients), Examples of such organic components, for example, various amino acids, for example, vitamins such as vitamin B _1, For example, required substances such as nucleic acids such as RNA, and further, for example, yeast extract.

  More specifically, such a medium includes LB medium.

  The culture conditions are not particularly limited. For example, when culturing E. coli, the culture temperature is, for example, 30 to 45 ° C., preferably 30 to 40 ° C., and the culture pH is aerobic. For example, it is 5 to 8, preferably 6.5 to 7.5, and the culture time is, for example, 16 to 72 hours, preferably 24 to 48 hours. For adjusting the pH, for example, an inorganic or organic acidic or alkaline substance, ammonia gas, or the like can be used.

  Recombinant cells (internally expressed cells, surface-expressing cells) grown in such a medium can be collected by, for example, centrifugation.

  In this method, the collected cells can be used as, for example, resting cells. However, if necessary, they can be crushed and used as a cell lysate (bacterial cell lysate).

  In preparing the cell disruption solution (bacterial cell disruption solution), a known method can be employed. More specifically, for example, the obtained internal expression cells and / or surface expression cells are first crushed by a method such as sonication, dynomill, French press, etc., and then cell debris is removed by centrifugation. To do.

  In this method, lysine decarboxylase can be purified from the obtained cell lysate, if necessary.

  The purification method of lysine decarboxylase is not particularly limited, and is a known method usually used for enzyme purification (for example, ammonium sulfate fractionation, ion exchange chromatography, hydrophobic chromatography, affinity chromatography, gel filtration chromatography, Isoelectric point precipitation, heat treatment, pH treatment, etc.) can be employed in combination as appropriate.

  In the decarboxylase reaction of lysine (or a salt thereof), the resting cells and / or cell lysate thus obtained are mixed with an aqueous solution of lysine (or a salt thereof), and the lysine desorbed in water. Carbonate acts on lysine (or its salt).

  The ratio of the dry cell equivalent mass of the cells (cells) used for the reaction to the total mass of lysine (or its salt) used for the reaction is that lysine (or its salt) is converted to pentamethylenediamine (or its salt). The amount is not particularly limited as long as it is sufficient for conversion, but is, for example, 0.01 or less, preferably 0.007 or less.

  The total mass of lysine (or salt thereof) used in the reaction is the mass of lysine (or salt thereof) present in the reaction system at the start of the reaction (lysine (or salt thereof) is added to the reaction system during the reaction) In some cases, the total amount of those lysines (or their salts).

  Moreover, the dry cell equivalent mass of a microbial cell is the mass of the microbial cell which dries and does not contain a water | moisture content. The dry cell equivalent mass of the bacterial cell is, for example, separated from the liquid containing the bacterial cell (bacterial cell liquid) by a method such as centrifugation or filtration, dried until the mass becomes constant, and the mass is measured. Can be obtained.

  The reaction temperature in the decarboxylase reaction of lysine (or a salt thereof) is, for example, 28 to 55 ° C., preferably 35 to 45 ° C., and the reaction time varies depending on the type of lysine decarboxylase employed. For example, it is 1 to 72 hours, preferably 12 to 36 hours. Moreover, reaction pH is 5.0-8.0, for example, Preferably, it is 5.5-6.5.

  Thereby, lysine (or a salt thereof) undergoes a decarboxylase reaction to be converted into pentamethylenediamine, and as a result, an aqueous solution of pentamethylenediamine is obtained.

  The reaction yield of pentamethylenediamine or a salt thereof is, for example, 10 to 100 mol%, preferably 70 to 100 mol%, more preferably 80 to 100 mol%, based on lysine (or a salt thereof). .

  Further, the concentration of pentamethylenediamine or a salt thereof in the aqueous solution of pentamethylenediamine (in the case of pentamethylenediamine salt, the concentration in terms of pentamethylenediamine) is, for example, 1 to 70% by mass, preferably 2 to 50% by mass, and more preferably. Is 5-40 mass%.

  In this reaction, since the obtained pentamethylenediamine is alkaline, the pH of the reaction solution may increase as lysine (or a salt thereof) is converted to pentamethylenediamine (or a salt thereof). In such a case, if necessary, an acidic substance (for example, an organic acid, for example, an inorganic acid such as hydrochloric acid) can be added to adjust the pH.

In this reaction, for example, vitamin B ₆ and / or a derivative thereof can be added to the reaction solution as necessary.

Examples of vitamin B ₆ and / or derivatives thereof include pyridoxine, pyridoxamine, pyridoxal, pyridoxal phosphate, and the like.

These vitamin B ₆ and / or derivatives thereof can be used alone or in combination of two or more.

Vitamin B ₆ and / or its derivatives are preferably pyridoxal phosphate.

By adding vitamin of B ₆ and / or its derivatives, it is possible to improve the production rate and yield of pentamethylene diamine.

  In this method, if necessary, a part of water is distilled off from the obtained pentamethylenediamine aqueous solution, and then pentamethylenediamine or a salt thereof is extracted. In extraction, for example, a liquid-liquid extraction method is employed.

  More specifically, for example, an aqueous pentamethylenediamine solution is heated (heat treated) under a pressure of 0.1 kPa to normal pressure by a distillation apparatus equipped with a continuous multistage distillation column, a batch multistage distillation column, etc. A pentamethylenediamine aqueous solution in which a part of is distilled off is obtained.

  The heating temperature is, for example, 25 ° C. or more and less than 90 ° C., preferably 25 ° C. or more and 85 ° C. or less, more preferably 25 ° C. or more and less than 80 ° C., more preferably 30 ° C. or more and 70 ° C. or less. is there.

  When the aqueous solution of pentamethylenediamine is heated at 90 ° C. or higher (heat treatment), the content of a nitrogen-containing six-membered ring compound having a C═N bond (described later) relative to the total amount of pentamethylenediamine or a salt thereof increases. The extraction rate of pentamethylenediamine or a salt thereof may decrease.

  Therefore, preferably, the aqueous solution of pentamethylenediamine is not heated (heat treatment) at 90 ° C. or higher, more preferably, it is not heated at 80 ° C. or higher, and more preferably, the aqueous solution of pentamethylene diamine is heated (heat treatment). Instead, as described later, pentamethylenediamine or a salt thereof is extracted as it is from the aqueous solution.

  In the pentamethylenediamine aqueous solution, the concentration of pentamethylenediamine is, for example, 5 to 80% by mass, preferably 15 to 60% by mass with respect to the total amount of the pentamethylenediamine aqueous solution.

  In the liquid-liquid extraction method, an extraction solvent (described later) is brought into contact with a pentamethylenediamine aqueous solution, and mixed and stirred to convert pentamethylenediamine or a salt thereof in the pentamethylenediamine aqueous solution into the extraction solvent (described later). Extract.

  The blending ratio of the pentamethylenediamine aqueous solution and the extraction solvent (described later) in the liquid-liquid extraction is such that the extraction solvent (described later) is, for example, 30 to 300 parts by mass with respect to 100 parts by mass of the pentamethylenediamine aqueous solution, It is 50-200 mass parts, More preferably, it is 60-150 mass, Especially preferably, it is 80-120 mass parts.

  In liquid-liquid extraction, an aqueous pentamethylenediamine solution and an extraction solvent (described later) are, for example, under normal pressure (atmospheric pressure), for example, 5 to 60 ° C., preferably 10 to 50 ° C., more preferably, At 15 to 40 ° C., for example, mixing is performed for 1 to 120 minutes, preferably 5 to 90 minutes, and more preferably 5 to 60 minutes.

  Thereby, pentamethylenediamine or a salt thereof is extracted into an extraction solvent (described later).

  Next, in this method, a mixture of pentamethylenediamine or a salt thereof and an extraction solvent (described later) is allowed to stand, for example, for 5 to 300 minutes, and then the extraction solvent from which pentamethylenediamine or a salt thereof has been extracted (that is, An extraction solvent (described later) and a mixture of pentamethylenediamine or a salt thereof are taken out by a known method.

  When pentamethylenediamine or a salt thereof cannot be sufficiently extracted by one liquid-liquid extraction, liquid-liquid extraction can be repeated a plurality of times (for example, 2 to 5 times).

  In the liquid-liquid extraction method, for example, pentamethylenediamine or a salt thereof can be continuously extracted using an extraction tower or the like. Examples of such an extraction tower include an extraction tower in which dozens of shelves are incorporated inside the tower, and an extraction tower having a rotating disk type shelf.

  Thereby, the pentamethylenediamine or its salt in the pentamethylenediamine aqueous solution can be extracted into an extraction solvent (described later).

  In the extraction solvent thus obtained (a mixture of the extraction solvent (described later) and pentamethylenediamine or a salt thereof), the concentration of pentamethylenediamine or a salt thereof is, for example, 0.2 to 40% by mass, preferably It is 0.3-35 mass%, More preferably, it is 0.4-30 mass%, Most preferably, it is 0.8-25 mass%.

  Moreover, the yield (extraction rate) of pentamethylenediamine or a salt thereof after extraction is, for example, 65 to 100 mol%, preferably 70 to 100 mol%, more preferably based on lysine (or a salt thereof). 80 to 100 mol%, particularly preferably 90 to 100 mol%.

  In this method, if necessary, the extraction solvent (described later) is removed from the mixture of the obtained extraction solvent (described later) and pentamethylenediamine or a salt thereof by a known method such as vacuum distillation, for example. A diamine or a salt thereof can also be isolated.

  In such extraction, examples of the extraction solvent include non-halogen organic solvents.

  Non-halogen organic solvents are organic solvents that do not contain halogen atoms (fluorine, chlorine, bromine, iodine, etc.) in their molecules, such as non-halogen aliphatic organic solvents, non-halogen alicyclic organic solvents, Non-halogen aromatic organic solvents are exemplified.

  Examples of non-halogen aliphatic organic solvents include linear non-halogen aliphatic organic solvents and branched non-halogen aliphatic organic solvents.

  Examples of the linear non-halogen aliphatic organic solvent include linear non-halogen aliphatic hydrocarbons, linear non-halogen aliphatic ethers, and linear non-halogen aliphatic alcohols. Is mentioned.

  Examples of linear non-halogen aliphatic hydrocarbons include n-hexane, n-heptane, n-nonane, n-decane, and n-dodecane.

  Examples of linear non-halogen aliphatic ethers include diethyl ether, dibutyl ether, dihexyl ether, and the like.

  Examples of linear non-halogen aliphatic alcohols include linear monohydric alcohols having 1 to 3 carbon atoms (for example, methanol, ethanol, n-propanol, isopropanol, etc.), linear carbon atoms of 4 To 7 monohydric alcohols (eg, n-butanol, n-pentanol, n-hexanol, n-heptanol, etc.), linear monohydric alcohols having 8 or more carbon atoms (eg, n-octanol, n-nonanol) , N-decanol, n-undecanol, n-dodecanol, etc.).

  Examples of branched non-halogen aliphatic organic solvents include branched non-halogen aliphatic hydrocarbons, branched non-halogen aliphatic ethers, branched non-halogen aliphatic monohydric alcohols, branched Non-halogen aliphatic polyhydric alcohols.

  Examples of branched non-halogen aliphatic hydrocarbons include 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, and 2,3-dimethylpentane. 2,4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethylhexane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2 , 4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 2-methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2 , 3,3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3,3-tetramethylbutane, 2,2,5-trimethylhexane, etc. It is.

  Examples of branched non-halogen aliphatic ethers include diisopropyl ether and diisobutyl ether.

  Examples of branched non-halogen aliphatic monohydric alcohols include branched monohydric alcohols having 4 to 7 carbon atoms (for example, 2-butanol, isobutanol, tert-butanol, 2-pentanol, 3-pentane). Tanol, isopentanol, 2-methyl-1-butanol, 2-methyl-3-butanol, 2,2-dimethyl-1-propanol, tert-pentanol, 2-hexanol, 3-hexanol, isohexanol, 2- Methyl-2-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, 3,3-dimethyl-1-butanol, 2-heptanol, 3-heptanol 4-heptanol, 5-methyl-1-hexanol, 4-methyl-1-hexanol, 3-methyl-1-he Sanol, 2-ethyl-2-methyl-1-butanol, etc., branched monohydric alcohols having 8 or more carbon atoms (for example, isooctanol, isononanol, isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2 -Hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, etc.).

  Examples of the branched non-halogen aliphatic polyhydric alcohols include 2-ethyl-1,3-hexanediol.

  These non-halogen aliphatic organic solvents can be used alone or in combination of two or more.

  The non-halogen aliphatic organic solvent is preferably a linear non-halogen aliphatic organic solvent, and more preferably a linear non-halogen aliphatic alcohol.

  When straight chain non-halogen aliphatic alcohols are used, pentamethylenediamine can be extracted in high yield.

  The non-halogen aliphatic organic solvent is preferably a monohydric alcohol having 4 to 7 carbon atoms (a linear monohydric alcohol having 4 to 7 carbon atoms or a branched monohydric alcohol having 4 to 7 carbon atoms). ).

  When a monohydric alcohol having 4 to 7 carbon atoms is used, pentamethylenediamine or a salt thereof can be efficiently extracted. Further, impurities of pentamethylenediamine or a salt thereof (nitrogen-containing six-membered having a C = N bond) The content ratio of the ring compound (described later) can be reduced.

  Examples of the non-halogen alicyclic organic solvent include non-halogen alicyclic hydrocarbons (for example, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, bicyclohexyl, etc.). .

  These non-halogen alicyclic organic solvents can be used alone or in combination of two or more.

  Non-halogen aromatic organic solvents include, for example, non-halogen aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, isopropylbenzene, 1,3,5-trimethylbenzene, 1,2,3,4- Tetrahydronaphthalene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, ethylbenzene and the like) and phenols (for example, phenol and cresol).

  These non-halogen aromatic organic solvents can be used alone or in combination of two or more.

  Examples of the non-halogen organic solvent include a mixture of aliphatic hydrocarbons and aromatic hydrocarbons. Examples of such a mixture include petroleum ether and petroleum benzine.

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

  As the extraction solvent, for example, a halogen-based organic solvent (an organic solvent containing a halogen atom in the molecule) can be used as long as the excellent effects of the present invention are not impaired.

  Examples of the halogen-based organic solvent include halogen-based aliphatic hydrocarbons (for example, chloroform, dichloromethane, carbon tetrachloride, tetrachloroethylene), halogen-based aromatic hydrocarbons (for example, chlorobenzene, dichlorobenzene, chlorotoluene, etc.) Etc.

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

  On the other hand, when a halogen-based organic solvent is used as the extraction solvent, the content of a nitrogen-containing six-membered ring compound (described later) having a C═N bond may increase with respect to the total amount of pentamethylenediamine or a salt thereof obtained. .

  In such a case, as will be described in detail later, pentamethylene diisocyanate (described later) is produced using the pentamethylenediamine or a salt thereof, and the pentamethylene diisocyanate (described later) is further reacted to produce an isocyanate-modified product. In the case of producing a polyurethane resin (described later) or a polyurethane resin (described later), the productivity and physical properties (for example, yellowing resistance) of the isocyanate-modified product (described later) may be inferior.

  Also, when a polyurethane resin is produced by reacting such a pentamethylene diisocyanate (described later) or an isocyanate-modified product (described later) with an active hydrogen compound (described later), the physical properties of the resulting polyurethane resin (for example, , Mechanical strength, chemical resistance, etc.).

  Therefore, the extraction solvent is preferably a non-halogen organic solvent, more preferably a non-halogen aliphatic organic solvent.

  When pentamethylenediamine or a salt thereof is extracted with a non-halogen aliphatic organic solvent, the content ratio of a nitrogen-containing six-membered ring compound (described later) having a C = N bond in pentamethylenediamine or a salt thereof is reduced. be able to.

  Therefore, in the case of producing pentamethylene diisocyanate using such pentamethylenediamine or a salt thereof, an isocyanate-modified product having excellent properties and a polyurethane resin having excellent properties can be efficiently produced. Pentamethylene diisocyanate can be produced.

  Moreover, in this invention, the boiling point of an extraction solvent is 60-250 degreeC, for example, Preferably, it is 80-200 degreeC, More preferably, it is 90-150 degreeC.

  When the boiling point of the extraction solvent is less than the above lower limit, separation from the extraction solvent may be difficult when pentamethylenediamine or a salt thereof is obtained by extraction from an aqueous pentamethylenediamine solution.

  On the other hand, when the boiling point of the extraction solvent exceeds the above upper limit, when obtaining pentamethylenediamine or a salt thereof from a mixture of the extraction solvent and pentamethylenediamine or a salt thereof, energy consumption in the separation step may increase. .

  Further, the method for obtaining pentamethylenediamine or a salt thereof from an aqueous pentamethylenediamine solution is not limited to the above extraction, and a known isolation and purification method such as distillation can also be employed.

  The pentamethylenediamine or salt thereof thus obtained does not contain a nitrogen-containing six-membered ring compound having a C═N bond (hereinafter sometimes referred to as C═N six-membered ring compound), Or the content is reduced.

  Examples of the C═N six-membered ring compound include a nitrogen-containing six-membered ring compound having an amino group and a C═N bond (hereinafter, sometimes referred to as an amino group-containing C═N six-membered ring compound), C. And a nitrogen-containing six-membered ring compound having an N bond and no amino group (hereinafter referred to as an amino group-free C = N six-membered ring compound).

  Examples of the amino group-containing C═N six-membered ring compound include compounds represented by the following formula (1).

(In the formula, X represents an aminomethyl group.)
More specifically, examples of the compound represented by the formula (1) include 2- (aminomethyl) -3,4,5,6-tetrahydropyridine.

  Examples of the amino group-free C═N six-membered ring compound include 2,3,4,5-tetrahydropyridine.

  In the present invention, the total amount of pentamethylenediamine or a salt thereof (pentamethylenediamine or a salt thereof and impurities (including an amino group-containing C = N six-membered ring compound and an amino group-free C = N six-membered ring compound) The content of these C = N six-membered ring compounds with respect to the total amount) (the total amount of amino group-containing C = N six-membered ring compounds and amino group-free C = N six-membered ring compounds) is 2% by mass or less, Preferably, it is 1.8 mass% or less, More preferably, it is 1.5 mass% or less, Most preferably, it is 1.2 mass% or less.

  When the content of the C = N six-membered ring compound exceeds the above upper limit, pentamethylene diisocyanate (described later) is produced using the pentamethylenediamine or a salt thereof, and the pentamethylene diisocyanate (described later) is further added. In the case of producing an isocyanate-modified product (described later) by reacting, the reaction rate of pentamethylene diisocyanate (described later) is not sufficient, and a large amount of catalyst may be required. In some cases, sufficient properties (for example, storage stability) of an isocyanate-modified product (described later) cannot be ensured.

  Also, when a polyurethane resin (described later) is produced by reacting pentamethylene diisocyanate (described later) or an isocyanate-modified product (described later) with an active hydrogen compound, the physical properties of the resulting polyurethane resin (described later) ( For example, mechanical strength, chemical resistance, etc.) may not be sufficiently ensured.

  On the other hand, if the content of the C = N six-membered ring compound is not more than the above upper limit, an isocyanate-modified product (described later) or a polyurethane resin (described later) having excellent properties can be produced efficiently. .

  The content of the amino group-containing C = N six-membered ring compound with respect to the total amount of pentamethylenediamine or a salt thereof is, for example, 1.5% by mass or less, preferably 1.2% by mass or less, more preferably 1% by mass or less, particularly preferably 0.8% by mass or less.

  Even when the content of the amino group-containing C = N six-membered ring compound exceeds the above upper limit, the pentamethylene diisocyanate (described later) is produced using the pentamethylenediamine or a salt thereof in the same manner as described above. Furthermore, in the case of producing an isocyanate-modified product (described later) by reacting the pentamethylene diisocyanate (described later), the reaction rate of pentamethylene diisocyanate (described later) is not sufficient, and a large amount of catalyst is required. In some cases, physical properties (for example, storage stability) of the resulting isocyanate-modified product (described later) may not be sufficiently ensured.

  Also, when a polyurethane resin (described later) is produced by reacting pentamethylene diisocyanate (described later) or an isocyanate-modified product (described later) with an active hydrogen compound, the physical properties of the resulting polyurethane resin (described later) ( For example, mechanical strength, chemical resistance, etc.) may not be sufficiently ensured.

  On the other hand, if the content of the amino group-containing C = N six-membered ring compound is less than or equal to the above upper limit, it will be described in detail later, but it is an isocyanate-modified product (described later) having an efficient and excellent property, and a polyurethane resin. (Described later) can be manufactured.

  The content of the amino group-free C═N six-membered ring compound with respect to the total amount of pentamethylenediamine or a salt thereof is, for example, 0.5% by mass or less, preferably 0.4% by mass or less, more preferably 0.3 mass% or less, particularly preferably 0.2 mass% or less.

  When the content of the amino group-free C = N six-membered ring compound exceeds the above upper limit, pentamethylene diisocyanate (described later) produced using the pentamethylenediamine or salt thereof, or pentamethylene diisocyanate (described later). ), The physical properties (for example, mechanical strength, chemical resistance, etc.) of the polyurethane resin (described later) obtained by reacting the resulting isocyanate-modified product (described later) with the active hydrogen compound cannot be sufficiently secured. There is.

  In this method, pentamethylene diisocyanate is synthesized from pentamethylenediamine or a salt thereof obtained as described above.

  As a method for synthesizing pentamethylene diisocyanate, for example, a method of phosgenating pentamethylenediamine or a salt thereof (hereinafter sometimes referred to as a phosgenation method), a pentamethylenediamine or a salt thereof is carbamate, and then And a method of thermal decomposition (hereinafter sometimes referred to as a carbamate method).

  More specifically, as the phosgenation method, for example, a method in which pentamethylenediamine is directly reacted with phosgene (hereinafter sometimes referred to as a cold two-stage phosgenation method), or a hydrochloride of pentamethylenediamine is inactive. Examples thereof include a method of suspending in a solvent (described later) and reacting with phosgene (hereinafter sometimes referred to as a phosgenation method of amine hydrochloride).

  In the cold two-stage phosgenation method, for example, first, an inert solvent is charged into a reactor that is capable of being stirred and equipped with a phosgene introduction tube, and the pressure in the reaction system is set at, for example, normal pressure to 1. 0.0 MPa, preferably normal pressure to 0.5 MPa, and the temperature is, for example, 0 to 80 ° C., preferably 0 to 60 ° C.

  Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and fatty acid esters such as ethyl acetate, butyl acetate, and amyl acetate, such as methyl salicylate, dimethyl phthalate, and phthalic acid. Aromatic carboxylic acid esters such as dibutyl and methyl benzoate, for example, chlorinated aromatic hydrocarbons such as monodichlorobenzene, orthodichlorobenzene, and trichlorobenzene, for example, chlorinated hydrocarbons such as chloroform and carbon tetrachloride Etc.

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

  The compounding amount (total amount) of the inert solvent is, for example, 400 to 3000 parts by mass, or preferably 500 to 2000 parts by mass with respect to 100 parts by mass of the raw material pentamethylenediamine.

  Next, in this method, phosgene is introduced into, for example, 1 to 10 times mol, preferably 1 to 6 times mol of one amino group of pentamethylenediamine, and pentamethylene dissolved in the above inert solvent. Add the diamine. During this time, the reaction solution is maintained at, for example, 0 to 80 ° C., preferably 0 to 60 ° C., and the generated hydrogen chloride is discharged out of the reaction system through a reflux condenser (cold phosgenation reaction). Thereby, the contents of the reactor are made into a slurry.

  In this cold phosgenation reaction, pentamethylene dicarbamoyl chloride and amine hydrochloride are produced.

  Next, in this method, the pressure in the reaction system is, for example, normal pressure to 1.0 MPa, preferably 0.05 to 0.5 MPa, for example, 30 minutes to 5 hours, for example, 80 to 180 ° C. The temperature is raised to a temperature range. After the temperature rise, for example, the reaction is continued for 30 minutes to 8 hours to completely dissolve the slurry (thermal phosgenation reaction).

  In the thermal phosgenation reaction, phosgene is appropriately introduced until the amount of reflux from the reflux cooler can be confirmed because dissolved phosgene vaporizes and escapes from the reaction system through the reflux cooler at the time of temperature rise and high temperature reaction.

  After completion of the thermal phosgenation reaction, an inert gas such as nitrogen gas is introduced and dissolved in the reaction system at, for example, 80 to 180 ° C., preferably 90 to 160 ° C. to dissolve excess phosgene and chloride. Purge hydrogen.

  In this thermal phosgenation reaction, pentamethylene dicarbamoyl chloride produced by the cold phosgenation reaction is thermally decomposed to produce pentamethylene diisocyanate, and further, amine hydrochloride of pentamethylenediamine is phosgenated to produce pentamethylene diisocyanate. Is done.

  On the other hand, in the phosgenation method of amine hydrochloride, the hydrochloride of pentamethylenediamine is sufficiently dried and finely pulverized, and then the hydrochloride of pentamethylenediamine is used in the same reactor as in the above-described cold and two-stage phosgenation method. Is stirred in the above inert solvent and dispersed into a slurry.

  Subsequently, in this method, the reaction temperature is maintained at, for example, 80 to 180 ° C., preferably 90 to 160 ° C., and the reaction pressure is maintained at, for example, normal pressure to 1.0 MPa, preferably 0.05 to 0.5 MPa. Then, phosgene is introduced over 1 to 10 hours so that the total amount of phosgene is 1 to 10 times the stoichiometric amount.

  Thereby, pentamethylene diisocyanate can be synthesized.

  The progress of the reaction can be estimated from the amount of the hydrogen chloride gas generated and the slurry insoluble in the above inert solvent disappearing, and the reaction solution becomes clear and uniform. Further, the generated hydrogen chloride is released out of the reaction system through, for example, a reflux condenser. At the end of the reaction, excess phosgene and hydrogen chloride dissolved by the above method are purged. Thereafter, the mixture is cooled and the inert solvent is distilled off under reduced pressure.

  Since pentamethylene diisocyanate tends to increase the concentration (HC) of hydrolyzable chlorine, when adopting the phosgenation method, when it is necessary to reduce HC, for example, a phosgenation reaction is performed. After removing the solvent, the pentamethylene diisocyanate distilled off is, for example, 150 ° C. to 200 ° C., preferably 160 ° C. to 190 ° C., for example, 1 to 8 while passing an inert gas such as nitrogen. Heat treatment is performed for a time, preferably 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).

  When the concentration of hydrolyzable chlorine exceeds 100 ppm, the reaction rate of trimerization (described later) decreases, and a large amount of trimerization catalyst (described later) may be required, and a large amount of trimerization catalyst (described later) is used. In some cases, the resulting polyisocyanate composition (described later) has a high degree of yellowing, the number average molecular weight is high, and the viscosity is high.

  When the concentration of hydrolyzable chlorine exceeds 100 ppm, the viscosity and hue may change greatly in the storage step of the polyisocyanate composition (described later) and the manufacturing process of the polyurethane resin (described later).

  Examples of the carbamate method include a urea method.

  In the urea method, for example, pentamethylenediamine is first carbamateized to produce pentamethylene dicarbamate (PDC).

  More specifically, pentamethylenediamine, urea and / or N-unsubstituted carbamic acid ester are reacted with alcohol.

  Examples of N-unsubstituted carbamic acid esters include N-unsubstituted carbamic acid aliphatic esters (for example, methyl carbamate, ethyl carbamate, propyl carbamate, iso-propyl carbamate, butyl carbamate, isocarbamate). -Butyl, sec-butyl carbamate, tert-butyl carbamate, pentyl carbamate, iso-pentyl carbamate, sec-pentyl carbamate, hexyl carbamate, heptyl carbamate, octyl carbamate, 2-ethylhexyl carbamate, carbamine Acid nonyl, decyl carbamate, isodecyl carbamate, dodecyl carbamate, tetradecyl carbamate, hexadecyl carbamate, etc.), N-unsubstituted carbamic acid aromatic esters (for example, Rubamin acid phenyl, tolyl carbamate, xylyl carbamate, carbamic acid biphenyl, naphthyl carbamate, anthryl carbamate, such as carbamic acid phenanthryl), and the like.

  These N-unsubstituted carbamic acid esters can be used alone or in combination of two or more.

  The N-unsubstituted carbamic acid ester is preferably N-unsubstituted carbamic acid aliphatic ester.

  Examples of the alcohol include 1 to 3 grade monohydric alcohols, and more specifically, for example, aliphatic alcohols and aromatic alcohols.

  Examples of aliphatic alcohols include linear aliphatic alcohols (for example, methanol, ethanol, n-propanol, n-butanol (1-butanol), n-pentanol, n-hexanol, n-heptanol, n-octanol (1-octanol), n-nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, etc., branched aliphatic alcohols (eg, iso-propanol, iso) -Butanol, sec-butanol, tert-butanol, iso-pentanol, sec-pentanol, 2-ethylhexanol, iso-decanol, etc.).

  Examples of aromatic alcohols include phenol, hydroxytoluene, hydroxyxylene, biphenyl alcohol, naphthalenol, anthracenol, phenanthrenol and the like.

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

  The alcohol is preferably an aliphatic alcohol, more preferably a linear aliphatic alcohol.

  The alcohol preferably includes the above-described monovalent alcohol having 4 to 7 carbon atoms (linear monovalent alcohol having 4 to 7 carbon atoms, branched monovalent alcohol having 4 to 7 carbon atoms). .

  Further, when an alcohol (such as a monohydric alcohol having 4 to 7 carbon atoms) is used as an extraction solvent in the above extraction, the alcohol is preferably used as a reaction raw material alcohol.

  In this method, pentamethylenediamine, urea and / or N-unsubstituted carbamic acid ester, and alcohol are blended and preferably reacted in a liquid phase.

  The blending ratio of pentamethylenediamine, urea and / or N-unsubstituted carbamic acid ester, and alcohol is not particularly limited and can be appropriately selected within a relatively wide range.

  Usually, the compounding amount of urea and N-unsubstituted carbamic acid ester and the compounding amount of alcohol should be equimolar or more with respect to the amino group of pentamethylenediamine. Therefore, urea and / or N- An unsubstituted carbamate or alcohol itself can also be used as a reaction solvent in this reaction.

  In addition, when an alcohol (such as a monohydric alcohol having 4 to 7 carbon atoms) is used as an extraction solvent in the above-described extraction, the alcohol is preferably used as it is as a reaction raw material and a reaction solvent.

  When urea and / or the above-mentioned N-unsubstituted carbamic acid ester or alcohol is also used as a reaction solvent, an excessive amount of urea and / or the above-mentioned N-unsubstituted carbamic acid ester or alcohol is used as necessary. However, if the excess amount is large, the energy consumption in the separation step after the reaction increases, which is not suitable for industrial production.

  Therefore, the blending amount of urea and / or the above-mentioned N-unsubstituted carbamic acid ester is 0.5 to 20 times mol with respect to one amino group of pentamethylenediamine from the viewpoint of improving the yield of carbamate, Preferably, it is 1 to 10 times mol, more preferably 1 to 5 times mol, and the compounding amount of alcohol is 0.5 to 100 times mol, preferably 1 amino group of pentamethylenediamine, It is 1-20 times mole, More preferably, it is 1-10 times mole.

  In this method, a catalyst can also be used.

  Although it does not restrict | limit especially as a catalyst, For example, according to periodic table group 1 (IUPAC Periodic Table of the Elements (version date 22 June 2007). The same applies hereafter) Metal compound (For example, lithium methanolate, lithium ethanolate, Lithium propanolate, lithium butanolate, sodium methanolate, potassium tert-butanolate, etc., Group 2 metal compounds (eg, magnesium methanolate, calcium methanolate, etc.), Group 3 metal compounds (eg, cerium oxide) (IV), uranyl acetate, etc.), Group 4 metal compounds (titanium tetraisopropanolate, titanium tetrabutanolate, titanium tetrachloride, titanium tetraphenolate, titanium naphthenate, etc.), fifth Metal compounds (eg, vanadium (III) chloride, vanadium acetylacetonate, etc.), Group 6 metal compounds (eg, chromium (III) chloride, molybdenum (VI), molybdenum acetylacetonate, tungsten (VI), etc.) , Group 7 metal compounds (eg, manganese (II) chloride, manganese (II) acetate, manganese (III) acetate, etc.), Group 8 metal compounds (eg, iron (II) acetate, iron (III) acetate, phosphorus Iron oxide, iron oxalate, iron chloride (III), iron bromide (III), etc., Group 9 metal compounds (eg, cobalt acetate, cobalt chloride, cobalt sulfate, cobalt naphthenate, etc.), Group 10 metal compounds (Eg, nickel chloride, nickel acetate, nickel naphthenate, etc.), Group 11 metal compounds (eg, copper (II) acetate, Copper (II) acid, copper (II) nitrate, bis- (triphenyl-phosphine oxide) -copper (II) chloride, copper molybdate, silver acetate, gold acetate, etc., Group 12 metal compounds (for example, zinc oxide) , Zinc chloride, zinc acetate, zinc acetonyl acetate, zinc octoate, zinc oxalate, zinc hexylate, zinc benzoate, zinc undecylate, etc.), Group 13 metal compounds (for example, aluminum acetylacetonate, aluminum- Isobutyrate, aluminum trichloride, etc.), Group 14 metal compounds (eg, tin (II) chloride, tin (IV) chloride, lead acetate, lead phosphate, etc.), Group 15 metal compounds (eg, antimony (III) chloride) , Antimony chloride (V), bismuth chloride (III), etc.).

Furthermore, as a catalyst, for example, Zn (OSO ₂ CF ₃ ) ₂ (another notation: Zn (OTf) ₂ , zinc trifluoromethanesulfonate), Zn (OSO ₂ C ₂ F ₅ ) ₂ , Zn (OSO ₂ C ₃ F ₇ ) ₂ , Zn (OSO ₂ C ₄ F ₉ ) ₂ , Zn (OSO ₂ C ₆ H ₄ CH ₃ ) ₂ (p-toluenesulfonic acid zinc), Zn (OSO ₂ C ₆ H ₅ ) ₂ , Zn ( BF ₄ ) ₂ , Zn (PF ₆ ) ₂ , Hf (OTf) ₄ (hafnium trifluoromethanesulfonate), Sn (OTf) ₂ , Al (OTf) ₃ , Cu (OTf) _{2 and the} like are also included.

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

  Moreover, the compounding quantity of a catalyst is 0.000001-0.1 mol with respect to 1 mol of pentamethylenediamine, Preferably, it is 0.00005-0.05 mol. Even if the amount of the catalyst is larger than this, no further significant reaction promoting effect is observed, but the cost may increase due to an increase in the amount of the catalyst. On the other hand, if the blending amount is less than this, the reaction promoting effect may not be obtained.

  In addition, the addition method of a catalyst does not affect reaction activity in any addition method of lump addition, continuous addition, and a plurality of intermittent additions, and is not particularly limited.

  In this reaction, a reaction solvent is not necessarily required. However, for example, when the reaction raw material is solid or a reaction product is precipitated, the operability can be improved by adding a solvent.

  Solvents that are inert or poorly reactive with pentamethylenediamine, urea and / or N-unsubstituted carbamic acid esters, which are reaction raw materials, and alcohol, and urethane compounds, which are reaction products. If it is, it will not restrict | limit in particular, For example, aliphatic hydrocarbons (for example, hexane, pentane, petroleum ether, ligroin, cyclododecane, decalins etc.), aromatic hydrocarbons (for example, benzene, toluene) , Xylene, ethylbenzene, isopropylbenzene, butylbenzene, cyclohexylbenzene, tetralin, chlorobenzene, o-dichlorobenzene, methylnaphthalene, chloronaphthalene, dibenzyltoluene, triphenylmethane, phenylnaphthalene, biphenyl, diethylbiphenyl, tri Tilbiphenyl, etc.), ethers (eg, diethyl ether, diisopropyl ether, dibutyl ether, anisole, diphenyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether), carbonates (Eg, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc.), nitriles (eg, acetonitrile, propionitrile, adiponitrile, benzonitrile, etc.), aliphatic halogenated hydrocarbons (eg, methylene chloride, chloroform) 1,2-dichloroethane, 1,2-dichloropro , 1,4-dichlorobutane etc.), amides (eg dimethylformamide, dimethylacetamide etc.), nitro compounds (eg nitromethane, nitrobenzene etc.), N-methylpyrrolidinone, N, N-dimethylimidazolidinone And dimethyl sulfoxide.

  Furthermore, examples of the reaction solvent include the extraction solvent in the above-described extraction.

  Of these reaction solvents, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used in view of economy and operability.

  The reaction solvent is preferably the extraction solvent in the above extraction.

  By using the extraction solvent as a reaction solvent, the extracted pentamethylene diisocyanate can be used for the carbamation reaction as it is, and the operability can be improved.

  Moreover, such a reaction solvent can be used individually or in combination of 2 or more types.

  The amount of the reaction solvent is not particularly limited as long as the target product pentamethylene dicarbamate is dissolved, but industrially, the reaction solvent needs to be recovered from the reaction solution. If the energy consumed for recovery is reduced as much as possible and the amount is large, the reaction substrate concentration decreases and the reaction rate slows down. More specifically, it is used in the range of usually 0.1 to 500 parts by mass, preferably 1 to 100 parts by mass with respect to 1 part by mass of pentamethylenediamine.

  In this reaction, the reaction temperature is appropriately selected, for example, in the range of 100 to 350 ° C, preferably 150 to 300 ° C. When the reaction temperature is lower than this, the reaction rate may decrease. On the other hand, when the reaction temperature is higher than this, side reaction may increase and the yield of the target product, pentamethylene dicarbamate may decrease.

  The reaction pressure is usually atmospheric pressure, but may be increased when the boiling point of the component in the reaction solution is lower than the reaction temperature, and further reduced as necessary.

  Moreover, reaction time is 0.1 to 20 hours, for example, Preferably, it is 0.5 to 10 hours. If the reaction time is shorter than this, the yield of the target product, pentamethylene dicarbamate, may decrease. On the other hand, if it is longer than this, it is unsuitable for industrial production.

  In this reaction, for example, pentamethylenediamine, urea and / or N-unsubstituted carbamic acid ester, alcohol, and, if necessary, a catalyst and a reaction solvent are charged in a reaction vessel and stirred or mixed. do it. Then, pentamethylene dicarbamate is produced in a short time, at a low cost and in a high yield under mild conditions.

  The obtained pentamethylene dicarbamate usually corresponds to the above pentamethylene diamine used as a raw material component, more specifically 1,5-pentamethylene dicarbamate, 1,4-pentamethylene dicarbamate, 1,3-pentamethylene dicarbamate, 2,5-pentamethylene dicarbamate, or a mixture thereof.

  That is, when 1,5-pentamethylenediamine obtained by decarboxylase reaction of lysine (or a salt thereof) is employed as a raw material component, 1,5-pentamethylene dicarbamate is obtained by carbamation.

  In this reaction, ammonia is by-produced.

  In this reaction, when an N-unsubstituted carbamic acid ester is blended, an alcohol corresponding to the ester is by-produced.

  In this reaction, either a batch type or a continuous type can be adopted as the reaction type.

  In addition, this reaction is preferably carried out while allowing ammonia produced as a by-product to flow out of the system. Furthermore, when N-unsubstituted carbamic acid ester is blended, the reaction is carried out while distilling off the alcohol produced as a by-product.

  Thereby, the production | generation of the pentamethylene dicarbamate which is a target product can be accelerated | stimulated, and the yield can be improved further.

  When the obtained pentamethylene dicarbamate is isolated, for example, excess (unreacted) urea and / or N-unsubstituted carbamic acid ester, excess (unreacted) alcohol, catalyst, pentamethylene dicarbamate. The pentamethylene dicarbamate may be separated from the reaction solution containing carbamate, reaction solvent, by-produced ammonia, and optionally by-produced alcohol by a known separation and purification method.

  Next, in this method for producing pentamethylene diisocyanate, the obtained pentamethylene dicarbamate is thermally decomposed to produce pentamethylene diisocyanate.

  That is, in such an isocyanate production method, the pentamethylene dicarbamate obtained as described above is thermally decomposed to produce pentamethylene diisocyanate and alcohol as a by-product.

  The obtained pentamethylene diisocyanate usually corresponds to the above-mentioned pentamethylenediamine used as a raw material component, and more specifically 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3 -Pentamethylene diisocyanate, 2,5-pentamethylene diisocyanate, or mixtures thereof.

  That is, when 1,5-pentamethylenediamine (or a salt thereof) obtained by a decarboxylase reaction of lysine (or a salt thereof) is employed as a raw material component, 1,5-pentamethylene diisocyanate is obtained by thermal decomposition. can get.

  Moreover, as alcohol, normally the alcohol of the same kind as the alcohol used as a raw material component is by-produced.

  This thermal decomposition is not particularly limited, and for example, a known decomposition method such as a liquid phase method or a gas phase method can be used.

  In the gas phase method, pentamethylene diisocyanate and alcohol produced by thermal decomposition can be separated from the gaseous product mixture by fractional condensation. In the liquid phase method, pentamethylene diisocyanate and alcohol produced by thermal decomposition can be separated by, for example, distillation or using a solvent and / or an inert gas as a support material.

  The thermal decomposition is preferably a liquid phase method from the viewpoint of workability.

  Since the thermal decomposition reaction of pentamethylene dicarbamate in the liquid phase method is a reversible reaction, it is preferable to suppress the reverse reaction of the thermal decomposition reaction (urethanization reaction of pentamethylene diisocyanate and alcohol). The pentamethylene diisocyanate and / or by-product alcohol is extracted from the reaction mixture as a gas, for example, and separated from the reaction mixture.

  As the reaction conditions for the thermal decomposition reaction, it is preferable that pentamethylene dicarbamate can be thermally decomposed satisfactorily, and pentamethylene diisocyanate and alcohol generated in the thermal decomposition evaporate, whereby the equilibrium of pentamethylene dicarbamate and pentamethylene diisocyanate is achieved. In addition, there may be mentioned conditions where side reactions such as polymerization of pentamethylene diisocyanate are suppressed.

  More specifically, as such reaction conditions, the thermal decomposition temperature is usually 350 ° C. or lower, preferably 80 to 350 ° C., more preferably 100 to 300 ° C. If it is lower than 80 ° C., a practical reaction rate may not be obtained, and if it exceeds 350 ° C., undesirable side reactions such as polymerization of pentamethylene diisocyanate may occur. In addition, the pressure during the pyrolysis reaction is preferably a pressure at which the generated alcohol can be vaporized with respect to the above pyrolysis reaction temperature. It is preferably 90 kPa.

  The pentamethylene dicarbamate used for the thermal decomposition may be purified, but the above reaction (that is, reaction of pentamethylenediamine with urea and / or N-unsubstituted carbamic acid ester with alcohol). Upon completion, excess (unreacted) urea and / or N-unsubstituted carbamic acid ester, excess (unreacted) alcohol, catalyst, reaction solvent, by-product ammonia, and optionally by-product alcohol are recovered and separated. The resulting raw material of pentamethylene dicarbamate may be subsequently pyrolyzed.

  Further, if necessary, a catalyst and an inert solvent may be added. Although these catalysts and inert solvents differ depending on their types, they may be added to the above reaction either before or after distillation separation after the reaction or before or after separation of pentamethylene dicarbamate.

  As a catalyst used for thermal decomposition, one kind selected from Sn, Sb, Fe, Co, Ni, Cu, Zn, Cr, Ti, Pb, Mo, Mn, etc., used for the urethanization reaction between isocyanate and hydroxyl group The metal simple substance or its oxides, halides, carboxylates, phosphates, organometallic compounds and the like are used. Among these, in this thermal decomposition, Fe, Sn, Co, Sb, and Mn are preferably used because they exhibit the effect of making it difficult to generate by-products.

  Examples of the Sn metal catalyst include tin oxide, tin chloride, tin bromide, tin iodide, tin formate, tin acetate, tin oxalate, tin octylate, tin stearate, tin oleate, tin phosphate, Examples include dibutyltin chloride, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxydistanoxane.

  Examples of the metal catalyst of Fe, Co, Sb, and Mn include acetates, benzoates, naphthenates, and acetylacetonates.

  In addition, the compounding quantity of a catalyst is 0.0001-5 mass% with respect to the reaction liquid as a metal simple substance or its compound, Preferably, it is the range of 0.001-1 mass%.

  The inert solvent is not particularly limited as long as it dissolves at least pentamethylene dicarbamate, is inert to pentamethylene dicarbamate and isocyanate, and is stable at the temperature in thermal decomposition. In order to carry out the reaction efficiently, the boiling point is preferably higher than that of the isocyanate to be produced. Examples of such inert solvents include esters such as dioctyl phthalate, didecyl phthalate, and didodecyl phthalate, such as dibenzyltoluene, triphenylmethane, phenylnaphthalene, biphenyl, diethylbiphenyl, and triethylbiphenyl. Aromatic hydrocarbons and aliphatic hydrocarbons that are commonly used as media.

  The inert solvent is also available as a commercial product. For example, barrel process oil B-01 (aromatic hydrocarbons, boiling point: 176 ° C.), barrel process oil B-03 (aromatic hydrocarbons, Boiling point: 280 ° C.), barrel process oil B-04AB (aromatic hydrocarbons, boiling point: 294 ° C.), barrel process oil B-05 (aromatic hydrocarbons, boiling point: 302 ° C.), barrel process oil B-27 (Aromatic hydrocarbons, boiling point: 380 ° C.), barrel process oil B-28AN (aromatic hydrocarbons, boiling point: 430 ° C.), barrel process oil B-30 (aromatic hydrocarbons, boiling point: 380 ° C.) , Barrel therm 200 (aromatic hydrocarbons, boiling point: 382 ° C.), barrel therm 300 (aromatic hydrocarbons, boiling point: 344 ° C.), barrel therm 400 (aromatic hydrocarbons) , Boiling point: 390 ° C.), barrel therm 1H (aromatic hydrocarbons, boiling point: 215 ° C.), barrel therm 2H (aromatic hydrocarbons, boiling point: 294 ° C.), barrel therm 350 (aromatic hydrocarbons, boiling point) : 302 ° C.), Barrel Therm 470 (aromatic hydrocarbons, boiling point: 310 ° C.), Barrel Therm PA (aromatic hydrocarbons, boiling point: 176 ° C.), Barrel Therm 330 (aromatic hydrocarbons, boiling point: 257) ° C), Barrel Therm 430 (aromatic hydrocarbons, boiling point: 291 ° C), (Made by Matsumura Oil Co., Ltd.), NeoSK-OIL1400 (aromatic hydrocarbons, boiling point: 391 ° C), NeoSK-OIL1300 (aromatic) Hydrocarbons, boiling point: 291 ° C), NeoSK-OIL330 (aromatic hydrocarbons, boiling point: 331 ° C), NeoSK-OIL170 (aromatic Hydrocarbons, boiling point: 176 ° C), NeoSK-OIL240 (aromatic hydrocarbons, boiling point: 244 ° C), KSK-OIL260 (aromatic hydrocarbons, boiling point: 266 ° C), KSK-OIL280 (aromatic hydrocarbons) Type, boiling point: 303 ° C.) (above, manufactured by Soken Techniques).

  The compounding amount of the inert solvent is in the range of 0.001 to 100 parts by mass, preferably 0.01 to 80 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 1 part by mass of pentamethylene dicarbamate. Range.

  This thermal decomposition reaction is a batch reaction in which pentamethylene dicarbamate, a catalyst and an inert solvent are charged all at once, or a continuous reaction in which pentamethylene dicarbamate is charged in an inert solvent containing a catalyst under reduced pressure. Either can be implemented.

  In thermal decomposition, pentamethylene diisocyanate and alcohol are generated, and side reactions may generate, for example, allophanate, amines, urea, carbonate, carbamate, carbon dioxide, etc. The obtained pentamethylene diisocyanate is purified by a known method.

  The carbamate method is not described in detail, but besides the urea method described above, a known carbonate method, that is, pentamethylene dicarbamate is synthesized from pentamethylenediamine and dialkyl carbonate or diaryl carbonate, and the pentamethylene is synthesized. A method of obtaining pentamethylene diisocyanate by thermally decomposing dicarbamate in the same manner as described above can also be employed.

  The purity of the pentamethylene diisocyanate of the present invention thus obtained is, for example, 95 to 100% by mass, preferably 97 to 100% by mass, more preferably 98 to 100% by mass, and particularly preferably 99 to 100% by mass. %, Most preferably 99.5 to 100% by mass.

  Moreover, a stabilizer etc. can be added to pentamethylene diisocyanate, for example.

  Examples of the stabilizer include an antioxidant, an acidic compound, a compound containing a sulfonamide group, and an organic phosphite.

  Examples of the antioxidant include hindered phenol-based antioxidants, and specific examples thereof include 2,6-di (t-butyl) -4-methylphenol, 2,4,6-triol, and the like. -T-butylphenol, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-thio-bis- (4-methyl-6-t-butylphenol), 4,4'- Thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis- (6-tert-butyl-3-methylphenol), 4,4′-methylidene-bis- (2,6 -Di-t-butylphenol), 2,2'-methylene-bis- [4-methyl-6- (1-methylcyclohexyl) -phenol], tetrakis- [methylene-3- (3,5-di-t- Butyl-4-hydroxy Phenyl) -propionyl] -methane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxyphenyl) -propionyl-methane, 1,3,5 -Trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) -benzene, N, N'-hexamethylene-bis- (3,5-di-t-butyl) -4-hydroxyhydrocinnamic amide, 1,3,5-tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3-tris- (5-t- Butyl-4-hydroxy-2-methylphenyl) -butane, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -mesitylene, ethylene glycol-bis- [3,3 -Bis- (3'-t- Tyl-4'-hydroxyphenyl) -butyrate, 2,2'-thiodiethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, di- (3-t-butyl-4 '-Hydroxy-5-methylphenyl) -dicyclopentadiene, 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 1,6-hexanediol-bis- (3,5-di- t-butyl-4-hydroxyphenyl) -propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, Diethyl-3,5-di-t-butyl-4-hydroxybezylphosphonate, triethylene glycol-bis-3- (t-butyl-4-hydroxy-5-methylphenol) Nil) -propionate, IRGANOX1010, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1726, IRGANOX245, IRGANOX3114, IRGANOX3790 (trade name, manufactured by BASF Japan Ltd.) and the like.

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

  Examples of the acidic compound include organic acidic compounds. Specifically, for example, phosphate ester, phosphite ester, hypophosphite ester, formic acid, acetic acid, propionic acid, hydroxyacetic acid, oxalic acid, lactic acid Citric acid, malic acid, sulfonic acid, sulfonic acid ester, phenol, enol, imide, oxime and the like.

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

  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.

  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 tris (2,3-dichloro-propyl) phosphite.

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

  The stabilizer preferably includes an antioxidant, an acidic compound, and a compound containing a sulfonamide group. More preferably, pentamethylene diisocyanate is blended with an antioxidant and an acidic compound and / or a compound containing a sulfonamide group.

  By adding these stabilizers, the storage stability of the pentamethylene diisocyanate, the reactivity with the active hydrogen compound (described later), and the reactivity when an isocyanate-modified product (described later) is produced using pentamethylene diisocyanate. Furthermore, the storage stability of the resulting isocyanate-modified product (described later) can be improved.

  The blending ratio of the stabilizer is not particularly limited, and is appropriately set according to necessity and application.

  Specifically, the mixing ratio of the antioxidant is, for example, 0.0005 to 0.05 parts by mass with respect to 100 parts by mass of pentamethylene diisocyanate.

  Moreover, the compounding ratio (the total amount when they are used together) of the compound containing an acidic compound and / or a sulfone and group is, for example, 0.0005 to 0.02 with respect to 100 parts by mass of pentamethylene diisocyanate. Part by mass.

  The pentamethylene diisocyanate of the present invention thus obtained is synthesized from pentamethylenediamine or a salt thereof which does not contain a nitrogen-containing six-membered ring compound having a C═N bond or whose content is reduced. Is done.

  Therefore, according to the pentamethylene diisocyanate of the present invention, an isocyanate-modified product having excellent properties can be produced efficiently.

  Moreover, according to the pentamethylene diisocyanate of this invention, the polyurethane resin provided with the outstanding property can also be manufactured.

  And the pentamethylene diisocyanate of this invention is used suitably in manufacture of an isocyanate modified body (polyisocyanate composition).

More specifically, the polyisocyanate composition is obtained by modifying pentamethylene diisocyanate and contains at least one functional group of the following (a) to (e).
(A) isocyanurate group (b) allophanate group (c) biuret group (d) urethane group (e) urea group The polyisocyanate composition containing the functional group (isocyanurate group) of the above (a) is pentamethylene diisocyanate. The trimer (trimer) can be obtained by, for example, reacting pentamethylene diisocyanate in the presence of a known isocyanuration catalyst and trimerization.

  The polyisocyanate composition containing the functional group (allophanate group) of the above (b) is an allophanate modified product of pentamethylene diisocyanate, and, for example, after reacting pentamethylene diisocyanate with a monoalcohol, a known allophanate is formed. It can be obtained by further reaction in the presence of a catalyst.

  The polyisocyanate composition containing the functional group (biuret group) of the above (c) is a biuret-modified product of pentamethylene diisocyanate, for example, pentamethylene diisocyanate, for example, water, tertiary alcohol (for example, t -Butyl alcohol, etc.), secondary amines (for example, dimethylamine, diethylamine, etc.) and the like are reacted and then further reacted in the presence of a known biuretization catalyst.

  The polyisocyanate composition containing the functional group (urethane group) of (b) is a polyol-modified product of pentamethylene diisocyanate, for example, pentamethylene diisocyanate and a polyol component (for example, trimethylolpropane, etc. ).

  The polyisocyanate composition containing the functional group (urea group) of (e) is a polyamine-modified product of pentamethylene diisocyanate, and for example, by reaction of pentamethylene diisocyanate with water, a polyamine component (described later), Obtainable.

  In addition, the polyisocyanate composition should just contain at least 1 type of the functional group of said (a)-(e), and can also contain 2 or more types. Such a polyisocyanate composition is produced by appropriately combining the above reactions.

  As the polyisocyanate composition, a trimer of pentamethylene diisocyanate (polyisocyanate composition containing an isocyanurate group) is preferably used.

  The trimer of pentamethylene diisocyanate contains a polyisocyanate having an iminooxadiazinedione group in addition to the isocyanurate group.

  As a method of trimerizing pentamethylene diisocyanate, a method of reacting pentamethylene diisocyanate with alcohols, then trimming in the presence of a trimerization catalyst, and then removing unreacted pentamethylene diisocyanate, for example, Examples thereof include a method in which only pentamethylene diisocyanate is subjected to a trimerization reaction, unreacted pentamethylene diisocyanate is removed, and the resulting trimer is reacted with an alcohol.

  Preferably, a polyisocyanate composition is obtained by a method in which pentamethylene diisocyanate is reacted with an alcohol, followed by a trimerization reaction in the presence of a trimerization 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, 2-ethylhexan-1-ol, isononanol, Isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, other branched alkanols (C (The number of carbon atoms, the same applies hereinafter) 5 to 20).

  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, and the blending ratio is 0.1 parts by weight with respect to 100 parts by weight of pentamethylene diisocyanate. -5 parts by mass, preferably 0.2-3 parts by mass.

  Further, in the trimerization reaction of pentamethylene diisocyanate, the alcohols described above and, for example, thiols, oximes, lactams, phenols, β, as long as they do not inhibit the excellent effects of the present invention. 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 may be 10-28 mass% in the polyisocyanate composition obtained, for example.

  In order 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 a trimerization catalyst, under predetermined reaction conditions. Trimerization reaction is performed.

  The trimerization catalyst is not particularly limited as long as it is an effective catalyst for trimerization. For example, tetraalkylammonium hydroxide such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium, and weak organic acids thereof. Salts such as trialkylhydroxyalkylammonium hydroxides and organic weak acid salts thereof such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium, for example acetic acid, caproic acid, octylic acid, myristic Alkali metal salts of alkyl carboxylic acids such as acids, for example, metals such as tin, zinc and lead of the above alkyl carboxylic acids , For example, metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone, for example, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, such as titanium tetrabutyrate, tributylantimony oxide, etc. An organometallic compound, for example, an aminosilyl group-containing compound such as hexamethylsilazane can be used.

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

  The trimerization catalyst is preferably N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate.

  The addition ratio of the trimerization catalyst is, for example, 0.0005 to 0.3 parts by mass, preferably 0.001 to 0.1 parts by mass, more preferably 0.001 to 100 parts by mass of pentamethylene diisocyanate. It is -0.05 mass part.

  In order to control trimerization, for example, an organic phosphite ester described in JP-A-61-129173 can be used as a cocatalyst.

  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-t- Diphosphites derived from bisphenol compounds such as butylphenyl-di-tridecyl) phosphite, polyphosphites such as hydrogenated bisphenol A phosphite polymer (molecular weight 2400-3000) Such as tris (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 alcohols have an equivalent ratio of isocyanate groups of pentamethylene diisocyanate to hydroxyl groups of alcohols (NCO / OH) of, for example, 20 or more, preferably 30 or more. Preferably, it is blended at a blending ratio of 40 or more, particularly preferably 60 or more, and usually 1000 or less.

  After reaching a predetermined isocyanate group concentration, the above trimerization catalyst is added to cause a trimerization reaction.

  In this reaction, the conversion rate of the isocyanate group is, for example, 5 to 35% by mass, preferably 5 to 30% by mass, and more preferably 5 to 25% 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. On the other hand, if the conversion rate is less than 5%, the productivity of the polyisocyanate composition may not be sufficient.

  The conversion rate of the isocyanate group can be measured based on, for example, high-speed GPC, NMR, isocyanate group concentration, refractive index, density, infrared spectrum, and 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.

  Further, as a method for obtaining a polyisocyanate composition, after trimerizing only pentamethylene diisocyanate, unreacted pentamethylene diisocyanate is removed, and the resulting trimer is reacted with alcohols (the latter method described above). Is employed, the reaction between the trimer 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.

  Further, the method for obtaining the polyisocyanate composition is not limited to the above method. For example, pentamethylene diisocyanate is used in the presence of the above trimerization catalyst in the presence of the above trimerization catalyst without using alcohols. A trimerization reaction can also be performed.

  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. On the other hand, if 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.

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

  The polyisocyanate composition thus obtained has an isocyanate group concentration of, for example, 10 to 28% by mass, preferably 15 to 28% by mass, and more preferably 20 to 28% by mass.

  Further, in the polyisocyanate composition thus obtained, an isocyanate-modified monomer having an isocyanate trimer (isocyanurate group (and optionally an iminooxadiazinedione group) and a molecular weight three times that of the isocyanate monomer). Body) (concentration excluding impurities such as unreacted pentamethylene diisocyanate) is, for example, 35 to 95% by mass, preferably 40 to 95% by mass, and more preferably 50 to 95% by mass.

  If the concentration of the isocyanate trimer is less than 35% by mass, the clay of the polyisocyanate composition may increase, resulting in problems such as reduced crosslinkability.

  In the polyisocyanate composition thus obtained, the isocyanate monomer concentration (concentration of unreacted pentamethylene diisocyanate) is, for example, 3% by mass or less, preferably 1.5% by mass or less, more preferably 1% by mass or less.

  The polyisocyanate composition thus obtained may contain allophanate bonds in addition to isocyanurate bonds and / or iminooxadiazinedione bonds. In such a case, the molar ratio of the isocyanurate group and iminooxadiazinedione group in the polyisocyanate composition to the allophanate group ((isocyanurate group (number of moles) + iminooxadiazinedione group (number of moles)) ) / Allophanate group (number of moles) is, for example, 1 to 3500, preferably 1 to 3000, and more preferably 1 to 1000.

  The molar ratio of the isocyanurate group and iminooxadiazinedione group to the allophanate group in the polyisocyanate composition can be measured by a known method. More specifically, for example, differential refractive index detection In a chromatogram (chart) of a gel permeation chromatograph (GPC) equipped with a vessel (RID), the peak ratio (area ratio) can be calculated by the NMR method or the like.

  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 2000 mPa · s.

  And the polyisocyanate composition of this invention is obtained by trimming said pentamethylene diisocyanate. Therefore, the polyisocyanate composition of the present invention can be produced efficiently and can have excellent storage stability.

  And the polyisocyanate composition thus obtained can be used for many industrial applications such as paints, adhesives, etc. without diluting with a solvent. If necessary, it can be dissolved in various organic solvents. It can also be used.

  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 can also be used as a blocked isocyanate in which free isocyanate groups contained in the molecule are blocked with a blocking agent.

  The blocked isocyanate can be produced, for example, by reacting a polyisocyanate composition with a blocking agent.

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

  Examples of the oxime blocking agent include formaldoxime, acetoaldoxime, methyl ethyl ketoxime, cyclohexanone oxime, acetoxime, diacetyl monooxime, benzophenoxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime. , Methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl ketone Oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4′-dimethoxybenzophenone oxime, 2 Such as cycloheptanone oxime, and the like.

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

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

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

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

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

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

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

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

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

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

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

  Moreover, as a blocking agent, it is not limited to the above, For example, other blocking agents, such as a benzoxazolone, an isatoic anhydride, tetrabutylphosphonium acetate, are mentioned.

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

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

  Then, the blocked isocyanate can be obtained by blending the polyisocyanate composition and the blocking agent in a ratio that the blocking agent is excessive with respect to the isocyanate group of the polyisocyanate composition and reacting them under known conditions. .

  The polyisocyanate composition of the present invention can be used as an aqueous blocked isocyanate in which free isocyanate groups contained in the molecule are blocked by a blocking agent and are dispersed or dissolved in water.

  The method for producing the aqueous blocked isocyanate is not particularly limited. For example, first, a polyisocyanate composition in which a part of free isocyanate groups in the polyisocyanate composition is blocked with a blocking agent (hereinafter referred to as partially blocked isocyanate) is used. Produced and then reacted with a free isocyanate group of the partially blocked isocyanate (an isocyanate group that remains unblocked by the blocking agent) and a compound having both a hydrophilic group and an active hydrogen group (hereinafter referred to as a hydrophilic group-containing active hydrogen compound) The method of letting it be mentioned.

  In this method, a part of free isocyanate groups of the polyisocyanate composition is first reacted with a blocking agent to produce a partially blocked isocyanate.

  Examples of the blocking agent include the same blocking agents as those described above.

  The partially blocked isocyanate can be obtained by blending the polyisocyanate composition and the blocking agent at a ratio in which the isocyanate group of the polyisocyanate composition is excessive with respect to the blocking agent and reacting them under known conditions. it can.

  Next, in this method, the free isocyanate group of the partially blocked isocyanate (the remainder of the isocyanate group) is reacted with the hydrophilic group-containing active hydrogen compound.

  The hydrophilic group-containing active hydrogen compound is a compound having both at least one hydrophilic group and at least one active hydrogen group. Examples of the hydrophilic group include an anionic group, a cationic group, and a nonionic group. Can be mentioned. The active hydrogen group is a group that reacts with an isocyanate group, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, and an epoxy group.

  More specifically, the hydrophilic group-containing active hydrogen compound is more specifically a carboxylic acid group-containing active hydrogen compound, a sulfonic acid group-containing active hydrogen compound, a hydroxyl group-containing active hydrogen compound, a hydrophilic group-containing polybasic acid, or a polyoxyethylene group-containing active hydrogen. Compound etc. are mentioned.

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

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

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

  Examples of the hydrophilic group-containing polybasic acid include polybasic acids containing sulfonic acid, more specifically, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (p-sulfophenoxy) isophthalic acid. Acid, 5- (sulfopropoxy) isophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfopropylmalonic acid, sulfosuccinic acid, 2-sulfobenzoic acid, 2,3-sulfobenzoic acid, 5-sulfosalicylic acid, In addition, alkyl esters of these carboxylic acids, and metal salts and ammonium salts of these sulfonic acids are also included. Preferably, the sodium salt of 5-sulfoisophthalic acid and the sodium salt of dimethyl 5-sulfoisophthalic acid are used.

  The polyoxyethylene group-containing active hydrogen compound is a compound having a polyoxyethylene group in the main chain or side chain and having at least one active hydrogen group.

  Examples of the polyoxyethylene group-containing active hydrogen compound include polyethylene glycol (for example, number average molecular weight 200 to 6000, preferably 300 to 3000) and polyoxyethylene side chain-containing polyol.

  The polyoxyethylene side chain-containing polyol is a compound having a polyoxyethylene group in the side chain and having two or more active hydrogen groups, and can be synthesized as follows.

  That is, first, diisocyanate (described later) and one-end-capped polyoxyethylene glycol (for example, alkoxyethylene glycol one-end-capped with an alkyl group having 1 to 4 carbon atoms, having a number average molecular weight of 200 to 6000, preferably 300 ˜3000) with respect to the hydroxyl group of the one-end-capped polyoxyethylene glycol at a ratio of diisocyanate (described later) in excess of the isocyanate group, and if necessary, removing unreacted diisocyanate (described later). To obtain a polyoxyethylene chain-containing monoisocyanate.

  Next, polyoxyethylene chain-containing monoisocyanate and dialkanolamine (for example, diethanolamine) are approximately equal in amount of the isocyanate group of polyoxyethylene group-containing monoisocyanate with respect to the secondary amino group of dialkanolamine. The urea reaction is carried out at a rate of

It does not restrict | limit especially as diisocyanate for obtaining a polyoxyethylene side chain containing polyol, A well-known diisocyanate can be used. More specifically, examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI), and 3-isocyanatomethyl. 3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate (IPDI)), 4,4'-methylenebis (cyclohexyl _isocyanate) (H 12 MDI), 2,6-bis (isocyanatomethyl) Norubonan (NBDI) And alicyclic diisocyanates.

  Moreover, as polyoxyethylene group-containing active hydrogen compounds, for example, monohydric alcohols added with ethylene oxide (for example, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, etc.), polyoxyethylene Containing sorbitan esters (eg, polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan ricinoleate, polyoxyethylene sorbitan oleate), polyoxyethylene containing alkylphenols (eg, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether) Polyethylene glycol-containing higher fatty acid esters (eg, polyethylene glycol laurate, polyethylene) Recall oleate, polyethylene glycol stearate), and also like.

  And aqueous block isocyanate mix | blends partial block isocyanate and a hydrophilic group containing active hydrogen compound in the ratio in which a hydrophilic group containing active hydrogen compound becomes excess with respect to the free isocyanate group of partial blocked isocyanate, and is on well-known conditions. It can be obtained by reacting.

  And this invention contains the polyurethane resin obtained by reaction of said pentamethylene diisocyanate and / or polyisocyanate composition, and an active hydrogen compound.

  Examples of the active hydrogen compound include polyol. The polyol is an organic compound having two or more hydroxyl groups, and examples thereof include a low molecular weight polyol and a macropolyol.

  Examples of the low molecular weight polyol include an organic compound having two or more hydroxyl groups and a number average molecular weight of less than 400, and a low molecular weight diol, a low molecular weight triol, and a low molecular weight polyol having four or more hydroxyl groups.

  Examples of the low molecular weight diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol (hereinafter abbreviated as NPG), 1,6-hexanediol, 2,2-diethyl-1,3-propane C2-22 alkanediols such as diol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, for example 2- Butene-1,4-diol, 2,6-dimethyl-1-octene-3,8-dio Aliphatic diols such as alkene diols such as Le, and the like. Further, examples of the low molecular weight diol include alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, or a C2-4 alkylene oxide adduct thereof. Examples of the low molecular weight diol include aromatics such as resorcin, xylylene glycol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, bisphenol A, bisphenol S, bisphenol F, and C2-4 alkylene oxide adducts of the above bisphenols. Diols are mentioned. Examples of the low molecular weight diol include ether diols such as diethylene glycol, triethylene glycol, and dipropylene glycol.

  Examples of the low molecular weight triol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, and trimethylolethane. , Trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and others And aliphatic triols (8 to 24 carbon atoms).

  Examples of the low molecular weight polyol having 4 or more hydroxyl groups include tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, D-mannitol and the like.

  As the macropolyol, for example, an organic compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, for example, polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, A fluorine polyol, polyolefin polyol, etc. are mentioned.

  The polyether polyol is a polyalkylene oxide, for example, polyethylene glycol, polypropylene glycol obtained by addition reaction of an alkylene oxide such as ethylene oxide and / or propylene oxide using the above low molecular weight polyol as an initiator. Polyethylene polypropylene glycol (random or block copolymer). Examples thereof include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

  As the polyester polyol, for example, a condensation reaction between a polyhydric alcohol selected from one or more of the above-described low molecular weight polyols, a polybasic acid, an alkyl ester thereof, an acid anhydride thereof, and an acid halide thereof. Or the polyester polyol obtained by transesterification is mentioned.

  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 aliphatic dicarboxylic acids (11 to 13 carbon atoms), hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid And het acid.

  Examples of the alkyl ester of polybasic acid include methyl ester and ethyl ester of polybasic acid described above.

  Examples of the acid anhydride include acid anhydrides derived from the above-mentioned polybasic acids. For example, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (carbon number 12-18) ) Succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride and the like.

  Examples of the acid halide include acid halides derived from the polybasic acids described above, and examples include oxalic acid 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, lactic acid, etc.) using the above-described low molecular weight polyol as an initiator. And vegetable oil-based polyester polyols obtained by condensation reaction of hydroxycarboxylic acids such as those under known conditions.

  Furthermore, the polyester polyol includes, for example, the above-described low molecular weight polyol as an initiator, for example, lactones such as ε-caprolactone and γ-valerolactone, and lactides such as L-lactide and D-lactide. Examples thereof include polyester polyols such as polycaprolactone polyol and polyvalerolactone polyol obtained by ring-opening polymerization.

  Examples of the polycarbonate polyol include polycarbonate polyols obtained by using the above-described low molecular weight polyol as an initiator and carbonates such as ethylene carbonate and dimethyl carbonate. The polycarbonate polyol includes an amorphous polycarbonate diol composed of a copolymer of 1,5-pentanediol and 1,6-hexanediol, and a copolymer of 1,4-butanediol and 1,6-hexanediol. An amorphous polycarbonate diol composed of amorphous polycarbonate diol and 3-methyl-1,5-pentanediol.

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

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

  Moreover, as another monomer copolymerizable therewith, for example, (meth) acrylic acid, alkyl (meth) acrylate (C1-12), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) -α-methylstyrene, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate.

  The acrylic polyol can be obtained by copolymerizing these monomers in the presence of an appropriate solvent and a polymerization initiator.

  Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

  Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.

  As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

  As the fluorine polyol, for example, in the copolymerization of the above-mentioned acrylic polyol, a copolymer containing a vinyl group-containing fluorine compound, for example, tetrafluoroethylene, chlorotrifluoroethylene, etc., as another copolymerizable monomer Etc.

  Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

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

  And the polyurethane resin of this invention can be manufactured by polymerization methods, such as bulk polymerization and solution polymerization, for example.

  In bulk polymerization, for example, an active hydrogen compound is added to a pentamethylene diisocyanate and / or polyisocyanate composition while stirring the pentamethylene diisocyanate and / or polyisocyanate composition, and the reaction temperature is 50 to 250 ° C., more preferably 50 to 200 ° C. Then, the reaction is carried out for about 0.5 to 15 hours.

  In solution polymerization, a pentamethylene diisocyanate and / or polyisocyanate composition and an active hydrogen compound are added to an organic solvent, and the reaction temperature is 50 to 120 ° C., preferably 50 to 100 ° C., and about 0.5 to 15 hours. React.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; 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. .

  Further, in the above polymerization reaction, for example, a known urethanization catalyst such as amines or organometallic compounds may be added as necessary, and free (unreacted) from the resulting isocyanate group-terminated prepolymer. The pentamethylene diisocyanate and / or polyisocyanate composition may be removed by known removal means such as distillation or extraction.

  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.

  In bulk polymerization and solution polymerization, for example, pentamethylene diisocyanate and an active hydrogen compound are converted into an equivalent ratio of an isocyanate group in pentamethylene diisocyanate to an active hydrogen group (hydroxyl group, mercapto group, amino group) in the active hydrogen compound (NCO / The active hydrogen group) is blended so as to be, for example, 0.75 to 1.3, preferably 0.9 to 1.1.

  When the polymerization reaction is more industrially performed, the polyurethane resin can be obtained by a known method such as a one-shot method or a prepolymer method.

  In the one-shot method, for example, pentamethylene diisocyanate and / or polyisocyanate composition and an active hydrogen compound are converted into pentamethylene diisocyanate and / or polyisocyanate for active hydrogen groups (hydroxyl group, mercapto group, amino group) in the active hydrogen compound. After formulating (mixing) the isocyanate group equivalent ratio (NCO / active hydrogen group) in the composition to be, 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 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, a pentamethylene diisocyanate and / or polyisocyanate composition is reacted with a part of an active hydrogen compound (preferably a high molecular weight polyol) to have an isocyanate group at the molecular end. An isocyanate group-terminated prepolymer is synthesized. 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, a pentamethylene diisocyanate and / or polyisocyanate composition and a portion of the active hydrogen compound are combined with the isocyanate in pentamethylene diisocyanate relative to the active hydrogen group in the portion of the active hydrogen compound. Formulation (mixing) is carried out so that the equivalent ratio of groups (NCO / active hydrogen group) is, for example, 1.1 to 20, preferably 1.3 to 10, more preferably 1.3 to 6. In the container, for example, 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. After the reaction is completed, if necessary, unreacted pentamethylene diisocyanate is distilled, extracted, or the like. It can also be removed by known removal means.

  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.

  Thereby, a polyurethane resin can be obtained.

  In the production of the polyurethane resin of the present invention, known additives such as a plasticizer, an antiblocking agent, a heat stabilizer, a light stabilizer, an antioxidant, and a release agent are added as necessary. In addition, a catalyst, and further, a pigment, a dye, a lubricant, a filler, a hydrolysis inhibitor and the like can be blended in an appropriate ratio. 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.

  And since such a polyurethane resin is manufactured using the pentamethylene diisocyanate of this invention and the polyisocyanate composition of this invention, it can be equipped with the outstanding property.

  Therefore, such a polyurethane resin can be widely used in various industrial fields as, for example, paints, adhesives, elastomers, sealants, foams, and the like. In particular, it can be suitably used for parts such as casing coats, automobiles, motorcycles, aircraft, repair paints, and the like.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Measurement methods used in production examples and the like are shown below.
<Reaction yield of pentamethylenediamine (unit: mol%)>
Using L-lysine monohydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) and purified pentamethylenediamine obtained by (distillation of pentamethylenediamine) described below, under the following HPLC (high performance liquid chromatograph) analysis conditions The concentration of pentamethylenediamine was calculated from the calibration curve created from the area value of the obtained chromatograph, and the ratio of the concentration of pentamethylenediamine to the total concentration of L-lysine monohydrochloride and pentamethylenediamine was calculated as pentamethylenediamine. Reaction yield.

Column: Asahipak ODP-50 4E (Showa Denko)
Column temperature: 40 ° C
Eluent: 0.2 mol / L sodium phosphate (pH 7.7) +2.3 mmol / L 1-octane sulfonate sodium flow rate: 0.5 mL / min
For detection of L-lysine monohydrochloride and pentamethylenediamine, a post-column derivatization method using orthophthalaldehyde [J. Chromatogr. 83, 353-355 (1973)].
<Puramethylenediamine purity (unit: mass%)>
The purity of pentamethylenediamine was calculated using a calibration curve created from the area values of the gas chromatogram obtained under the following gas chromatographic analysis conditions using the purified pentamethylenediamine obtained in (Distillation of pentamethylenediamine) described later. .

Apparatus; GC-6890 (manufactured by Agilent Technologies)
Column; WCOT FUSED SILICA CP-SIL 8CB FOR AMINES (Varian)
Oven temperature: held at 40 ° C. for 3 minutes, heated from 40 ° C. to 300 ° C. at 10 ° C./min, held at 300 ° C. for 11 minutes Inlet temperature: 250 ° C.
Detector temperature: 280 ° C
Carrier gas; helium detection method; FID
<Extraction rate (unit: mass%)>
In order to determine the extraction rate of pentamethylenediamine with the extraction solvent, the same measurement as the above (purity of pentamethylenediamine) was performed, the concentration of pentamethylenediamine in the aqueous solution of pentamethylenediamine before the extraction operation, and the extraction solvent after the extraction operation The concentration of pentamethylenediamine was measured.

And the extraction rate was computed with the following formula | equation.
(A) Mass of pentamethylenediamine in extraction solvent = Pentamethylenediamine concentration in extraction solvent × Mass of extraction solvent / 100
(B) Mass of pentamethylenediamine in the prepared pentamethylenediamine aqueous solution = diaminopentane concentration of pentamethylenediamine aqueous solution before extraction operation × mass of prepared pentamethylenediamine aqueous solution / 100
Extraction rate (mass%) = (a) / (b) × 100
<Total content (unit: mass%) of the compound having a cyclic structure containing a C = N bond>
It calculated | required by the total value of (2,3,4,5-tetrahydropyridine density | concentration) mentioned later and (2- (aminomethyl) -3,4,5,6-tetrahydropyridine density | concentration).
<2,3,4,5-tetrahydropyridine concentration (unit: mass%)>
Area value of gas chromatogram obtained by measurement under the same conditions as described in (Pentamethylenediamine purity) using 2,3,4,5-tetrahydropyridine obtained in (Structural analysis of unknown substance) described later The 2,3,4,5-tetrahydropyridine concentration was calculated from the calibration curve created from
<2- (Aminomethyl) -3,4,5,6-tetrahydropyridine concentration (unit: mass%)>
Using 2- (aminomethyl) -3,4,5,6-tetrahydropyridine obtained in (Structural analysis of unknown substance) described later, and obtained by measurement under the same conditions as described in (Puramethylenediamine purity). The concentration of 2- (aminomethyl) -3,4,5,6-tetrahydropyridine was calculated from a calibration curve created from the area values of the obtained gas chromatogram.
<Puramethylene diisocyanate purity (unit: mass%)>
The purity of pentamethylene diisocyanate was calculated from the isocyanate group concentration measured by the n-dibutylamine method in accordance with JIS K-1556 using a potentiometric titrator.
<Pentamethylene diisocyanate concentration (unit: mass%)>
Using the pentamethylene diisocyanate (a) obtained in Example 1 to be described later, a calibration curve prepared from the area value of the chromatogram obtained under the following HPLC analysis conditions was used to determine the pentamethylene diisocyanate in the polyisocyanate composition. Concentration was calculated.

Equipment; Prominence (manufactured by Shimadzu Corporation)
1) Pump LC-20AT
2) Degasser DGU-20A3
3) Autosampler SIL-20A
4) Column thermostat COT-20A
5) Detector SPD-20A
Column; SHISEIDO SILICA SG-120
Column temperature: 40 ° C
Eluent: n-hexane / methanol / 1,2-dichloroethane = 90/5/5 (volume ratio)
Flow rate: 0.2 mL / min
Detection method: UV 225 nm
<Purity of bis (butoxycarbonylamino) pentane (unit: mass%)>
The purity of bis (butoxycarbonylamino) pentane was calculated using a calibration curve created from the area values of the chromatogram obtained under the following HPLC analysis conditions.

Apparatus; alliance 2695 separation module (manufactured by Waters)
Detector 2414 RI detector column; Unison UK C-18 manufactured by Imtakt
Column temperature: 40 ° C
Eluent: acetonitrile / distilled water = 45/55 (volume ratio)
Flow rate: 1.0 mL / min
Detection method: RI
<Yield of bis (butoxycarbonylamino) pentane (unit: mass%)
The yield of bis (butoxycarbonylamino) pentane was calculated using the following formula.

_{(W 2 × C 2/100} ) / (W 1 × C 1/100 × M 2 / M 1) × 100
M ₁ : Molecular weight of pentamethylenediamine M ₂ : Molecular weight of bis (butoxycarbonylamino) pentane C ₁ : Concentration of n-butanol solution of pentamethylenediamine C ₂ : Purity of bis (butoxycarbonylamino) pentane W ₁ : Pentamethylene Charged part by mass of n-butanol solution of diamine W ₂ : part by mass of bis (butoxycarbonylamino) pentane obtained <purity of pentamethylene diisocyanate (unit: mass%)>
The purity of pentamethylene diisocyanate was measured by an n-dibutylamine method based on JIS K-1603-1 using a potentiometric titrator.
<Yield of thermal decomposition reaction (unit: mass%)>
The yield of the thermal decomposition reaction was calculated using the following formula.

_{(W 4 × C 3/100} ) / (W 3 × C 2/100 × M 3 / M 2) × 100
M ₃ : Molecular weight of pentamethylene diisocyanate C ₃ : Purity of pentamethylene diisocyanate W ₃ : Charged mass part of bis (butoxycarbonylamino) pentane W ₄ : Mass part of the obtained pentamethylene diisocyanate <Yield of pentamethylene diisocyanate ( (Unit: mass%)>
The yield of pentamethylene diisocyanate was calculated using the following formula.

A x B / 100
A: Yield of bis (butoxycarbonylamino) pentane B: Yield of thermal decomposition reaction <Conversion rate of isocyanate group (unit:%)>
The conversion rate of the isocyanate group is the ratio of the area of the peak on the high molecular weight side of the peak of pentamethylene diisocyanate to the total peak area, based on the chromatogram obtained under the following GPC measurement conditions, 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 Flow rate: 0.8 mL / min
Detection method: Differential refractive index Standard material: Polyethylene oxide (manufactured by Tosoh Corporation, trade name: TSK standard polyethylene oxide)
<Isocyanate trimer concentration (unit: mass%)>
The measurement similar to the above (conversion rate of isocyanate group) was performed, and a peak area ratio corresponding to a molecular weight three times that of pentamethylene diisocyanate was defined as an isocyanate trimer concentration.
<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.
<Viscosity (unit: mPa · s)>
The viscosity at 25 ° C. of the polyisocyanate composition was measured using an E-type viscometer TV-30 manufactured by Toki Sangyo Co., Ltd.
<Hue (unit: APHA)>
The hue of the polyisocyanate composition was measured by a method based on JIS K-0071.
(Distillation of pentamethylenediamine)
Into a four-necked flask equipped with a thermometer, a distillation tower, a cooling pipe, and a nitrogen introduction pipe, pentamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) is charged and further refluxed under conditions of a tower top temperature of 111 to 115 ° C. and 10 KPa. Then, rectification was performed to obtain purified pentamethylenediamine. The pentamethylenediamine purified by distillation had a gas chromatography area ratio of 100%.

Preparation Example 1 (Preparation of cell disruption solution)
(Cloning of lysine decarboxylase gene (cadA))
Genomic DNA prepared from Escherichia coli W3110 strain (ATCC 27325) according to a conventional method was used as a PCR template.

  As primers for PCR, oligonucleotides having the nucleotide sequences shown in SEQ ID NOs: 1 and 2 designed based on the nucleotide sequence of lysine decarboxylase gene (cadA) (GenBank Accession No. AP009048) (consigned to Invitrogen) Synthesized). These primers have restriction enzyme recognition sequences for KpnI and XbaI, respectively, near the 5 'end.

  Using 25 μL of a PCR reaction solution containing 1 ng / μL of genomic DNA and 0.5 pmol / μL of each primer, denaturation: 94 ° C., 30 seconds, annealing: 55 ° C., 30 seconds, extension reaction: 68 ° C., from 2 minutes PCR was performed under the following reaction cycle of 30 cycles.

  The PCR reaction product and plasmid pUC18 (Takara Shuzo) were digested with KpnI and XbaI and ligated using Ligation High (Toyobo), then Escherichia coli DH5α (Toyobo) Made). The transformant was cultured on an LB agar medium containing 100 μg / mL of ampicillin (Am) and X-Gal (5-bromo-4-chloro-3-indolyl-β-D-galactoside), and was Am-resistant and white colony. The resulting transformant was obtained. A plasmid was extracted from the transformant thus obtained.

  In accordance with the usual method for determining the base sequence, it was confirmed that the base sequence of the DNA fragment introduced into the plasmid was the base sequence shown in SEQ ID NO: 3.

The obtained plasmid having DNA encoding lysine decarboxylase was named pCADA. By culturing E. coli transformed with pCADA, lysine decarboxylase having the amino acid sequence shown in SEQ ID NO: 4 could be produced.
(Production of transformants)
Escherichia coli W3110 strain was transformed with pCADA by a conventional method, and the resulting transformant was named W / pCADA.

  This transformant was inoculated into 500 ml of LB medium containing 100 μg / mL of Am in a baffled Erlenmeyer flask, shake-cultured at 30 ° C. until OD (660 nm) became 0.5, and then IPTG (isopropyl-β-thio). Galactopyranoside) was added at 0.1 mmol / L, and the mixture was further cultured with shaking for 14 hours. The culture solution was centrifuged at 8000 rpm for 20 minutes to obtain bacterial cells. The cells were suspended in a 20 mmol / L sodium phosphate buffer (pH 6.0), and then ultrasonically disrupted to prepare a cell disruption solution.

Preparation Example 2 (Production of pentamethylenediamine aqueous solution)
In a flask, L-lysine monohydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added so that the final concentration was 45 mass%, and pyridoxal phosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared with a final concentration of 0.15 mmol / L. 120 parts by mass of the prepared substrate solution was added. Next, the above-mentioned W / pCADA cell disruption solution (the weight of charged dry cell equivalent 0.3 g) was added to initiate the reaction. The reaction conditions were 37 ° C. and 200 rpm. The pH of the reaction solution was adjusted to pH 6 with 6 mol / L hydrochloric acid. The reaction yield of pentamethylenediamine after 24 hours reached 99%. The reaction solution after 24 hours of the reaction was adjusted to pH 2 with 6 mol / L hydrochloric acid, 0.6 parts by mass of activated carbon (powdered activated carbon PM-SX manufactured by Mikura Kasei Co., Ltd.) was added, and the mixture was heated at 25 ° C. for 1 hour. After stirring, filtration was performed with a filter paper (5C manufactured by ADVANTEC). Next, this filtrate was adjusted to pH 12 with sodium hydroxide to obtain a pentamethylenediamine aqueous solution (17.0 mass% aqueous solution).

Production Example 1 (Preparation of pentamethylenediamine (a))
A separating funnel was charged with 100 parts by mass of an aqueous pentamethylenediamine solution and 100 parts by mass of n-butanol, mixed for 10 minutes, and then allowed to stand for 30 minutes. The lower layer which is an aqueous layer was extracted, and then the upper layer which was an organic layer was extracted. As a result of measuring the extraction rate, it was 91.8%.

  Next, 80 parts by mass of the organic layer extract was charged into a four-necked flask equipped with a thermometer, a distillation column, a cooling tube, and a nitrogen introduction tube, the oil bath temperature was 120 ° C., and n-butanol was added under a reduced pressure of 10 kPa. Distilled to obtain pentamethylenediamine (a) having a purity of 99.9% by mass.

  That is, pentamethylenediamine (a) could be prepared by solvent extraction of an aqueous solution of pentamethylenediamine with n-butanol and further distilling off n-butanol.

  The obtained pentamethylenediamine (a) contained impurities including 2,3,4,5-tetrahydropyridine.

Production Example 2 (Preparation of pentamethylenediamine (b))
Solvent extraction was performed in the same manner as in Production Example 1 except that 100 parts by mass of chloroform was used instead of 100 parts by mass of n-butanol. As a result of measuring the extraction rate, it was 62.0%.

  Subsequently, chloroform was distilled off in the same manner as in Production Example 1 to obtain pentamethylenediamine (b) having a purity of 97.8% by mass.

  That is, pentamethylenediamine (b) could be prepared by subjecting an aqueous pentamethylenediamine solution to solvent extraction with chloroform and further distilling off chloroform.

  The resulting pentamethylenediamine (b) contained 2,3,4,5-tetrahydropyridine and impurities including unknown substances.

Production Example 3 (Preparation of pentamethylenediamine (c))
100 parts by mass of pentamethylenediamine (a) obtained as described above and 100 parts by mass of pentamethylenediamine (b) were blended and mixed to produce pentamethylenediamine (c).

  The obtained pentamethylene diamine (c) contained 2,3,4,5-tetrahydropyridine and impurities including unknown substances.

Production Example 4 (Preparation of pentamethylenediamine (d))
100 parts by mass of pentamethylenediamine (a) obtained as described above and 200 parts by mass of pentamethylenediamine (b) were blended and mixed to produce pentamethylenediamine (d).

  The obtained pentamethylenediamine (d) contained impurities including 2,3,4,5-tetrahydropyridine and unknown substances.

Production Example 5 (Preparation of pentamethylenediamine (e) (n-butanol solution of 1,5-pentamethylenediamine))
A separating funnel was charged with 100 parts by mass of an aqueous pentamethylenediamine solution and 100 parts by mass of n-butanol, mixed for 10 minutes, and then allowed to stand for 30 minutes. The lower layer which is an aqueous layer was extracted, and then the upper layer which was an organic layer was extracted. As a result of measuring the extraction rate, it was 91.7%, almost the same as in Production Example 1.

  Next, 80 parts by mass of the organic layer extract is charged into a four-necked flask equipped with a thermometer, distillation tower, cooling pipe, and nitrogen introduction pipe, and heated at normal pressure until the liquid temperature reaches 139 ° C., And n-butanol was distilled off and 17 mass parts of n-butanol solutions of 1,5-pentamethylenediamine were obtained. Next, 17 parts by mass of an n-butanol solution of 1,5-pentamethylenediamine was charged into a four-necked flask equipped with a thermometer, a distillation tower, a cooling tube, and a nitrogen introduction tube, and the liquid temperature was 65 at 1.7 kPa. It heated until it reached to degree C, and pentamethylenediamine (e) (n-butanol solution of 1,5-pentamethylenediamine) was obtained as a distillate. The purity of pentamethylenediamine of pentamethylenediamine (e) was 33.5%.

Production Example 6 (Preparation of pentamethylenediamine (f) (isobutanol solution of 1,5-pentamethylenediamine))
A separating funnel was charged with 100 parts by mass of an aqueous pentamethylenediamine solution and 100 parts by mass of isobutanol, mixed for 10 minutes, and then allowed to stand for 30 minutes. The lower layer which is an aqueous layer was extracted, and then the upper layer which was an organic layer was extracted. As a result of measuring the extraction rate, it was 85.8%.

  Next, 80 parts by mass of the organic layer extract is charged into a four-necked flask equipped with a thermometer, a distillation column, a cooling tube, and a nitrogen introduction tube, and heated at normal pressure until the liquid temperature reaches 130 ° C., And isobutanol was distilled off to obtain 16 parts by mass of an isobutanol solution of 1,5-pentamethylenediamine. Next, 16 parts by mass of an isobutanol solution of 1,5-pentamethylenediamine was charged into a four-necked flask equipped with a thermometer, a distillation tower, a cooling tube, and a nitrogen introduction tube, and the liquid temperature was 65 ° C. at 1.7 kPa. The purity of pentamethylenediamine in pentamethylenediamine (f) obtained as a distillate was pentamethylenediamine (f) (an isobutanol solution of 1,5-pentamethylenediamine) was 33.9%. Met.

Test Example 1 (Structural analysis of unknown substance contained in pentamethylenediamine)
Impurities contained in pentamethylenediamine were separated using a solid-phase extraction cartridge (VARIAN, model 1225-6067), and structural analysis was performed by GC-MS analysis and NMR analysis.

  In order to condition the solid phase extraction cartridge, a mixed solution of 50 mL of methanol and 450 mL of chloroform was passed. After dissolving 500 mg of pentamethylenediamine (b) in a mixed solution of 50 mL of methanol and 450 mL of chloroform, the solution was passed through a solid phase extraction cartridge to obtain an effluent. Subsequently, the mixed solution of methanol and chloroform at the ratio shown below was passed through 5 times, and the effluent from the solid phase extraction cartridge was collected.

First time: Mixed solution of methanol 100 mL and chloroform 900 mL Second time; Mixed solution of methanol 50 mL and chloroform 450 mL Third time: Mixed solution of methanol 100 mL and chloroform 400 mL Fourth time: Mixed solution of methanol 100 mL and chloroform 400 mL Fifth time; Mixed solution of chloroform (400 mL) The solvent was removed from the first and second effluents by nitrogen purge, and the resulting compound was measured under the conditions of GC-MS analysis 1 below. As a result, pentamethylenediamine was not detected, and 2,3,4,5-tetrahydropyridine having an area ratio of 99% was detected.

  The compound obtained from the third time was measured by GC-MS analysis 1 in the same manner as in the first and second effluents. As a result, pentamethylenediamine was not detected, but 2,3,4,5-tetrahydropyridine and an unknown substance were detected.

  The compounds obtained from the fourth and fifth times were measured by GC-MS analysis 1 in the same manner as in the first and second effluents. As a result, pentamethylenediamine and 2,3,4,5-tetrahydropyridine were not detected, and an unknown substance with an area ratio of 99% was detected.

  The chromatogram of GC-MS analysis 1 of the 4th and 5th compound is shown in FIG.

  In FIG. 1, the peak at 4:08 is chloroform and the peak at 13:26 is an unknown substance.

  Moreover, the spectrum of the GC-MS analysis 1 of the 4th and 5th time compound is shown in FIG.

  Next, in order to determine the chemical formula of the unknown substance, the distilled and purified pentamethylenediamine obtained in the above (distillation of pentamethylenediamine) was added as a standard substance to the fourth and fifth compounds, and the following GC-MS analysis 2 It measured on condition of this. The obtained chromatogram is shown in FIG.

  In FIG. 3, the 11:61 peak is pentamethylenediamine, and the 13:34 peak is an unknown substance.

From the results of GC-MS analysis 2, it was confirmed that the chemical formula of the unknown substance was C ₆ H ₁₂ N ₂ .

  Subsequently, in order to perform the structural analysis of the unknown substance, the fourth and fifth compounds were measured under the following NMR analysis conditions.

4 shows the results of ¹ H-NMR of the unknown substance, FIG. 5 shows the results of ¹³ C-NMR, FIG. 6 shows the results of COSY, FIG. 7 shows the results of HMQC, and FIGS. 8 and 9 show the results of HMBC. Shown in FIG. 9 shows an enlarged view of the result shown in FIG.

  From the results of GC-MS analysis and NMR analysis, it was confirmed that the unknown substance was 2- (aminomethyl) -3,4,5,6-tetrahydropyridine.

In addition, the apparatus and conditions of GC-MS analysis and NMR analysis are shown below.
<GC-MS analysis 1>
Device: Q1000GC K9 (manufactured by JEOL Ltd.)
Ionization method; EI
Column; WCOT FUSED SILICA CP-SIL 8CB FOR AMINES (Varian), 0.25 mmφ × 30 m
Oven temperature: held at 40 ° C. for 3 minutes, heated from 40 ° C. to 300 ° C. at 10 ° C./min, held at 300 ° C. for 11 minutes Inlet temperature: 250 ° C.
He flow rate: 0.7 mL / min
Injection mode; split <GC-MS analysis 2>
Device: JMS-T100GC (manufactured by JEOL)
Ionization method; FI
Column; WCOT FUSED SILICA CP-SIL 8CB FOR AMINES (Varian), 0.25 mmφ × 30 m
Oven temperature: held at 40 ° C. for 3 minutes, heated from 40 ° C. to 300 ° C. at 10 ° C./min, held at 300 ° C. for 11 minutes Inlet temperature: 250 ° C.
He flow rate: 0.7 mL / min
Injection mode; split <NMR analysis>
Equipment: Nuclear magnetic resonance system ECA500 (manufactured by JEOL)
Measurement method: ¹ H-NMR, ¹³ C-NMR, COSY, HMQC, HMBC
Test Example 2 (Measurement of impurity concentration)
The concentration of impurities (2,3,4,5-tetrahydropyridine and 2- (aminomethyl) -3,4,5,6-tetrahydropyridine) contained in the pentamethylenediamine obtained in each production example is Calculation was performed by the following method.

  That is, the purified pentamethylene obtained by the above-mentioned (distillation of pentamethylenediamine) so that the concentration of 2,3,4,5-tetrahydropyridine was 2% by mass, 0.5% by mass, and 0.05% by mass. Diamine and 2,3,4,5-tetrahydropyridine obtained in Test Example 1 were mixed. Next, as an internal standard substance, a certain amount of o-dichlorobenzene (hereinafter sometimes abbreviated as ODCB) and a solution of methanol as a solvent were added three times to the purity of pentamethylenediamine. Calibration curve with the same conditions as described, with the horizontal axis representing the area ratio of ODCB and 2,3,4,5-tetrahydropyridine and the vertical axis representing the concentration ratio of ODCB to 2,3,4,5-tetrahydropyridine It was created.

  A certain amount of ODCB and a solvent methanol were added to the pentamethylenediamine obtained in each production example, and the same conditions as described in (Pentamethylenediamine purity) were measured. The 5-tetrahydropyridine concentration was calculated.

  The concentration of 2- (aminomethyl) -3,4,5,6-tetrahydropyridine was calculated in the same manner as the 2,3,4,5-tetrahydropyridine concentration calculation method.

  As a result, the 2,3,4,5-tetrahydropyridine concentration of pentamethylenediamine (a) was 0.1% by mass, and the 2- (aminomethyl) -3,4,5,6-tetrahydropyridine concentration was detected. It was less than the limit (detection limit: 0.0006% by mass), and the total amount thereof (total amount in the detectable range) was 0.1% by mass.

  The 2,3,4,5-tetrahydropyridine concentration of pentamethylenediamine (b) is 0.6% by mass, and the concentration of 2- (aminomethyl) -3,4,5,6-tetrahydropyridine is 1.6% by mass. %, And their total amount was 2.2% by mass.

  The 2,3,4,5-tetrahydropyridine concentration of pentamethylenediamine (c) is 0.4 mass%, and the concentration of 2- (aminomethyl) -3,4,5,6-tetrahydropyridine is 0.8 mass%. %, And their total amount was 1.2% by mass.

  The 2,3,4,5-tetrahydropyridine concentration of pentamethylenediamine (d) is 0.4% by mass, and the concentration of 2- (aminomethyl) -3,4,5,6-tetrahydropyridine is 1.1% by mass. %, And their total amount was 1.5% by mass.

  The 2,3,4,5-tetrahydropyridine concentration of pentamethylenediamine (e) is 0.03% by mass, and the 2- (aminomethyl) -3,4,5,6-tetrahydropyridine concentration is below the detection limit. The total amount thereof was 0.03% by mass.

  The 2,3,4,5-tetrahydropyridine concentration of pentamethylenediamine (f) is 0.03% by mass, and the concentration of 2- (aminomethyl) -3,4,5,6-tetrahydropyridine is below the detection limit. The total amount thereof was 0.03% by mass.

  Table 1 shows the concentration of each impurity in each of these pentamethylenediamines.

Example 1 (Production of pentamethylene diisocyanate (a))
A mixture of 51 parts by mass of pentamethylenediamine (a), 72 parts by mass of urea and 222 parts by mass of n-butanol was charged into a SUS autoclave equipped with a pressure control valve, a reflux condenser, a gas-liquid separator, and a stirrer. The gas was allowed to react for 3 hours while adjusting the internal pressure with a pressure control valve so as to keep the reaction temperature at 215 ° C. while stirring the gas at a flow rate of 0.3 L per minute at 500 rpm. The obtained reaction solution was distilled under reduced pressure at 0.5 KPa and 150 ° C. to cut light boiling components, and 150 parts by mass of bis (butoxycarbonylamino) pentane having a purity of 96.1% was obtained.

  Next, a four-necked flask equipped with a rectifying column equipped with a stirrer, a thermometer and a cooler was used as a reactor, warm water at 80 ° C. was passed through the cooler, and the receiver was passed through a cold trap cooled with cold acetone. Connected to vacuum line. The flask was charged with 70 parts by weight of bis (butoxycarbonylamino) pentane, 70 parts by weight of barrel process oil B-30 (manufactured by Matsumura Oil Co., Ltd.), and 0.14 parts by weight of dibutyltin dilaurate. After the reaction system was purged with nitrogen, the pressure was reduced to 3.0 kPa, and the reaction solution was heated to 250 ° C. and reacted for 2 hours. After completion of the reaction, the reaction solution collected in the receiver was quantified by gas chromatography. As a result, pentamethylene diisocyanate (a) having a purity of 99.9% by mass was obtained.

  The analysis conditions for gas chromatography are shown below.

Device: GC-14B (manufactured by Shimadzu Corporation)
Column; UA-20EX-2.0F, 1.2 mmφ × 20 m (manufactured by Frontier Laboratories)
Oven temperature: held at 100 ° C. for 2 minutes, raised from 100 ° C. to 240 ° C. at 10 ° C./min, held at 240 ° C. for 14 minutes Inlet temperature: 250 ° C.
Detector temperature: 250 ° C
Carrier gas; helium detection method; FID
Example 2 (Production of pentamethylene diisocyanate (b))
2000 parts by mass of o-dichlorobenzene 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 pentamethylenediamine (a) in 2600 parts by mass of o-dichlorobenzene 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.

  Subsequently, after o-dichlorobenzene was distilled off under reduced pressure, pentamethylene diisocyanate was also distilled off under reduced pressure.

  Subsequently, the distilled pentamethylene diisocyanate was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, and at 200 ° C. under atmospheric pressure while introducing nitrogen. Heat treatment was performed for a time.

  Next, the heat-treated pentamethylene diisocyanate 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), reflux ratio Further reflux under conditions of 127 to 132 ° C. and 2.7 KPa using a distillation tower equipped with a control timer (manufactured by Shibata Kagaku Co., Ltd., trade name: distillation head K type) and a rectifier equipped with a condenser. Then, rectification was performed to obtain 450 parts by mass of pentamethylene diisocyanate (b) having a purity of 99.8% by mass.

Example 3 (Production of pentamethylene diisocyanate (c))
A pentamethylene diisocyanate (c) having a purity of 99.4% by mass was obtained under the same conditions and operation as in Example 1 except that pentamethylenediamine (c) was used instead of pentamethylenediamine (a). Example 4 (Production of pentamethylene diisocyanate (d))
A pentamethylene diisocyanate (d) having a purity of 99.3% by mass was obtained under the same conditions and operation as in Example 1 except that pentamethylenediamine (d) was used instead of pentamethylenediamine (a).

Comparative Example 1 (Production of pentamethylene diisocyanate (e))
A pentamethylene diisocyanate (e) having a purity of 98.7% by mass was obtained under the same conditions and operation as in Example 1 except that pentamethylenediamine (b) was used instead of pentamethylenediamine (a).

Comparative Example 2 (Production of pentamethylene diisocyanate (f))
A pentamethylene diisocyanate (f) having a purity of 98.4% by mass was obtained under the same conditions and operation as in Example 2 except that pentamethylenediamine (b) was used instead of pentamethylenediamine (a).

Example 5 (Production of pentamethylene diisocyanate (g))
In a SUS autoclave equipped with a pressure control valve, a reflux condenser, a gas-liquid separator, and a stirrer, pentamethylenediamine (e) obtained in Production Example 5 (n-butanol solution of 1,5-pentamethylenediamine) A mixture of 152 parts by mass, 72 parts by mass of urea, and 121 parts by mass of n-butanol was charged, and the internal pressure was controlled to keep the reaction temperature at 215 ° C. while stirring nitrogen gas at a flow rate of 0.3 L per minute at 500 rpm. The reaction was allowed to proceed for 3 hours while adjusting. The obtained reaction solution was distilled under reduced pressure at 0.5 KPa and 150 ° C. to cut light boiling, and 150 parts by mass of bis (butoxycarbonylamino) pentane having a purity of 96.2% by mass was obtained with a yield of 95.6 masses. %.

  Next, a four-necked flask equipped with a rectifying column equipped with a stirrer, a thermometer and a cooler was used as a reactor, warm water at 80 ° C. was passed through the cooler, and the receiver was passed through a cold trap cooled with cold acetone. Connected to vacuum line. The flask was charged with 150 parts by mass of bis (butoxycarbonylamino) pentane, 150 parts by mass of barrel process oil B-30 (manufactured by Matsumura Oil Co., Ltd.), and 0.3 parts by mass of dibutyltin dilaurate. After substituting the reaction system with nitrogen, the pressure was reduced to 3.0 kPa, the reaction solution was heated to 250 ° C. and subjected to a pyrolysis reaction for 2 hours, and 70 parts by mass of pentamethylene diisocyanate (g) having a purity of 99.9% by mass was performed. Obtained. The yield of the thermal decomposition reaction was 95.1% by mass, and the yield of pentamethylene diisocyanate (g) was 91.0% by mass.

Example 6 (Production of pentamethylene diisocyanate (h))
In a SUS autoclave equipped with a pressure control valve, a reflux condenser, a gas-liquid separator, and a stirrer, pentamethylenediamine (f) obtained in Production Example 6 (isobutanol solution of 1,5-pentamethylenediamine) 150 Charge a mixture of parts by mass, 72 parts by mass of urea, and 123 parts by mass of n-butanol, and with a pressure control valve to keep the reaction temperature at 215 ° C. while stirring nitrogen gas at 0.3 L / min and 500 rpm. The reaction was allowed to proceed for 3 hours while adjusting. The obtained reaction solution was distilled under reduced pressure at 0.5 KPa and 150 ° C. to cut light boiling components, and 150 parts by mass of bis (butoxycarbonylamino) pentane having a purity of 89.8% by mass was obtained with a yield of 89.3 masses. %.

  Next, a four-necked flask equipped with a rectifying column equipped with a stirrer, a thermometer and a cooler was used as a reactor, warm water at 80 ° C. was passed through the cooler, and the receiver was passed through a cold trap cooled with cold acetone. Connected to vacuum line. The flask was charged with 150 parts by mass of bis (butoxycarbonylamino) pentane, 150 parts by mass of barrel process oil B-30 (manufactured by Matsumura Oil Co., Ltd.), and 0.3 parts by mass of dibutyltin dilaurate. After the atmosphere in the reaction system was replaced with nitrogen, the pressure was reduced to 3.0 kPa, the reaction solution was heated to 250 ° C. and subjected to thermal decomposition for 2 hours, and 63 parts by mass of pentamethylene diisocyanate (h) having a purity of 99.9% by mass was obtained. Obtained. The yield of the thermal decomposition reaction was 91.9% by mass, and the yield of pentamethylene diisocyanate (h) was 82.1% by mass.

Example 7 (Production of pentamethylene diisocyanate (i))
With respect to 100 parts by mass of the reaction solution obtained in Example 1, 0.005 part by mass of 2,6-di (tert-butyl) -4-methylphenol, 0.001 part by mass of p-toluenesulfonamide, tris (tridecyl) ) 0.01 parts by mass of phosphite was added to obtain pentamethylene diisocyanate (i) having a purity of 99.9% by mass.

  Next, pentamethylene diisocyanate (i) was transferred to a sample bottle, purged with nitrogen, and allowed to stand in an oven at 50 ° C. for 14 days to perform a storage stability test. The purity of pentamethylene diisocyanate (i) after the test was 99.8% by mass.

Example 8 (Production of pentamethylene diisocyanate (j))
To 100 parts by mass of the reaction solution obtained in Example 1, 0.005 part by mass of 2,6-di (tert-butyl) -4-methylphenol was added, and pentamethylene diisocyanate having a purity of 99.9% by mass ( j) was obtained.

  Next, pentamethylene diisocyanate (j) was transferred to a sample bottle, purged with nitrogen, and left in an oven at 50 ° C. for 14 days to perform a storage stability test. The purity of pentamethylene diisocyanate (j) after the test was 99.4% by mass.

  Table 2 shows the purity of pentamethylene diisocyanate obtained in each example and each comparative example.

Example 9 (Production of polyisocyanate composition (A))
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate (a) and 0,2,6-di (tert-butyl) -4-methylphenol were added. .25 parts by mass and 0.25 part by mass of tris (tridecyl) phosphite were charged, and the temperature was raised to 60 ° C. Next, 0.1 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added as a trimerization catalyst. After reacting for 1 hour, 0.12 parts by mass of o-toluenesulfonamide was added (conversion rate of isocyanate group: 10% 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 pentamethylene diisocyanate, and further, o-based on 100 parts by mass of the obtained composition. 0.02 parts by mass of toluenesulfonamide was added to obtain a polyisocyanate composition (A).

  This polyisocyanate composition (A) has a pentamethylene diisocyanate concentration of 0.3% by mass, an isocyanate trimer concentration of 63% by mass, an isocyanate group concentration 1 of 25.9% by mass, and a viscosity 1 at 25 ° C. of 1530 mPa · s. Hue 1 was APHA20. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Subsequently, the polyisocyanate composition (A) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to perform a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 25.5% by mass, a viscosity 2 at 25 ° C. of 1650 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Example 10 (Production of polyisocyanate composition (B))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate (a), 1,3-butanediol (hereinafter abbreviated as 1,3-BG). 3.9 parts by mass), 0.25 parts by mass of 2,6-di (tert-butyl) -4-methylphenol, and 0.25 parts by mass of tris (tridecyl) phosphite. The reaction was carried out at 80 ° C. for 3 hours. After the temperature of this solution was lowered to 60 ° C., 0.1 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added as a trimerization catalyst. After reacting for 1 hour, 0.12 parts by mass of o-toluenesulfonamide was added (conversion rate of isocyanate group: 10% 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 pentamethylene diisocyanate, and further, o-based on 100 parts by mass of the obtained composition. 0.02 parts by mass of toluenesulfonamide was added to obtain a polyisocyanate composition (B).

  This polyisocyanate composition (B) has a pentamethylene diisocyanate concentration of 0.4 mass%, an isocyanate trimer concentration of 46 mass%, an isocyanate group concentration 1 of 24.0 mass%, and a viscosity 1 at 25 ° C. of 1930 mPa · s. Hue 1 was APHA20. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (B) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to conduct a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 23.5% by mass, a viscosity 2 at 25 ° C. of 2100 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Example 11 (Production of polyisocyanate composition (C))
A polyisocyanate composition (C) was obtained in the same manner as in Example 10 except that pentamethylene diisocyanate (b) was used instead of pentamethylene diisocyanate (a).

  This polyisocyanate composition (C) has a pentamethylene diisocyanate concentration of 0.6% by mass, an isocyanate trimer concentration of 43% by mass, an isocyanate group concentration 1 of 23.5% by mass, and a viscosity 1 at 25 ° C. of 2120 mPa · s. Hue 1 was APHA30. These measured values are shown in Table 2 as measured values before the heating acceleration test.

  Next, the polyisocyanate composition (C) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to carry out a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 23.0% by mass, a viscosity 2 at 25 ° C. of 2370 mPa · s, and a hue 2 of APHA40. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Example 12 (Production of polyisocyanate composition (D))
A polyisocyanate composition (D) was obtained in the same manner as in Example 10 except that pentamethylene diisocyanate (c) was used instead of pentamethylene diisocyanate (a).

  This polyisocyanate composition (D) has a pentamethylene diisocyanate concentration of 0.6% by mass, an isocyanate trimer concentration of 42% by mass, an isocyanate group concentration 1 of 21.8% by mass, and a viscosity 1 at 25 ° C. of 2350 mPa · s. Hue 1 was APHA40. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (D) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to conduct a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 21.1% by mass, a viscosity 2 at 25 ° C. of 2830 mPa · s, and a hue 2 of APHA60. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Example 13 (Production of polyisocyanate composition (E))
A polyisocyanate composition (E) was obtained in the same manner as in Example 10 except that pentamethylene diisocyanate (d) was used instead of pentamethylene diisocyanate (a).

  This polyisocyanate composition (E) has a pentamethylene diisocyanate concentration of 0.7% by mass, an isocyanate trimer concentration of 40% by mass, an isocyanate group concentration 1 of 20.9% by mass, and a viscosity 1 at 25 ° C. of 2420 mPa · s. Hue 1 was APHA50. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (E) was transferred to a metal container, purged with nitrogen, and allowed to stand in an oven at 60 ° C. for 4 days, and a heating acceleration test was performed. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 20.1% by mass, a viscosity 2 at 25 ° C. of 2930 mPa · s, and a hue 2 of APHA70. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Comparative Example 3 (Production of polyisocyanate composition (F))
Instead of pentamethylene diisocyanate (a), pentamethylene diisocyanate (e) was used and a trimerization reaction was carried out in the same manner as in Example 10, but it was confirmed from the measurement of isocyanate group concentration that the reaction rate was low. Therefore, 0.2 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added to obtain a polyisocyanate composition (F).

  This polyisocyanate composition (F) has a pentamethylene diisocyanate concentration of 0.7% by mass, an isocyanate trimer concentration of 34% by mass, an isocyanate group concentration 1 of 19.1% by mass, and a viscosity 1 at 25 ° C. of 2870 mPa · s. Hue 1 was APHA100. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (F) was transferred to a metal container, purged with nitrogen, and then allowed to stand in an oven at 60 ° C. for 4 days to conduct a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 17.0% by mass, a viscosity 2 at 25 ° C. of 3790 mPa · s, and a hue 2 of APHA150. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Comparative Example 4 (Production of polyisocyanate composition (G))
Instead of pentamethylene diisocyanate (a), pentamethylene diisocyanate (f) was used and a trimerization reaction was carried out in the same manner as in Example 10. However, it was confirmed from the measurement of isocyanate group concentration that the reaction rate was low. Therefore, 0.2 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added. After measurement of the isocyanate group concentration, 0.1 parts by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was further added to obtain a polyisocyanate composition (G). .

  This polyisocyanate composition (G) has a pentamethylene diisocyanate concentration of 0.8% by mass, an isocyanate trimer concentration of 32% by mass, an isocyanate group concentration 1 of 18.4% by mass, and a viscosity 1 at 25 ° C. of 3010 mPa · s. Hue 1 was APHA150. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (G) was transferred to a metal container, purged with nitrogen, and allowed to stand in an oven at 60 ° C. for 4 days, and a heating acceleration test was performed. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 15.6% by mass, a viscosity 2 at 25 ° C. of 4180 mPa · s, and a hue 2 of APHA200. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Example 14 (Production of polyisocyanate composition (H))
A polyisocyanate composition (H) was obtained in the same manner as in Example 10 except that pentamethylene diisocyanate (i) was used instead of pentamethylene diisocyanate (a).

  This polyisocyanate composition (H) has a pentamethylene diisocyanate concentration of 0.3% by mass, an isocyanate trimer concentration of 45% by mass, an isocyanate group concentration 1 of 23.9% by mass, and a viscosity 1 at 25 ° C. of 2000 mPa · s. Hue 1 was APHA20. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (H) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to perform a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 23.4% by mass, a viscosity 2 at 25 ° C. of 2200 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 3.

Example 15 (Production of polyisocyanate composition (I))
Polyisocyanate composition (I) was obtained in the same manner as in Example 10 except that pentamethylene diisocyanate (j) was used instead of pentamethylene diisocyanate (a).

  This polyisocyanate composition (I) has a pentamethylene diisocyanate concentration of 0.5% by mass, an isocyanate trimer concentration of 42% by mass, an isocyanate group concentration 1 of 22.3% by mass, and a viscosity 1 at 25 ° C. of 2250 mPa · s. Hue 1 was APHA20. These measured values are measured values before the heating acceleration test and are shown in Table 3.

  Next, the polyisocyanate composition (I) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to carry out a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 21.6% by mass, a viscosity 2 at 25 ° C. of 2670 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 3.

(Discussion)
The pentamethylene diisocyanate (i) used in Example 14 contains an antioxidant, an acidic compound, and a compound having a sulfonamide group, so that it is stored in advance (50 ° C., 14 days) at a high temperature. However, the polyisocyanate composition obtained using the pentamethylene diisocyanate was able to ensure the same level of storage stability as other polyisocyanate compositions in which pentamethylene diisocyanate was not stored.

Example 16 (Production of polyisocyanate composition (J))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate (a), 24 parts by mass of isobutanol, 2,6-di (t-butyl) 0.3 parts by mass of -4-methylphenol and 0.3 parts by mass of tris (tridecyl) phosphite were charged, the temperature was raised to 85 ° C., and a urethanization reaction was performed for 3 hours. Next, 0.02 parts by mass of lead octylate as an allophanatization catalyst was added and the reaction was carried out until the isocyanate group concentration reached the calculated value, and then 0.02 parts by mass of o-toluenesulfonamide was added. The obtained reaction liquid was passed through a thin-film distillation apparatus (vacuum degree 0.093 KPa, temperature 150 ° C.) to remove unreacted pentamethylene diisocyanate, and further, o-based on 100 parts by mass of the obtained composition. 0.02 part by mass of toluenesulfonamide was added to obtain a polyisocyanate composition (J).

  The polyisocyanate composition (J) had a pentamethylene diisocyanate concentration of 0.2% by mass, an isocyanate group concentration 1 of 20.4% by mass, a viscosity 1 at 25 ° C. of 200 mPa · s, and a hue 1 of APHA20. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (J) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to conduct a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 19.9% by mass, a viscosity 2 at 25 ° C. of 220 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Comparative Example 5 (Production of polyisocyanate composition (K))
In place of pentamethylene diisocyanate (a), pentamethylene diisocyanate (e) was used, and urethanization and allophanate reaction were carried out in the same manner as in Example 16, but the reaction rate was low from the measurement of isocyanate group concentration. Therefore, 0.01 parts by mass of lead octylate was further added to obtain a polyisocyanate composition (K).

  The polyisocyanate composition (K) had a pentamethylene diisocyanate concentration of 0.2% by mass, an isocyanate group concentration 1 of 16.5% by mass, a viscosity 1 at 25 ° C. of 320 mPa · s, and a hue 1 of APHA80. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (K) was transferred to a metal container, purged with nitrogen, and allowed to stand in an oven at 60 ° C. for 4 days, and a heating acceleration test was performed. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 14.5% by mass, a viscosity 2 at 25 ° C. of 420 mPa · s, and a hue 2 of APHA120. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Example 17 (Production of polyisocyanate composition (L))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 500 parts by mass of pentamethylene diisocyanate (a), 0.2 parts by mass of tris (tridecyl) phosphite, and 8 parts of trimethyl phosphoric acid 5 parts by mass of water and 5 parts by mass of water were charged, the temperature was raised to 130 ° C., and the reaction was performed until the isocyanate group concentration reached the calculated value. The obtained reaction liquid was passed through a thin film distillation apparatus (vacuum degree: 0.093 KPa, temperature: 150 ° C.) to remove unreacted pentamethylene diisocyanate to obtain a polyisocyanate composition (L).

  The polyisocyanate composition (L) had a pentamethylene diisocyanate concentration of 0.6% by mass, an isocyanate group concentration 1 of 24.8% by mass, a viscosity 1 at 25 ° C. of 2810 mPa · s, and a hue 1 of APHA30. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (L) was transferred to a metal container, purged with nitrogen, and allowed to stand in an oven at 60 ° C. for 4 days, and a heating acceleration test was performed. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 24.0% by mass, a viscosity 2 at 25 ° C. of 3200 mPa · s, and a hue 2 of APHA40. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Comparative Example 6 (Production of polyisocyanate composition (M))
Instead of pentamethylene diisocyanate (a), pentamethylene diisocyanate (e) was used and the reaction was carried out in the same manner as in Example 17 to obtain a polyisocyanate composition (M).

  The polyisocyanate composition (M) had a pentamethylene diisocyanate concentration of 0.7% by mass, an isocyanate group concentration 1 of 20.5% by mass, a viscosity 1 at 25 ° C. of 3820 mPa · s, and a hue 1 of APHA70. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (M) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to carry out a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 18.0% by mass, a viscosity 2 at 25 ° C. of 4980 mPa · s, and a hue 2 of APHA100. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Example 18 (Production of polyisocyanate composition (N))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate (a) of Production Example and trimethylolpropane (abbreviation: TMP) as a low molecular weight polyol 50 parts by mass were charged (equivalent ratio (NCO / OH) = 5.8). The temperature was raised to 75 ° C. in a nitrogen atmosphere, and after confirming that trimethylolpropane was dissolved, the reaction was allowed to proceed at 83 ° C. until the isocyanate group concentration reached the calculated value.

  Next, after the reaction solution was cooled to 55 ° C., 350 parts by mass of a mixed extraction solvent (n-hexane / ethyl acetate = 90/10 (mass ratio)) was added, stirred for 10 minutes, and allowed to stand for 10 minutes. The extraction solvent layer was removed. The same extraction operation was repeated 4 times.

  Thereafter, the reaction solution obtained was heated to 80 ° C. under reduced pressure to remove the extraction solvent remaining in the reaction solution. Furthermore, ethyl acetate was added, and it prepared so that the density | concentration of a polyisocyanate composition might be 75 mass%, and obtained the polyisocyanate composition (N). This polyisocyanate composition (N) has a pentamethylene diisocyanate concentration of 0.3% by mass, an isocyanate group concentration 1 of 20.5% by mass, a viscosity 1 at 25 ° C. of 500 mPa · s, and hue 1 of APHA20. Met. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (N) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to carry out a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 20.0% by mass, a viscosity 2 at 25 ° C. of 530 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Comparative Example 7 (Production of polyisocyanate composition (O))
Instead of pentamethylene diisocyanate (a), pentamethylene diisocyanate (e) was used and the reaction was carried out in the same manner as in Example 18 to obtain a polyisocyanate composition (O).

  This polyisocyanate composition (O) had a pentamethylene diisocyanate concentration of 0.4% by mass, an isocyanate group concentration 1 of 17.0% by mass, a viscosity 1 at 25 ° C. of 680 mPa · s, and a hue 1 of APHA40. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (O) was transferred to a metal container, purged with nitrogen, and left in an oven at 60 ° C. for 4 days to carry out a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 15.4% by mass, a viscosity 2 at 25 ° C. of 820 mPa · s, and a hue 2 of APHA70. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Example 19 (Production of polyisocyanate composition (P))
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 500 parts by mass of pentamethylene diisocyanate (a) and 0,2,6-di (tert-butyl) -4-methylphenol were added. .3 parts by mass, 0.3 parts by mass of tris (tridecyl) phosphite, and 130 parts by mass of methoxypolyethylene ether glycol having an average molecular weight of 400 were charged and reacted at 85 ° C. for 3 hours in a nitrogen atmosphere. Next, 0.1 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added as a trimerization catalyst. After reacting for 1 hour, 0.12 parts by mass of o-toluenesulfonamide was added (conversion rate of isocyanate group: 10% 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 pentamethylene diisocyanate, and further, o-based on 100 parts by mass of the obtained composition. 0.02 part by mass of toluenesulfonamide was added to obtain a polyisocyanate composition (P).

  The polyisocyanate composition (P) had a pentamethylene diisocyanate concentration of 0.1% by mass, an isocyanate group concentration 1 of 13.2% by mass, a viscosity 1 at 25 ° C. of 280 mPa · s, and a hue 1 of APHA20. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Subsequently, the polyisocyanate composition (P) was transferred to a metal container, purged with nitrogen, and then allowed to stand in an oven at 60 ° C. for 4 days to conduct a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 12.8% by mass, a viscosity 2 at 25 ° C. of 310 mPa · s, and a hue 2 of APHA30. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Comparative Example 8 (Production of polyisocyanate composition (Q))
Instead of pentamethylene diisocyanate (a), pentamethylene diisocyanate (e) was used, and a trimerization reaction was carried out in the same manner as in Example 19, but it was confirmed from the measurement of isocyanate group concentration that the reaction rate was low. Therefore, 0.2 part by mass of N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate was added and the reaction was continued for 2 hours to obtain a polyisocyanate composition (Q). It was.

  The polyisocyanate composition (Q) had a pentamethylene diisocyanate concentration of 0.2% by mass, an isocyanate group concentration 1 of 10.8% by mass, a viscosity 1 at 25 ° C. of 410 mPa · s, and a hue 1 of APHA90. These measured values are measured values before the heating acceleration test and are shown in Table 4.

  Next, the polyisocyanate composition (Q) was transferred to a metal container, and after purging with nitrogen, the polyisocyanate composition (Q) was left in an oven at 60 ° C. for 4 days to conduct a heating acceleration test. The polyisocyanate composition after the test had an isocyanate group concentration 2 of 9.7% by mass, a viscosity 2 at 25 ° C. of 540 mPa · s, and a hue 2 of APHA140. These measured values are measured values after the heating acceleration test and are shown in Table 4.

Example 20 (Production of polyurethane resin (A))
The polyisocyanate composition (A) obtained in Example 5 and the acrylic polyol (Mitsui Chemicals, trade name: Takelac UA-702, hereinafter abbreviated as UA-702) are hydroxyl groups in the acrylic polyol. Was added at a ratio such that the equivalent ratio of isocyanate groups (NCO / OH) in the polyisocyanate composition to 1.0 was 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. Curing for 1 hour gave a polyurethane resin (A) having a thickness of about 45 μm.

  The obtained polyurethane resin (A) was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.

Example 21 (Production of polyurethane resin (B))
A polyurethane resin having a thickness of about 45 μm in the same conditions and operation as in Example 20 except that the polyisocyanate composition (B) obtained in Example 6 was used instead of the polyisocyanate composition (A). B) was obtained.

  The obtained polyurethane resin (B) was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.

Example 22 (Production of polyurethane resin (C))
A polyurethane resin having a thickness of about 45 μm in the same conditions and operation as in Example 20 except that the polyisocyanate composition (C) obtained in Example 7 was used instead of the polyisocyanate composition (A). C) was obtained.

  The obtained polyurethane resin (C) was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.

Comparative Example 9 (Production of polyurethane resin (D))
A polyurethane resin having a thickness of about 45 μm was obtained under the same conditions and operation as in Example 10 except that the polyisocyanate composition (F) obtained in Comparative Example 3 was used instead of the polyisocyanate composition (A). D) was obtained.

  The obtained polyurethane resin (D) was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.

Example 23 (Production of polyurethane resin (E))
A polyurethane resin having a thickness of about 45 μm was obtained under the same conditions and operation as in Example 20 except that the polyisocyanate composition (D) obtained in Example 12 was used instead of the polyisocyanate composition (A). E) was obtained.

  The obtained polyurethane resin (E) was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.

Example 24 (Production of polyurethane resin (F))
A polyurethane resin having a thickness of about 45 μm was obtained under the same conditions and operation as in Example 20 except that the polyisocyanate composition (E) obtained in Example 13 was used instead of the polyisocyanate composition (A). F) was obtained.

  The obtained polyurethane resin (F) was allowed to stand for 7 days in a room at 23 ° C. and a relative humidity of 55%.

Evaluation of Physical Properties Martens hardness, breaking strength, solvent resistance and scratch hardness of the polyurethane resins (hereinafter abbreviated as “coating films”) obtained in the respective Examples and Comparative Examples were measured by the following methods. The results are shown in Table 5.
<Martens hardness (unit: N / mm ² )>
Using the ultra-hardness meter (Shimadzu Corp., DUH-211), the indentation type: Triangular 115, test mode: load-unloading test, test force: 10. Martens hardness (HMT115) was measured under the conditions of 00 mN, load speed of 3.0 mN / sec, and load holding time: 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 solution was ethyl acetate, toluene, and methyl ethyl ketone.

Claims (12)

Pentamethylene diisocyanate synthesized from pentamethylenediamine or a salt thereof,
A pentamethylene diisocyanate, wherein the content of a nitrogen-containing six-membered ring compound having a C = N bond is 2% by mass or less based on the total amount of pentamethylenediamine or a salt thereof.   A pentamethylene diisocyanate, wherein the content of a nitrogen-containing six-membered ring compound having an amino group and a C = N bond is 1.5% by mass or less based on the total amount of pentamethylenediamine or a salt thereof.   The pentagonal compound according to claim 2, wherein the nitrogen-containing six-membered ring compound having an amino group and a C = N bond is 2- (aminomethyl) -3,4,5,6-tetrahydropyridine. Methylene diisocyanate.   The pentamethylene diisocyanate according to any one of claims 1 to 3, which is obtained by phosgenating pentamethylenediamine or a salt thereof. Obtained by carbamation and pyrolysis of pentamethylenediamine or a salt thereof,
An antioxidant,
The pentamethylene diisocyanate according to any one of claims 1 to 3, comprising an acidic compound and / or a compound having a sulfonamide group. A polyisocyanate composition obtained by modifying the pentamethylene diisocyanate according to any one of claims 1 to 5 and containing at least one of the following functional groups (a) to (e): object.
(A) isocyanurate group (b) allophanate group (c) biuret group (d) urethane group (e) urea group It is a manufacturing method of pentamethylene diisocyanate as described in any one of Claims 1-5,
A method for producing pentamethylene diisocyanate, characterized in that pentamethylenediamine or a salt thereof is extracted with a non-halogen aliphatic organic solvent and then isocyanated.   The method for producing pentamethylene diisocyanate according to claim 7, wherein the non-halogen aliphatic organic solvent is a linear monohydric alcohol having 4 to 7 carbon atoms.   The method for producing pentamethylene diisocyanate according to claim 7 or 8, wherein pentamethylenediamine or a salt thereof is extracted from an aqueous solution containing pentamethylenediamine or a salt thereof.   The method for producing pentamethylene diisocyanate according to claim 9, wherein an aqueous solution containing pentamethylenediamine or a salt thereof is obtained by a decarboxylase reaction of lysine or a salt thereof.   A polyurethane resin obtained by reacting the pentamethylene diisocyanate according to any one of claims 1 to 5 with an active hydrogen compound.   A polyurethane resin obtained by reacting the polyisocyanate composition according to claim 6 with an active hydrogen compound.