[0001]The present invention is polycarbodiimide composition, a method of manufacturing a polycarbodiimide composition, aqueous dispersion composition, the solution composition, a resin composition and a cured resin.
Background technique
[0002]Traditionally, paint in the areas such as adhesives, coatings, base resin and the resin composition is known containing a curing agent, as a curing agent, for example, a carbodiimide-based curing agents are known.
[0003]
　More specifically, examples of the carbodiimide-based curing agent, for example, hexamethylene diisocyanate (HDI) 673 g, and a polyethylene glycol monomethyl ether 800g of average molecular weight 400 reacted at 120 ° C., further carbodiimidization catalyst (3 - methyl-1-phenyl-2-phospholene-1-oxide) was added 13.5 g, further polycarbodiimide composition was allowed to react for 5 hours at 185 ° C. has been proposed (e.g., Patent Document 1 (synthesis example 82) reference.).
[0004]
　Then, such a polycarbodiimide composition (curing agent) and a resin composition comprising a base resin, followed by drying and curing, it is possible to obtain a resin cured product such as a coating film.
CITATION
Patent Document
[0005]
Patent Document 1: Japanese Patent Publication 10-316930
Summary of the Invention
Problems that the Invention is to Solve
[0006]
　On the other hand, the resin composition, the improvement of production efficiency, in view of improvement of workability, at relatively low temperatures (e.g., 80 ° C. or less), to cure in a relatively short period of time (e.g., 10 minutes or less) ( that is, low-temperature rapid curability) is required.
[0007]
　However, when a polycarbodiimide composition described in Patent Document 1, not the low-temperature rapid curability is insufficient resin composition, a relatively low temperature and in a relatively short time conditions, the resulting cured resin product physical properties (for example, water resistance, chemical resistance) there is a problem that is not enough.
[0008]
　An object of the present invention is polycarbodiimide composition having excellent low-temperature fast curing, a method of manufacturing the polycarbodiimide composition, also the polycarbodiimide composition aqueous dispersion composition comprising a and solution composition, also polycarbodiimide composition resin composition comprising, furthermore, to provide a resin cured product obtained by curing the resin composition.
Means for Solving the Problems
[0009]
　The present invention [1], a polyisocyanate having a primary isocyanate groups, the reaction product of an alcohol, and a carbodiimide group and the uretonimine groups, in the infrared absorption spectrum, the stretching vibration derived from carbodiimide group 2120cm -1 vicinity absorbance IR of CI of, 1720 cm from stretching vibration of uretonimine groups and urethane groups -1 absorbance IR near UI + U intensity ratio (IR CI / IR UI + U ) is 1.5 to 4.5, It contains polycarbodiimide composition.
[0010]
　The present invention [2], in the polycarbodiimide composition, the proportion of uretonimine groups to the total moles of the carbodiimide group and the uretonimine groups is 15 mol% or less 1.5 mol%, according to the above [1] It contains polycarbodiimide composition.
[0011]
　The present invention [3], to the hydroxyl group of the alcohol, the equivalent ratio of the isocyanate groups of the polyisocyanate (NCO / OH), exceed 2 is 16 or less, according to the above [1] or [2] It contains polycarbodiimide composition.
[0012]
　The present invention [4], the alcohols, containing alcohols containing oxyethylene group three or more consecutive, the content of oxyethylene groups to three or more consecutive, with respect to the polycarbodiimide composition, 10 wt% or more and 40 mass% or less, contains a polycarbodiimide composition according to any one of the above [1] to [3].
[0013]
　The present invention [5], the alcohols, containing alcohols containing oxyethylene group three or more consecutive, the content of the alcohol containing three or more consecutive oxyethylene groups, the alcohol based on the total moles, 5 mol% or less than 50 mol%, includes the above-mentioned [1] to polycarbodiimide composition according to any one of [4].
[0014]
　The present invention [6], wherein the polyisocyanate is an aliphatic polyisocyanate includes the [1] to polycarbodiimide composition according to any one of [5].
[0015]
　The present invention [7], wherein the aliphatic polyisocyanate is a pentamethylene diisocyanate includes polycarbodiimide composition according to [6].
[0016]
　The present invention [8], [1] to [7] A method for producing a polycarbodiimide composition according to any one of, urethanization to urethanization reaction between the alcohol and the polyisocyanate a step, the reaction product in the urethanization step, by heating in the presence of a carbodiimide catalyst, and a carbodiimidization step of carbodiimidization reaction includes a method for manufacturing a polycarbodiimide composition.
[0017]
　The present invention [9], the reaction temperature in the carbodiimidization reaction is 125 ° C. or higher 160 ° C. or less, contains a method for producing a polycarbodiimide composition according to the above [8].
[0018]
　The present invention [10], said to carbodiimidization reaction under reflux, and includes a method for manufacturing a polycarbodiimide composition according to the above [8] or [9].
[0019]
　The present invention [11], [1] to [7] or polycarbodiimide composition according to one found aqueous dispersion dispersed in water at a ratio of solids concentration of 5 to 90 mass% of a liquid contains a water-dispersed composition.
[0020]
　The present invention [12], the [1] to polycarbodiimide composition according to any one of [7], dissolved in an organic solvent in a proportion of less than 90 wt% solids concentration of 5 mass% or more solution in it, it contains a solution composition.
[0021]
　The present invention [13], the main agent having a carboxyl group, containing a curing agent comprising the above-mentioned [1] to polycarbodiimide composition according to any one of [7] contains a resin composition .
[0022]
　The present invention [14] is a cured product of the resin composition according to [13], containing the cured resin.
Effect of the invention
[0023]
　The polycarbodiimide composition of the present invention, 2120 cm from stretching vibration of the carbodiimide groups -1 absorbance IR near CI of, 1720 cm from stretching vibration of uretonimine groups and urethane groups -1 absorbance IR near UI + U intensity ratio (IR CI / IR UI Tasu U ) is in a particular range.
[0024]
　Therefore, polycarbodiimide composition of the present invention, the solution composition of the aqueous dispersion composition and the invention of the present invention comprising the polycarbodiimide composition The resin composition of the present invention comprising a polycarbodiimide composition, low speed excellent curability.
[0025]
　According to the manufacturing method of polycarbodiimide composition of the present invention, a polycarbodiimide composition of the present invention, it can be efficiently produced.
[0026]
　Further, the cured resin of the present invention is a cured product of the resin composition having excellent low-temperature rapid curability. Therefore, the resin cured product of the present invention, relatively low temperatures and relatively short time to obtain, and is excellent in various properties (e.g., water resistance, chemical resistance, etc.).
BRIEF DESCRIPTION OF THE DRAWINGS
[0027]
[1] Figure 1 shows an infrared absorption spectrum of the polycarbodiimide composition in Example 6.
FIG. 2 is a polycarbodiimide obtained composition in Example 20 13 shows a C-NMR spectrum.
DESCRIPTION OF THE INVENTION
[0028]
　Polycarbodiimide composition of the present invention, polyisocyanates having a primary isocyanate group (hereinafter, simply referred to as polyisocyanates.), The reaction products of alcohols.
[0029]
　Primary isocyanate group, the carbon atom to which the isocyanate group (-NCO) is attached (C), 1 monovalent functional group wherein a hydrogen atom (H) is bonded two (-CH 2 and defined NCO) that.
[0030]
　Polyisocyanates having a primary isocyanate groups, it is sufficient that at least one has a primary isocyanate group, for example, secondary isocyanate groups, may have such a tertiary isocyanate group.
[0031]
　Secondary isocyanate groups, the carbon atom to which the isocyanate group (-NCO) is attached (C), the divalent functional group (-CHR-NCO (R hydrogen atom (H) is bonded one substituent represents a group.)) to be defined.
[0032]
　Further, tertiary isocyanate groups, the carbon atom to which the isocyanate group (-NCO) is attached (C), 3-valent functional group wherein a hydrogen atom (H) is not bound (-CR 1 R 2 -NCO ( R 1 and R 2 represents a substituent of the same or different.)) to be defined.
[0033]
　Polyisocyanates having a primary isocyanate group, for example, aliphatic polyisocyanates having a primary isocyanate group, an alicyclic polyisocyanate having a primary isocyanate groups, such as aromatic aliphatic polyisocyanates include having primary isocyanate groups It is.
[0034]
　Aliphatic polyisocyanate having a primary isocyanate group, a chain having a primary isocyanate group (linear or branched: acyclic) an aliphatic polyisocyanate, for example, 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 capsule benzoate, the descriptor diisocyanate, Ok Diisocyanate, and aliphatic diisocyanates such as dodecamethylene diisocyanate.
[0035]
　The alicyclic polyisocyanate having a primary isocyanate group, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 1,3 or 1,4-bis (isocyanatomethyl Natomechiru) cyclohexane or mixtures thereof (hydrogenated XDI), an alicyclic diisocyanate such as norbornane diisocyanate (NBDI) and the like.
[0036]
　Examples of the aromatic aliphatic polyisocyanates having a primary isocyanate group, for example, aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI) and the like.
[0037]
　Polyisocyanates containing these primary isocyanate group may be used alone or in combination of two or more.
[0038]
　Polyisocyanate having a primary isocyanate groups, lightfastness, from the viewpoints of fluidity and water-dispersible, preferably an aliphatic polyisocyanate having a primary isocyanate groups, alicyclic polyisocyanates having a primary isocyanate group include It is, more preferably, include aliphatic polyisocyanates having a primary isocyanate group.
[0039]
　Aliphatic polyisocyanates having a primary isocyanate group, from the viewpoint of easy availability, preferably, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI) and the like, more preferably , 1,5-pentamethylene diisocyanate (PDI) and the like.
[0040]
　1,5-pentamethylene diisocyanate, less carbon atoms than the 1,6-hexamethylene diisocyanate, low molecular weight. Therefore, when manufacturing polycarbodiimide composition of the same molecular weight, the use of 1,5-pentamethylene diisocyanate, compared with the case of using 1,6-hexamethylene diisocyanate, increasing the carbodiimide group concentration in the polycarbodiimide composition be able to. As a result, it is possible to obtain an excellent polycarbodiimide composition low-temperature fast curing, furthermore, it is possible to obtain various properties (water resistance, chemical resistance, etc.) excellent cured resin (to be described later). Further, 1,5-pentamethylene diisocyanate carbon atoms is odd, compared with 1,6-hexamethylene diisocyanate which is an even number of carbon atoms, because of low crystallinity by amorphous structure derived from an odd number of carbon atoms, flow excellent sex and dispersibility is believed that the physical properties of the resulting cured resin (described later) is improved.
[0041]
　Furthermore, 1,5 With pentamethylene diisocyanate, compared with the case of using 1,6-hexamethylene diisocyanate, tends to occur thermal decomposition of uretonimine to be described later, therefore, the polycarbodiimide composition can be obtained in good yield it can. Further, since it handled even at low temperatures, it is believed to be able to suppress the molecular weight of the uretonimine.
[0042]
　Further, when used in combination polyisocyanates having a primary isocyanate group of two or more is preferably used in combination with aliphatic polyisocyanates having a primary isocyanate group, and an alicyclic polyisocyanate having primary isocyanate groups .
[0043]
　Aliphatic polyisocyanates having a primary isocyanate group, a primary when combined and alicyclic polyisocyanates having an isocyanate group, storage stability and pot life derived from the reaction of low alicyclic polyisocyanate the improvement can be achieved, and it is possible to improve the rapid curability derived from high reactivity of aliphatic polyisocyanates. That is, it is possible to achieve a storage stability and pot life, the balance between rapid curability.
[0044]
　Aliphatic polyisocyanates having a primary isocyanate group, combination ratio in the case of the alicyclic polyisocyanate is used in combination with a primary isocyanate groups, relative to the aliphatic polyisocyanate 100 parts by mass having a primary isocyanate groups , for example, aliphatic polyisocyanates having a primary isocyanate group, for example, 20 parts by mass or more, or preferably 30 parts by mass or more, for example, 90 parts by mass or less, preferably 50 parts by mass or less.
[0045]
　Further, when used in combination polyisocyanates having a primary isocyanate group of two or more, the timing of mixing them is not particularly limited, each step (first urethanization step described below, carbodiimidization step and the second urethanization step it may be any of).
[0046]
　Specifically, for example, in the first urethanization step (described later), it can be used as a mixture of two or more polyisocyanates.
[0047]
　Further, for example, two or more polyisocyanates individually urethanization after (first urethanization step (described later)), the carbodiimidization step (described later), and mixing them urethanized two or more polyisocyanates it can be used Te.
[0048]
　Further, for example, in two or more polyisocyanates individually urethanization (first urethanization step (described later)) and a carbodiimidization (carbodiimidization step (described later)) and then, second urethanization step (described later), they the urethanization and carbodiimidized two or more polyisocyanates may be used as a mixture.
[0049]
　Furthermore, for example, of two or more urethanization some types of of polyisocyanate (first urethanization step (described later)), and then its urethanization polyisocyanates, of two or more polyisocyanates of the remaining types of polyisocyanate and (urethanization are not even polyisocyanate) are mixed, may be subjected to carbodiimidization step (described later).
[0050]
　Further, the above method is not limited to the case of using a polyisocyanate two or more, can be employed when used alone polyisocyanate. For example, a single type of polyurethane a part of the polyisocyanate after the (first urethanization step (described later)), and the urethanization polyisocyanates, alone type of the remainder of the polyisocyanate (urethanization are not even polyisocyanate ) were mixed, it may be subjected to carbodiimidization step (described later).
[0051]
　As the alcohols, for example, alcohols containing oxyethylene group three or more consecutive, and other alcohol (i.e., alcohol not containing an oxyethylene group three or more consecutive) and the like.
[0052]
　The alcohol containing three or more consecutive oxyethylene groups, for example, a polyol containing oxyethylene group three or more consecutive, such as monool containing oxyethylene group three or more consecutive.
[0053]
　Polyols containing three or more consecutive oxyethylene groups is an organic compound having both oxyethylene groups successive in one molecule three or more, two or more and hydroxyl, for example, polyoxyethylene polyols, etc. and the like.
[0054]
　Polyoxyethylene polyols, for example, as an initiator and a low molecular weight polyol, as the number of repeating units of oxyethylene groups is 3 or more, by the addition reaction of ethylene oxide, can be obtained.
[0055]
　Low molecular weight polyol is a compound having a molecular weight of less than 60 or more 500 having two or more hydroxyl groups, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol , 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl pentanediol, 3,3 - dimethylol heptane, alkanes (C7 ~ 20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol, and mixtures thereof, hydrogenated bisphenol a , 1,4-dihydroxy-2-butene, 2,6-di Chill-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dihydric alcohols such as dipropylene glycol, for example, glycerol, trimethylolpropane, trihydric alcohols such as triisopropanolamine, for example, tetra methylol methane (pentaerythritol), tetravalent alcohols such as diglycerin, for example, pentavalent alcohols such as xylitol, for example, sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, hexahydric alcohols such as dipentaerythritol, for example, 7-valent alcohols such as perseitol, for example, 8 monohydric alcohol and sucrose. These may be used alone or in combination of two or more kinds.
[0056]
　As low molecular weight polyol, preferably, a dihydric alcohol.
[0057]
　As the method of addition reaction of ethylene oxide to these low molecular weight polyol is not particularly limited, it may be a known method.
[0058]
　Also, functionality polyoxyethylene polyol (number of hydroxyl groups) is the same as the functionality of the initiator (such as a low molecular weight polyol) (number of hydroxyl groups), for example, in the case of using a dihydric alcohol as initiator, as polyoxyethylene polyol, polyoxyethylene glycol is obtained.
[0059]
　Polyol containing oxyethylene groups consecutive three or more may be used alone or in combination of two or more kinds.
[0060]
　As polyols containing three or more consecutive oxyethylene groups, preferably polyoxyethylene glycol.
[0061]
　Monools containing three or more consecutive oxyethylene groups is an organic compound having both oxyethylene groups successive in one molecule three or more, and one hydroxyl group, for example, one end sealing polyoxy ethylene glycol.
[0062]
　One end sealing polyoxyethylene glycol, the one of the terminal hydroxyl groups of the polyoxyethylene glycol, polyethylene glycol monoalkyl ethers substituted by oxyalkylene groups.
[0063]
　In polyethylene glycol monoalkyl ether, the carbon number of the alkyl group is 1 or more, e.g., 20 or less, preferably 8 or less, more preferably 6 or less, more preferably, 4 or less, especially preferably 2 or less it is. That is, the alkyl group for sealing the one end, and methyl group, an ethyl group. Such polyethylene glycol monoalkyl ethers include polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether.
[0064]
　Monools containing oxyethylene groups consecutive three or more may be used alone or in combination of two or more kinds.
[0065]
　Alcohols containing oxyethylene groups consecutive three or more may be used alone or in combination of two or more kinds.
[0066]
　As alcohols containing three or more consecutive oxyethylene groups, preferably monools containing oxyethylene group three or more consecutive, more preferably, polyethylene glycol monoalkyl ether, more preferably, polyethylene glycol monomethyl ether and the like.
[0067]
　Further, in the alcohol containing oxyethylene group three or more consecutive, number of repeating units of oxyethylene groups is 3 or more, preferably, 5 or more, more preferably 10 or more, for example, 60 or less, preferably , it is 50 or less.
[0068]
　If a repeating unit number is the range of oxyethylene groups, it is possible to achieve the stability of the synthesis, the improvement of the water-dispersible polycarbodiimide composition.
[0069]
　The molecular weight of alcohols containing oxyethylene group three or more consecutive (number average molecular weight) is, for example, 100 or more, 200 or more, more preferably, 300 or more, further preferably 400 or more, For example, 5000 or less, preferably 3000 or less, more preferably 2000 or less, more preferably 1000 or less.
[0070]
　If three or more molecular weight (number average molecular weight) is within the above range alcohols containing oxyethylene groups consecutive, it is possible to achieve the stability of the synthesis, the improvement of the water-dispersible polycarbodiimide composition.
[0071]
　Other alcohols, an alcohol excluding alcohols containing oxyethylene group three or more consecutive mentioned above, specifically, is an alcohol with no have an oxyethylene group continuous in the molecule three or more . In other words, other alcohols either do not contain oxyethylene groups, or, three or more consecutive non oxyethylene group (e.g., two consecutive oxyethylene groups, such as single oxyethylene group) it is an alcohol containing.
[0072]
　Other alcohols, specifically, a polyol except the polyols containing oxyethylene groups contiguous the three or more (hereinafter, referred to as other polyols.), Containing oxyethylene group consecutive said three or more mono monool except ol (hereinafter, referred to as other monol.) and the like.
[0073]
　Other polyols, not without having three or more consecutive oxyethylene groups per molecule and an alcohol having two or more hydroxyl groups in one molecule, for example, decanediol (10 carbon atoms ), dodecanediol (12 carbon atoms), tetradecane diol (14 carbon atoms), hexadecane diol (16 carbon atoms), octadecane diol (18 carbon atoms), no oxyethylene groups, such as Eiko Sanji ol (20 carbon atoms) no aliphatic polyols include, for example, one or two with ether polyol oxyethylene groups, such as diethylene glycol. These other polyols can be used alone or in combination of two or more.
[0074]
　Other monool has no more than three consecutive oxyethylene groups per molecule and an alcohol having one hydroxyl group in one molecule, for example, methanol, ethanol, propanol, isopropanol , butanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol (10 carbon atoms), lauryl alcohol (12 carbon atoms), cetyl alcohol (14 carbon atoms), stearyl alcohol ( 18 carbon atoms), oleyl alcohol (18 carbon atoms), eicosanol (aliphatic monools having no oxyethylene groups, such as the number 20) atoms, for example, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , diethylene glycol Monoethyl ether (also known as Carbitol) oxyethylene group from 1 to 2 with ether monool such as, for example, phenol and its derivatives, benzyl alcohol and its derivatives, phenethyl alcohol and its derivatives, aromatic such as naphthol and derivatives thereof such as alcohol and the like. These other monols can be used alone or in combination of two or more.
[0075]
　Other alcohols may be used alone or in combination of two or more kinds.
[0076]
　Other alcohols, preferably, other mono-ol, more preferably, aliphatic monools having no oxyethylene groups, include ether monool having one or two oxyethylene groups, improvement of water-dispersible from the viewpoint of, further preferably, ethers monool having one or two oxyethylene groups, particularly preferably, include 1-methoxy-2-propanol.
[0077]
　These alcohols may be used alone or in combination of two or more kinds.
[0078]
　Alcohols, from the viewpoint of improving the water-dispersible, preferably, contain an alcohol containing oxyethylene group three or more consecutive, from the viewpoint of compatibility with water-dispersible and water resistance, more preferably, and alcohols containing three or more consecutive oxyethylene groups, and other alcohols having both.
[0079]
　That, alcohols, if containing alcohol containing three or more consecutive oxyethylene groups, it is possible to improve the hydrophilicity, it is possible to improve the water-dispersible polycarbodiimide composition can, aqueous dispersion composition (described later) can be obtained with good efficiency.
[0080]
　Also, if the alcohol has contain alcohol containing oxyethylene group three or more consecutive, the content of oxyethylene groups consecutive its three or more, with respect to polycarbodiimide composition, for example, 5 mass% 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.
[0081]
　If the content is above the range of oxyethylene groups, low-temperature rapid curability of the polycarbodiimide composition and it is possible to improve the water dispersibility, also possible to obtain a resin cured product excellent in water resistance (described below) can.
[0082]
　Incidentally, the content of the oxyethylene group is a content of oxyethylene groups in the alcohols containing oxyethylene group three or more consecutive oxyethylene groups other polyols contains (e.g., oxyethylene group the oxyethylene groups in ether monool having one or two) is not included.
[0083]
　Further, the content of oxyethylene groups consecutive three or more, can be calculated from the charged amount.
[0084]
　Further, alcohols, contain the alcohol containing oxyethylene group three or more consecutive, when containing and other alcohol, based on the total moles of alcohols, three or more consecutive oxyethylene groups alcohol the content ratio, for example, 5 mol% or more, preferably not 12 mol% or more, for example, 50 mol% or less, preferably not more than 48 mol%. Further, the content of other alcohols, for example, 50 mol% or more, preferably not 52 mol% or more, for example, 95 mol% or less, or preferably 88 mol% or less.
[0085]
　And alcohols containing three or more consecutive oxyethylene groups, if the content is above the range of the other alcohols, it is possible to improve the low-temperature rapid curability and water-dispersible polycarbodiimide composition and , it is possible to obtain a resin cured product excellent in water resistance (described below).
[0086]
　On the other hand, alcohols does not contain alcohol containing oxyethylene group three or more consecutive, may contain only other alcohols.
[0087]
　In such a case, it is possible to improve the lipophilicity, it is possible to improve the solubility in organic solvents polycarbodiimide composition can be obtained with a solution composition (described later) efficiency.
[0088]
　The polycarbodiimide composition of the above polyisocyanate and the alcohol are reacted under predetermined conditions, further by carbodiimidization reaction, can be obtained.
[0089]
　Hereinafter, a manufacturing method of the polycarbodiimide composition will be described in detail.
[0090]
　In this method, first, to urethanization reaction of the above polyisocyanate and the alcohol (urethanization step).
[0091]
　In the urethanization step, the reaction ratio of the polyisocyanate and the alcohol is to the hydroxyl group of the alcohol, the equivalent ratio of the isocyanate groups of the polyisocyanate (NCO / OH) is, for example, exceed 2, preferably 3 or more, more preferably 4 or more, for example, 16 or less, preferably 14 or less, more preferably 10 or less. That is, in the urethanization step, preferably, the isocyanate groups are reacted so that the ratio of excess relative to the hydroxyl group.
[0092]
　Within the reaction rate is above the range of polyisocyanates with alcohols, it is possible to achieve water dispersibility and low-temperature rapid curability of polycarbodiimide composition.
[0093]
　Further, in this reaction, if necessary, for example, it may be added a known urethanization catalyst such as amine or an organometallic compound.
[0094]
　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.
[0095]
　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.
[0096]
　Further, as a urethanization catalyst, for example, potassium carbonate, potassium acetate, potassium salts such as potassium octoate.
[0097]
　These urethanization catalysts may be used alone or in combination of two or more kinds.
[0098]
　The mixing ratio of the urethane-forming catalyst is not particularly limited, depending on the purpose and application, are set appropriately.
[0099]
　Moreover, the reaction conditions in the urethanization step is, for example, atmospheric pressure and inert gas (e.g., nitrogen gas) in the atmosphere, reaction temperature, e.g., 30 ° C. or more, preferably, 60 ° C. or higher, for example, 200 ° C. or less, preferably 180 ° C. or less. The reaction time is, for example, 1 hour or more, preferably, not less than 3 hours, for example, 50 hours or less, preferably more than 40 hours.
[0100]
　This makes it possible to obtain a urethane-modified products of polyisocyanates (alcohol modified product). Incidentally, urethane-modified products of polyisocyanates (alcohol modified product) has an isocyanate group at the molecular terminal.
[0101]
　Next, in this method, the reaction solution containing the reaction product in the above urethanization step, by heating in the presence of a carbodiimide catalyst, to carbodiimidization reaction (carbodiimide formation step).
[0102]
　The carbodiimidization catalyst is not particularly limited, for example, trialkyl phosphate ester compounds, phosphonium alkylene oxide-based compounds, phosphonium sulfide compounds, phosphine oxide-based compound, and a phosphine compound.
[0103]
　The trialkyl phosphate esters, e.g., trimethyl phosphate, triethyl phosphate, tri-alkyl phosphoric acid ester compound having a carbon number of 3 to 24, such as trioctyl phosphate.
[0104]
　The phosphonium alkylene oxide compounds, for example, 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phospholene-1-oxide (EMPO), 1 , 3-dimethyl-2-phospholene 1-oxide, 1-phenyl-2-phospholene-1-oxide, 1-methyl-2-phospholene 1-oxide, 1-ethyl-2-phospholene-1-oxide and their double phosphonium alkylene oxide compounds having 4 to 18 carbon atoms, such as bond isomers, and the like.
[0105]
　The phosphonium sulfide compounds, such as 1-phenyl-2-phospholene-1-phosphotransferase sulfide compound having 4 to 18 carbon atoms, such as sulfides and the like.
[0106]
　The phosphine oxide compounds, e.g., triphenyl phosphine oxide, phosphine oxide-based compound having a carbon number of 3 to 21, such as tri-tolyl phosphine oxide, and the like.
[0107]
　The phosphine compounds include, for example, bis (oxa diphenylphosphino) phosphine compound having 3 to 30 carbon atoms, such as ethane.
[0108]
　These carbodiimidization catalysts can be used alone or in combination of two or more.
[0109]
　As carbodiimidization catalyst, preferably, include phosphonium alkylene oxide-based compound, more preferably, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene - 1-oxide, and the like.
[0110]
　Using the above carbodiimidization catalyst, to improve the activity of the carbodiimidization reaction temperature can be lowered, also to suppress the side reactions such as uretonimine reduction, to the polycarbodiimide composition high yield it can be, also, it is possible to improve the content of the carbodiimide group.
[0111]
　As carbodiimidization catalyst, from the viewpoint of obtaining a resin cured product excellent in water resistance (described below), especially preferably include 3-methyl-1-phenyl-2-phospholene-1-oxide.
[0112]
　The mixing ratio of the carbodiimidization catalyst, relative to (polyisocyanate used in the urethanization step) 100 parts by weight of polyisocyanate, for example, 0.01 parts by mass or more, or preferably, 0.05 parts by mass or more, e.g. , 20 parts by mass or less, preferably 10 parts by mass or less.
[0113]
　Moreover, the reaction conditions in the carbodiimidization step, the content of the carbodiimide group of polycarbodiimide resulting composition is set to be the specific range to be described later. More specifically, work to progress of carbodiimidization reaction, from the viewpoint of reducing the uretonimine, under normal pressure and an inert gas (such as nitrogen gas) atmosphere, reaction temperature, e.g., 125 ° C. or higher, preferably, 130 ° C. or higher, more preferably at 135 ° C. or higher, for example, 160 ° C. or less, preferably, 155 ° C. or less, more preferably, less than 155 ° C.. The reaction time is, for example, 1 hour or more, preferably, not less than 3 hours, for example, 50 hours or less, preferably more than 40 hours.
[0114]
　By reaction under such conditions, it is possible to react the product obtained in the urethanization step (urethane modified product of polyisocyanate) are combined decarboxylation condensation via an isocyanate group, to produce efficiently carbodiimide groups .
[0115]
　More specifically, if the reaction temperature is lower than the lower limit, the resulting uretonimine is while facilitating the decomposition reaction of the carbodiimide and isocyanate groups, it is possible to proceed carbodiimidization reaction. If it is a temperature below the lower limit, the thermal decomposition reaction is less likely to occur in very increases the amount of uretonimine content of carbodiimide group is reduced. Also, increased molecular weight due to the increase of uretonimine, there is a case where the reaction liquid is solidified. On the other hand, the reaction temperature is not more than the above upper limit, it is possible to reduce the polymerization loss. If exceeds the upper limit temperature, carbodiimidization, is accelerated polymerization reaction other than uretonimine reduction, not only the content of the carbodiimide group is reduced, the reaction mixture tends to solidify by increasing the molecular weight.
[0116]
　Further, in the carbodiimidization process smoothly by carbodiimidization reaction, also, from the viewpoint of promoting decarboxylation condensation, preferably in the presence of an organic solvent, and refluxed the reaction solution. That is, under reflux, to carbodiimidization reaction.
[0117]
　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 methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methylate Ether acetate (PMA), 3- methyl-3-methoxybutyl acetate, ethyl-3-glycol ether esters such as ethoxy propionate such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethers such as ethylene glycol diethyl ether 1,2-diethoxyethane, 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'Jimechirua Toamido, dimethyl sulfoxide, such as a polar aprotic such as hexamethylphosphoric phosphonyl amides. These organic solvents may be used alone or in combination of two or more kinds.
[0118]
　As the organic solvent, preferably, the temperature at reflux, the organic solvent and the like is within the range of the reaction temperature as described above.
[0119]
　As such organic solvents, specifically, xylene, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate.
[0120]
　The mixing ratio of the organic solvent is not particularly limited, with respect to (polyisocyanate used in the urethanization step) 100 parts by weight of polyisocyanate, for example, 50 parts by mass or more, or preferably 100 parts by mass or more, e.g. , below 2000 parts by weight, preferably at most 500 parts by mass.
[0121]
　By refluxing the reaction mixture in the presence of an organic solvent, while promoting the degradation reaction of uretonimine, smoothly it can be carbodiimidization reaction and to desorb carbon dioxide gas caused by the carbodiimidization of the isocyanate groups it is possible, it is possible to enhance the carbodiimidization.
[0122]
　Then, by such a method, a polycarbodiimide composition is obtained which contains the urethane group, carbodiimide and uretonimine.
[0123]
　More specifically, first, in the urethanization step, urethane groups derived from the isocyanate group of the polyisocyanate is formed.
[0124]
　Then, the reaction product obtained by the urethanization step (urethane modified product of polyisocyanate) is, when it is heated in the carbodiimidization process, generated by the carbodiimide group derived from an isocyanate group at the molecular ends, generated by the carbodiimide groups some react with the isocyanate groups at the molecular terminal, uretonimine groups is produced.
[0125]
　Then, a part of the uretonimine group, is thermally decomposed by heating in the carbodiimidization process is continued, and carbodiimide groups, and playback and an isocyanate group at the molecular ends, further, carbodiimide groups derived from the isocyanate groups at the molecular terminal There is generated.
[0126]
　In this manner, the isocyanate groups of the polyisocyanate is converted urethane group, a carbodiimide and uretonimine. As a result, polycarbodiimide composition is obtained which contains the urethane group, carbodiimide and uretonimine.
[0127]
　Then, in the manufacturing method of the polycarbodiimide composition than the proportion of the isocyanate groups are converted into urethane and uretonimine groups, who rate the isocyanate groups are converted into carbodiimide groups, which is relatively large .
[0128]
　More specifically, in the infrared absorption spectrum of the polycarbodiimide composition, 2120 cm from stretching vibration of the carbodiimide groups -1 absorbance IR near CI of, 1720 cm from stretching vibration of uretonimine groups and urethane groups -1 absorbance around IR UI + U intensity ratio (IR CI / IR UI + U ) is 1.5 or more, preferably, 1.8 or higher, more preferably at least 2.4, 4.5 or less, preferably 4.2 or less , more preferably, it is 3.6 or less.
[0129]
　In polycarbodiimide composition, the intensity ratio of the (IR CI / IR UI + U is), if below the above lower limit, because the carbodiimide group relatively small, not a low-temperature rapid curability is insufficient, the resin composition various physical properties when cured at relatively low temperatures and relatively short time (described later), the resulting cured resin product (described later), among others, poor chemical resistance.
[0130]
　The intensity ratio of the (IR CI / IR UI + U ) is, if they exceed the above upper limit, although carbodiimide groups increases relatively, the molecular weight becomes higher, dispersibility in water, and an organic solvent have poor solubility, there is a problem that can not be produced aqueous dispersion composition (described later) and the solution composition (described later).
[0131]
　For these, the intensity ratio of the (IR CI / IR UI + U if any)
[0132]
　Incidentally, infrared absorption spectrum of the polycarbodiimide composition can be measured in accordance with Examples described later.
[0133]
　Further, the polycarbodiimide composition, the proportion of uretonimine groups to the total moles of the carbodiimide group and the uretonimine groups, for example, 1 mol% or more, preferably, exceed 1 mol%, more preferably, 1.5 mol% or more, more preferably 2 mol% or more, especially preferably, is 4 mol% or more, for example, 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, more preferably, 8 is less than or equal to mol%.
[0134]
　In polycarbodiimide composition, if the proportion of uretonimine groups to the total moles of the carbodiimide group and the uretonimine within specific ranges described above, it is possible to improve the low-temperature rapid curability and cured resin excellent in various properties it is possible to obtain an object (described later). Furthermore, the water-dispersible composition in (described later), it is also possible to improve the water-dispersible.
[0135]
　The ratio of uretonimine groups to the total moles of the carbodiimide group and the uretonimine groups, in conformity with the examples described below, 13 can be determined from the C-NMR
[0136]
　Further, in this method, if desired, the polycarbodiimide composition obtained in carbodiimidization step described above, the alcohol may be further reacted. In the following, the previous urethanization processes carbodiimide step, referred to as a first urethanization step, also, there is a case where the urethanization step after the carbodiimidization process, referred to as a second urethanization process.
[0137]
　Specifically, polycarbodiimide composition obtained in carbodiimidization step further, if having an isocyanate group at the molecular terminal, by reacting the polycarbodiimide composition and alcohols, the molecular end isocyanate it can be urethanization group.
[0138]
　In the second urethanization step, as the alcohol, other alcohols as described above (i.e., alcohols not containing an oxyethylene group three or more consecutive) and the like.
[0139]
　The mixing ratio of alcohol in the second urethanization step with alcohols used in the first urethanization process, the total amount of alcohol used in the second urethanization step, the polyisocyanate used in the first urethanization step as is adjusted a predetermined ratio with respect to.
[0140]
　Specifically, the hydroxyl group of alcohol used in the first urethanization step, based on the total amount of the alcohol hydroxyl groups of the employed in the second urethane step, the equivalent ratio of the isocyanate groups of the polyisocyanate (NCO / OH ) is, for example, exceed 2, preferably 3 or more, more preferably 4 or more, for example, 16 or less, preferably 14 or less, more preferably 10 or less.
[0141]
　Further, in this reaction, if necessary, it may be added urethane catalyst as described above. The mixing ratio of the urethane-forming catalyst is not particularly limited, depending on the purpose and application, are set appropriately.
[0142]
　Moreover, the reaction conditions in the second urethanization step, urethane groups polycarbodiimide composition obtained, the content of carbodiimide and uretonimine groups, is set to a predetermined range as described above. The reaction conditions in the second urethanization process, atmospheric pressure and inert gas (e.g., nitrogen gas) in the atmosphere, reaction temperature, is preferably the same range as the reaction temperature of the carbodiimide process. The reaction time is, for example, 15 minutes or more, preferably not more than 30 minutes, for example, 5 hours or less, preferably less than 1 hour.
[0143]
　Thus, an isocyanate group at the molecular ends of polycarbodiimide composition has a hydroxyl groups of alcohols is reacted urethanization.
[0144]
　As a result, no isocyanate group at the molecular end, or, polycarbodiimide composition isocyanate groups at the molecular ends is reduced is obtained.
[0145]
　The polycarbodiimide composition obtained in this manner, a urethane group, a carbodiimide and uretonimine and contains a predetermined ratio described above. That is, the intensity ratio of the (IR CI / IR UI + U ) is in a particular range. Therefore, the adjusted molecular weight, water-dispersed composition (described below) and solution composition (described later) can easily be obtained, also by relatively large carbodiimide group, the resin composition having excellent low-temperature rapid curability can be obtained (see below), further, by hardening of the resin composition, a cured resin excellent in various properties (described later) can be obtained at relatively low temperatures and relatively short time.
[0146]
　Incidentally, when the second urethanization step is performed, the more by-products derived from alcohols, and the molecular weight increases rapidly fluidity decreases, water-dispersible, if the low-temperature rapid curability is lowered is there. Therefore, preferably, without performing the second urethanization step, performed only the first urethanization process and carbodiimide process.
[0147]
　The manufacturing method of polycarbodiimide composition is not limited to the above, for example, a polyisocyanate and a carbodiimidization catalyst and an alcohol collectively blending, can be heated.
[0148]
　Further, if necessary, from polycarbodiimide composition, for example, unreacted polyisocyanate, alcohols unreacted low molecular weight compound (by-product), an organic solvent, carbodiimidization catalyst, and a urethane catalyst, distillation , extraction, may be removed by a known method such as filtration.
[0149]
　Further, the polycarbodiimide composition, optionally further, known additives, for example, storage stabilizer (o-toluenesulfonamide, p- toluenesulfonamide, etc.), plasticizers, antiblocking agents, heat stabilizers agents, light stabilizers, antioxidants, mold release agents, catalysts, pigments, dyes, lubricants, fillers, etc. hydrolysis inhibitor may be added at an appropriate timing. The addition proportion of the additive is not particularly limited, depending on the purpose and application, are set appropriately.
[0150]
　Further, polycarbodiimide composition can be used alone or in combination of two or more kinds.
[0151]
　And, in such a polycarbodiimide composition, 2120 cm from stretching vibration of the carbodiimide groups -1 absorbance IR near CI of, 1720 cm from stretching vibration of uretonimine groups and urethane groups -1 absorbance IR near UI + U intensity ratio ( IR CI / IR UI Tasu U ) is in a particular range. Therefore, such a polycarbodiimide composition is excellent in low-temperature rapid curability.
[0152]
　According to the manufacturing method of the polycarbodiimide composition, the polycarbodiimide composition can be efficiently produced.
[0153]
　The polycarbodiimide composition is excellent in low-temperature rapid curability, it is suitably used as a curing agent in the resin composition.
[0154]
　Resin composition contains a curing agent containing a polycarbodiimide composition, the main agent having a carboxyl group.
[0155]
　Curing agent, if it contains polycarbodiimide composition is not particularly limited, for example, polycarbodiimide composition aqueous dispersion dispersed in water (hereinafter, referred to as water-dispersed composition.) And polycarbodiimide composition object is dissolved in an organic solvent solution (hereinafter referred to as the solution composition.) is prepared as such.
[0156]
　Aqueous dispersion composition contains a water polycarbodiimide composition.
[0157]
　As polycarbodiimide composition in aqueous dispersion composition, preferably, polycarbodiimide composition of the reaction product obtained by carbodiimidization reaction of an alcohol and polyisocyanates containing alcohols containing oxyethylene group three or more consecutive thing, and the like.
[0158]
　That is, in the production of polycarbodiimide composition, if alcohols containing oxyethylene group three or more consecutive is used, polycarbodiimide composition contains an oxyethylene group to three or more consecutive. Such polycarbodiimide compositions are the hydrophilic, it is readily dispersed in water.
[0159]
　The polycarbodiimide composition as a method of dispersing in water is not particularly limited, water is added to the polycarbodiimide composition, stirred and method of water was added to the polycarbodiimide composition, and a method of stirring . Preferably, water is added to the polycarbodiimide composition.
[0160]
　Ratio of the water polycarbodiimide composition is not particularly limited, polycarbodiimide composition in aqueous dispersion composition concentration (resin component) (i.e., solid concentration) of, for example, 5 wt% or more, it is 10 mass% or more, e.g., 90 wt% or less, preferably 80 mass% or less.
[0161]
　If the curing agent is a water-dispersed composition, it is possible to improve the compatibility with the aqueous resin (main agent), it can also be obtained a cured product having excellent water resistance and solvent resistance. Moreover, such solutions composition because it contains the polycarbodiimide composition, excellent low-temperature rapid curability.
[0162]
　The solution composition contains a polycarbodiimide composition and an organic solvent.
[0163]
　As polycarbodiimide composition in solution composition, preferably, polycarbodiimide composition obtained reaction product with other polyol and polyisocyanate are reacted carbodiimidization and the like.
[0164]
　That is, in the production of polycarbodiimide composition, if alcohols containing oxyethylene group three or more consecutive is not used, polycarbodiimide composition contains no oxyethylene group three or more consecutive. Such polycarbodiimide compositions are the hydrophobic, are readily soluble in organic solvents.
[0165]
　In the production of polycarbodiimide composition, alcohol is used containing oxyethylene group three or more consecutive, polycarbodiimide composition, even when it contains more than three consecutive oxyethylene groups, in an organic solvent it is dissolved.
[0166]
　As the organic solvent, it includes organic solvents mentioned above, preferably, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene.
[0167]
　As a method for dissolving the polycarbodiimide composition in an organic solvent is not particularly limited, adding an organic solvent to polycarbodiimide composition, stirred and method of, in an organic solvent by adding polycarbodiimide composition, a method of stirring, etc. and the like. Preferably, the addition of an organic solvent to polycarbodiimide composition.
[0168]
　Ratio of the polycarbodiimide composition and the organic solvent is not particularly limited, the concentration (i.e., solid concentration) of the polycarbodiimide composition in solution composition (resin component), for example, 5 wt% or more, it is 10 mass% or more, e.g., 90 wt% or less, preferably 80 mass% or less.
[0169]
　If hardener solution composition, it is possible to improve the compatibility with oil-based resin (main agent), it can also be obtained a cured product having excellent water resistance and solvent resistance. Moreover, such solutions composition because it contains the polycarbodiimide composition, excellent low-temperature rapid curability.
[0170]
　The main agent having a carboxyl group, an aqueous resin having a carboxyl group and an oil-based resin having a carboxyl group.
[0171]
　The aqueous resin having a carboxyl group include, for example, a hydrophilic polymer having a carboxyl group, specifically, a hydrophilic polyester resin having a carboxyl group, a hydrophilic polyamide resin having a carboxyl group, a carboxyl group hydrophilic polyurethane resins, hydrophilic acrylic resin having a carboxyl group, a hydrophilic polyolefin having a carboxyl group (e.g., polypropylene, polyethylene, polypropylene - polyethylene (random block) copolymer, other 4 or more carbon atoms of the repeating units etc. polyolefin) resins. Aqueous resin having these carboxyl groups can be used alone or in combination of two or more.
[0172]
　As an aqueous resin having a carboxyl group, preferably a hydrophilic polyurethane resin having a carboxyl group, and a hydrophilic acrylic resin having a carboxyl group.
[0173]
　As the oil-based resin having a carboxyl group include, for example, a hydrophobic polymer having a carboxyl group, specifically, a hydrophobic polyester resin having a carboxyl group, a hydrophobic polyamide resin having a carboxyl group, a carboxyl group hydrophobic polyurethane resins, hydrophobic acrylic resin having a carboxyl group, a hydrophobic polyolefin (e.g., polypropylene having a carboxyl group, polyethylene, polypropylene having - polyethylene (random block) copolymer, other carbon atoms of the repeating units 4 like more polyolefins) resin. Oil-based resins having these carboxyl groups can be used alone or in combination of two or more.
[0174]
　As an oil-based resin having a carboxyl group, preferably a hydrophobic polyurethane resin having a carboxyl group, and hydrophobic acrylic resin having a carboxyl group.
[0175]
　These may be used alone or in combination of two or more.
[0176]
　As the main agent and curing agent, preferably, the base resin is an aqueous resin, and a combination curing agent is a water-dispersed composition. Also, preferably, the base resin is an oil-based resin, curing agents also combined a solution composition.
[0177]
　As the resin composition, to reduce the organic solvent, from the viewpoint of protecting the global environment, preferably, a combination of a water-based main agent and the water-dispersed composition.
[0178]
　The resin composition, if containing a curing agent as main agent and the mentioned above is not particularly limited, the main agent and the curing agent is prepared separately, be a two-pack type which is mixed at the time of use well, also, the main agent and the curing agent may be a one-pack type that is pre-mixed.
[0179]
　As the resin composition, preferably, a resin composition of two-pack type.
[0180]
　Main agent and the content of the curing agent with respect to their total 100 parts by weight base resin is, for example, 10 parts by weight or more, preferably, is 30 parts by mass or more, for example, 99.5 parts by mass or less, preferably , or less 95.0 parts by weight. Further, the curing agent, for example, 0.5 parts by mass or more, or preferably 5 parts by mass or more, for example, 90 parts by weight or less, or preferably 70 parts by mass or less.
[0181]
　Further, to the carboxyl groups in the base resin, the molar ratio of carbodiimide groups in the curing agent is, for example, 0.1 or more, preferably is 0.2 or more, for example, 2.0 or less, preferably, 1.5 less.
[0182]
　Further, the main agent and curing agent, as necessary, to either one or both thereof, for example, epoxy resins, catalysts, coating improvers, leveling agents, antifoaming agents, such as antioxidants and ultraviolet absorbers stabilizers, plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, a fungicide may be blended with additives such as a silane coupling agent. The amount of these additives is appropriately determined according to the purpose and application.
[0183]
　Further, as the main component, an aqueous resin having a carboxyl group described above, and / or an oil-based resin having a carboxyl group as described above, other resins (e.g., hydroxyl group-containing polyurethane resin, hydroxyl group-containing acrylic resin, hydroxyl group-containing polyester resins, It may be used in combination with melamine resins, etc.).
[0184]
　Furthermore, it as a curing agent, a polycarbodiimide composition described above, other curing agent (e.g., polyisocyanate-based resins, and epoxy resins) may be used in combination with.
[0185]
　And, in such a resin composition, as a curing agent, since the polycarbodiimide composition mentioned above is used, excellent low-temperature rapid drying property and excellent cured resin physical properties (water resistance and solvent resistance) it is possible to obtain.
[0186]
　As a method for producing a cured resin is not particularly limited, for example, when the resin composition is a one-pack type as the resin composition is applied to the object to be coated or deposits. In the case of the resin composition two-liquid type by mixing the main agent and curing agent, the resulting mixture is applied to the object to be coated or deposits. Then, by heat curing the resin composition, the cured resin is obtained.
[0187]
　In the above resin composition, a curing temperature is relatively low, specifically, for example, 100 ° C. or less, preferably 80 ° C. or less. Further, for example, 20 ° C. or more, preferably, 30 ° C. or higher.
[0188]
　Further, a relatively short curing time, specifically, for example, 1 hour or less, preferably 30 minutes or less. Further, for example, more than 1 minute, preferably more than 5 minutes.
[0189]
　Further, if necessary, a heat cured resin cured product, may be further dried.
[0190]
　In such a case, the drying temperature may be a room temperature, e.g., 10 ° C. or higher, preferably not 15 ℃ or higher, e.g., 40 ° C. or less, preferably 30 ° C. or less.
[0191]
　The drying time is, for example, more than 1 minute, preferably not less than 5 minutes, for example, 2 hours or less, preferably not more than 1 hour.
[0192]
　Then, the resulting cured resin are the cured product of the resin composition having excellent low-temperature fast curing, relatively low temperatures and relatively short time to obtain, and various physical properties (e.g., water resistance, chemical excellent sex, etc.).
[0193]
　Further, polycarbodiimide Where the composition is obtained by using an aliphatic polyisocyanate, a resin cured product obtained by using the polycarbodiimide composition, excellent in light resistance (weathering resistance).
[0194]
　Therefore, the resin composition and the cured resin, coating material, adhesive material (adhesive), adhesive material (adhesive), inks, sealants, molding materials, foams and optical materials, further, polyesters, polylactic acid, polyamide, in various fields such as a resin modifier for modifying the resin such as polyimide, it is preferably used.
[0195]
　When used as a coating material, for example, plastics coatings, automotive exterior coatings, automobile interior paints, electric and electronic materials for paints, coatings for optical materials (lenses, etc.), building materials paints, glass coating composition, woodworking paints, film coating paints, inks paints, artificial and synthetic leather coatings (coating agent), cans paint (coating agent), such as paper coating composition and the like.
[0196]
　As the plastic coating, for example, a plastic material (e.g., polyolefins, ABS, polycarbonates, polyamides, polyesters and these various polymer materials such as complex) for a molded article paints used, specifically, , housing (mobile phone, smartphone, computer, tablet, etc.) for paint, automobile parts (such as automobile interior materials and head lamp) for paints, household appliances paints, paint robots materials, furniture paint, stationery for paint , rubber, elastomers and flexible coatings for materials such as a gel, eyewear materials (lenses, etc.) paints, the optical lens coatings of electronic devices (surface-coating agent), and the like.
[0197]
　Further, as the automobile exterior paints, for example, for new cars (intermediate, base, top, etc.) coatings, automotive repair (intermediate, base, top, etc.) paints, paint exterior parts (aluminum wheels, bumpers, etc.) and the like.
[0198]
　When using the above-mentioned resin composition as an automotive exterior coatings, the main agent can be used oil-based resin having a water-based resin, a carboxyl group described above having a carboxyl group described above. Preferably, an aqueous resin having a carboxyl group is used.
[0199]
　As an aqueous resin having a carboxyl group, a hydrophilic Preferably, the hydrophilic acrylic resin having a carboxyl group, a hydrophilic polyurethane resin having a carboxyl group, and a hydrophilic polyester resin having a carboxyl group, more preferably, having a carboxyl group sexual acrylic resins, hydrophilic polyester resin having a carboxyl group. Furthermore, it can be used in combination an aqueous resin having a carboxyl group as the two or more types.
[0200]
　Further, as the main component, an aqueous resin having a carboxyl group described above, and / or an oil-based resin having a carboxyl group as described above, other resins (e.g., hydroxyl group-containing polyurethane resin, hydroxyl group-containing acrylic resin, hydroxyl group-containing polyester resins, It may be used in combination with melamine resins, etc.).
[0201]
　When using the above-mentioned resin composition as an automotive exterior coatings, the solid concentration of the base resin is usually 5 wt% or more, preferably 20 mass% or more, more preferably, not less than 30 mass%, for example, 80 wt% or less, preferably 70 wt% or less, more preferably 60 mass% or less.
[0202]
　The acid value of the solid content basis of the main agent, for example, 5 mgKOH / g or more, preferably not 10 mgKOH / g or more, for example, 200 mg KOH / g or less, preferably not more than 100 mg KOH / g.
[0203]
　As the curing agent, polycarbodiimide the above composition can be mentioned, also be a polycarbodiimide composition, other curing agent (e.g., polyisocyanate-based resins, and epoxy resins) may be used in combination with.
[0204]
　Further, as the film coating paint, for example, an optical member (an optical film, such as an optical sheet) coating, the coating material for optical fiber coatings, electronic and electrical materials for paints, food packaging coatings, medical film coatings, cosmetics package for paint, decorative film for the paint, and the like paint for a release film.
[0205]
　As the adhesive, for example, packaging materials for adhesives, electric appliances adhesives, adhesives for liquid crystal display (LCD), a glue for an organic EL display, an organic EL illumination adhesives, display device (electronic paper, plasma displays etc.) adhesives, LED adhesives, in automotive exteriors adhesives, consumer electronics adhesives, adhesives for solar cell back sheet, such as adhesive for various batteries (lithium ion battery) can be mentioned.
[0206]
　Further, as the ink resin, various inks include vehicles (plate ink, screen ink, flexographic inks, gravure inks, jet inks, etc.).
[0207]
　Incidentally, application of the polycarbodiimide composition is not limited to the above, for example, as a solid, polyester or polyamide resin or polylactic acid, or as a liquid, hydrolysis preventing agent such as polyester polyols, acid-modified, for example, complexation with maleic acid modified polyolefin, or a polyolefin emulsion an acid-modified polyolefin dispersed in water, complexing and curing agent of acrylic emulsion containing acid sites, converging material for various fiber such as carbon fiber or glass fiber, CFRP Ya as such a reinforcing material or sizing agent and the curing agent of the fiber-reinforced plastics such as FRP, it can be preferably used.
Example
[0208]
　Next, the present invention, manufacturing examples will be described with reference to examples and comparative examples, the present invention is not limited by the examples below. Incidentally, "parts" and "%", unless specifically stated, it is by weight. The mixing ratio used in the following description (content), physical properties, the specific values ​​of such parameters are described in the "Description of the Invention" section above, the blending ratio corresponding to them ( content), physical properties, the upper limit of such appropriate according parameter ( "hereinafter" substitute defined numerical are) or the lower limit value as "less than" ( "or" numerical values ​​is defined as "excess") be able to.
[0209]
　In addition, a variety of measurement methods described below.
[0210]
　　 　polycarbodiimide composition was distilled off the organic solvent used in the reaction (hereinafter. Referred to as "desolvated product") according to an ordinary method at the following apparatus under the following conditions IR spectra were measured.
[0211]
　Then, 2120 cm from stretching vibration of the carbodiimide groups -1 absorbance IR near CI of, 1720 cm from C = O stretching vibration of uretonimine groups and urethane groups -1 absorbance IR near UI + U intensity ratio (IR CI / IR UI + U ) It was calculated.
[0212]
　IR Measurement apparatus: Perkin Elmer Co., Ltd. Frontier FT-IR
　measurement method: ATR (reflection method)　　
　wavenumber range: 4000 ~ 400 cm -1　　
　resolution 4 cm -1　　
　Regarding polycarbodiimide composition of Example 6 described below, resulting in the analysis the obtained infrared absorption spectrum shown in FIG.
[0213]
　　
　using desolvation products at device and conditions below 13 measures the C-NMR, Incidentally, as a reference for the chemical shift ppm, CDCL 3 using tetramethylsilane in a solvent (0 ppm).
Device; ECA-500 (manufactured by JEOL)
conditions; measurement frequency: 125 MHz, solvent: CDCL 3 , solute concentration: 50 wt%
Measurement temperature: room temperature, number of scans 8500 times
repetition time: 3.0 sec, pulse width: 30 ° (3.70μ sec)
carbon attributions peak of carbodiimide group (N = C = N group in the carbodiimide group): 139 ppm
uretonimine attributable peaks (3H) carbon groups (C = O group in the uretonimine): 155 ppm
　　uretonimine mole% of groups / (uretonimine + carbodiimide group) = (integral value of attribution peak of carbon uretonimine groups) / (integration value of attribution peak integrated value + carbodiimide group attribution peak of carbon uretonimine groups) × 100
　Note that the polycarbodiimide composition of example 20 described below were obtained in the analysis 13The C-NMR spectrum shown in Figure 2.
[0214]
　　
　content of the oxyethylene groups with respect to polycarbodiimide composition was calculated from the charged amounts and chemical structure.
[0215]
　　
　content of alcohols containing oxyethylene group three or more consecutive to the total moles of alcohols, It was calculated from the charged amounts and chemical structure.
[0216]
　　Production Example 1 (production of pentamethylene diisocyanate)
　when in the same manner as in Example 1 in the specification of International Publication Pamphlet No. WO2012 / 121291, abbreviated to 99.9 wt% of 1,5-pentamethylene diisocyanate (hereinafter PDI was obtained there.) it is.
[0217]
　More specifically, an electromagnetic induction stirrer, an automatic pressure control valve, a thermometer, a nitrogen inlet line, a phosgene inlet line, a condenser, jacketed pressure reactor equipped with a raw material feed pump, o- dichlorobenzene 2000 Weight He was charged with part. Then added phosgene 2300 parts by mass of phosgene inlet line and stirring was started. The reactor jacket through cold water, the internal temperature was maintained at about 10 ° C.. Thereto, a solution of pentamethylene diamine (a) 400 parts by weight of the o- dichlorobenzene 2600 parts by weight, was fed over a period of 60 minutes at the feed pump, 30 ° C. or less, was started cold phosgenation under normal pressure . After completion of the feeding, pressurized reactor became pale brownish white slurry solution.
[0218]
　Then, while the internal solution in the reactor was gradually raised to 160 ° C., pressurized to 0.25 MPa, further pressure 0.25 MPa, and 90 minutes heat phosgenation at a reaction temperature of 160 ° C.. Incidentally, during the hot phosgenation, the phosgene 1100 parts by weight was further added. In the course of hot phosgenation, the pressurized reactor solution became pale brown clear solution. After completion of heat phosgenation, at 100 ~ 140 ° C., a nitrogen gas was bubbled when 100L /, degassed.
[0219]
　Then, after distilled off under reduced pressure in o- dichlorobenzene, also by distilling off pentamethylene diisocyanate under reduced pressure, 98.7% purity of pentamethylene diisocyanate (a 0 was obtained)
[0220]
　Then, pentamethylene diisocyanate (a 0 ) 558 parts by weight, and tris (tridecyl) phosphite (Johoku Chemical Co., trade name: JP-333E) 0.02 parts by weight to 100 parts by weight pentamethylene diisocyanate and stirrer , thermometer, reflux condenser, and was charged into a four-necked flask equipped with a nitrogen inlet tube, while introducing nitrogen, under normal pressure, 190 ° C., for 2 hours of heat treatment, purity 98.2% of penta methine diisocyanate (a 1 a) to give 553 parts by weight. The yield of pentamethylene diisocyanate in the heat treatment was 99.4%.
[0221]
　Then, pentamethylene diisocyanate after the heat treatment (a 1 a), were charged to a glass flask, fill (Sumitomo Heavy Industries Ltd., trade name: Sumitomo / Sulzer Labo Packing EX type) was 4 packing elements Distilled tube, reflux ratio adjusted timer was mounted distillation column (Shibata scientific Co., Ltd., trade name: distillation head K type), and, using a rectification apparatus equipped with a condenser, 127 ~ 132 ° C., the conditions of 2.7KPa lower, fractionated while further refluxing, the fraction of distillate rate 20-80% were collected, to give a pentamethylene diisocyanate (a).
[0222]
　　Example 1
　preparation of poly carbodiimide composition
　stirrer, thermometer, reflux condenser, and a four-necked flask equipped with a nitrogen inlet tube, at room temperature, 100.0 pentamethylene diisocyanate obtained in Production Example 1 parts by weight 40.0 parts by mass of UNIOX M550 (manufactured by NOF Corporation polyethylene glycol monomethyl ether molecular weight 550) was charged 6.0 parts by weight of 1-methoxy-2-propanol. While introducing nitrogen, warmed to 80 ° C. under normal pressure, and stirred for 6 hours (first urethanization step).
[0223]
　Subsequently, 306.5 parts by weight of xylene, 3-methyl-1-phenyl-2-phospholene-1-oxide and (MPPO) and 2.0 parts by weight charged, and stirred for 8 hours under reflux (141 ° C.) (carbodiimide step).
[0224]
　Further still under reflux, 1-methoxy-2-propanol was charged 6.8 parts by weight, and stirred for 30 minutes, the reaction was terminated (second urethanization step).
[0225]
　After completion of the reaction, was cooled to 80 ° C., the xylene was distilled off under reduced pressure to obtain a polycarbodiimide composition. Some of the resulting polycarbodiimide composition was taken out, as a result of measuring an IR spectrum, IR intensity ratio (IR CI / IR UI + U ) was 2.83. Also, 13 the results of measuring the C-NMR,
[0226]
　Water dispersion of polycarbodiimide composition (aqueous dispersion composition) Preparation of
　polycarbodiimide composition was placed in a flask, heated to 80 ° C., was slowly added distilled water so that the resin solid content of 40% . After stirring for 5 min, cooled to room temperature. This gave an aqueous dispersion of a polycarbodiimide composition. Then, to evaluate the water-dispersibility in a manner described below.
[0227]
　Preparation of the resin composition
　aqueous dispersion of the polycarbodiimide obtained composition was used as a curing agent. Then, a curing agent, 1.5 parts by mass of a polyurethane dispersion as the main agent (solid content 30% by mass, the carboxyl group equivalent 3100 g / mol) was mixed with 98.5 parts by mass, to prepare a resin composition.

claims

[Claim 1]A polyisocyanate having a primary isocyanate groups, the reaction product of an alcohol,
　and a carbodiimide group and the uretonimine groups,
　in the infrared absorption spectrum,
　　2120 cm from stretching vibration of the carbodiimide groups -1 absorbance IR nearby CI of,
　　1720 cm from stretching vibration of uretonimine groups and urethane groups -1 absorbance IR near UI + U intensity ratio (IR CI / IR UI + U ) is 1.5 to 4.5
, wherein the polycarbodiimide Composition.
[Claim 2]
　In the polycarbodiimide composition, the proportion of uretonimine groups to the total moles of the carbodiimide group and the uretonimine groups is less than or equal to 15 mol% 1.5 mol% or more
, characterized in that, polycarbodiimide composition of claim 1 Stuff.
[Claim 3]
　To the hydroxyl group of the alcohol, the equivalent ratio of the isocyanate groups of the polyisocyanate (NCO / OH), characterized in that it is less exceed 2 16,
polycarbodiimide composition of claim 1.
[Claim 4]
　Said alcohols, containing alcohols containing oxyethylene group three or more consecutive,
　the content of oxyethylene groups consecutive three or more, with respect to the polycarbodiimide composition, 10 wt% to 40 wt% or less
and wherein the polycarbodiimide composition of claim 1.
[Claim 5]
　Said alcohols, containing alcohols containing oxyethylene group three or more consecutive,
　the content of the alcohol containing three or more consecutive oxyethylene groups, based on the total moles of said alcohol, 5 mol% or more and 50 mol% or less
, wherein the polycarbodiimide composition of claim 1.
[Claim 6]
　The polyisocyanate is an aliphatic polyisocyanate
, characterized in that, polycarbodiimide composition of claim 1.
[Claim 7]
　The aliphatic polyisocyanate is pentamethylene diisocyanate
, wherein the polycarbodiimide composition of claim 6.
[8.]
　A method of manufacturing a polycarbodiimide composition of claim 1,
　wherein the urethanization step of urethanization reaction of the alcohol with a polyisocyanate,
　the reaction product in the urethanization step, the carbodiimidization catalyst was heated in the presence, of a carbodiimidization step of carbodiimidization
, characterized in that it comprises a method for producing a polycarbodiimide composition.
[Claim 9]
　The reaction temperature in the carbodiimidization reaction is less than or equal 160 ° C. 125 ° C. or more
manufacturing methods, wherein the polycarbodiimide composition of claim 8.
[Claim 10]
　Wherein the reacting the carbodiimidization under reflux method for producing a polycarbodiimide composition of claim 8.
[Claim 11]
　Polycarbodiimide composition of claim 1,
　a water dispersion liquid dispersed in water at a ratio of less than 90 wt% solids concentration of 5 mass% or more
and wherein the water-dispersed composition.
[Claim 12]
　Polycarbodiimide composition of claim 1,
　a solution in an organic solvent in a proportion of less than 90 wt% solids concentration of 5 mass% or more
, characterized in that, the solution composition.
[Claim 13]
　A base resin having a carboxyl group,
　and a curing agent comprising a polycarbodiimide composition according to claim 1
, characterized in that it contains a resin composition.
[Claim 14]
　Characterized in that it is a cured product of the resin composition according to claim 13, cured resin.