0001]The present invention relates to a polyurethane resin and a manufacturing method thereof.
BACKGROUND
[0002]Conventionally, polyurethane resins are obtained by the reaction of a polyisocyanate component and a polyol component, it is widely used in various industrial fields. On the other hand, the polyurethane resin, in some applications, there is a case where the light-transmitting from the viewpoint of design properties (transparency) are required.
[0003]
　Therefore, optical transparency have been studied polyurethane resin having (transparency) is, for example, a polyisocyanate component comprising a modified product of an aliphatic polyisocyanate, an average hydroxyl value is an average functionality of at 280 ~ 1240mgKOH / g and 2 is exceeded less than 5 polyol component, optical polyurethane resin obtained by reacting in the presence of a bismuth based catalysts have been proposed.
[0004]
　More specifically, the average functionality 3.8 to a mixture of hexamethylene diisocyanate trimer (isocyanurate modified product) and allophanate modified product of hexamethylene diisocyanate, sorbitol and glycerin as an initiator, the average hydroxyl value 550mgKOH / g and a polyether polyol, optical polyurethane resin obtained by reacting in the presence of bismuth octylate has been proposed (e.g., see Patent Document 1 (example 11).).
CITATION
Patent Document
[0005]
Patent Document 1: JP 2011-12141 Publication
Summary of the Invention
Problems that the Invention is to Solve
[0006]
　On the other hand, as described in Patent Document 1, a three When a mixture of dimers and allophanate modified product is used, the content of the allophanate modified product is too high, optical transparency and durability (e.g., humidity and heat resistance test there is a case before and after the haze change evaluation) is not sufficient.
[0007]
　Further, the polyurethane resin having optical transparency, depending on the application, mechanical strength (e.g., ratings hardness) in some cases is required.
[0008]
　An object of the present invention is excellent in optical transparency, further is to provide a polyurethane resin and a manufacturing method thereof excellent in durability and mechanical strength.
Means for Solving the Problems
[0009]
　The present invention [1], a polyisocyanate component, a reaction product of a polyol component, wherein the polyisocyanate component contains a derivative of an aliphatic polyisocyanate, derivatives of the aliphatic polyisocyanates include isocyanurates having a group and allophanate groups, the content of allophanate groups, relative to isocyanurate groups 100 moles is 10 moles or more and 90 mol or less, wherein the polyol component has a hydroxyl value of 100 mg KOH / g or more 600 mg KOH / g or less of and triols, hydroxyl value contains the following diol 100 mg KOH / g or more 300 mgKOH / g, the triol, the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene triols, and / or, and polybasic acids / or its alkyl ester A polyester triol which is a reaction product of a polyhydric alcohol, said diol, the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene diols, and / or polybasic acids and / or their alkyl esters and multi a polyester diol is the reaction product of a polyhydric alcohol, contains a polyurethane resin.
[0010]
　The present invention [2], the aliphatic polyisocyanate, including a pentamethylene diisocyanate, includes polyurethane resins according to [1].
[0011]
　The present invention [3], the average functionality of the polyol component is from 2.1 to 2.9, it contains a polyurethane resin according to [1] or [2].
[0012]
　The present invention [4], the total amount of the polyol component, the total amount of the content of the polyester diol and the polyester triol, 5 is equivalent percent to 70 equivalent percent or less, the above-mentioned [1] to [3] It contains polyurethane resin of any one.
[0013]
　The present invention [5], comprising a polyisocyanate component, a step of reacting a polyol component, wherein the polyisocyanate component contains a derivative of an aliphatic polyisocyanate, derivatives of the aliphatic polyisocyanates, isocyanurate group and having allophanate groups, the content of allophanate groups, relative to isocyanurate groups 100 moles is 10 moles or more and 90 mol or less, wherein the polyol component has a hydroxyl value of 100 mg KOH / g or more 600 mg KOH / g or less of triol When the hydroxyl value is contained and less diol 100 mg KOH / g or more 300 mgKOH / g, the triol, the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene triols, and / or polybasic acids and / or its alkyl ester A polyester triol which is a reaction product of a polyhydric alcohol, said diol, the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene diols, and / or a polybasic acid and / or its alkyl ester a polyester diol is the reaction product of a polyhydric alcohol, the equivalent ratio of the isocyanate groups of the polyisocyanate component to the hydroxyl group of the polyol component (NCO / OH) is 0.9 to 1.1, a polyurethane resin it includes methods of manufacturing.
Effect of the invention
[0014]
　Polyurethane resin of the present invention, derivatives of aliphatic polyisocyanate is used containing isocyanurate groups and allophanate groups in a specific ratio, and, since the polyol component contains a specific proportion of specific triols and certain diols, light excellent transparency, further, is excellent in durability and mechanical strength.
[0015]
　According to the manufacturing method of the polyurethane resin of the present invention is excellent in optical transparency, further, it is possible to a polyurethane resin excellent in durability and mechanical strength, efficiently produced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016]
[1] Figure 1 is a graph showing the proportion of allophanate groups to isocyanurate groups, the relationship between the haze (optical transparency) and hardness (mechanical strength).
FIG. 2 is a graph showing the proportion of allophanate groups to isocyanurate groups, the relationship between the haze after the wet heat test (optical transparency).
FIG. 3 is a graph showing the proportion of allophanate groups to isocyanurate groups, the relationship between the amount of change in the haze (optical transparency) before and after the wet heat test.
DESCRIPTION OF THE INVENTION
[0017]
　Polyurethane resin of the present invention, a polyisocyanate component, a reaction product of a polyol component.
[0018]
　The polyisocyanate component contains a derivative of an aliphatic polyisocyanate.
[0019]
　Examples of the aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate ), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4 or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl Cap benzoate , and aliphatic diisocyanates such as dodecamethylene diisocyanate.
[0020]
　These aliphatic polyisocyanates may be used alone or in combination of two or more kinds.
[0021]
　As aliphatic polyisocyanates, in view of easy availability, preferably, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI) and the like, more preferably, 1,5-penta diisocyanate (PDI) and the like.
[0022]
　More specifically, 1,5-pentamethylene diisocyanate (PDI) is 1,6 compared to hexamethylene diisocyanate (HDI), methylene chain low crystallinity because of asymmetry due to the odd and crosslinking of the polyurethane resin it is possible to improve the density, it can be achieved by using 1,5-pentamethylene diisocyanate as aliphatic polyisocyanate (PDI), optically transparent polyurethane resin, the improvement of the durability and mechanical strength.
[0023]
　Incidentally, aliphatic polyisocyanates, containing no alicyclic polyisocyanates containing alicyclic (described later).
[0024]
　Further, derivatives of aliphatic polyisocyanates containing isocyanurate groups and allophanate groups.
[0025]
　That is, in the present invention, derivatives of aliphatic polyisocyanate is a derivative compositions of aliphatic polyisocyanates, mainly containing isocyanurate derivatives of aliphatic polyisocyanates, further comprising isocyanurate derivatives of aliphatic polyisocyanate alcohol containing allophanate modified isocyanurate derivatives of aliphatic polyisocyanate is the reaction product of (below), optionally the reaction product of (unreacted) aliphatic polyisocyanate with an alcohol (described later) fat containing allophanate derivatives families polyisocyanate.
[0026]
　In derivatives of such aliphatic polyisocyanates, the content ratio (molar ratio) of isocyanurate groups and allophanate groups, optical transparency, in view of the durability and mechanical strength, and is adjusted to a predetermined range.
[0027]
　Specifically, in the derivatives of aliphatic polyisocyanates, the content of allophanate groups, to the isocyanurate group 100 mol, 10 mol or more, preferably 12 mol or more, more preferably 20 mol or more, more preferably is 30 mol or more, especially preferably is 40 mol or more, 90 mol or less, preferably 80 mol or less, more preferably 70 mol or less, more preferably 60 mol or less.
[0028]
　In a case where the content of allophanate groups with monohydric alcohols in the preparation of derivatives of aliphatic polyisocyanates to be described later below the above lower limit, excessive trifunctional isocyanurate groups relative bifunctional allophanate groups since the crosslinking density increases, it decreases the light transmittance of the polyurethane resin.
[0029]
　On the other hand, the content of allophanate groups in a case of using a monohydric alcohol in the preparation of derivatives of aliphatic polyisocyanates to be described later exceeds the above upper limit, the allophanate groups is excessive relative to the isocyanurate group, the crosslinking density It becomes low, and decreases the mechanical strength of the polyurethane resin (such as hardness), inferior in durability.
[0030]
　For these, if the content of the above range of allophanate groups, it is possible to properly adjust the crosslink density, can be obtained optical transparency, durability and excellent polyurethane resins mechanical strength.
[0031]
　Further, in the derivatives of aliphatic polyisocyanates, the content of allophanate groups, based on 100 moles of isocyanurate groups and allophanate groups, for example, 9 mol or more, preferably 11 mol or more, more preferably, 17 mol or more, more preferably, 23 mol or more, particularly preferably not 29 mol or more, for example, 47 mol or less, preferably 44 mol or less, more preferably 41 mol or less, more preferably, is 38 mol or less .
[0032]
　In derivatives of aliphatic polyisocyanates, the content of isocyanurate groups, based on 100 moles of isocyanurate groups and allophanate groups, for example, 53 mol or more, preferably 56 mol or more, more preferably, 59 mol , more preferably not 62 mol or more, for example, 91 mol or less, preferably 89 mol or less, more preferably 83 mol or less, more preferably 77 mol or less, particularly preferably is 71 mol or less.
[0033]
　Incidentally, the content of isocyanurate groups and allophanate groups in conformity with Examples below, the derivatives of aliphatic polyisocyanate, 13 C-NMR allophanate groups and isocyanurate groups obtained from the measured NMR chart under the law it can be calculated from the molar ratio of.
[0034]
　To produce such derivatives of aliphatic polyisocyanates, for example, first, the above-mentioned aliphatic polyisocyanate and alcohol by urethanization reaction, then reacting the isocyanurate in the presence of isocyanurate catalyst and, for example, firstly, the aliphatic polyisocyanate is the isocyanurate of, then, a method for urethanization reaction include blended with alcohol.
[0035]
　Preferably, first, the above-described aliphatic polyisocyanate and alcohol by urethanization reaction, then reacted isocyanurate in the presence of an isocyanurate-forming catalyst.
[0036]
　Examples of the alcohol include monohydric alcohols, such as dihydric alcohols.
[0037]
　The monovalent alcohol, for example, monohydric alcohols of linear, like branched monohydric alcohol.
[0038]
　The monovalent 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, C, such as eicosanol (carbon number, hereinafter the same) include monohydric alcohols having 1 to 20 straight-chain.
[0039]
　The branched monohydric alcohols, such as isopropanol, isobutanol (isobutyl alcohol), sec-butanol, tert- butanol, iso-pentanol, isohexanol, iso heptanol, isooctanol, 2-ethyl-hexan-1-ol , 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 (C5 ~ 20) 1 monohydric alcohol C3 ~ 20 branched such as and the like.
[0040]
　Examples of the divalent alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol (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 alcohols linear, such as a diol, e.g., 1,2-propanediol, 1 3- butanediol (1,3-butylene glycol), 1,2-butanediol (1,2-butylene glycol), neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2 trimethyl pentanediol, 3,3-dimethylol heptane, 2,6-dimethyl-1-octenyl 3,8-diol, other branched alkane (C7 ~ 20) 2 dihydric alcohols branched, such as diols, e.g., 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3 - or 1,4-cyclohexanediol, and mixtures thereof, hydrogenated bisphenol a, include divalent alcohols C2 ~ 20 such as bisphenol a.
[0041]
　These alcohols may be used alone or in combination of two or more kinds.
[0042]
　As the alcohol, from the viewpoint of low viscosity derivatives of aliphatic polyisocyanates, preferably, monohydric alcohols, more preferably monohydric alcohols C1 ~ 20 linear, C3 ~ 20 monohydric alcohols branched in and the like. More preferably, it includes monohydric alcohols C3 ~ 20 branched, particularly preferably, include isobutyl alcohol.
[0043]
　If derivatives of aliphatic polyisocyanates long been low viscosity, it is possible to improve the compatibility with the polyol component, also can be improved optically transparent polyurethane resin.
[0044]
　The mixing ratio of the alcohol per 100 parts by mass of the aliphatic polyisocyanate, for example, 0.05 parts by mass or more, preferably, 0.1 parts by mass or more, more preferably, 0.2 parts by mass or more, more preferably , exceed 0.5 part by weight, for example, 4.0 parts by mass or less, preferably, 2.5 parts by mass or less, and more preferably not more than 1.5 parts by mass.
[0045]
　Within compounding ratio within the above range alcohol, relative isocyanurate derivatives of aliphatic polyisocyanates, aliphatic polyisocyanates, the content of the allophanate-modified isocyanurate derivatives and / or allophanate derivative (i.e., aliphatic polyisocyanate it is possible to adjust the content ratio) of allophanate groups in the derivative.
[0046]
　The urethanization reaction conditions, for example, an inert gas atmosphere such as nitrogen gas, at normal pressure (atmospheric pressure), reaction temperature, e.g., room temperature (e.g., 25 ° C.) or higher, preferably, be 40 ° C. or higher , for example, 100 ° C. or less, preferably 90 ° C. or less. The reaction time is, for example, 0.5 hour or more, preferably, not less than 1 hour, for example, 10 hours or less, preferably 6 hours or less, and more preferably not more than 3 hours.
[0047]
　In the above urethanization reaction, a known urethane catalyst (e.g., amines (described later), an organometallic compound (described later), etc.) may be compounded. The mixing ratio of the urethane-forming catalyst is not particularly limited, depending on the purpose and application, are set appropriately.
[0048]
　Thus, some of urethane-modified aliphatic polyisocyanate (i.e., a urethane-modified aliphatic polyisocyanate, (unreacted) aliphatic polyisocyanate composition comprising an aliphatic polyisocyanate) to obtain a it can.
[0049]
　Then, part of the urethane-modified aliphatic polyisocyanate is reacted isocyanurate in the presence of an isocyanurate-forming catalyst.
[0050]
　The isocyanurate catalysts, e.g., tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium, hydroxide or organic weak acid salt of tetraalkylammonium such as tributyl benzyl ammonium, e.g., trimethyl hydroxypropyl ammonium (aka: N-(2-hydroxypropyl) -N, N, N-trimethyl ammonium), trimethyl hydroxyethyl ammonium, triethyl hydroxypropyl ammonium hydroxide or organic weak acid salt of trialkylhydroxyalkylammonium such as triethyl hydroxyethyl ammonium (e.g. , N-(2-hydroxypropyl) -N, N, N- trimethylammonium-2-ethyl Etc. hexanoate), 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, etc. lead salt), for example, aluminum acetylacetone, metal chelate compounds such β- diketones such as lithium acetylacetonate, for example, aluminum chloride, Friedel-Crafts catalysts such as boron trifluoride, for example, titanium tetrabutylate, various organic, such as tributyl antimony oxide metal compounds, e.g., aminosilyl group-containing compound such as hexamethyl disilazane and the like.
[0051]
　These isocyanurate catalysts may be used alone or in combination of two or more kinds.
[0052]
　As isocyanurate catalysts, preferably, it includes organic weak acid salt of trialkylhydroxyalkylammonium, more preferably, N-(2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethyl hexanoate and the like.
[0053]
　The mixing ratio of the isocyanurate-forming catalyst (active component 100% basis) per 100 parts by mass of the aliphatic polyisocyanate, for example, 0.001 parts by mass or more, or preferably, 0.003 part by weight or more, For example, 0.1 parts by mass or less, preferably at most 0.05 parts by weight.
[0054]
　The reaction conditions of the isocyanurate-forming reaction, for example, an inert gas atmosphere such as nitrogen gas, normal pressure (atmospheric pressure), reaction temperature, e.g., 50 ° C. or higher, preferably, 70 ° C. or higher, more preferably, and at 80 ° C. or higher, for example, 120 ° C. or less, preferably 100 ° C. or less. The reaction time is, for example, 5 minutes or more, preferably, 10 minutes or more, more preferably, not less than 15 minutes, for example, 120 minutes or less, preferably not more than 60 minutes.
[0055]
　Then, in the above isocyanurate reaction, upon reaching a predetermined reaction rate (isocyanate group conversion), for example, phosphoric acid, monochloroacetic acid, benzoyl chloride, dodecylbenzenesulfonic acid, toluenesulfonic acid (o-or p - toluenesulfonic acid) and its derivatives (e.g., o- or p- toluenesulfonic acid methyl etc.), by adding a reaction terminator such as toluene sulfonamide (o-or p- toluenesulfonamide) in the reaction mixture, the catalyst the was quenched to stop the isocyanurate reaction. In this case, such a chelate resin or an ion exchange resin, catalyst was added an adsorbent that adsorbs, it is also possible to stop the isocyanurate reaction.
[0056]
　Conversion of the isocyanate groups when stopping the isocyanuration reaction, for example, 1 mass% or more, preferably, 5% by mass or more, e.g., 20 wt% or less, preferably 15 mass% or less.
[0057]
　Incidentally, the conversion of the isocyanate groups are, for example, high-speed GPC, NMR, isocyanate group concentration, refractive index, density, etc. on the basis of the infrared spectrum can be measured.
[0058]
　Thus, it is possible to react an isocyanurate of an aliphatic polyisocyanate.
[0059]
　Further, in this isocyanuration, since a part is isocyanurate of a urethane-modified aliphatic polyisocyanate, with isocyanurate derivatives described above, also generates allophanate modified isocyanurate derivatives.
[0060]
　In the above-described isocyanurate reaction, in order to adjust the isocyanuration, for example, an organic phosphite ester as described in JP-A-61-129173, it is formulated as a cocatalyst It can also be.
[0061]
　The organic phosphites, for example, organic phosphoric acid diesters, include such organic phosphite triester, more specifically, for example, triethyl phosphite, tributyl phosphite, tridecyl phosphite, tris ( tridecyl) phosphite, triphenyl phosphite, tris (mono-phosphites such as nonylphenyl) phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, diphenyl (tridecyl) phosphite, for example, di stearyl pentaerythrityl-diphosphite, tripentaerythritol, triethylene phosphite, di derived from a polyhydric alcohol such as tetraphenyl dipropylene glycol diphosphite, and the like tri or tetra phosphites.
[0062]
　These organic phosphites may be used alone or in combination of two or more kinds.
[0063]
　As organic phosphites, preferably mono- phosphites and the like, more preferably, tridecyl phosphite include tris (tridecyl) phosphite.
[0064]
　The mixing ratio of the organic phosphite per 100 parts by mass of the aliphatic polyisocyanate, for example, 0.01 parts by mass or more, preferably, 0.05 parts by mass or more, more preferably, 0.10 parts by mass or more , and the example, 1.0 parts by mass or less, preferably not more than 0.50 parts by mass.
[0065]
　In the above isocyanurate reaction, if necessary, a hindered phenol-based antioxidant include 2,6-di (tert- butyl) 4-methylphenol (BHT), Irganox 1010, Irganox 1076, Irganox 1135, Irganox 245 (or, BASF Japan Ltd., trade name) may also be blended reaction stabilizers such.
[0066]
　The mixing ratio of the reactive stabilizer, relative to 100 parts by weight of aliphatic polyisocyanate, for example, 0.01 parts by mass or more, or preferably, 0.05 parts by mass or more, for example, 1.0 parts by mass or less, preferably is 0.10 parts by mass.
[0067]
　Further, a cocatalyst and reaction stabilizers above can also be added during the urethanization reaction described above.
[0068]
　In the above isocyanurate reaction, if necessary, it may be blended a known reaction solvent.
[0069]
　After completion of the reaction, when the resulting reaction mixture, unreacted aliphatic polyisocyanates (catalyst, blending the reaction solvent and / or catalyst deactivator, catalyst, reaction solvent and / or catalyst deactivator also included), for example, distillation or the like thin film distillation (Smith distillation), is removed by a known method such as extraction, derivatives of aliphatic polyisocyanate is obtained.
[0070]
　Further, after removal of the unreacted aliphatic polyisocyanate, the derivative of the resulting aliphatic polyisocyanate, can also be added in any addition rate of reaction inhibitor described above as a stabilizer.
[0071]
　And, thereby, derivatives of aliphatic polyisocyanate is obtained.
[0072]
　Derivatives of the resulting aliphatic polyisocyanate is contained isocyanurate groups and allophanate groups, and their content is adjusted within the above range. Therefore, according to the derivatives of aliphatic polyisocyanates can be light transmissive, durability and improved mechanical strength.
[0073]
　Further, derivatives of aliphatic polyisocyanates, if the content of isocyanurate groups and allophanate groups long as it is adjusted within the above range, not limited to the above manufacturing method, for example, the different formulations of aliphatic polyisocyanate derivatives can also be prepared by blending two or more kinds.
[0074]
　More specifically, for example, the isocyanurate derivatives of aliphatic polyisocyanates, the allophanate derivatives of aliphatic polyisocyanates, each prepared separately by mixing them, containing isocyanurate groups and allophanate groups it can be obtained derivatives of aliphatic polyisocyanate (derivative composition).
[0075]
　Isocyanurate derivatives of aliphatic polyisocyanates has contain isocyanurate groups and do not contain allophanate groups, or, trace (described below) is a derivative containing.
[0076]
　Isocyanurate derivatives of aliphatic polyisocyanate containing no allophanate groups, for example, in the isocyanurate forming reaction as described above, without compounding the alcohol, reacting the isocyanurate of aliphatic polyisocyanates in the presence of isocyanurate catalyst it makes it possible to obtain. Incidentally, the reaction conditions in the isocyanuration reaction is the same as above.
[0077]
　However, isocyanurate group is readily formed by way of the urethane reaction. Therefore, by blending traces of alcohol, it is possible to promote the isocyanuration reaction. In such a case, allophanate groups isocyanurate derivatives of aliphatic polyisocyanates containing trace obtained.
[0078]
　Isocyanurate derivatives of aliphatic polyisocyanates with allophanate groups containing trace amounts, for example, the method described above (first, the above-mentioned aliphatic polyisocyanate and alcohol by urethanization reaction, then isocyanate in the presence of isocyanurate catalyst a method) to isocyanurate reaction to relatively small amount of alcohol.
[0079]
　In such a case, the mixing ratio of alcohol with respect to 100 parts by weight of aliphatic polyisocyanate, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, for example, 0.5 parts by mass or less, preferably, at most 0.3 parts by weight.
[0080]
　Thus, it is possible to suppress the generation amount of allophanate groups by reaction with aliphatic polyisocyanate and alcohol.
[0081]
　Then, the resulting reaction product is reacted isocyanurate in the presence of an isocyanurate-forming catalyst. Incidentally, the reaction conditions in the isocyanuration reaction is the same as above.
[0082]
　In isocyanurate derivatives of aliphatic polyisocyanates, the content of allophanate groups, to the isocyanurate group 100 mol, e.g., less than 10 mol, preferably 8 mol or less, more preferably 7 or mole or less, , usually, it is 0 mole or more.
[0083]
　Allophanate derivatives of aliphatic polyisocyanates has contain allophanate groups and either not containing isocyanurate groups, or, trace (described below) is a derivative containing.
[0084]
　Allophanate derivatives of aliphatic polyisocyanates, for example, by reacting a monohydric alcohol mentioned above and the aliphatic polyisocyanate, then by allophanatization reaction in the presence of an allophanate catalyst, can be obtained.
[0085]
　The monovalent alcohol, the same alcohol can be mentioned monohydric alcohols mentioned above (monohydric alcohol in isocyanurating), can be used alone or in combination of two or more. As monohydric alcohols, preferably, it includes branched monohydric alcohol, more preferably, isobutanol (also known as iso-butyl alcohol) and the like.
[0086]
　When producing allophanate derivatives of aliphatic polyisocyanate, the mixing ratio of alcohol with respect to 100 parts by weight of aliphatic polyisocyanate, for example, exceeds 3 parts by mass, preferably 3.2 parts by mass or more, more preferably is 3.5 parts by mass or more, for example, 50 parts by weight or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
[0087]
　Further, in this reaction, the better does not inhibit the effect scope of the present invention, if necessary, a monohydric alcohol as described above, for example, thiols, oximes, lactams, phenols, such as β-diketones it can be used in combination with an active hydrogen group-containing compound.
[0088]
　The reaction conditions in the reaction of an aliphatic polyisocyanate and an alcohol, for example, an inert gas atmosphere such as nitrogen gas, at normal pressure (atmospheric pressure), reaction temperature, e.g., 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.
[0089]
　Thus, reacting urethanization an alcohol aliphatic polyisocyanate.
[0090]
　In the above urethanization reaction, if necessary, a known urethane catalyst (e.g., amines (described later), an organometallic compound (described later), etc.) may be compounded. The mixing ratio of the urethane-forming catalyst is not particularly limited, depending on the purpose and application, are set appropriately.
[0091]
　Then, in this method, the reaction solution obtained, by blending the allophanate catalyst, the reaction product of an aliphatic polyisocyanate with an alcohol, thereby allophanatization reaction.
[0092]
　The allophanatization catalysts, for example, an organic carboxylic bismuth salt such as bismuth octylate, for example, an organic carboxylic San'namarishio such octylate lead.
[0093]
　These allophanatization catalysts may be used alone or in combination of two or more kinds.
[0094]
　As allophanatization catalyst, preferably an organic carboxylic San'namarishio the like, and more preferably include lead octylate.
[0095]
　The addition ratio of the allophanatization catalyst per 100 parts by mass of the aliphatic polyisocyanate, for example, 0.001 parts by mass or more, preferably 0.002 parts by mass or more, more preferably, be 0.01 part by mass or more , for example, 0.3 parts by mass or less, preferably, 0.05 parts by mass or less, and more preferably not more than 0.03 parts by mass.
[0096]
　The reaction conditions for the allophanate reaction, for example, an inert gas atmosphere such as nitrogen gas, normal pressure (atmospheric pressure), reaction temperature, 0 ° C. or more, or preferably, 20 ° C. or higher, for example, 160 ° C. or less , preferably it is 120 ° C. or less. The reaction time is, for example, 30 minutes or more, or preferably 60 minutes or more, e.g., 1200 minutes or less, or preferably 600 minutes or less.
[0097]
　Then, the allophanatization reaction described above, at the time of reaching a predetermined reaction rate (isocyanate group conversion), the reaction terminator was added to the reaction solution, the catalyst was deactivated by stopping the allophanatization reaction. In this case, such a chelate resin or an ion exchange resin, catalyst was added an adsorbent that adsorbs, it is also possible to stop the allophanatization reaction. The reaction terminator to stop the allophanate reaction, for example, the same as the reaction stopper to stop the isocyanurate reaction.
[0098]
　Conversion of the isocyanate groups when stopping the allophanatization reaction, for example, 1 mass% or more, preferably, 5% by mass or more, e.g., 20 wt% or less, preferably 15 mass% or less.
[0099]
　Incidentally, the conversion of the isocyanate groups are, for example, high-speed GPC, NMR, isocyanate group concentration, refractive index, density, etc. on the basis of the infrared spectrum can be measured.
[0100]
　Thus, it is possible to react allophanatization aliphatic polyisocyanate.
[0101]
　In the above reaction, in order to adjust the urethanization and allophanatization, for example, an organic phosphite ester as described above, it may also be formulated as a cocatalyst. Organic phosphites may be used alone or in combination of two or more kinds. As organic phosphites, preferably mono- phosphites, and more preferably include tris (tridecyl) phosphite.
[0102]
　The addition ratio of the organic phosphite per 100 parts by mass of the aliphatic polyisocyanate, for example, 0.01 parts by mass or more, preferably, 0.02 parts by mass or more, more preferably, 0.03 parts by mass or more , and the example, 0.2 parts by mass or less, preferably, 0.15 parts by mass or less, and more preferably not more than 0.1 part by weight.
[0103]
　Further, a cocatalyst and reaction stabilizers above can also be added during the urethanization reaction described above.
[0104]
　In the above isocyanurate reaction, if necessary, it may be blended a known reaction solvent.
[0105]
　After completion of the reaction, when the resulting reaction mixture, unreacted aliphatic polyisocyanates (catalyst, blending the reaction solvent and / or catalyst deactivator, catalyst, reaction solvent and / or catalyst deactivator also included), for example, distillation or the like thin film distillation (Smith distillation), is removed by a known method such as extraction, allophanate derivatives of aliphatic polyisocyanate is obtained. Further, after removal of the unreacted aliphatic polyisocyanate, the allophanate derivatives of the resultant aliphatic polyisocyanate, can also be added in any addition rate of reaction inhibitor described above as a stabilizer.
[0106]
　In allophanate derivatives of aliphatic polyisocyanates, the content of allophanate groups, to the isocyanurate group 100 mol, 3000 mol or more, or preferably 3500 mol, more preferably, 4000 moles or more, and generally, 100000 is mol or less.
[0107]
　Then, the isocyanurate derivative of the aliphatic polyisocyanate, the allophanate derivatives of the aliphatic polyisocyanate, by mixing in a known manner, as their mixture (composition), isocyanurate groups and allophanate groups it can be obtained derivatives of aliphatic polyisocyanates having.
[0108]
　The mixing ratio of the isocyanurate derivatives of aliphatic polyisocyanates, allophanate derivatives of aliphatic polyisocyanate, the proportion of allophanate groups and isocyanurate groups in the resulting mixture is adjusted to a predetermined range.
[0109]
　Specifically, the isocyanurate derivatives of aliphatic polyisocyanate, the total amount of 100 parts by mass of the allophanate derivatives of aliphatic polyisocyanates, isocyanurate derivatives of aliphatic polyisocyanates, for example, 50 parts by mass or more, preferably is 60 parts by mass or more, more preferably 80 parts by mass or more, for example, 96 parts by mass or less, preferably not more than 90 parts by mass. Further, allophanate derivatives of aliphatic polyisocyanates, for example, 4 parts by mass or more, preferably is at least 10 parts by weight, for example, 50 parts by weight or less, preferably 40 parts by mass or less, more preferably 20 parts by weight less.
[0110]
　Further, derivatives of aliphatic polyisocyanate (derivative compositions), the unreacted aliphatic polyisocyanate monomer, with respect to 100 parts by weight derivatives of aliphatic polyisocyanates, for example, 1.0 parts by mass or less, also allowed to contain 0.5 parts by mass or less.
[0111]
　Furthermore, derivatives of aliphatic polyisocyanates, for example, can contain derivatives excluding isocyanurate derivatives and allophanate derivatives of aliphatic polyisocyanate (hereinafter, referred to as other derivatives.).
[0112]
　Other derivatives, for example, biuret derivatives (e.g., aliphatic polyisocyanate described above, such as biuret derivatives produced by the reaction of water and amines.), Urea derivatives (e.g., aliphatic polyisocyanate and a diamine as described above such urea derivative formed by the reaction of.), oxadiazinetrione derivative (e.g., oxadiazinetrione derivative formed by the reaction of an aliphatic polyisocyanate and carbon dioxide as described above.), carbodiimide derivatives (fatty described above carbodiimide derivatives produced by decarboxylation condensation reaction of family polyisocyanate.), polyol derivatives (for example, a low molecular weight polyol (preferably to be described later and aliphatic polyisocyanate described above, the low molecular weight triol, described later) for generating from the reaction of Po Ol derivative (alcohol adduct), was the (preferably below the molecular weight polyol) low molecular weight polyols and / or below the molecular weight polyol to be described later aliphatic polyisocyanate said polyol derivatives produced from reaction with), more , iminooxadiazinedione derivatives of aliphatic polyisocyanates, like uretdione derivatives of aliphatic polyisocyanates.
[0113]
　These other derivatives can be used alone or in combination of two or more kinds.
[0114]
　Other derivatives, in view of optical transparency, preferably, a biuret derivatives of aliphatic polyisocyanates.
[0115]
　The form in which other derivatives is contained, is not particularly limited, for example, each of the reactions described above (urethanization reaction, an isocyanurate-forming reaction, such as the allophanatization reaction) other derivatives as by-products in the generation, other derivative may be contained in the aliphatic polyisocyanate derivative. Further, for example, other derivatives, which are separately prepared, may be added to the polyisocyanate derivative.
[0116]
　Content of other derivatives, the proportion of allophanate groups and isocyanurate groups in the aliphatic polyisocyanate derivative (derivative compositions) may, if it is adjusted so that the above range is not particularly limited, aliphatic poly based on 100 parts by weight of derivatives of isocyanates, for example, 1 part by mass or more, or preferably 5 parts by mass or more, for example, 50 parts by weight or less, or preferably 40 parts by mass or less.
[0117]
　The polyisocyanate component may contain solely the derivatives of aliphatic polyisocyanates, it is also possible in addition to the derivatives of aliphatic polyisocyanates, contain other polyisocyanates and / or derivatives thereof.
[0118]
　Other polyisocyanates and / or derivatives thereof, for example, polyisocyanate monomers (here, excluding the aliphatic polyisocyanates), polyisocyanate derivative (here, except for derivatives of aliphatic polyisocyanate) include .
[0119]
　The polyisocyanate monomers, for example, aromatic polyisocyanates, araliphatic polyisocyanates, such as polyisocyanates, such as an alicyclic polyisocyanate.
[0120]
　Examples of the aromatic polyisocyanates, for example, m- or p- phenylene diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 4,4 '-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI ) and aromatic diisocyanates such.
[0121]
　Examples of the aromatic aliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), omega, such as aromatic aliphatic diisocyanates such as ω'- diisocyanate-1,4-diethylbenzene, and the like.
[0122]
　Examples of the alicyclic polyisocyanates, such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4 '-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof (hydrogenated XDI), an alicyclic diisocyanate such as norbornane diisocyanate (NBDI) and the like.
[0123]
　These polyisocyanate monomers can be used alone or in combination of two or more kinds.
[0124]
　The polyisocyanate derivatives, for example, polyisocyanate monomers mentioned above, multimer (e.g., dimers, trimers, pentamers, heptamers, etc..), Allophanate derivatives (e.g., polyisocyanates described above a monomer, such as allophanate derivatives produced from reaction with an alcohol.), biuret derivatives (e.g., a polyisocyanate monomer described above, such as biuret derivatives produced by the reaction of water and amines.), urea derivatives (e.g., urea derivatives formed by the reaction of a polyisocyanate monomer and a diamine as described above.), oxadiazinetrione derivative (e.g., Okisajia produced by reaction of the polyisocyanate monomers with carbon dioxide as described above such as Jintorion derivatives.), carbodiimide derivatives (Porii described above Carbodiimide derivatives produced by decarboxylation condensation reaction of cyanate monomers.), From the reaction of a polyol derivative (e.g., polyisocyanate monomer and a low molecular weight polyol to be described later (preferably as described above, the low molecular weight triol, which will be described later) resulting polyol derivative (alcohol adduct), the above-mentioned polyisocyanate monomer with (preferably, below the molecular weight polyol) low molecular weight polyols and / or below the molecular weight polyol to be described later polyol derivative produced from the reaction of ( poly isocyanate terminated prepolymer) and the like.) and the like.
[0125]
　These polyisocyanates derivatives can be used alone or in combination of two or more kinds.
[0126]
　These other polyisocyanates and / or its derivatives can be used alone or in combination of two or more.
[0127]
　In the polyisocyanate component, the content of components excluding aliphatic polyisocyanate derivative (other polyisocyanates and / or its derivatives), of the total amount of aliphatic polyisocyanate derivatives, for example, less than 50 wt%, preferably, 30 wt% or less, more preferably 10 mass% or less, especially preferably 0 mass%.
[0128]
　That is, the polyisocyanate component preferably contains alone aliphatic polyisocyanate derivative.
[0129]
　Then, the isocyanate group equivalent of the polyisocyanate component prepared in this way, for example, 150 or more, preferably, is 200 or more, and is, for example, 750 or less, preferably 500 or less.
[0130]
　Note that the isocyanate group equivalent is synonymous with an amine equivalent weight, the A method or B method JIS K 1603-1 (2007), (hereinafter the same) which can be obtained.
[0131]
　The average functionality of the polyisocyanate component is, for example, 2.00 or more, preferably not 2.10 or more, and is, for example, 2.90 or less, preferably 2.80 or less.
[0132]
　Also, isocyanate group content of the polyisocyanate component is, for example, 18 mass% or more, preferably not less than 20 wt%, e.g., 30 wt% or less, preferably not more than 28 wt%.
[0133]
　Incidentally, an isocyanate group content, the n- dibutylamine method conforming to JIS K 1556 (2006), can be obtained (hereinafter the same).
[0134]
　The polyol component includes a diol having a hydroxyl value of 100 to 300, a hydroxyl value contains a 100 or more and 600 or less of triol.
[0135]
　The diol, the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene diols, and / or, a polyester diol is the reaction product of a polybasic acid and / or its alkyl ester and a polyhydric alcohol .
[0136]
　The polyoxyalkylene diol carbon atoms of oxyalkylene group is 2 to 3, for example, low molecular weight diol, addition polymer of low molecular weight diamines such as the initiator and the alkylene oxide having 2 to 3 carbon atoms (two or more of including random and / or block copolymers of alkylene oxide) and the like.
[0137]
　Low molecular weight diol (preferably, less than 400) number average molecular weight is less than 300 usually more than 40, a bifunctional low molecular weight polyol having two hydroxyl groups, for example, aliphatic diols, alicyclic diols, and aromatic diols.
[0138]
　Examples of the aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2 - methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethylpentane - 1,3-diol, 1,6-hexane diol, neopentyl glycol, 1,5-heptane diol, 1,7-heptane diol, 3,3'-dimethylol heptane, 1,8-octanediol, 1,9 - nonanediol, 1,10-decanediol, 1,11-undecane Diol, 1,12-undecane diol, such as 12-hydroxy stearyl alcohol.
[0139]
　Examples of the alicyclic diols such as hydrogenated bisphenol A, hydrogenated xylylenediol, cyclohexanediol, cyclohexanedimethanol, and hydrogenated dimer diols.
[0140]
　Examples of the aromatic diols include bisphenol A, bis-hydroxyethyl terephthalate, catechol, resorcinol, hydroquinone, 1,3-or 1,4-xylylene ol.
[0141]
　These low molecular weight diol may be used alone or in combination of two or more kinds.
[0142]
　Low molecular weight diamines (preferably, less than 400) number average molecular weight is less than 300 usually more than 40, a compound having two amino groups, such as ethylenediamine, 1,3-propanediamine, 1,3 or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethane diamine , 2,5 (2,6) - bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, o, m or p- tolylene diamine (TDA, OTD), and the like.
[0143]
　These low molecular weight diamines may be used alone or in combination of two or more.
[0144]
　As an initiator, preferably, a low molecular weight diol.
[0145]
　The alkylene oxide having 2 to 3 carbon atoms, e.g., ethylene oxide (also known as oxirane), trimethylene oxide (also known oxetane), propylene oxide (also known as oxirane), and the like.
[0146]
　These alkylene oxides may be used alone or in combination of two or more kinds.
[0147]
　As alkylene oxide, preferably ethylene oxide, propylene oxide and the like, more preferably, propylene oxide.
[0148]
　Such polyoxyalkylene diol, specifically, for example, polyethylene glycol, polypropylene glycol, propylene oxide - ethylene oxide copolymer diol (random and / or block copolymer) and the like.
[0149]
　These polyoxyalkylene diols can be used alone or in combination of two or more.
[0150]
　As polyoxyalkylene diols, preferably, a polypropylene glycol.
[0151]
　The hydroxyl value of the polyoxyalkylene diol is, 100 mg KOH / g or more as described above, preferably, 105 mgKOH / g or more, more preferably, 150 mgKOH / g or more, as described above 300 mgKOH / g or less, preferably, 290MgKOH / g or less, and more preferably not more than 250 mgKOH / g.
[0152]
　The hydroxyl value of the polyoxyalkylene diol is within the above range, it is possible to improve the optical transparency, durability and mechanical strength of the polyurethane resin.
[0153]
　The hydroxyl value is measured according to the description of JIS K-1557-1 (2007 years) (hereinafter the same.).
[0154]
　The number average molecular weight of polyoxyalkylene diols, for example, 300 or more, 400 or more, more preferably 500 or more, for example, 1200 or less, preferably 1000 or less.
[0155]
　The number average molecular weight, (hereinafter the same), which is calculated by the following equation.
[0156]
　The number average molecular weight = 56100 × average functionality / hydroxyl value
　also polyoxyalkylene diols of CPR (controlled polymerization rate) is, for example, 5 or less, preferably, 3 or less, more preferably 2 or less, more preferably, 1 or less, for example, 0 or more, preferably 0.01 or more, more preferably 0.1 or more.
[0157]
　Incidentally, CPR, based on the method of JIS K 1557-4 (2007) described, is measured (hereinafter the same).
[0158]
　The polyester diol, the reaction product of a polybasic acid and / or its alkyl esters with polyhydric alcohols. More specifically, as the polyester diol, a dibasic acid and / or its alkyl esters, reaction products of dihydric alcohols.
[0159]
　The dibasic acids, such as oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxylate propane, 3-methyl-3-ethyl glutaric acid , azelaic acid, sebacic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, aliphatic dibasic acids such as HET acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalene dicarboxylic acid, dimer acid and aromatic dibasic acids such as, and these acid anhydrides, such as their acid halides and the like. The acid anhydrides, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl succinic acid (having 12 to 18 carbon atoms), and the like tetrahydrophthalic anhydride. As the acid halide, such as oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.
[0160]
　These dibasic acids may be used alone or in combination of two or more kinds.
[0161]
　The alkyl esters of dibasic acids, methyl esters of dibasic acids mentioned above, such as ethyl esters.
[0162]
　Alkyl esters of these dibasic acids may be used alone or in combination of two or more kinds.
[0163]
　As the divalent alcohol, for example, low molecular weight diol as described above. These dihydric alcohols may be used alone or in combination of two or more kinds.
[0164]
　The polyester diols are the condensation reaction of dihydric alcohol described above and dibasic acids mentioned above, or, by transesterification of dihydric alcohol described above and an alkyl ester of a dibasic acid mentioned above, obtained as a reaction product It is. As the polyester diol, preferably, the reaction product by condensation reaction of dibasic acids and dihydric alcohols.
[0165]
　Incidentally, the condensation reaction or ester exchange reaction, if necessary, under known catalyst can be carried out in a known reaction conditions.
[0166]
　Hydroxyl value of the polyester diol, as described above 100 mg KOH / g or more, preferably, 105 mgKOH / g or more, and more preferably not 150 mgKOH / g or more, as described above 300 mgKOH / g or less, preferably, 290mgKOH / g or less, more preferably not more than 250 mgKOH / g.
[0167]
　Hydroxyl value of the polyester diol is within the above range, it is possible to improve the optical transparency, durability and mechanical strength of the polyurethane resin.
[0168]
　The number average molecular weight of the polyester diols are, for example, 300 or more, 400 or more, more preferably 500 or more, for example, 1200 or less, preferably 1000 or less.
[0169]
　The diols, the polyoxyalkylene diols, and / or are the polyester diols, preferably, the polyoxyalkylene diol and the like.
[0170]
　By using such a diol, optically transparent polyurethane resin, it is possible to improve the durability and mechanical strength.
[0171]
　The hydroxyl value of the diol, the 100 mg KOH / g or more as described above, preferably, 105 mgKOH / g or more, and more preferably not 150 mgKOH / g or more, or less 300 mgKOH / g as described above, preferably, 290mgKOH / g or less , more preferably not more than 250 mgKOH / g.
[0172]
　The number average molecular weight diols, for example, 300 or more, 400 or more, more preferably 500 or more, for example, 1200 or less, preferably 1000 or less.
[0173]
　The triol, the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene triols, and / or a polyester triol which is a reaction product of a polybasic acid and / or its alkyl ester and a polyhydric alcohol .
[0174]
　Oxy As the polyoxyalkylene triols carbon number of 2-3 alkylene group, for example, low molecular weight triol, addition polymer of low molecular weight triamine such as the initiator and the alkylene oxide having 2 to 3 carbon atoms (two or more of including random and / or block copolymers of alkylene oxide) and the like.
[0175]
　Low molecular weight triols (preferably, less than 300) number average molecular weight is less than 400 usually more than 40, a trifunctional low molecular weight polyols having three hydroxyl groups.
[0176]
　The low molecular weight triols, such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethyl pentane, 1,2,6-hexanetriol, trimethylol ethane , trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and other and aliphatic triols (8-24 carbon atoms) can be mentioned, preferably, trimethylolpropane.
[0177]
　These low molecular weight triols can be used alone or in combination of two or more.
[0178]
　Low molecular weight triamines, number average molecular weight is less than 300 (preferably less than 400) typically of 40 or more, a compound having three amino groups, such as diethylenetriamine, 4-amino-1,8-octane diamine 2,2 ', 2' '- triamino triethylamine, tris-1,1,1-aminoethyl ethane, 1,2,3-aminopropane, tris - (3-aminopropyl) - amine, N, N , N ', N'-tetrakis - (2-aminoethyl) - such as ethylenediamine.
[0179]
　These low molecular weight triamines may be used alone or in combination of two or more kinds.
[0180]
　As an initiator, preferably, a low molecular weight triol.
[0181]
　The alkylene oxide having 2 to 3 carbon atoms include alkylene oxide mentioned above.
[0182]
　These alkylene oxides may be used alone or in combination of two or more kinds.
[0183]
　As alkylene oxide, preferably ethylene oxide, propylene oxide and the like, more preferably, propylene oxide.
[0184]
　Such polyoxyalkylene triols, specifically, for example, polyethylene triol, polypropylene triol, propylene oxide - ethylene oxide copolymer triol (random and / or block copolymer) and the like.
[0185]
　These polyoxyalkylene triols may be used alone or in combination of two or more kinds.
[0186]
　As polyoxyalkylene triols, preferably, a polypropylene triol.
[0187]
　The hydroxyl value of the polyoxyalkylene triols is, 100 mg KOH / g or more as described above, preferably, 109mgKOH / g or more, more preferably, 150 mgKOH / g or more, as described above 600 mg KOH / g or less, preferably, 590MgKOH / g or less, and more preferably not more than 570MgKOH / g.
[0188]
　The hydroxyl value of the polyoxyalkylene triols is within the above range, it is possible to improve the optical transparency, durability and mechanical strength of the polyurethane resin.
[0189]
　The number average molecular weight of polyoxyalkylene triols, for example, 300 or more, 400 or more, more preferably 500 or more, for example, 2000 or less, preferably 1700 or less.
[0190]
　Further, polyoxyalkylene triols of CPR (controlled polymerization rate) is, for example, 5 or less, preferably, 3 or less, more preferably 2 or less, more preferably, 1 or less, for example, 0 or more, 0.01 or more, more preferably 0.1 or more.
[0191]
　The polyester triol, reaction products of polybasic acids and / or their alkyl esters and polyhydric alcohols. More specifically, as the polyester triol, and dibasic acids and / or their alkyl esters, reaction products of trihydric alcohols and dihydric alcohols.
[0192]
　The dibasic acid and / or its alkyl ester, dibasic acid and / or its alkyl ester include the above-mentioned. These polybasic acids and / or their alkyl esters may be used alone or in combination of two or more.
[0193]
　Examples of the divalent alcohol, a divalent alcohol described above are exemplified, and specific examples thereof include low molecular weight diol as described above. These dihydric alcohols may be used alone or in combination of two or more kinds.
[0194]
　Examples of the trivalent alcohols, for example, low molecular weight triols as described above can be mentioned. These trihydric alcohols may be used alone or in combination of two or more kinds.
[0195]
　Then, the polyester triol, for example, firstly, a trihydric alcohol mentioned above and dibasic acids mentioned above, to a condensation reaction so that the ratio of excess relative dibasic acid hydroxyl carboxyl groups of 3 monohydric alcohol, then the resulting reaction product either by further reaction (reaction liquid) and the dihydric alcohol, or a trihydric alcohol mentioned above and alkyl esters of dibasic acids mentioned above, 2 alkyl ester group of the alkyl esters of dibasic acids There is an ester exchange reaction so that the ratio of excess relative to the hydroxyl group of the trihydric alcohol, then, by further reacting the reaction product obtained with (reaction liquid) and dihydric alcohols, obtained as a reaction product.
[0196]
　Incidentally, the condensation reaction or ester exchange reaction, if necessary, under known catalyst can be carried out in a known reaction conditions.
[0197]
　The hydroxyl value of the polyester triol, as described above 100 mg KOH / g or more, preferably, 109mgKOH / g or more, and more preferably not 150 mgKOH / g or more, as described above 600 mg KOH / g or less, preferably, 590mgKOH / g or less, more preferably not more than 570mgKOH / g.
[0198]
　The hydroxyl value of the polyester triol is within the above range, it is possible to improve the optical transparency, durability and mechanical strength of the polyurethane resin.
[0199]
　The number average molecular weight of the polyester triol, for example, 300 or more, 400 or more, more preferably 500 or more, for example, 2000 or less, preferably 1700 or less.
[0200]
　Incidentally, a polyester diol and polyester triols of the present invention is a reaction product of a polybasic acid and / or its alkyl ester and a polyhydric alcohol, as an initiator of low molecular weight polyol, a ring-opening polymerization of lactones or lactides ring-opening polymerization type polyester polyols obtained by (polycaprolactone polyols, polyvalerolactone polyols, etc.) are not included.
[0201]
　As polyester diols and polyester triols, rather than the ring-opening polymerization type polyester polyols, by using a reaction product of a polybasic acid and / or its alkyl esters with polyhydric alcohols, improvement in optical transparency, durability and mechanical strength it can be achieved.
[0202]
　Then, the triol, the polyoxyalkylene triols, and / or are the polyester triol, preferably, the polyoxyalkylene triols and the like.
[0203]
　By using such a triol, optically transparent polyurethane resin, it is possible to improve the durability and mechanical strength.
[0204]
　The hydroxyl value of the triol to 100 mg KOH / g or more as described above, preferably, 109mgKOH / g or more, and more preferably not 150 mgKOH / g or more, or less 600 mg KOH / g as described above, preferably, 590mgKOH / g or less , more preferably not more than 570mgKOH / g.
[0205]
　The hydroxyl value of the polyoxyalkylene triols is within the above range, it is possible to improve the optical transparency, durability and mechanical strength of the polyurethane resin.
[0206]
　The number average molecular weight of polyoxyalkylene triols, for example, 300 or more, 400 or more, more preferably 500 or more, for example, 2000 or less, preferably 1700 or less.
[0207]
　The polyol component contains the above diol and the triol.
[0208]
　In the polyol component, preferably, hydroxyl group derived from triols, and may include more than hydroxyl group derived from a diol. In other words, preferably, the chemical equivalent of triol contained in the polyol component (hydroxyl equivalent mass / triol triol) is from the chemical equivalent of the diol contained in the polyol component (hydroxyl equivalent mass / diol of the diol) It is mentioned often.
[0209]
　The hydroxyl equivalent weight (hereinafter the same), which is calculated by the following equation.
[0210]
　Hydroxyl group equivalent = 56100 / hydroxyl number
　More specifically, based on the total amount of the polyol component, the content of the triol (chemical equivalent basis), for example, 10 equivalent percent or more, preferably 20 equivalent% or more, more preferably is 30 equivalent% or more, more preferably 40 equivalent% or more, more preferably 50 equivalent% or more, more preferably, exceed 50 equivalent%, particularly preferably not 60 equivalent% or more, for example, 99 equivalent percent or less, preferably, 97 equivalent percent or less, more preferably 95 equivalent percent or less, more preferably 94 equivalent percent or less, more preferably 93 equivalent percent or less, more preferably 90 equivalent percent or less, more preferably is 80 equivalent percent or less, more preferably, 75 equivalent percent or less, especially preferably 70 or less equivalent%.
[0211]
　Further, based on the total amount of the polyol component, the content of the diol (chemical equivalent basis), for example, 1 equivalent percent or more, preferably, 3 equivalent percent or more, more preferably, 5 equivalent percent or more, more preferably, 6 equivalent percent or more, more preferably, 7 equivalent% or more, more preferably 10 equivalent% or more, more preferably 20 equivalent% or more, more preferably, 25 equivalent% or more, especially preferably 30 equivalent% or more There, for example, 90 equivalent percent or less, preferably, 80 equivalent percent or less, more preferably 70 equivalent percent or less, more preferably, 60 equivalent percent or less, more preferably, 50 equivalent percent or less, more preferably 50 equivalents less than%, especially preferably 40 or less equivalent%.
[0212]
　If the content is within the above range of content and diols triols, it is possible to improve the light transmittance of the polyurethane resin, durability and mechanical strength.
[0213]
　Further, the polyol component of CPR (controlled polymerization rate) is, for example, 5 or less, preferably, 3 or less, for example, 0 or more, preferably 0.01 or more, more preferably 0.1 or more.
[0214]
　If CPR is above the upper limit, i.e., when the polyol component contains too much a basic substance that acts as a urethanization catalyst may reaction rate with the polyisocyanate component and the polyol component is too fast Therefore, there are cases where local crystallization in the resulting polyurethane resin occurs, resulting in turbidity occurs in the polyurethane resin, there are cases where optical transparency is lowered.
[0215]
　On the other hand, if the CPR is too low, i.e., when the content of the basic substance which acts as a urethanization catalyst is too low, the reaction rate with the polyisocyanate and polyol components is relatively slow, localized can inhibit Do crystallization, although the optical transparency can be secured, the crosslinking density decreases, the mechanical strength (hardness, etc.) may be lowered.
[0216]
　In this respect, if CPR is within the above range, it is possible to adjust the reaction rate with the polyisocyanate component and the polyol component in a suitable range, it is possible to suppress the local crystallization, and sufficient crosslinking can be secured density, excellent in optical transparency, further, it is possible to obtain a polyurethane resin excellent in durability and mechanical strength.
[0217]
　Further, the polyol component preferably contains a polyester diol and / or polyester triol.
[0218]
　That is, the polyol component can also contain only the polyether component (polyoxyalkylene diols and polyoxyalkylene triols) preferably contains a polyester component (polyester diols and / or polyester triol).
[0219]
　If polyester diols and / or polyester triol is used, the polyol component, the total amount of the content of the polyester diol and polyester triol (chemical equivalent basis), for example, 3 equivalent percent or more, preferably, 5 equivalent percent or more, more preferably it is 10 equivalent% or more, more preferably 15 equivalent% or more, e.g., 70 equivalent percent or less, preferably, 65 equivalent percent or less, more preferably 60 equivalent percent, more preferably at most 50 equivalent% or less.
[0220]
　Content of polyester diols and polyester triols, within the above range, the polyurethane resin hardness, improvement of mechanical strength and heat resistance, it is possible to suppress the shrinkage.
[0221]
　In the following, to the polyol component, there is a case where the total amount of content of the polyester diol and polyester triol (chemical equivalent basis), referred to as an ester equivalent (eq%).
[0222]
　Further, the polyol component is in excellent does not inhibit the effect scope of the present invention, the polyol excluding the diol and the triol (hereinafter, referred to as other polyols.) Can contain.
[0223]
　Other polyols, for example, a number average molecular weight include known polymeric polyols of 300 to 5000, specifically, for example, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyols, polyolefin polyols, such as polyurethane polyols, and the like.
[0224]
　As the other polyols, in addition to the above, for example, hydroxyl value diol of less than 100 mg KOH / g, diol hydroxyl value exceeds 300 mgKOH / g, hydroxyl value triol of less than 100 mg KOH / g or hydroxyl value, such triol in excess of 600 mg KOH / g and the like, further, (preferably, less than 400) number average molecular weight is less than 300 usually over 40, and a low molecular weight polyol having four or more hydroxyl groups.
[0225]
　These other polyols can be used alone or in combination of two or more.
[0226]
　Other polyols, preferably diols hydroxyl value exceeds 300 mgKOH / g, hydroxyl value include triol exceeds 600 mg KOH / g.
[0227]
　The diol hydroxyl value exceeds 300 mgKOH / g, for example, low molecular weight diol described above may be mentioned, may be used alone or in combination of two or more.
[0228]
　The triols hydroxyl value exceeds 600 mg KOH / g, for example, low molecular weight triols as described above can be mentioned, it can be used alone or in combination of two or more.
[0229]
　Other polyols, more preferably, include diol hydroxyl value exceeds 300 mgKOH / g, more preferably, low molecular weight diol and the like, more preferably, include aliphatic diols, especially preferably di propylene glycol.
[0230]
　Content of other polyol (chemical equivalent basis), based on the total amount of the polyol component, 10 equivalent percent or less, preferably not more than 5 equivalent percent, and more preferably 0 equivalent%.
[0231]
　Average functionality of the polyol component, for example, 2.1 or more, preferably, 2.2 or more, more preferably, 2.3 or more, further preferably 2.4 or more, and is, for example, 2.9 or less, preferably 2.8 or less, more preferably 2.7 or less, still more preferably 2.6 or less. Average functionality of the polyol component, within the above range, the polyurethane resin hardness, mechanical strength, can be improved heat resistance and moist heat resistance.
[0232]
　Then, polyurethane resin, and the polyisocyanate component and the polyol component, for example, by polymerizing (reaction) in the polymerization method such as bulk polymerization or solution polymerization, obtained as a reaction product.
[0233]
　In bulk polymerization, for example, under a stream of nitrogen, with stirring polyisocyanate component, which, in addition to the polyol component, the reaction temperature 50 ~ 250 ° C., further preferably 50 ~ 200 ℃, 0.5 ~ 15 hours to the extent reaction.
[0234]
　In solution polymerization, the polyisocyanate component, a polyol component in addition to the organic solvent, the reaction temperature 50 ~ 120 ° C., preferably at 50 ~ 100 ° C., the reaction about 0.5 to 15 hours.
[0235]
　As the organic solvent, such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, for example, nitriles such as acetonitrile, methyl acetate, ethyl acetate, butyl acetate, alkyl esters such as isobutyl acetate, for example, n- hexane, n- heptane, aliphatic hydrocarbons such as octane, for example, alicyclic hydrocarbons such as methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, for example, 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-methoxide Glycol ether esters such as butyl acetate, ethyl 3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, for example, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodide methylene, halogenated aliphatic hydrocarbons such as dichloroethane, for example, N- methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethyl sulfoxide, and the like polar aprotic such as hexamethylphosphoramide sulfonylamide .
[0236]
　Further, as the organic solvent, for example, a non-polar solvent (non-polar organic solvent). Examples of these non-polar solvents, aliphatic, naphthenic hydrocarbon organic solvent, aniline point, for example, 10 to 70 ° C., preferably of 12 ~ 65 ° C., a weak or non-polar organic solvent dissolving power with low toxicity, and the like vegetable oils typified by turpentine oil.
[0237]
　Such non-polar organic solvents are commercially available, as such commercially available products, for example, house (Shell Chemical Co., aniline point 15 ° C.), Swasol 310 (Maruzen Oil Co., Ltd., aniline point 16 ° C.), Essonafusa No. 6 (Exxon Chemical Co., aniline point 43 ° C.), Laws (Shell Chemical Co., aniline point 43 ° C.), Essonafusa No. 5 (manufactured by Exxon, aniline point 55 ° C.), Pegazoru 3040 petroleum hydrocarbon organic solvents such as (Mobil Oil Ltd., aniline point 55 ° C.), other, methylcyclohexane (aniline point 40 ° C.), ethylcyclohexane (aniline point 44 ° C. ), Gamuterepin N (Yasuhara Yushi, aniline point 27 ° C.), and the like turpentine oils such as.
[0238]
　These organic solvents may be used alone or in combination of two or more kinds.
[0239]
　Further, in the above polymerization reaction, if necessary, for example, it may be added a known urethanization catalyst such as amines and organic metal compounds at an appropriate ratio.
[0240]
　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.
[0241]
　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, dibutyltin dineodecanoate, 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, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compound such as octene copper, for example, bismuth octylate, organic bismuth compounds such as bismuth neodecanoate, organic zinc compounds, organic zirconium compound, Lead acetylacetonate, bismuth (2-ethylhexanoate), bismuth neodecanoate, zinc 2-ethylhexanoate, zinc neodecanoate, bismuth tetramethylheptanedionate benzoate, furthermore, mixtures thereof.
[0242]
　Further, as a urethanization catalyst, for example, potassium carbonate, potassium acetate, potassium salts such as potassium octoate.
Potassium salts such as potassium and the like.

claims

A polyisocyanate component, a reaction product of a polyol component,
　wherein the polyisocyanate component contains a derivative of an aliphatic polyisocyanate,
　derivatives of the aliphatic polyisocyanate has an isocyanurate group and allophanate groups , the content of allophanate groups, relative to isocyanurate groups 100 moles is 10 moles or more and 90 mol or less,
　the polyol component,
　　the hydroxyl value and the following triol 100 mg KOH / g or more 600 mg KOH / g,
　　hydroxyl value of 100 mg KOH / g and more 300 mgKOH / g or less of diols
containing,
　said triol is
　　a polyoxyalkylene triol number of carbon atoms of oxyalkylene group is 2-3, and / or,
　　polybasic acids and / or their alkyl esters and multi and polyhydric alcohol Polyester triol which is a reaction product
is,
　the diol,
　　the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene diols, and / or,
　　polybasic acid and / or its alkyl ester and a polyvalent alcohol a polyester diol which is a reaction product
, wherein the polyurethane resin.
[Requested item 2]
　The aliphatic polyisocyanate, characterized in that it comprises a pentamethylene diisocyanate, polyurethane resin according to claim 1.
[Requested item 3]
　Average functionality of the polyol component is from 2.1 to 2.9
, wherein the polyurethane resin according to claim 1.
[Requested item 4]
　The total amount of the polyol component,
　the total amount of the content of the polyester diol and the polyester triol, 5 equivalent percent or more and 70 or less equivalent%
, wherein the polyurethane resin according to claim 1.
[Requested item 5]
　Comprising a polyisocyanate component, a step of reacting a polyol component,
　wherein the polyisocyanate component contains a derivative of an aliphatic polyisocyanate,
　derivatives of the aliphatic polyisocyanate has an isocyanurate group and allophanate groups, content of allophanate groups, relative to isocyanurate groups 100 moles is 10 moles or more and 90 mol or less,
　the polyol component,
　　a hydroxyl value of 100 mg KOH / g or more 600 mg KOH / g or less of triol,
　　a hydroxyl value of 100 mg KOH / and following diols g to 300 mgKOH / g
and containing,
　the triol,
　　the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene triols, and / or,
　　polybasic acid and / or its alkyl ester and a polyhydric alcohol Polyester triol which is a reaction product
is,
　the diol,
　　the number of carbon atoms of the oxyalkylene group is 2-3 polyoxyalkylene diols, and / or,
　　polybasic acid and / or its alkyl ester and a polyhydric alcohol a polyester diol which is a reaction product,
　Wherein the equivalent ratio of the isocyanate groups of the polyisocyanate component to the hydroxyl group of the polyol component (NCO / OH) is 0.9 to 1.1, the production method of the polyurethane resin.