[0001]
　The present invention, the polyisocyanate composition, derived from the polyisocyanate polyurethane resin obtained from the composition, two-component curable polyurethane composition comprising a polyisocyanate component comprising a polyisocyanate composition, and its two-part curing polyurethane resin It relates to a coating material that is.
Background technique
[0002]
　Polyurethane resins are usually produced by reacting a polyisocyanate with an active hydrogen group-containing compound, for example, coating materials, paints, adhesive materials, adhesive materials, as such as an elastomer, are widely used in various industrial fields .
[0003]
　The polyisocyanate used in the production of polyurethane resins, for example, xylylene diisocyanate and derivatives thereof, such as hexamethylene diisocyanate and derivatives thereof are known, also, it is known to use a mixture of them.
[0004]
　Such polyisocyanates are, for example, is used as a curing agent, such as paints and adhesives. Specifically, for example, a polyol-30 to 90% by weight of xylylene diisocyanate, 10 to 70% by weight of hexamethylene diisocyanate curing agent containing a biuret modified product and / or trimers of the proposed is (e.g., see Patent Document 1.).
[0005]
　According to such a curing agent, adhesion, acid-alkali resistance, solvent resistance, stain resistance, can be obtained two-component curable polyurethane composition having excellent weather resistance.
CITATION
Patent Literature
[0006]
Patent Document 1: JP 2010-24386 JP
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　On the other hand, in the field of polyurethane resins, depending on the application, there is a case where further improvement of weather resistance is required.
[0008]
　As the polyurethane resin, further, and chemical resistance, mechanical properties (such as hardness), further it may like design properties such as smoothness is required.
[0009]
　An object of the present invention include mechanical properties, the polyisocyanate compositions obtainable polyurethane resin excellent in design properties and durability, polyurethane resins obtained from the polyisocyanate composition, the polyisocyanate component comprising a polyisocyanate composition two-component curable polyurethane composition, and is to provide a coating material obtained from the two-component curable polyurethane resin.
Means for Solving the Problems
[0010]
　The present invention [1], modified xylylene diisocyanate, and contain a denatured product of the pentamethylene diisocyanate, and / or contain a denatured product consisting of xylylene diisocyanate and pentamethylene diisocyanate, xylylene diisocyanate and pentaerythritol proportion of pentamethylene diisocyanate to the total amount of the diisocyanate is a polyisocyanate composition is 60 mol% to 95 mol% or less, and comprise.
[0011]
　The present invention [2], the modified product is a multi-molecule comprising a diisocyanate and / or pentamethylene diisocyanate 2 or more molecules, content of the multimolecular of more than 4 molecules in the polyisocyanate composition, the polyisocyanate composition according to [1] 30% by mass or less than 65 wt%, and comprise.
[0012]
　The present invention [3], the 4 or more molecules of the multimolecular body, the multi-molecule of 4 or more molecules of xylylene diisocyanate, are contained in a proportion of 5 mass% or more and 45 mass% or less [2] the polyisocyanate composition according to, and comprise.
[0013]
　The present invention [4], the modified product is in any one of the following (a) ~ [1] containing at least one functional group selected from the group consisting of (i) ~ [3] the polyisocyanate composition according and comprise.
(A) isocyanurate groups
(b) an allophanate group
(c) biuret groups
(d) a urethane group
(e) urea group
(f) uretdione groups
(g) iminooxadiazinedione groups
(h) uretonimine groups
(i) carbodiimide group
　the present invention [5], the [1] and the polyisocyanate composition according to any one of to [4], a polyurethane resin obtained by reacting an active hydrogen group-containing compounds, which comprise.
[0014]
　The present invention [6], a polyisocyanate component containing the above-mentioned [1] - Polyisocyanate composition according to any one of [4], the two-component curable polyurethane composition containing a polyol component, which comprise.
[0015]
　The present invention [7], a coating material obtained from the two-component curable polyurethane composition according to [6], which comprise.
Effect of the invention
[0016]
　According to the polyisocyanate composition of the present invention, (such as hardness) mechanical properties, design and durability (chemical resistance, weather resistance) can be obtained a polyurethane resin excellent in.
[0017]
　Further, the polyurethane resin of the present invention, two-component curable polyurethane composition and the coating material (such as hardness) mechanical properties, excellent design and durability (chemical resistance, weather resistance, etc.).
BRIEF DESCRIPTION OF THE DRAWINGS
[0018]
[1] Figure 1 is a graph showing the molar ratio of pentamethylene diisocyanate modified product, a relationship between Delta] E.
DESCRIPTION OF THE INVENTION
[0019]
　Polyisocyanate composition of the present invention, modified xylylene diisocyanate, and either containing a denatured product of the pentamethylene diisocyanate, and / or contain a denatured product consisting of xylylene diisocyanate and pentamethylene diisocyanate.
[0020]
　That is, the polyisocyanate composition of the present invention is composed of only modified product consisting of (1) and a modified body of xylylene diisocyanate, or consisting of a modified product of pentamethylene diisocyanate, (2) xylylene diisocyanate and pentamethylene diisocyanate or consists of (3) and modified products modified products and / or pentamethylene diisocyanate xylylene diisocyanate, a modified product consisting of xylylene diisocyanate and pentamethylene diisocyanate.
[0021]
　(1) and a modified body of xylylene diisocyanate, the polyisocyanate composition consisting of a modified product of pentamethylene diisocyanate, detail.
[0022]
　Modified products of xylylene diisocyanate is a multi-molecule comprising a diisocyanate 2 or more molecules, by denaturing in a manner depending on the functional group to be described later xylylene diisocyanate can be obtained.
[0023]
　The xylylene diisocyanate, 1,2-xylylene diisocyanate (o-xylylene diisocyanate (o-XDI)), 1,3- xylylene diisocyanate (m-xylylene diisocyanate (m-XDI)), 1,4- xylylene diisocyanate (p- xylylene diisocyanate (p-XDI)) may be mentioned as structural isomers.
[0024]
　These xylylene diisocyanate can be used alone or in combination of two or more. As xylylene diisocyanate, preferably 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and more preferably, include 1,3-xylylene diisocyanate.
[0025]
　Modified products of xylylene diisocyanate preferably contains at least one functional group selected from the group consisting of the following (a) ~ (i).
(A) isocyanurate groups
(b) an allophanate group
(c) biuret groups
(d) a urethane group
(e) urea group
(f) uretdione groups
(g) iminooxadiazinedione groups
(h) uretonimine groups
(i) carbodiimide group
　modified products containing a functional group of the (a) (isocyanurate group) is a xylylene diisocyanate trimer (trimer), for example, reacting a diisocyanate in the presence of a known isocyanurate catalyst it is, by trimerization can be obtained.
[0026]
　The modified products containing a functional group (allophanate group) of (b) is a allophanate modified product of xylylene diisocyanate, for example, after a xylylene diisocyanate and alcohol and (below) is reacted, known allophanate by further reaction in the presence of a catalyst, it can be obtained.
[0027]
　Modified products containing a functional group of the (c) (biuret) is a biuret-modified product of xylylene diisocyanate, for example, a xylylene diisocyanate, for example, water, tertiary alcohols (e.g., t- butyl alcohol), secondary amine (e.g., dimethylamine, by reacting diethylamine, etc.) and can be obtained.
[0028]
　Polyisocyanate compositions containing a functional group (urethane groups) (d) above is a xylylene diisocyanate polyol modifications thereof (polyol derivatives), e.g., xylylene diisocyanate and the polyol component (e.g., trimethylolpropane, etc. trihydric alcohols by reaction with (described later)), can be obtained.
[0029]
　Modified products containing the functional group (urea groups) of (e) is a polyamine-modified product of xylylene diisocyanate, e.g., xylylene diisocyanate and water, the reaction such as the polyamine component, can be obtained.
[0030]
　The modified products containing a functional group (uretdione groups) of (f), the uretdione modified product of xylylene diisocyanate (dimer, dimer) a, for example, the presence of xylylene diisocyanate known dimerization catalyst it is reacted in the, by dimerization, can be obtained.
[0031]
　The modified products containing a functional group (iminooxadiazinedione groups) of (g) is a xylylene diisocyanate trimer (trimer), for example, xylylene diisocyanate known iminooxadiazinedione of are reacted in the presence of a catalyst, by trimerization can be obtained.
[0032]
　Modified products containing a functional group (uretonimine) above (h) is a uretonimine-modified product of xylylene diisocyanate, for example, by reaction with a diisocyanate and a carbodiimide compound can be obtained.
[0033]
　Modified products containing a functional group (carbodiimide group) (i) above is a carbodiimide modified product of xylylene diisocyanate, for example, by decarboxylation condensation reaction of xylylene diisocyanate can be obtained.
[0034]
　Incidentally, modified xylylene diisocyanate, the above (a) need only contain at least one functional group of ~ (i), may also contain two or more. Such modified products, by suitably used in combination the above reaction is produced.
[0035]
　As modified product xylylene diisocyanate, preferably, a trimer of diisocyanate, polyol-xylylene diisocyanate (polyol derivative), and more preferably include, trimer of xylylene diisocyanate. In other words, modified xylylene diisocyanate preferably contains trimer of xylylene diisocyanate, and more preferably, consists of trimer of xylylene diisocyanate.
[0036]
　The use of trimer of xylylene diisocyanate, it is possible to obtain a polyurethane resin excellent in mechanical properties (hardness, etc.) and durability (chemical resistance, weather resistance, etc.).
[0037]
　Trimer xylylene diisocyanate is modified products containing isocyanurate groups of the (a) and (hereinafter referred to. Isocyanurate derivatives), modified products containing iminooxadiazinedione groups of the (g) (hereinafter referred to. as iminooxadiazinedione derivative) and a.
[0038]
　And these isocyanurate derivatives and iminooxadiazinedione derivative, a relationship between structural isomers, isocyanurate derivatives are symmetrical trimer, iminooxadiazinedione derivatives are asymmetric trimers.
[0039]
　Incidentally, in the production of isocyanurate derivatives, may iminooxadiazinedione derivative as a by-product is produced, also, in some cases at the time of manufacture of iminooxadiazinedione derivatives, isocyanurate derivatives occur as a by-product.
[0040]
　Isocyanurate derivatives of xylylene diisocyanate, as described above, xylylene diisocyanate, in the presence of an isocyanurate-forming catalyst obtained by isocyanuration.
[0041]
　In the present invention, the isocyanurate catalyst, if the catalyst which activates the isocyanurate-forming is not particularly limited, for example, triethylamine, tributylamine, triethylenediamine, 2 amine copolymer (e.g., dialkyl amines such as secondary amines and secondary amine monomers copolymerizable with (e.g., phenol, formaldehyde, etc.) polycondensate) tertiary amines such as, for example, 2-dimethylamino-methylphenol, 2,4, 6- tris (dimethylaminomethyl) Mannich bases such as phenol, e.g., tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium, hydroxide of tetraalkylammonium such as tributyl benzyl ammonium The organic weak acid salt, for example, trimethyl hydroxypropyl ammonium (also known as: N-(2-hydroxypropyl) -N, N, N-trimethyl ammonium), trimethyl hydroxyethyl ammonium, triethyl hydroxypropyl ammonium, birds such as triethyl hydroxyethyl ammonium hydroxide or organic weak acid salt of an alkyl hydroxyalkyl ammonium, for example, acetic acid, caproic acid, octyl acid, myristic acid, metal salts of alkyl carboxylic acids such as naphthenic acids (e.g., alkali metal salts, magnesium salts, tin salts, zinc salts, lead salts), for example, aluminum acetylacetonate, metal chelate compounds such β- diketones such as lithium acetylacetonate, for example, aluminum chloride, such as boron trifluoride Friedel-Crafts catalysts, e.g., titanium tetrabutylate, various organometallic compounds such as tributyl antimony oxide, e.g., aminosilyl group-containing compound such as hexamethyldisilazane, halogenated organic phosphorus such as hydrogen difluoride tetrabutylphosphonium such compounds.
[0042]
　These isocyanurate catalysts may be used alone or in combination of two or more kinds.
[0043]
　As isocyanurate catalysts, preferably hydroxide of tetraalkylammonium, include hydroxide of trialkylhydroxyalkylammonium, more preferably, hydroxide of tetraalkylammonium and the like, more preferably, the trimethylbenzylammonium hydroxide, include hydroxide of tetrabutylammonium.
[0044]
　As isocyanurate catalysts, the use of the above catalyst, for a xylylene diisocyanate can be isocyanurating with especially good reaction rates, excellent production efficiency.
[0045]
　Also, isocyanurate catalysts may be used as a 100% solids, also alcohols (e.g., methanol, isopropyl alcohol, isobutyl alcohol, and ethylene glycol) in an organic solvent such as, be diluted with an appropriate ratio it may be.
[0046]
　The mixing ratio of the isocyanurate-forming catalyst (solids), based on xylylene diisocyanate 100 parts by weight, for example, 0.001 parts by weight (phr) or more, or preferably 0.01 parts by weight (phr) or more, For example, 0.1 parts by weight (phr) or less, preferably, 0.05 parts by weight (phr) or less.
[0047]
　And in this way, by blending isocyanurate catalyst to xylylene diisocyanate at a mixing ratio mentioned above, by heating, to isocyanuration reaction.
[0048]
　The reaction conditions of xylylene diisocyanate isocyanurate reaction, for example, an inert gas atmosphere such as nitrogen gas, normal pressure (atmospheric pressure), the reaction temperature (ultimate maximum temperature), for example, 40 ° C. or higher, preferably it is at 60 ° C. or higher, e.g., 90 ° C. or less, preferably 80 ° C. or less. The reaction time is, for example, 30 minutes or more, or preferably 60 minutes or more, for example, 600 minutes or less, preferably not more than 480 minutes.
[0049]
　In the above reaction, in order to adjust the isocyanuration, for example, an organic phosphite ester as described in JP-A-61-129173, it can also be formulated as a cocatalyst .
[0050]
　The organic phosphites, aliphatic organic phosphites, and the like aromatic organic phosphites.
[0051]
　The aliphatic organic phosphites, e.g., triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, tristearyl phosphite alkyl mono phosphites such as, for example, distearyl pentaerythrityl-diphosphite, di-dodecyl-pentaerythritol diphosphite, di-tridecyl-pentaerythritol-diphosphite, aliphatic polyhydric alcohols such as tripentaerythritol-triphosphite induced di-, tri- or tetra phosphite, further, hydrogenated bisphenol a phosphite polymer (molecular weight 2400-3000) alicyclic polyphosphite, such as bets Such as scan (2,3-dichloro-propyl) phosphite.
[0052]
　The aromatic organic phosphites, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, diphenyl decyl phosphite, diphenyl (tridecyl) aryl mono- phosphite phosphite, for example, di-nonylphenyl-pentaerythritol diphosphite, tetraphenyl tetra-tridecyl-pentaerythrityl-tetra phosphites, aromatic such as tetraphenyl dipropylene glycol diphosphite polyhydric alcohol induced di-, tri- or tetra phosphite from further example, di-alkyl-bisphenol a · diphosphite having 1 to 20 carbon atoms, 4,4'-butylidene - bis (3-methyl -6-t-Buchirufu Eniru - such diphosphite derived from bisphenol compounds, such as di-tridecyl) phosphite.
[0053]
　These organic phosphites may be used alone or in combination of two or more kinds.
[0054]
　As organic phosphites, preferably, it includes aromatic organic phosphites, and more preferably, di derived from aromatic polyhydric alcohol, include tri- or tetra phosphite, more preferably, tetra include phenyl, dipropyleneglycol diphosphite.
[0055]
　The mixing ratio of the organic phosphite ester, relative xylylene diisocyanate 100 parts by weight, for example, 0.001 parts by weight (phr) or more, or preferably 0.005 parts by weight (phr) or more, e.g. , 0.05 parts by weight (phr) or less, preferably, 0.03 parts by weight (phr) or less.
[0056]
　By blending the organic phosphite in the above proportions as a co-catalyst, it is possible to improve the reaction rate and the reaction rate, can also suppress the gelation.
[0057]
　In the above reaction, hindered phenolic antioxidants, for example, 2,6-di (tert- butyl) -4-methylphenol (also known as dibutylhydroxytoluene, hereinafter sometimes abbreviated as BHT.) , can be IRGANOX 1010, IRGANOX 1076, IRGANOX 1135, IRGANOX 245 (or more, Ciba Japan Co., Ltd., trade name) is also possible to add a stabilizer such as.
[0058]
　The mixing ratio of the stabilizer, relative xylylene diisocyanate 100 parts by weight, for example, 0.01 parts by weight (phr) or more, or preferably 0.02 parts by weight (phr) or more, for example, 0.05 part (phr) or less, preferably, 0.03 parts by weight (phr) or less.
[0059]
　In the above reaction, if necessary, it may be blended a known reaction solvent, and further, a known catalyst deactivator at any time (e.g., phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, ortho-toluene sulfonic acid, benzoyl chloride, p- toluenesulfonamide, o- toluenesulfonamide, etc.) may be added.
[0060]
　After completion of the reaction, xylylene diisocyanate Unreacted optionally, it can be removed by a known method.
[0061]
　Specifically, after completion of the above isocyanurate reaction, and isocyanurate derivatives of the resulting xylylene diisocyanate, a mixture reaction of xylylene diisocyanate monomer, a diisocyanate monomer unreacted example, thin-film distillation ( it can be removed Smith distillation) distillation or the like, by a known method such as extraction.
[0062]
　In the present invention, when the thin film distillation after isocyanuration completion of xylylene diisocyanate, and the yield of the thin film distillation by obtained isocyanurate derivative (distillation yield), relative to the mass of the reaction mixture, xylylene diisocyanate diisocyanate is the mass of the isocyanurate derivatives, for example, 15 mass% or more, preferably 25 wt% or more, more preferably 40 mass% or more, e.g., 70 wt% or less, preferably 65 wt% or less, more preferably is 60 wt% or less.
[0063]
　Incidentally, the distillation yield of isocyanurate derivatives of xylylene diisocyanate can be obtained by in conformity with the examples described below, it calculates the ratio of the mass of the isocyanurate derivative of xylylene diisocyanate to the mass of the reaction mixture .
[0064]
　In the above reaction, if necessary, it may be blended alcohols. That is, isocyanurate derivatives can be modified with alcohols.
[0065]
　As the alcohols, for example, aliphatic alcohols, and aromatic alcohols can be mentioned, preferably, it includes aliphatic alcohol.
[0066]
　Examples of the aliphatic alcohols, e.g., monohydric aliphatic alcohols, divalent aliphatic alcohols, trihydric aliphatic alcohols, and the like tetravalent or more aliphatic alcohols.
[0067]
　The monovalent aliphatic alcohols, for example, monohydric aliphatic alcohols of linear, like branched monohydric aliphatic alcohols.
[0068]
　The monovalent aliphatic alcohol, linear, for example, methanol, ethanol, n- propanol, n- butanol, n- pentanol, n- hexanol, n- heptanol, n- octanol, n- nonanol, n- decanol , n- undecanol, n- dodecanol (lauryl alcohol), n- tridecanol, n- tetradecanol, n- pentadecanol, n- hexadecanol, n- heptadecanol, n- octadecanol (stearyl alcohol) , n- nonadecanol, and the like eicosanol.
[0069]
　Examples of the branched monohydric aliphatic alcohols, such as isopropanol (also known as isopropyl alcohol, IPA), isobutanol (also known as iso-butyl alcohol, IBA), sec-butanol, tert- butanol, iso-pentanol, isohexanol, iso heptanol, isooctanol, 2-ethylhexanol (also known as 2-ethylhexyl alcohol, 2-EHA), isononanol, isodecanol, 5-ethyl-2-nonanol, trimethyl nonyl alcohol, 2-hexyl decanol, 3,9-diethyl -6 - tridecanol, 2-iso-heptyl isophthalate undecanol, 2-octyl dodecanol, other branched alkanols (C (carbon number, hereinafter the same) 5-20), and the like.
[0070]
　Examples of the divalent aliphatic alcohols include ethylene glycol, 1,3-propanediol (1,3-PG), 1,4- butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1 , 4-dihydroxy-2-butene, diethylene glycol, triethylene glycol, dipropylene glycol, other linear alkane (C7 ~ 20) 2 dihydric aliphatic alcohols linear, such as diols, such as 1,2 propanediol, 1,3-butylene glycol (also known as 1,3-butanediol), 1,2-butylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol (MPD), 2,2,4 - trimethyl-1,3-pentanediol (TMPD), 3,3-dimethylol heptane, 2,6-dimethyl Le-1-octene-3,8-diol, other branched alkane (C7 ~ 20) branched divalent aliphatic alcohol such as a diol, e.g., 1,3- or 1,4-cyclohexane dimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol, and mixtures thereof, such as dihydric aliphatic alcohols alicyclic such as hydrogenated bisphenol a and the like.
[0071]
　Examples of the trivalent aliphatic alcohols, for example, glycerin, trimethylolpropane.
[0072]
　The tetravalent or more aliphatic alcohols, for example, tetra methylol methane, D- sorbitol, xylitol, etc. D- mannitol.
[0073]
　These alcohols, as long as it has one or more hydroxy groups in a molecule, it molecular structures other than as long as it does not inhibit the excellent effects of the present invention is not particularly limited, for example, in the molecule in may have an ester group, an ether group, a cyclohexane ring, and an aromatic ring. Such alcohols include, for example, in the above-mentioned monohydric alcohol and an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) adducts polymer of (random and / or block polymers of two or more alkylene oxide) ether group-containing monovalent alcohols, the monohydric alcohol and a lactone (e.g., .epsilon.-caprolactone, .delta.-valerolactone, etc.) such as an ester group-containing monohydric alcohol is an addition polymer of the like.
[0074]
　These alcohols may be used alone or in combination of two or more kinds.
[0075]
　As alcohols, preferably include aliphatic alcohols, more preferably, include monovalent and divalent aliphatic alcohol, more preferably, divalent aliphatic alcohols.
[0076]
　Further, as the aliphatic alcohols, preferably aliphatic alcohols having 1 to 20 carbon atoms, more preferably an aliphatic alcohol having a carbon number of 2 to 20, more preferably, an aliphatic alcohol having 2 to 8 carbon atoms and the like.
[0077]
　Further, as the aliphatic alcohols, preferably branched monovalent and divalent aliphatic alcohols can be mentioned, more preferably, include branched divalent aliphatic alcohol, especially preferably 1,3 - it includes butane diol.
[0078]
　Alcohols, in isocyanurate derivatives of xylylene diisocyanate, are formulated such that the average functionality is two or more, the mixing ratio, with respect xylylene diisocyanate 100 parts by mass, alcohols, for example, 0. 1 part by mass or more, preferably, 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and is, for example, 10 parts by mass or less, preferably not more than 5.0 parts by mass.
[0079]
　Further, in this reaction, the xylylene diisocyanate and alcohol, for hydroxy group of an alcohol, the equivalent ratio of the isocyanate groups of the diisocyanate (NCO / OH) is, for example, 5 or more, preferably 10 or more, more preferably, 20 or more, usually 1000 or less, preferably, 100 or less, more preferably, at proportions of 50 or less is formulated.
[0080]
　Isocyanurate derivatives of xylylene diisocyanate, as a method of modifying the alcohols, for example, firstly, reacting a xylylene diisocyanate and alcohol, then was allowed to isocyanuration reaction in the presence of isocyanurate catalyst , a method of removing diisocyanate unreacted example, first, only the xylylene diisocyanate was isocyanurate-forming in the manner described above, to remove xylylene diisocyanate unreacted Thereafter, the resulting polyisocyanurate and a method of reacting an alcohol with.
[0081]
　Preferably, first, reacting a xylylene diisocyanate and alcohol, and then was reacted isocyanurate in the presence of a isocyanurate catalyst, removing xylylene diisocyanate unreacted.
[0082]
　Specifically, in this method, first, a xylylene diisocyanate and alcohol, mixed and reacted.
[0083]
　Reaction between xylylene diisocyanate and alcohol are urethane reaction (including allophanatization reaction), the reaction conditions, for example, an inert gas atmosphere such as nitrogen gas, at normal pressure (atmospheric pressure), the reaction temperature is, for example, room temperature (e.g., 25 ° C.) or higher, preferably not 40 ° C. or higher, for example, 100 ° C. or less, preferably 90 ° C. or less. The reaction time is, for example, 0.05 hours or more, preferably not less than 0.2 hours, for example, 10 hours or less, preferably 6 hours or less, and more preferably not more than 3 hours.
[0084]
　In the above urethanization reaction, if necessary, for example, it may be added a known urethanization catalyst such as amine or an organometallic compound.
[0085]
　The amines, e.g., triethylamine, triethylenediamine, bis - (2-dimethylaminoethyl) ether, tertiary amines such as N- methylmorpholine, for example, quaternary ammonium salts such as tetraethyl hydroxyl ammonium, such as imidazole, and 2-ethyl-4-imidazoles such as methylimidazole.
[0086]
　As an organic metal compound, for example, tin acetate, octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyl tin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dilaurate dibutyltin (IV)), dibutyltin neodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, organotin compounds such as dibutyltin dichloride, for example, lead octoate, organic lead compounds such as lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example, an organic cobalt compounds such as cobalt naphthenate, for example, organic copper compound such as octene copper, for example, bismuth octylate, and organic bismuth compounds such as bismuth neodecanoate ani It is.
[0087]
　Further, as a urethanization catalyst, for example, potassium carbonate, potassium acetate, potassium salts such as potassium octoate.
[0088]
　These urethanization catalysts may be used alone or in combination of two or more kinds.
[0089]
　Then, in this method, the reaction solution obtained, the isocyanurate catalyst were blended at the mixing ratio described above, the reaction product of xylylene diisocyanate and alcohol, to isocyanuration reaction. Incidentally, the reaction conditions in the isocyanurate-forming are the same as above. After completion of the reaction, the unreacted xylylene diisocyanate is necessary, by a known removal method such as distillation, removed.
[0090]
　Thus, it is possible to obtain modified with alcohols, the isocyanurate derivative of xylylene diisocyanate.
[0091]
　Further, for example, after isocyanurating only xylylene diisocyanate, in the case of adopting the method of removing the xylylene diisocyanate unreacted reacting the resulting polyisocyanate and the alcohol (above the latter method) includes isocyanurate derivatives and alcohols xylylene diisocyanate reacts. Note that this reaction is also a urethane-forming reaction, under reaction conditions of the urethane reaction as described above.
[0092]
　This also can be prepared modified with alcohols, the isocyanurate derivative of xylylene diisocyanate.
[0093]
　Incidentally, isocyanurate derivatives of xylylene diisocyanate is the case where it is modified by alcohol may allophanate derivatives of xylylene diisocyanate is obtained as a by-product. In such a case, isocyanurate derivatives of xylylene diisocyanate as auxiliary components contained in the inevitable, allophanate derivatives of xylylene diisocyanate. In other words, isocyanurate derivatives of xylylene diisocyanate is the case where it is modified by alcohols, and isocyanurate derivatives of xylylene diisocyanate, isocyanurate composition containing allophanate derivatives of xylylene diisocyanate is obtained.
[0094]
　Modified with an alcohol, in the isocyanurate derivative of xylylene diisocyanate, modification amount of alcohol for the isocyanurate derivative (alcohol-modified ratio of isocyanurate derivatives), for example, 0.5 mass% or more, preferably 1. 0 wt% or more, more preferably, 3.0 mass% or more, still more preferably 4.0 mass% or more, e.g., 15 wt% or less, preferably 10 wt% or less, more preferably, 6. it is 0 mass% or less.
[0095]
　Incidentally, modification amount of alcohol for the isocyanurate derivative (alcohol modification ratio) can be calculated by the following equation.
[0096]
　　Alcohol-modified ratio of isocyanurate derivatives (wt%) = (alcohol-modified ratio in the reaction mixture (wt%) / distilled yield (wt%)) × 100
　The alcohol modification ratio in the reaction mixture, the reaction mixture a modification of alcohol against xylylene diisocyanate and isocyanurate derivatives can be calculated as a proportion of the charge mass of alcohol based on the charged weight of xylylene diisocyanate.
[0097]
　Also, in general, alcohol-modified rate 1 can be calculated by H-NMR
[0098]
　The isocyanurate derivative of xylylene diisocyanate, isocyanurate derivatives essentially diisocyanate which is not modified by an alcohol, and may be either of the isocyanurate derivative of the modified xylylene diisocyanate by alcohol but preferably, isocyanurate derivatives of the modified diisocyanate with an alcohol.
[0099]
　In the present invention, the essentially isocyanurate derivatives which are not modified with alcohols, are defined as derivatives that do not actively incorporating the active hydrogen group-containing compound as a modifying agent such as the alcohols, for example, in isocyanurate derivatives during manufacture, inevitably active hydrogen group-containing compound to be mixed (e.g., solvent isocyanurate catalysts (e.g., methanol, etc.) and water, etc.) based on the modified group to the isocyanurate derivatives (e.g., urethane group, containing such urea groups) is allowed, and so forth.
[0100]
　Isocyanurate derivatives of xylylene diisocyanate, isocyanurate reaction mixture isocyanate group concentration (before distillation) (solid content 100 wt%), for example, 5 wt% or more, preferably 10 mass% or more, more preferably, is 15 mass% or more, e.g., 50 wt% or less, preferably 40 wt% or less, more preferably 35 mass% or less.
[0101]
　Note that the isocyanate group concentration of the isocyanurate derivative of xylylene diisocyanate (solid content 100 wt%) can be determined in conformity with the examples described below.
[0102]
　In the isocyanurate derivative of xylylene diisocyanate, diisocyanate monomer concentration (concentration of xylylene diisocyanate unreacted) is, for example, 2 wt% or less, preferably 1 mass% or less, more preferably 0.5 mass % or less.
[0103]
　Further, the isocyanurate derivative of xylylene diisocyanate, the conversion of isocyanate groups (reaction rate) is, for example, 5 wt% or more, preferably 10 mass% or more, more preferably 15 mass% or more, for example, 50 wt% or less, preferably 40 wt% or less, more preferably 35 mass% or less.
[0104]
　Incidentally, isocyanurate derivatives of xylylene diisocyanate is, when not modified by essentially alcohols, conversion of isocyanate groups (reaction rate) is substantially the isocyanurate conversion (trimer conversion) to be the same.
[0105]
　That is, isocyanurate conversion (trimer conversion) is, for example, 5 wt% or more, preferably 10 mass% or more, more preferably 15 mass% or more, e.g., 50 wt% or less, preferably , 40 wt% or less, more preferably 35 mass% or less.
[0106]
　On the other hand, isocyanurate derivatives of xylylene diisocyanate is, if it is denatured by the alcohol, the conversion of the isocyanate groups (reaction rate) is a urethane conversion by alcohol, isocyanurate conversion (trimer conversion which is the total value of the rate).
[0107]
　In such cases, urethanes conversion, for example, 1 mass% or more, preferably 3 wt% or more, more preferably 5 mass% or more, e.g., 30 wt% or less, preferably 20 wt% or less , more preferably 10 mass% or less.
[0108]
　Also, isocyanurate conversion (trimer conversion) is, for example, 5 wt% or more, preferably 10 mass% or more, more preferably 15 mass% or more, e.g., 50 wt% or less, preferably , 40 wt% or less, more preferably 35 mass% or less.
[0109]
　Incidentally, the conversion of the isocyanate groups of the diisocyanate, urethane conversion and isocyanurate conversion, in compliance with the embodiment described later, to the isocyanate group concentration of xylylene diisocyanate of time of charging, the isocyanate group concentration of the reaction solution it can be determined by calculating the reduction rate.
[0110]
　Further, modified xylylene diisocyanate are multimolecular comprising a xylylene diisocyanate 4 or more molecules (hereinafter referred to as 4 or more molecules body.) Can contain.
[0111]
　For example, modified xylylene diisocyanate is when an isocyanurate derivative, 4 or more molecules body, the isocyanurate mononuclear body (specifically, 3-xylylene diisocyanate molecules to form one isocyanurate ring compounds are, that is, 3 molecular entity) of xylylene diisocyanate via an isocyanurate ring, furthermore, is a multi-molecule having a xylylene diisocyanate molecules that reacted (4 molecular sieve) or more molecular weight. Specifically, for example, dinuclear body (5 molecular entity), Sankakutai (7 molecular sieve) · · · n karyoplast ((2n + 1) molecular entity), and the like.
[0112]
　In modified product xylylene diisocyanate, the content of 4 or more molecules body, relative to the total amount of the modified product of xylylene diisocyanate, for example, 20 mass% or more, preferably 25 mass% or more, more preferably, 30 mass % or more, more preferably, 33 mass% or more, especially preferably not less than 35 wt%, e.g., 80 wt% or less, preferably 70 wt% or less, more preferably 65 wt% or less, more preferably , 60 wt% or less, especially preferably at most 55 mass%.
[0113]
　Note that in the modified product of xylylene diisocyanate, the content of 4 or more molecules body, the molecular weight distribution of the modified product of xylylene diisocyanate, based on the calibration curve of standard polyethylene oxide, equipped differential refractive index detector (RID) determined by gel permeation chromatography (GPC), as the peak area in the chromatogram obtained (chart) ratio (relative area ratio of the modified product of xylylene diisocyanate, the area ratio of 4 or more molecules form), it is calculated it can.
[0114]
　Further, in the modified product of xylylene diisocyanate, the area ratio of 4 or more molecules body can be determined as an area ratio corresponding to the polyethylene oxide equivalent molecular weight of 600 or more.
[0115]
　In modified product xylylene diisocyanate, if the content of the above range of 4 or more molecules bodies (such as hardness) mechanical properties, design and durability (chemical resistance, weather resistance, etc.) in excellent polyurethane resin (described later) it is possible to obtain.
[0116]
　Further, modified xylylene diisocyanate, when such organic phosphite is used as a co-catalyst, which may contain phosphorus.
[0117]
　Phosphorus concentration of denaturing of xylylene diisocyanate (composition), for example, 5 ppm or more, preferably not less 10ppm or more, for example, 500 ppm or less, preferably 300ppm or less.
[0118]
　Incidentally, the phosphorus concentration may be in conformity with the examples described below are obtained.
[0119]
　Modified products of pentamethylene diisocyanate is a multi-molecule comprising a pentamethylene diisocyanate 2 or more molecules, by denaturing in a manner depending on the functional group to be described later pentamethylene diisocyanate, can be obtained.
[0120]
　The pentamethylene diisocyanate, e.g., 1,5-pentamethylene diisocyanate, 1,4-pentamethylene diisocyanate, 1,3-pentamethylene diisocyanate.
[0121]
　These pentamethylene diisocyanates can be used alone or in combination of two or more.
[0122]
　As pentamethylene diisocyanate, preferably, 1,5-pentamethylene diisocyanate.
[0123]
　Pentamethylene diisocyanate, for example, can also be obtained commercially known methods, for example, biochemical means (for example, lysine and / or decarboxylase reactions salt thereof) pentamethylene diamine or the like that to produce a salt, the pentamethylene diamine or a salt thereof, phosgenation, by isocyanate reaction by a method such as carbamate Act can be produced.
[0124]
　Further, pentamethylene diisocyanate, if necessary, rectification (distillation) and purified by known methods such as extraction.
[0125]
　The purity of pentamethylene diisocyanate, e.g., 95 wt% or more, preferably 98 mass% or more, more preferably, 99 mass% or more, more preferably, 99.5 mass% or higher, especially preferably 99.9 not less than%, usually is 100% by mass.
[0126]
　The concentration of hydrolyzable chlorine of pentamethylene diisocyanate (hereinafter sometimes abbreviated as HC.) Is, 200 ppm or less, preferably, 100 ppm or less, more preferably, 80 ppm or less, more preferably, 70 ppm or less, usually it is 1ppm or more.
[0127]
　Modified products of pentamethylene diisocyanate, preferably, as in the modified product of the above diisocyanate, containing at least one functional group selected from the group consisting of the above (a) ~ (i).
(A) isocyanurate groups
(b) an allophanate group
(c) biuret groups
(d) a urethane group
(e) urea group
(f) uretdione groups
(g) iminooxadiazinedione groups
(h) uretonimine groups
(i) carbodiimide group
　the modified products containing a functional group (isocyanurate group) of (a) is a trimer of pentamethylene diisocyanate (trimer), for example, reacting a pentamethylene diisocyanate in the presence of a known isocyanurate catalyst it is, by trimerization can be obtained.
[0128]
　Modified products containing a functional group of the (b) (allophanate group) is a allophanate modified product of pentamethylene diisocyanate, e.g., after reacting a pentamethylene diisocyanate and the alcohol, known allophanatization catalyst by further reaction in the presence, it can be obtained.
[0129]
　Modified products containing a functional group of the (c) (biuret) is a biuret modified product of pentamethylene diisocyanate, e.g., a pentamethylene diisocyanate, e.g., water, tertiary alcohols (e.g., t- butyl alcohol), secondary amine (e.g., dimethylamine, by reacting diethylamine, etc.) and the like, can be obtained.
[0130]
　Polyisocyanate composition containing a functional group of the (d) (urethane groups) is a polyol-pentamethylene diisocyanate (polyol derivatives), e.g., pentamethylene diisocyanate and a polyol component (e.g., trimethylolpropane, etc. can be of a reaction of the trivalent alcohol), it obtained.
[0131]
　Modified products containing a functional group (urea group) of the (e) is a polyamine modified product of pentamethylene diisocyanate, e.g., pentamethylene diisocyanate and water, the reaction such as the polyamine component, can be obtained.
[0132]
　The modified products containing a functional group (uretdione groups) of (f), the uretdione modified product of pentamethylene diisocyanate (dimer-dimer) a, for example, the presence pentamethylene diisocyanate known dimerization catalyst it is reacted in the, by dimerization, can be obtained.
[0133]
　The modified products containing a functional group (iminooxadiazinedione groups) of (g) is a pentamethylene diisocyanate trimer (trimer), for example, a pentamethylene diisocyanate known iminooxadiazinedione of are reacted in the presence of a catalyst, by trimerization can be obtained.
[0134]
　Modified products containing a functional group of the (h) (uretonimine groups) is a uretonimine-modified product of pentamethylene diisocyanate, e.g., by reaction with pentamethylene diisocyanate and carbodiimide compounds, can be obtained.
[0135]
　Modified products containing a functional group (carbodiimide group) (i) above is a carbodiimide modified product of pentamethylene diisocyanate, e.g., by decarboxylation condensation reaction of pentamethylene diisocyanate, can be obtained.
[0136]
　Incidentally, it modified pentamethylene diisocyanate, the above (a) need only contain at least one functional group of ~ (i), may also contain two or more. Such modified products, by suitably used in combination the above reaction is produced.
[0137]
　As modified product of pentamethylene diisocyanate, preferably, a trimer of pentamethylene diisocyanate. In other words, modified pentamethylene diisocyanate is preferably contained trimer of pentamethylene diisocyanate, and more preferably, consists of trimer of pentamethylene diisocyanate.
[0138]
　The use of trimer of pentamethylene diisocyanate, it is possible to obtain a polyurethane resin excellent in mechanical properties (hardness, etc.) and durability (chemical resistance, weather resistance, etc.).
[0139]
　Incidentally, trimers pentamethylene diisocyanate, modified products containing isocyanurate groups of the (a) and (isocyanurate derivatives), modified products containing iminooxadiazinedione groups of the (g) (Iminookisa It contains Jiajinjion derivative) and.
[0140]
　And these isocyanurate derivatives and iminooxadiazinedione derivative, a relationship between structural isomers, isocyanurate derivatives are symmetrical trimer, iminooxadiazinedione derivatives are asymmetric trimers.
[0141]
　Incidentally, in the production of isocyanurate derivatives, may iminooxadiazinedione derivative as a by-product is produced, also, in some cases at the time of manufacture of iminooxadiazinedione derivatives, isocyanurate derivatives occur as a by-product.
[0142]
　As trimer of pentamethylene diisocyanate, preferably, isocyanurate derivatives.
[0143]
　Isocyanurate derivatives of pentamethylene diisocyanate, e.g., pentamethylene diisocyanate described above, in the presence of an isocyanurate-forming catalyst obtained by isocyanuration.
[0144]
　The isocyanurate catalysts, exemplified isocyanurate catalysts is mentioned as catalyst in the isocyanuration reaction of xylylene diisocyanate.
[0145]
　As isocyanurate catalysts, preferably, include organic weak acid salt of trialkylhydroxyalkylammonium, more preferably, it includes organic weak acid salt of trimethyl hydroxypropyl ammonium.
[0146]
　The mixing ratio of the isocyanurate-forming catalyst (solids) per 100 parts by mass of pentamethylene diisocyanate, e.g., 0.001 parts by weight (phr) or more, preferably, 0.005 parts by weight (phr) or more, more preferably is 0.01 parts by weight (phr) or more, for example, 0.1 parts by weight (phr) or less, preferably, 0.05 parts by weight (phr) or less, more preferably, 0.03 parts by weight (phr ) is less than or equal to.
[0147]
　The reaction conditions of the isocyanurate-forming reaction of pentamethylene diisocyanate, e.g., an inert gas atmosphere such as nitrogen gas, normal pressure (atmospheric pressure), the reaction temperature (ultimate maximum temperature), for example, 40 ° C. or higher, preferably , and at 60 ° C. or higher, for example, 120 ° C. or less, preferably, 110 ° C. or less, more preferably 100 ° C. or less. The reaction time is, for example, 5 minutes or more, preferably, not less than 10 minutes, for example, 180 minutes or less, preferably 120 minutes or less, and more preferably not more than 90 minutes.
[0148]
　In the above reaction, like the isocyanuration reaction of xylylene diisocyanate as described above, the organic phosphite ester as described above, it may also be formulated as a cocatalyst.
[0149]
　As organic phosphites, preferably, it includes aliphatic organic phosphites, and more preferably an alkyl mono- phosphites and the like, more preferable example is tridecyl phosphite.
[0150]
　The mixing ratio of the organic phosphite per 100 parts by mass of pentamethylene diisocyanate, e.g., 0.01 parts by weight (phr) or more, or preferably 0.03 parts by weight (phr) or more, e.g. , 0.5 parts by weight (phr) or less, preferably, 0.3 part by weight (phr) or less.
[0151]
　The mixing ratio of the organic phosphite ester, relative pentamethylene diisocyanate, 200 ppm or more, preferably not less 300ppm or more, e.g., 5000 ppm or less, preferably 2000ppm or less.
[0152]
　The amount of organic phosphite, relative to the chlorine equivalent amount of hydrolyzable chlorine in pentamethylene diisocyanate, e.g., 0.4 or more equivalents, preferably 0.7 equivalent or more, for example, 2.5 equivalents or less, preferably 1.5 equivalents or less.
[0153]
　By blending the organic phosphite in the above proportions as a co-catalyst, it is possible to improve the reaction rate and the reaction rate, can also suppress the gelation.
[0154]
　In the above reaction, as with xylylene diisocyanate isocyanurate reaction, it may be added a stabilizer such as a hindered phenol antioxidant described above.
[0155]
　The mixing ratio of the stabilizer with respect to 100 parts by mass of pentamethylene diisocyanate, e.g., 0.01 parts by weight (phr) or more, or preferably 0.02 parts by weight (phr) or more, for example, 0.1 part (phr) or less, preferably, 0.08 parts by weight (phr) or less.
[0156]
　In the above reaction, if necessary, it may be blended a known reaction solvent, and further, a known catalyst deactivator at any time (e.g., phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, ortho-toluene sulfonic acid, benzoyl chloride, p- toluenesulfonamide, o- toluenesulfonamide, etc.) may be added.
[0157]
　After completion of the reaction, pentamethylene diisocyanate Unreacted optionally, it can be removed by a known method.
[0158]
　Specifically, after the above-mentioned isocyanurate reaction completion, the isocyanurate derivative of pentamethylene diisocyanate obtained from a mixed reaction solution of pentamethylene diisocyanate monomer, pentamethylene diisocyanate unreacted monomer, for example, thin-film distillation ( it can be removed Smith distillation) distillation or the like, by a known method such as extraction.
[0159]
　In the present invention, when the thin film distillation after isocyanuration completion of pentamethylene diisocyanate, and the yield of the thin film distillation by obtained isocyanurate derivative (distillation yield), relative to the mass of the reaction mixture, isocyanurate of pentamethylene diisocyanate is the mass of the isocyanurate derivatives, for example, 5 wt% or more, preferably 10 mass% or more, more preferably 15 mass% or more, e.g., 70 wt% or less, preferably 65 wt% or less, more preferably is 60 wt% or less.
[0160]
　Incidentally, the distillation yield of isocyanurate derivatives pentamethylene diisocyanate can be determined by in conformity with the examples described below, calculates the ratio of the mass of the isocyanurate derivative of pentamethylene diisocyanate to the mass of the reaction mixture .
[0161]
　In the above reaction, if necessary, it may be blended alcohols. That is, isocyanurate derivatives can be modified with alcohols.
[0162]
　The alcohols, exemplified alcohols are mentioned as alcohols in the isocyanuration reaction of xylylene diisocyanate.
[0163]
　As alcohols, preferably include aliphatic alcohols, more preferably, include monovalent to trivalent aliphatic alcohol, more preferable example is a monovalent aliphatic alcohol.
[0164]
　Further, as the aliphatic alcohols, preferably aliphatic alcohols having 1 to 20 carbon atoms, more preferably an aliphatic alcohol having a carbon number of 2 to 20, more preferably, an aliphatic alcohol having 2 to 8 carbon atoms and the like.
[0165]
　Further, as the aliphatic alcohols, preferably branched monovalent aliphatic alcohols, divalent aliphatic alcohols, include trivalent aliphatic alcohol, more preferably, isobutanol (also known as iso-butyl alcohol, IBA ), 1,3-butanediol, include trimethylol propane, more preferably, isobutanol (also known as iso-butyl alcohol, IBA) and the like.
[0166]
　Alcohols, in isocyanurate derivatives of pentamethylene diisocyanate, formulated as the average number of functional groups is 2 or more, the mixing ratio with respect to 100 parts by mass of pentamethylene diisocyanate, alcohols, for example, 0. 1 part by mass or more, preferably, 0.2 part by weight or more, and is, for example, 10 parts by mass or less, preferably, 5.0 parts by mass or less, and more preferably not more than 1.0 part by weight.
[0167]
　Further, in this reaction, the pentamethylene diisocyanate and alcohol, for hydroxy group of an alcohol, the equivalent ratio of the isocyanate groups of pentamethylene diisocyanate (NCO / OH) is, for example, 5 or more, preferably 10 or more, more preferably, 20 or more, usually 1000 or less, preferably 600 or less, more preferably, under the compounding ratio to form 500 or less, are blended.
[0168]
　Isocyanurate derivatives of pentamethylene diisocyanate, as a method of modifying the alcohol, as well as the isocyanurate-forming reaction of xylylene diisocyanate as described above, for example, firstly, reacting a pentamethylene diisocyanate and alcohol, then isocyanurate after isocyanuration reaction in the presence of a catalyst, and a method of removing pentamethylene diisocyanate unreacted example, first, only pentamethylene diisocyanate and isocyanurate of in the manner described above, the unreacted pentamethylene diisocyanate was removed, then, and a method of reacting a polyisocyanurate obtained and the alcohol.
[0169]
　Preferably, first, reacting a pentamethylene diisocyanate and alcohol, and then was reacted isocyanurate in the presence of a isocyanurate catalyst, removing pentamethylene diisocyanate unreacted.
[0170]
　Reaction between pentamethylene diisocyanate and alcohol are urethane reaction (including allophanatization reaction), the reaction conditions, for example, an inert gas atmosphere such as nitrogen gas, at normal pressure (atmospheric pressure), the reaction temperature is, for example, room temperature (e.g., 25 ° C.) or higher, preferably not 40 ° C. or higher, for example, is 100 ° C. or less. The reaction time is, for example, 0.05 hours or more, preferably not less than 0.2 hours, for example, 10 hours or less, preferably 4 hours or less.
[0171]
　In the above urethanization reaction, if necessary, for example, it may be added to the urethane catalysts such as amines or organometallic compounds.
[0172]
　Then, in this method, the reaction solution obtained, the isocyanurate catalyst were blended at the mixing ratio described above, the reaction product of pentamethylene diisocyanate and alcohol, to isocyanuration reaction. Incidentally, the reaction conditions in the isocyanurate-forming are the same as above. After completion of the reaction, pentamethylene diisocyanate Unreacted necessary, by a known removal method such as distillation, removed.
[0173]
　Thus, it is possible to obtain modified with alcohols, the isocyanurate derivative of pentamethylene diisocyanate.
[0174]
　Further, for example, after isocyanurating only pentamethylene diisocyanate, in the case of adopting the method of removing the pentamethylene diisocyanate unreacted reacting the resulting polyisocyanate and the alcohol (above the latter method) includes isocyanurate derivatives and alcohols pentamethylene diisocyanate reacts. Note that this reaction is also a urethane-forming reaction, under reaction conditions of the urethane reaction as described above.
[0175]
　This also can be prepared modified with alcohols, the isocyanurate derivative of pentamethylene diisocyanate.
[0176]
　Incidentally, isocyanurate derivatives of pentamethylene diisocyanate, if it is denatured by the alcohol may allophanate derivatives of pentamethylene diisocyanate, obtained as a by-product. In such a case, isocyanurate derivatives of pentamethylene diisocyanate, as a sub-component contained in the inevitable, allophanate derivatives of pentamethylene diisocyanate. In other words, isocyanurate derivatives of pentamethylene diisocyanate, if it is denatured by the alcohol has a isocyanurate derivatives pentamethylene diisocyanate, isocyanurate composition containing allophanate derivatives of pentamethylene diisocyanate is obtained.
[0177]
　Modified with an alcohol, in the isocyanurate derivative of pentamethylene diisocyanate, modification amount of alcohol for the isocyanurate derivative (alcohol-modified ratio of isocyanurate derivatives), e.g., 0.01 wt% or more, preferably, 0. 1 mass% or more, more preferably 1.0 mass% or more, e.g., 35 wt% or less, preferably 30 wt% or less, more preferably 25 wt% or less, more preferably, 20 mass% or less it is.
[0178]
　In isocyanurate derivatives of pentamethylene diisocyanate, if alcohol modification ratio is within the above range, (such as hardness) mechanical properties, to obtain a design and durability (chemical resistance, weather resistance) polyurethane resin (described later) having excellent can.
[0179]
　Incidentally, modification amount of alcohol for the isocyanurate derivative (alcohol modification ratio) is in the isocyanurate derivative of xylylene diisocyanate as described above, it can be obtained by the equation similar to the alcohol-modified rate.
[0180]
　Further, the Like, alcohol modification rate, 1 can be calculated by H-NMR measurement.
[0181]
　The isocyanurate derivative of pentamethylene diisocyanate, essentially isocyanurate derivatives of pentamethylene diisocyanate which is not modified with alcohols, and may be either of the isocyanurate derivative of pentamethylene diisocyanate modified with an alcohol but preferably, isocyanurate derivatives of pentamethylene diisocyanate modified with an alcohol.
[0182]
　Isocyanurate derivatives of pentamethylene diisocyanate, isocyanate group concentration (solid content 100 wt%) is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably at 22 mass% or more, for example, 30 mass% or less, or preferably less 26 wt%.
[0183]
　Note that the isocyanate group concentration of the isocyanurate derivative of pentamethylene diisocyanate (solid content 100 wt%) can be determined in conformity with the examples described below.
[0184]
　In the isocyanurate derivative of pentamethylene diisocyanate, isocyanate monomer concentration (concentration of pentamethylene diisocyanate unreacted) is, for example, 2 wt% or less, preferably 1 mass% or less, more preferably 0.5 mass % or less.
[0185]
　Further, the isocyanurate derivative of pentamethylene diisocyanate, conversion of isocyanate groups (reaction rate) is, for example, 5 wt% or more, preferably 7 mass% or more, more preferably 10 mass% or more, for example, 40 wt% or less, preferably 35 wt% or less, and more preferably not more than 30 wt%.
[0186]
　Incidentally, isocyanurate derivatives of pentamethylene diisocyanate, if not modified by essentially alcohols, conversion of isocyanate groups (reaction rate) is substantially the isocyanurate conversion (trimer conversion) to be the same.
[0187]
　That is, isocyanurate conversion (trimer conversion) is, for example, 5 wt% or more, preferably 7 mass% or more, more preferably 10 mass% or more, e.g., 40 wt% or less, preferably , 35 wt% or less, and more preferably not more than 30 wt%.
[0188]
　On the other hand, isocyanurate derivatives of pentamethylene diisocyanate, if they are modified with alcohols, conversion of isocyanate groups (reaction rate) is a urethane conversion by alcohol, isocyanurate conversion (trimer conversion which is the total value of the rate).
[0189]
　In such cases, urethanes conversion, for example, 0.1 mass% or more, preferably 0.5 mass% or more, more preferably at least 1 mass%, for example, 10 wt% or less, preferably, 8 wt% or less, and more preferably not more than 5 wt%.
[0190]
　Also, isocyanurate conversion (trimer conversion) is, for example, 5 wt% or more, preferably 7 mass% or more, more preferably 10 mass% or more, e.g., 40 wt% or less, preferably , 35 wt% or less, and more preferably not more than 30 wt%.
[0191]
　Incidentally, the conversion of the isocyanate groups of pentamethylene diisocyanate, urethane conversion and isocyanurate conversion, like xylylene diisocyanate, in conformity with the examples described below, with respect to the isocyanate group concentration of pentamethylene diisocyanate time of charging, the reaction it can be determined by calculating the reduction rate of the isocyanate group concentration of the liquid.
[0192]
　Further, it modified pentamethylene diisocyanate, multimolecular comprising pentamethylene diisocyanate 4 or more molecules (hereinafter referred to as 4 or more molecules body.) Can contain.
[0193]
　For example, modified pentamethylene diisocyanate, if an isocyanurate derivative, 4 or more molecules body, the isocyanurate mononuclear body (specifically, 3-pentamethylene diisocyanate molecules to form one isocyanurate ring compounds are, i.e., the 3 molecules of pentamethylene diisocyanate) through an isocyanurate ring, furthermore, is a multi-molecule having a 1 which pentamethylene diisocyanate molecules had reacted (4 molecular sieve) or more molecular weight. Specifically, for example, dinuclear body (5 molecular entity), Sankakutai (7 molecular sieve) · · · n karyoplast ((2n + 1) molecular entity), and the like.
[0194]
　In modified product of pentamethylene diisocyanate, the content of 4 or more molecules body, relative to the total amount of the modified product of pentamethylene diisocyanate, e.g., 20 wt% or more, preferably 25 mass% or more, more preferably, 30 mass % or more, more preferably, 33 mass% or more, especially preferably not less than 35 wt%, e.g., 80 wt% or less, preferably 70 wt% or less, more preferably 65 wt% or less, more preferably , 60 wt% or less, especially preferably at most 55 mass%.
[0195]
　Note that in the modified product of pentamethylene diisocyanate, the content of 4 or more molecules body, the molecular weight distribution of the modified product of pentamethylene diisocyanate, based on the calibration curve of standard polyethylene oxide, equipped differential refractive index detector (RID) determined by gel permeation chromatography (GPC), as the peak area in the chromatogram obtained (chart) ratio (relative area ratio of the modified product of pentamethylene diisocyanate, the area ratio of 4 or more molecules form), it is calculated it can.
[0196]
　Further, in the modified product of pentamethylene diisocyanate, the area ratio of 4 or more molecules body can be determined as an area ratio equal to at least polyethylene oxide molecular weight in terms of 600.
[0197]
　In modified product of pentamethylene diisocyanate, if the content of the above range of 4 or more molecules bodies (such as hardness) mechanical properties, design and durability (chemical resistance, weather resistance, etc.) in excellent polyurethane resin (described later) it is possible to obtain.
[0198]
　Further, it modified pentamethylene diisocyanate, when such organic phosphite is used as a co-catalyst, which may contain phosphorus.
[0199]
　Phosphorus concentration of denaturing of pentamethylene diisocyanate (composition), for example, 5 ppm or more, preferably not less 10ppm or more, for example, 500 ppm or less, preferably 300ppm or less.
[0200]
　Incidentally, the phosphorus concentration may be in conformity with the examples described below are obtained.
[0201]
　The polyisocyanate composition is, if made of a modified product of xylylene diisocyanate, and modified products of pentamethylene diisocyanate (i.e., if the mode of the above (1)), the polyisocyanate composition, modification of xylylene diisocyanate and body, and a modified product of pentamethylene diisocyanate, by blending and mixing in a known manner, can be obtained.
[0202]
　In such a case, the proportion of each component in the polyisocyanate composition (specifically, a xylylene diisocyanate monomer, the proportion of the pentamethylene diisocyanate monomer) ratio of raw material monomers of the respective components as, It is adjusted.
[0203]
　More specifically, with respect to the total amount of xylylene diisocyanate and pentamethylene diisocyanate (total moles), xylylene diisocyanate is 5 mol% or more, preferably 10 mol% or more, more preferably, 15 mol% or more , and the 40 mole% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Further, pentamethylene diisocyanate, 60 mol% or more, preferably 70 mol% or more, more preferably 75 mol% or more, 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol % or less.

WE CLAIM
[Claim 1]
　Modified products of xylylene diisocyanate, and contain a denatured product of the pentamethylene diisocyanate
, and / or,
　modified products made of xylylene diisocyanate and pentamethylene diisocyanate
containing,
　penta to the total amount of the xylylene diisocyanate and pentamethylene diisocyanate ratio of diisocyanate is less 95 mol% 60 mol% or more
and wherein the polyisocyanate composition.
[Claim 2]
　The modified product is a multi-molecule comprising a diisocyanate and / or pentamethylene diisocyanate 2 or more molecules,
　content of the multimolecular of more than 4 molecules in the polyisocyanate composition is 30 mass% or more 65 wt% or less
and wherein the polyisocyanate composition according to claim 1.
[Claim 3]
　The four molecules or more of the multimolecular body,
　the multi-molecule of 4 or more molecules of xylylene diisocyanate, characterized in that it contains a proportion of 5 mass% or more and 45 mass% or less, according to claim 2 of the polyisocyanate composition.
[Claim 4]
　The modified body,
　characterized in that it contains at least one functional group selected from the group consisting of the following (a) ~ (i), the polyisocyanate composition according to claim 1.
(A) isocyanurate groups
(b) an allophanate group
(c) biuret groups
(d) a urethane group
(e) urea group
(f) uretdione groups
(g) iminooxadiazinedione groups
(h) uretonimine groups
(i) carbodiimide group
[Claim 5]
　A polyisocyanate composition according to claim 1,
　with an active hydrogen group-containing compound
characterized in that it is obtained by reaction of a polyurethane resin.
[Claim 6]
　A polyisocyanate component containing the polyisocyanate composition according to claim 1,
　and a polyol component
, characterized in that it contains, two-component curable polyurethane composition.
[Claim 7]
　Characterized in that it is obtained from a two-component curable polyurethane composition according to claim 6, the coating material.