Technical field
[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
[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, a 673g hexamethylene diisocyanate (HDI), and polyethylene glycol monomethyl ether 800g of average molecular weight 400 reacted at 120 ° C., further carbodiimidization catalyst ( was added 3-methyl-1-phenyl-2-phospholene-1-oxide) 13.5 g, further polycarbodiimide compound reacted for 5 hours at 185 ° C. has been proposed (e.g., Patent Document 1 (synthesis example 82) reference.).
[0004]
　Then, such a polycarbodiimide compound (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 above-mentioned polycarbodiimide compounds are not storage stable enough, or when the flowability is decreased by storing, sometimes solidified.
[0007]
　Further, the cured resin, such coating film obtained by using a polycarbodiimide compound, film forming property and various physical properties such as water resistance and chemical resistance is required.
[0008]
　The present invention is excellent in storage stability, also polycarbodiimide composition can be obtained film-forming properties, water resistance and the resin cured product excellent in chemical resistance, a method of manufacturing the polycarbodiimide composition also, the poly carbodiimide composition aqueous dispersion composition comprising a and solution composition and a resin composition comprising a polycarbodiimide composition further is 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, the alcohol is at least one oxyethylene-containing alcohol containing oxyethylene groups, oxyethylene and at least one polyoxyethylene-free alcohol not containing group, at least one said solubility parameter of polyoxyethylene-free alcohol is, 11.20 (cal / cm 3 ) 1/2 or less, polycarbodiimide it includes compositions.
[0010]
　The present invention [2], the content of oxyethylene groups, wherein the relative polycarbodiimide composition is 35 wt% or less than 10 wt%, contains a polycarbodiimide composition according to [1] .
[0011]
　The present invention [3], the solubility parameter is 11.20 (cal / cm 3 ) 1/2 the polyoxyethylene-free alcohol or less is a primary alcohol and / or secondary alcohol, the [1 contains polycarbodiimide composition according to] or [2].
[0012]
　The present invention [4], the solubility parameter is 11.20 (cal / cm 3 ) 1/2 the polyoxyethylene-free alcohol or less is a monovalent alcohol containing less 12 or 4 or more carbon atoms, contains polycarbodiimide composition according to any one of the above [1] to [3].
[0013]
　The present invention [5], the solubility parameter is 11.20 (cal / cm 3 ) 1/2 or less the polyoxyethylene-free alcohol,
　isobutanol, 2-butanol, 2-methyl-1-butanol, 2, 2-dimethyl-1-propanol, 3-methoxy-1-butanol, is at least one 1-octanol, are selected from the group consisting of 2-ethyl-1-hexanol and 1-dodecanol, the above-mentioned [1] to [ It contains 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 polyisocyanate is a pentamethylene diisocyanate, contain the [1] to polycarbodiimide composition according to any one of [6].
[0016]
　The present invention [8], a polyisocyanate having a primary isocyanate group, and urethanization step of reacting urethanization and alcohols, the reaction product in the urethanization step, by heating in the presence of a carbodiimidization catalyst, and a carbodiimidization step of carbodiimidization reaction include the alcohols, and at least one oxyethylene-containing alcohol containing oxyethylene groups, and at least one polyoxyethylene-free alcohol not containing an oxyethylene group at least one solubility parameter of the polyoxyethylene-free alcohol is, 11.20 (cal / cm 3 ) 1/2 or less include a method for producing a polycarbodiimide composition.
[0017]
　The present invention [9], to the hydroxyl group of the alcohol, the equivalent ratio of the isocyanate groups of the polyisocyanate (NCO / OH) is in excess of 2 10 or less, polycarbodiimide composition according to the above [8] it includes methods of manufacturing.
[0018]
　The present invention [10], [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.
[0019]
　The present invention [11], 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.
[0020]
　The present invention [12], 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 .
[0021]
　The present invention [13] is a cured product of the resin composition according to [12], containing the cured resin.
The invention's effect
[0022]
　Polycarbodiimide composition of the present invention, there in a polyisocyanate having a primary isocyanate group, at least one oxyethylene-containing alcohol and, the reaction product of an alcohol containing at least one polyoxyethylene-free alcohol Te solubility parameter of at least one polyoxyethylene-free alcohol is no more than the predetermined value.
[0023]
　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, storage stability excellent sex, also, it is possible to obtain a film forming property, water resistance and the resin cured product excellent in chemical resistance.
[0024]
　According to the manufacturing method of polycarbodiimide composition of the present invention, a polycarbodiimide composition of the present invention, it can be efficiently produced.
[0025]
　Further, the cured resin of the present invention, film-forming property, excellent water resistance and chemical resistance.
DESCRIPTION OF THE INVENTION
[0026]
　Polycarbodiimide composition of the present invention, polyisocyanates having a primary isocyanate group (hereinafter, simply referred to as polyisocyanates.), The reaction products of alcohols.
[0027]
　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.
[0028]
　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.
[0029]
　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.
[0030]
　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.
[0031]
　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.
[0032]
　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.
[0033]
　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.
[0034]
　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.
[0035]
　Polyisocyanates containing these primary isocyanate group may be used alone or in combination of two or more.
[0036]
　Polyisocyanate having a primary isocyanate groups, lightfastness, from the viewpoints of handling property and water-dispersible, preferably an aliphatic polyisocyanate having a primary isocyanate groups, alicyclic polyisocyanates having a primary isocyanate group include It is, from the viewpoint of chemical resistance, and more preferably, include aliphatic polyisocyanates having a primary isocyanate group.
[0037]
　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.
[0038]
　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 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, handling excellent sex and dispersibility, properties of the resin cured product obtained (described later) can be improved.
[0039]
　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 can be suppressed molecular weight of uretonimine.
[0040]
　Alcohols, alcohols containing oxyethylene groups in the molecule (hereinafter. Referred oxyethylene-containing alcohol), the alcohol not containing an oxyethylene group in the molecule (hereinafter, referred to as polyoxyethylene-free alcohol.) And contains and de, and more specifically, contains at least one oxyethylene-containing alcohol, at least one of a polyoxyethylene-free alcohol.
[0041]
　Oxyethylene group (-CH 2 CH 2 O-) has two carbon atoms, a group of four hydrogen atoms and one oxygen atom.
[0042]
　That is, an oxyethylene group (-CH 2 CH 2 O-) are those in which one or more hydrogen atoms have been substituted with other atomic group (e.g., oxypropylene group (-CH (CH 3 ) CH 2 O-) and the like), are distinguished.
[0043]
　Furthermore, an oxyethylene group (-CH 2 CH 2 O-), the carbon atom of the terminal, those bonded to a hydrogen atom or a hydrocarbon group (e.g., ethyl ether groups (H-CH 2 CH 2 O-), propyl ether groups (CH 3 -CH 2 CH 2 with O-), etc.), are distinguished.
[0044]
　Such an oxyethylene group (-CH 2 CH 2 alcohol having O-) structure in the molecule, is defined as a polyoxyethylene-containing alcohol.
[0045]
　Furthermore, an oxyethylene group (-CH 2 CH 2 alcohol having no O-) structure in the molecule, is defined as a polyoxyethylene-free alcohol.
[0046]
　The oxyethylene content alcohol, polyol containing oxyethylene groups in the molecule (hereinafter, referred to as polyoxyethylene-containing polyols.) Monool containing oxyethylene groups in the molecule (hereinafter, referred to as polyoxyethylene-containing monools.) and the like.
[0047]
　Oxyethylene-containing polyol comprises one or more oxyethylene groups in the molecule, an organic compound having both at least two hydroxyl groups, for example, polyoxyethylene polyols, polyoxyethylene-polyoxypropylene (Random and / or block) oxyethylene-containing polymer polyols and copolymers thereof.
[0048]
　Polyoxyethylene polyols, for example, as an initiator and a low molecular weight polyol, by addition reaction of ethylene oxide, can be obtained. Polyoxyethylene-polyoxypropylene copolymers, for example, as an initiator and a low molecular weight polyol, by addition reaction of ethylene oxide and propylene oxide can be obtained.
[0049]
　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.
[0050]
　As low molecular weight polyol, preferably, a dihydric alcohol.
[0051]
　As the method of addition reaction of ethylene oxide (and propylene oxide) to these low molecular weight polyol is not particularly limited, it may be a known method.
[0052]
　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. Further, polyoxyethylene-polyoxypropylene (random and / or block) copolymer of functional groups (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 an initiator, as the polyoxyethylene-polyoxypropylene copolymer, divalent polyoxyethylene-polyoxypropylene copolymer.
[0053]
　Further, the oxyethylene-containing polyol, and one or more oxyethylene groups in the molecule, if the both of an two or more hydroxyl groups, is not limited to polyoxyethylene-containing polymer polyols described above, such as ethylene glycol (HO-CH 2 CH 2 -OH), diethylene glycol (HO-CH 2 CH 2 -O-CH 2 CH 2 oxyethylene-containing monomer polyols, such as -OH) can also be mentioned.
[0054]
　Further, if the oxyethylene-containing polyol contains two or more oxyethylene groups, they oxyethylene group may be continuous, also may not be contiguous. In other words, if the oxyethylene-containing polyol contains two or more oxyethylene groups, between which an oxyethylene group, another group (e.g., oxypropylene group) may be interposed, also, it may not have been interposed.
[0055]
　These oxyethylene-containing polyols may be used alone or in combination of two or more kinds.
[0056]
　As oxyethylene-containing polyol, preferably, a polyoxyethylene-containing polymer polyol.
[0057]
　Further, as the polyoxyethylene-containing polyols, preferably, include polyols containing oxyethylene groups consecutive two or more in a molecule, more preferably, polyol containing oxyethylene groups successive in the molecule three or more Among them, more preferable example is polyoxyethylene glycol containing oxyethylene group three or more consecutive.
[0058]
　Oxyethylene content monols and one or more oxyethylene groups in the molecule, an organic compound having both one hydroxyl group, for example, polyoxyethylene-containing polymer mono- such one end sealing polyoxyethylene glycol such as All, and the like.
[0059]
　One end sealing polyoxyethylene glycol, the one of the terminal hydroxyl groups of the polyoxyethylene glycol, polyethylene glycol monoalkyl ethers substituted by oxyalkylene groups.
[0060]
　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.
[0061]
　Furthermore, an oxyethylene-containing monols and one or more oxyethylene groups in the molecule, if the both of an and one hydroxyl group is not limited to the aforementioned oxyethylene-containing polymer monools oxyethylene content monomer mono-ol may also be mentioned. The oxyethylene-containing monomers monool, such as 2-methoxyethanol (CH 3 O-CH 2 CH 2 -OH), 2- ethoxyethanol (CH 3 CH 2 O-CH 2 CH 2 -OH), diethylene glycol monoethyl ether (also known as carbitol) (CH 3 O-CH 2 CH 2 -O-CH 2 CH 2 , etc. -OH) primary alcohols and the like.
[0062]
　Further, if the oxyethylene content monol contains two or more oxyethylene groups, they oxyethylene group may be continuous, also may not be contiguous. In other words, if the oxyethylene content monol contains two or more oxyethylene groups, between which an oxyethylene group, another group (e.g., oxypropylene group) may be interposed, also it may not have been interposed.
[0063]
　These oxyethylene content monols can be used alone or in combination of two or more.
[0064]
　These oxyethylene content alcohols can be used alone or in combination of two or more.
[0065]
　As oxyethylene content alcohol, preferably oxyethylene content monools, more preferably, oxyethylene-containing polymer monools, more preferably, polyethylene glycol monoalkyl ethers, especially preferably polyethylene glycol monomethyl ether.
[0066]
　Furthermore, an oxyethylene-containing alcohol, if having a repeating unit of oxyethylene groups, the number of the repeating units, for example, 2 or more, 3 or more, more preferably, 5 or more, more preferably, be 10 or more , for example, 60 or less, preferably 50 or less.
[0067]
　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.
[0068]
　The molecular weight of oxyethylene-containing alcohol (number average molecular weight) is, for example, 100 or more, preferably, 200 or more, more preferably, 300 or more, more preferably, is 400 or more, for example, 5000 or less, preferably, 3000 or less, more preferably, 2,000 or less, more preferably, 1,000 or less.
[0069]
　If the molecular weight (number average molecular weight) is within the above range oxyethylene-containing alcohol, it is possible to achieve the stability of the synthesis, the improvement of the water-dispersible polycarbodiimide composition.
[0070]
　Polyoxyethylene-free alcohol, an alcohol excluding the oxyethylene-containing alcohol mentioned above, specifically, an alcohol not containing an oxyethylene group in the molecule.
[0071]
　Polyoxyethylene-free alcohol has a solubility parameter (Solubility Parameter: SP value) 11.20 (cal / cm 3 ) 1/2 or less is polyoxyethylene-free alcohol (hereinafter referred to as low SP polyoxyethylene-free alcohol. ) and it contains at least one.
[0072]
　In other words, in the present invention, as polyoxyethylene-free alcohol, the solubility parameter (SP value) 11.20 (cal / cm 3 ) 1/2 or less of the alcohol is selected at least one.
[0073]
　It should be noted that, as the solubility parameter (SP value), Fedors method (Polymer Engineering and Science, February, 1974, Vol.14, No.2 P.147 ~ 154 (A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids) ) values ​​calculated by the method described in is adopted.
[0074]
　As such a low SP polyoxyethylene-free alcohol, specifically, polyoxyethylene-free polyols containing no oxyethylene group in the molecule (hereinafter. Referred low SP oxyethylene-free polyol), polyoxyethylene in the molecule monools containing no group (hereinafter, referred to as low SP oxyethylene-free monools.) and the like, preferably, a low SP oxyethylene-free monol.
[0075]
　Low SP oxyethylene-free monool has no oxyethylene groups per molecule and an alcohol having one hydroxyl group in one molecule, for example, isobutanol (SP value 11.11 (cal / cm 3 ) 1/2 ), 2-butanol (SP value 11.11 (cal / cm 3 ) 1/2 ), 2-methyl-1-butanol (SP value 10.77 (cal / cm 3 ) 1/2 ), 3-methoxy-1-butanol (SP value 10.92 (cal / cm 3 ) 1/2 ), 1-pentanol (SP value 10.96 (cal / cm 3 ) 1/2 ), 2,2-dimethyl-1-propanol (also known as neopentyl alcohol) (SP value 10.58 (cal / cm 3 ) 1/2 ), 1-hexanol (SP value 10.68 (cal / cm 3 ) 1/2 ), 1- Heptanol (SP value 10.46 (Cal / Cm 3 ) 1/2 ), 1-octanol (SP value 10.28 (cal / cm 3 ) 1/2 ), 2-ethyl-1-hexanol (SP value 10.14 (cal / cm 3 ) 1/2 ), 1 - dodecanol (SP value 9.81 (cal / cm 3 ) 1/2 ), 1-octadecanol (SP value 9.45 (cal / cm 3 ) 1/2 ) primary alcohols such as, for example, di propylene glycol monomethyl ether (SP value 10.42 (cal / cm 3 ) 1/2 ), tripropylene glycol monomethyl ether (SP value 9.99 (cal / cm 3 ) 1/2 ), cyclooctanol (SP value 10. 93 (cal / cm 3 ) 1/2 ) secondary alcohol, such as, for example, tert- butanol (SP value 10.90 (cal / cm 3 ) 1/2) And the like tertiary alcohols such. These low SP oxyethylene-free monols can be used alone or in combination of two or more.
[0076]
　Low SP oxyethylene free alcohol can be used alone or in combination of two or more kinds.
[0077]
　Low SP oxyethylene free alcohols preferably contain a low SP oxyethylene-free monol. Content of low SP oxyethylene-free monol, based on the total amount of oxyethylene-free alcohols, for example, 25 mass% or more, preferably at least 50 wt%, for example, is 100% by mass.
[0078]
　Further, as a low SP polyoxyethylene-free alcohol, preferably a primary alcohol, secondary alcohol.
[0079]
　Low SP polyoxyethylene-free alcohol, primary If alcohol and / or secondary alcohol (in other words, if a tertiary alcohol), excellent production efficiency of the polycarbodiimide composition, also, the storage stability also excellent in sex.
[0080]
　Further, as a low SP polyoxyethylene-free alcohol, preferably, it includes monohydric alcohols containing less 12 or 4 or more carbon atoms, more preferably, isobutanol, 2-butanol, 2-methyl-1-butanol , 3-methoxy-1-butanol, 1-pentanol, 2,2-dimethyl-1-propanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, and 1-dodecanol . By using these, excellent inter alia, to improve the reactivity in the urethanization step described later, excellent efficiency can be obtained polycarbodiimide composition, also on the storage stability of the polycarbodiimide obtained composition .
[0081]
　The low SP polyoxyethylene-free alcohol solubility parameter (SP value), as described above, 11.20 (cal / cm 3 ) 1/2 or less, preferably, 11.17 (cal / cm 3 ) 1/2 or less, more preferably, 11.15 (cal / cm 3 ) 1/2 or less, more preferably, 11.13 (cal / cm 3 ) 1/2 or less, especially preferably 11.11 ( cal / cm 3 ) 1/2 or less, for example, 9.50 (cal / cm 3 ) 1/2 or more, preferably, 9.70 (cal / cm 3 ) 1/2 or more, more preferably, 10 .00 (cal / cm 3 ) 1/2 or more, more preferably, 10.10 (cal / cm 3 ) 1/2 or more, particularly preferably, 10.15 (cal / cm 3 ) 1/2 is at least.
[0082]
　If low SP polyoxyethylene-free alcohol solubility parameter (SP value) is within the above range, excellent storage stability and can be obtained film-forming properties, water resistance and the resin cured product excellent in chemical resistance.
[0083]
　As the polyoxyethylene-free alcohol, it can optionally be used in combination with a low SP polyoxyethylene-free alcohol above, and other polyoxyethylene-free alcohol. Other oxyethylene-free alcohol is, in other words, the solubility parameter (SP value) of 11.20 (cal / cm 3 ) 1/2 alcohol in excess of (hereinafter referred to as high SP polyoxyethylene-free alcohol.) a is a high SP oxyethylene-free monol, and a high SP polyoxyethylene-free polyols. That is, as the polyoxyethylene-free alcohol, and the with low SP polyoxyethylene-free alcohol (low SP oxyethylene-free monol and / or low SP oxyethylene-free polyol), if necessary, the effect of the present invention within a range that does not inhibit, it may be used in combination with high SP oxyethylene-free monol and / or high SP oxyethylene-free polyols.
[0084]
　These alcohols may be used alone or in combination of two or more kinds.
[0085]
　In alcohols, the content of the oxyethylene-containing alcohol and polyoxyethylene-free alcohol, as the content of oxyethylene groups polycarbodiimide composition obtained becomes a predetermined range is adjusted.
[0086]
　Specifically, the content of oxyethylene groups polycarbodiimide composition, for example, 5 wt% or more, preferably 10 mass% or more, more preferably 15 mass% or more, for example, less than 50 wt% , preferably 40 wt% or less, more preferably 35 mass% or less.
[0087]
　If the content is above the range of oxyethylene groups, the polycarbodiimide composition, solubility in solvents and can improve water dispersibility, also be a resin cured product excellent in water resistance (described below) be able to.
[0088]
　Incidentally, the content of oxyethylene groups can be calculated from the charged amount.
[0089]
　Then, the content of oxyethylene groups polycarbodiimide composition so that the above-mentioned range, the content of the oxyethylene-containing alcohol and polyoxyethylene-free alcohol in an alcohol is adjusted.
[0090]
　Specifically, based on the total moles of alcohol, the content of oxyethylene-containing alcohol, e.g., 5 mol% or more, or preferably 12 mol% or more, for example, 50 mol% or less, preferably, is less than or equal to 48 mol%. Further, the content of oxyethylene-free alcohol, for example, 50 mol% or more, preferably not 52 mol% or more, for example, 95 mol% or less, or preferably 88 mol% or less.
[0091]
　If the content is above the range of the oxyethylene-containing alcohol and polyoxyethylene-free alcohol in the alcohol, it is possible to improve the solubility and water dispersibility to a solvent polycarbodiimide composition, also the water resistance it can be obtained excellent cured resin (to be described later).
[0092]
　The polycarbodiimide composition of the above polyisocyanate and the alcohol are reacted under predetermined conditions, further by carbodiimidization reaction, can be obtained.
[0093]
　Hereinafter, a manufacturing method of the polycarbodiimide composition will be described in detail.
[0094]
　In this method, first, to urethanization reaction of the above polyisocyanate and the alcohol (urethanization step).
[0095]
　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.
[0096]
　Within the reaction rate is above the range of polyisocyanates with alcohols, excellent storage stability and can be obtained a cured resin excellent in water resistance (described below).
[0097]
　Further, in this reaction, if necessary, for example, it may be added a known urethanization catalyst such as amine or an organometallic compound.
[0098]
　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.
[0099]
　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.
[0100]
　Further, as a urethanization catalyst, for example, potassium carbonate, potassium acetate, potassium salts such as potassium octoate.
[0101]
　These urethanization catalysts may be used alone or in combination of two or more kinds.
[0102]
　The mixing ratio of the urethane-forming catalyst is not particularly limited, depending on the purpose and application, are set appropriately.
[0103]
　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.
[0104]
　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.
[0105]
　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).
[0106]
　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.
[0107]
　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.
[0108]
　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.
[0109]
　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.
[0110]
　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.
[0111]
　The phosphine compounds include, for example, bis (oxa diphenylphosphino) phosphine compound having 3 to 30 carbon atoms, such as ethane.
[0112]
　These carbodiimidization catalysts can be used alone or in combination of two or more.
[0113]
　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.
[0114]
　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.
[0115]
　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.
[0116]
　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.
[0117]
　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.
[0118]
　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 .
[0119]
　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.
[0120]
　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.
[0121]
　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, amyl acetate, e.g. , 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 grayed Call ether acetate (PMA), 3- methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate glycol ether esters such as, for example, 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 , methylene iodide, halogenated aliphatic hydrocarbons such as dichloroethane, for example, N- methylpyrrolidone, dimethylformamide, N, N ' Dimethylacetamide, 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.
[0122]
　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.
[0123]
　As such organic solvents, specifically, xylene, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate.
[0124]
　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.
[0125]
　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.
[0126]
　Then, by such a method, a urethane group and a carbodiimide group, and polycarbodiimide composition containing uretonimine groups optionally can be obtained.
[0127]
　More specifically, first, in the urethanization step, urethane groups derived from the isocyanate group of the polyisocyanate is formed.
[0128]
　Then, the reaction product obtained by the urethanization step (urethane modified product of polyisocyanate) is, when it is heated in the carbodiimidization process, carbodiimide groups derived from the isocyanate groups at the molecular terminal is produced, also optionally, some of the resulting carbodiimide groups react with the isocyanate groups at the molecular terminal, uretonimine groups is produced. Incidentally, uretonimine groups, is thermally decomposed by heating in the carbodiimidization process is continued, and carbodiimide groups, and isocyanate groups at the molecular terminal is reproduced, further, carbodiimide groups derived from the isocyanate groups at the molecular ends to produce .
[0129]
　In this manner, the isocyanate groups of the polyisocyanate is converted to urethane groups and carbodiimide groups (and, optionally uretonimine groups).
[0130]
　As a result, a urethane group and a carbodiimide group, and polycarbodiimide composition containing uretonimine groups optionally can be obtained.
[0131]
　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.
[0132]
　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.
[0133]
　In the second urethanization step, as the alcohol, polyoxyethylene-free alcohol include the above-mentioned.
[0134]
　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.
[0135]
　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.
[0136]
　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.
[0137]
　As 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.
[0138]
　Thus, an isocyanate group at the molecular ends of polycarbodiimide composition has a hydroxyl groups of alcohols is reacted urethanization.
[0139]
　As a result, no isocyanate group at the molecular end, or, polycarbodiimide composition isocyanate groups at the molecular ends is reduced is obtained.
[0140]
　Incidentally, when the second urethanization step is performed, the more by-products derived from alcohols, and when the molecular weight is increased drastically reduced fluidity, decreases the workability, addition, water-dispersible composition there are cases where dispersibility in the object is reduced. Therefore, preferably, without performing the second urethanization step, performed only the first urethanization process and carbodiimide process.
[0141]
　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.
[0142]
　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.
[0143]
　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.
[0144]
　Further, polycarbodiimide composition can be used alone or in combination of two or more kinds.
[0145]
　The content of oxyethylene groups polycarbodiimide composition thus obtained, as described above, for example, 5 wt% or more, preferably 10 mass% or more, more preferably 15 mass% or more, For example, 50 wt% or less, preferably 40 wt% or less, more preferably 35 mass% or less.
[0146]
　If the content is above the range of oxyethylene groups polycarbodiimide composition can be obtained both water-dispersed composition (described below) and solution composition.
[0147]
　And, in such a polycarbodiimide composition, primary polyisocyanate having an isocyanate group, a reaction product of an alcohol containing oxyethylene-containing alcohols and polyoxyethylene-free alcohols, the polyoxyethylene-free alcohol solubility parameter is less than or equal to the predetermined value.
[0148]
　Therefore, such a polycarbodiimide composition, film forming property, water resistance and chemical resistance and excellent cured resin can be obtained (see below), and excellent storage stability.
[0149]
　Specifically, by using a polycarbodiimide composition before storage, it is possible to obtain film-forming properties, water resistance and chemical resistance and excellent cured resin (to be described later). Further, it is possible to suppress a decrease in handling properties when stored the polycarbodiimide composition. Furthermore, in the case of using the polycarbodiimide composition after storage, it is possible to obtain film-forming properties, water resistance and chemical resistance and excellent cured resin (to be described later).
[0150]
　According to the manufacturing method of the polycarbodiimide composition, the polycarbodiimide composition can be efficiently produced.
[0151]
　The polycarbodiimide composition is excellent in storage stability and film forming property, it is possible to obtain the water resistance and the resin cured product excellent in chemical resistance, is preferably used as a curing agent in the resin composition.
[0152]
　Resin composition contains a curing agent containing a polycarbodiimide composition, the main agent having a carboxyl group.
[0153]
　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.
[0154]
　Aqueous dispersion composition contains a water polycarbodiimide composition.
[0155]
　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.
[0156]
　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.
[0157]
　If the curing agent is a water-dispersed composition, it is possible to improve the compatibility with the aqueous resin (main agent), also can be obtained film-forming properties, water resistance and the cured product excellent in chemical resistance . Moreover, such solutions composition because it contains the polycarbodiimide composition is excellent in storage stability.
[0158]
　The solution composition contains a polycarbodiimide composition and an organic solvent.
[0159]
　As the organic solvent, it includes organic solvents mentioned above, preferably, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene.
[0160]
　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.
[0161]
　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.
[0162]
　If hardener solution composition, it is possible to improve the compatibility with oil-based resin (main agent), also can be obtained film-forming properties, water resistance and the cured product excellent in chemical resistance . Moreover, such solutions composition because it contains the polycarbodiimide composition is excellent in storage stability.
[0163]
　The main agent having a carboxyl group, an aqueous resin having a carboxyl group and an oil-based resin having a carboxyl group.
[0164]
　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.
[0165]
　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.
[0166]
　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.
[0167]
　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.
[0168]
　These may be used alone or in combination of two or more.
[0169]
　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.
[0170]
　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.
[0171]
　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.
[0172]
　As the resin composition, preferably, a resin composition of two-pack type.
[0173]
　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.
[0174]
　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.
[0175]
　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.
[0176]
　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.).
[0177]
　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.
[0178]
　And, in such a resin composition, obtained as a curing agent, since the polycarbodiimide composition mentioned above is used, excellent storage stability and film forming property, water resistance and the resin cured product excellent in chemical resistance be able to.
[0179]
　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.
[0180]
　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.
[0181]
　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.
[0182]
　Further, if necessary, a heat cured resin cured product, may be further dried.
[0183]
　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.
[0184]
　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.
[0185]
　Then, the resulting cured resin are the cured product of the resin composition having excellent storage stability, is excellent in productivity, also film-forming property, excellent water resistance and chemical resistance.
[0186]
　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).
[0187]
　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, polyimide, resin modifier for modifying the resin such as polyvinyl alcohol, textile treatment agents, in various fields such as fiber treatment agent, is preferably used.
[0188]
　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), a paper coating composition, and the like thermal paper coating composition.
[0189]
　As the plastic coatings, 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 includes a 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 robot material, furniture coatings, for stationery paints, 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.
[0190]
　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.
[0191]
　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.
[0192]
　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.
[0193]
　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.).
[0194]
　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.
[0195]
　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.
[0196]
　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.
[0197]
　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.
[0198]
　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.) for the adhesive, LED adhesives, exterior-friendly adhesive in the automotive, consumer electronics adhesives, adhesive for building materials, adhesive for solar battery back sheets, various types of batteries (such as a lithium-ion battery) for the adhesive, such as and the like.
[0199]
　Further, as the ink resin, various inks (plate ink, screen ink, flexographic inks, gravure inks, jet inks, printing inks and the like) and the vehicle.
[0200]
　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
[0201]
　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.
[0202]
　　
　content of the oxyethylene groups with respect to polycarbodiimide composition was calculated from the charged amounts and chemical structure.
[0203]
　　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.
[0204]
　　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 34.6 parts by mass of UNIOX M400 (manufactured by NOF Corporation polyethylene glycol monomethyl ether molecular weight 400), and 9.6 parts by weight of charged isobutanol. While introducing nitrogen, warmed to 80 ° C. under normal pressure, and stirred for 6 hours (urethanization step).
[0205]
　Subsequently, PMA 302.8 parts by weight (propylene glycol monomethyl ether acetate), 3-methyl-1-phenyl-2-phospholene-1-oxide and (MPPO) and 2.0 parts by mass loading, reflux (150 ° C.) in was stirred for 7 hours, the reaction was terminated (carbodiimide step).
[0206]
　After completion of the reaction, was cooled to 80 ° C., the PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition. Some of the resulting polycarbodiimide composition was taken out and the measurement results of the E-type viscosity at 25 ° C., was 1100 mPa · s. Furthermore, some 2 months at 25 ° C. The resulting polycarbodiimide composition, after storage under a nitrogen atmosphere, the results of measurement of the E-type viscosity at 25 ° C., was 2500 mPa · s.
[0207]
　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. Further, 2 months at 25 ° C., for even polycarbodiimide composition was stored under nitrogen atmosphere, an aqueous dispersion was prepared in the same manner.
[0208]
　Preparation of solution (solution composition) of polycarbodiimide composition
　polycarbodiimide composition was placed in a flask, heated to 80 ° C., was added slowly butyl acetate so that the resin solid content of 40%. After stirring for 5 min, cooled to room temperature. This gave a solution of the polycarbodiimide composition. Further, 2 months at 25 ° C., for even polycarbodiimide composition was stored under nitrogen atmosphere, an aqueous dispersion was prepared in the same manner.
[0209]
　Preparation of the resin composition of the aqueous
　aqueous dispersion of a polycarbodiimide composition obtained 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.
[0210]
　Preparation of solvent-based resin composition
　solution of the polycarbodiimide obtained composition was used as a curing agent. Then, a curing agent 1.0 part by mass, the acrylic resin as the main agent (solid content 50 mass%, the carboxyl group equivalent 2004g / mol solids) and 39.2 parts by mass, 59.8 parts by weight of butyl acetate as solvent mixing the door, to prepare a resin composition.
[0211]
　Example 2
　except for using 9.6 parts by mass charged to 2-butanol instead of isobutanol to give a polycarbodiimide composition in the same manner as in Example 1.
[0212]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0213]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0214]
　Example 3
　11.4 parts by weight of 2-methyl-1-butanol in place of isobutanol, except that charged 306.5 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0215]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0216]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0217]
　Example 4
　11.4 parts by weight of 2,2-dimethyl-1-propanol in place of iso-butanol, except that charged 306.5 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0218]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0219]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0220]
　Example 5
　13.5 parts by mass of 3-methoxy-1-butanol in place of isobutanol, except that charged 310.8 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0221]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0222]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0223]
　Example 6
　16.9 parts by weight of 1-octanol instead of isobutanol, except that charged 317.8 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0224]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0225]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0226]
　Example 7
　16.9 parts by mass of 2-ethyl-1-hexanol in place of isobutanol, except that charged 317.8 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0227]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0228]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0229]
　Example 8
　24.2 parts by weight of 1-dodecanol instead of isobutanol, except that charged 332.9 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0230]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0231]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0232]
　Example 9
　35.1 parts by mass of 1-octadecanol in place of isobutanol, except that charged 355.5 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0233]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0234]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition. However, two months at 25 ° C., polycarbodiimide composition was stored under a nitrogen atmosphere would be solidified (hardened product was waxy), it was not possible to obtain aqueous dispersion.
[0235]
　Example 10
　UNIOX M400 43.2 parts by weight 24.0 parts by weight of isobutanol, the PMA was charged 350.6 parts by weight, the embodiment except that the reaction time of the carbodiimidization step 6.5 hours to obtain a polycarbodiimide composition in the same manner as example 1.
[0236]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0237]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0238]
　Example 11
　23.1 parts by mass of UNIOX M400, 6.4 parts by weight of isobutanol, the PMA was charged 272.2 parts by weight, except for changing the reaction time of the carbodiimidization step 8 hours Example 1 to obtain a polycarbodiimide composition in the same manner as.
[0239]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0240]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0241]
　Example 12
　12.4 parts by weight of UNIOX M400, 13.7 parts by weight of isobutanol, except that charged 265.2 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0242]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0243]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and was prepared a resin composition for water dispersion, slightly hard spots was confirmed. Thereafter, to prepare a resin composition in the same manner as in Example 1.
[0244]
　Example 13
　a UNIOX M400 74.1 parts by weight 2.3 parts by weight of isobutanol, except that charged 369.5 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0245]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0246]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0247]
　Example 14
　9.6 parts by mass charged tert- butanol in place of isobutanol, except that the reaction time of the urethanization step 12 hours to obtain a polycarbodiimide composition in the same manner as in Example 1.
[0248]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0249]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0250]
　Example 15
　stirrer, thermometer, reflux condenser, and a four-necked flask equipped with a nitrogen inlet tube, at room temperature, 1,3-xylylene 100.0 parts by mass of isocyanate, the Uniox M400 28.3 parts by weight, and 7.9 parts by weight of charged isobutanol. While introducing nitrogen, warmed to 80 ° C. under normal pressure, and stirred for 2 hours (urethanization step).
[0251]
　Subsequently, 286.2 parts by weight of xylene, 3-methyl-1-phenyl-2-phospholine-1-oxide and 2.0 parts by mass charged, 3 hours and stirred at reflux (141 ° C.), the reaction It was allowed to end (carbodiimide step).
[0252]
　After completion of the reaction, was cooled to 80 ° C., the xylene was distilled off under reduced pressure to obtain a polycarbodiimide composition.
[0253]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0254]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0255]
　Example 16
　stirrer, thermometer, reflux condenser, and a four-necked flask equipped with a nitrogen inlet tube, at room temperature, 1,3-bis 100.0 parts by mass of (isocyanatomethyl) cyclohexane, Uniox M400 27.5 parts by mass, and 7.6 parts by weight of charged isobutanol. While introducing nitrogen, warmed to 80 ° C. under normal pressure, and stirred for 7 h (urethanization step).
[0256]
　Subsequently, 283.9 parts by mass of PMA, 3- methyl-1-phenyl-2-phospholine-1-oxide and 2.0 parts by mass charged, and stirred for 9 hours under reflux (0.99 ° C.), the reaction It was allowed to end (carbodiimide step).
[0257]
　After completion of the reaction, was cooled to 80 ° C., the PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition.
[0258]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0259]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0260]
　Example 17
　stirrer, thermometer, reflux condenser, and a four-necked flask equipped with a nitrogen inlet tube, at room temperature, 100.0 parts by weight of isophorone diisocyanate, the UNIOX M400 33.0 parts by weight of isobutanol was 8.1 parts by weight charged. While introducing nitrogen, warmed to 80 ° C. under normal pressure, and stirred for 7 h (urethanization step).
[0261]
　Subsequently, 296.2 parts by mass of PMA, 3- methyl-1-phenyl-2-phospholine-1-oxide and 2.0 parts by mass charged, and stirred for 9 hours under reflux (0.99 ° C.), the reaction It was allowed to end (carbodiimide step).
[0262]
　After completion of the reaction, was cooled to 80 ° C., the PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition.
[0263]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0264]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0265]
　Example 18
　100 parts by weight of hexamethylene diisocyanate instead of pentamethylene diisocyanate, 31.7 parts by mass of UNIOX M400, 8.8 parts by weight of isobutanol, except that charged 295.1 parts by weight of PMA Example to obtain a polycarbodiimide composition in the same manner as 1.
[0266]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0267]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and to prepare a resin composition.
[0268]
　Comparative Example 1
　4.2 part by weight of methanol instead of isobutanol, except that charged 291.5 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0269]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0270]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and is to prepare a resin composition, 2 months, polycarbodiimide composition was stored under nitrogen atmosphere at 25 ° C. The solidified will be (solidified product was rubbery), it was not possible to obtain aqueous dispersions and solutions.
[0271]
　Comparative Example 2
　except that 9.6 parts by mass charged 1-butanol instead of isobutanol to give a polycarbodiimide composition in the same manner as in Example 1.
[0272]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0273]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and is to prepare a resin composition, 2 months, polycarbodiimide composition was stored under nitrogen atmosphere at 25 ° C. The solidified will be (solidified product was rubbery), it was not possible to obtain aqueous dispersions and solutions.
[0274]
　Comparative Example 3
　11.7 weight parts of 1-methoxy-2-propanol in place of iso-butanol, except that charged 307.1 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0275]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0276]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and is to prepare a resin composition, 2 months, polycarbodiimide composition was stored under nitrogen atmosphere at 25 ° C. The solidified will be (solidified product was rubbery), it was not possible to obtain aqueous dispersions and solutions.
[0277]
　Comparative Example 4
　13.0 parts by weight of cyclohexanol instead of isobutanol, except that charged 309.8 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0278]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0279]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and is to prepare a resin composition, 2 months, polycarbodiimide composition was stored under nitrogen atmosphere at 25 ° C. The solidified will be (solidified product was rubbery.), it was not possible to obtain aqueous dispersions and solutions.
[0280]
　Comparative Example 5
　14.0 parts by weight of benzyl alcohol in place of isobutanol, except that charged 311.9 parts by weight of PMA was obtained polycarbodiimide composition in the same manner as in Example 1.
[0281]
　Further, the obtained polycarbodiimide composition, the viscosity was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.
[0282]
　Further, in the same manner as in Example 1, aqueous dispersions of polycarbodiimides composition and was prepared and is to prepare a resin composition, 2 months, polycarbodiimide composition was stored under nitrogen atmosphere at 25 ° C. The solidified will be (solidified product was rubbery), it was not possible to obtain aqueous dispersions and solutions.
[0283]
　Comparative Example 6
　16.1 parts by weight of 4-methoxyphenol in place of isobutanol, but except that 316.2 parts by mass charged PMA was obtained polycarbodiimide composition in the same manner as in Example 1, under reduced pressure to PMA when you are evaporated under gradually thickened, since it had solidified (solidified product was rubbery), it was not possible to obtain aqueous dispersion of the polycarbodiimide and solutions.
[0284]
　　Comparative Example 7
　The method described in JP-A-10-316930 Synthesis Example 83 of Japanese were synthesized polycarbodiimide composition reference.
[0285]
　Specifically, stirrer, thermometer, reflux condenser, and a four-necked flask equipped with a nitrogen inlet tube, at room temperature, 1008 parts by weight of hexamethylene diisocyanate, Uniox M400 (manufactured by NOF Corporation polyethylene glycol monomethyl the ether molecular weight 400) was 800 parts by mass charged. While introducing nitrogen, heated to 120 ° C. under normal pressure, and stirred for 1 hour. Subsequently, a 3-methyl-1-phenyl-2-phospholene-1-oxide and 13.5 parts by mass charged, tried stirring warmed 5 hours 185 ° C. in a nitrogen stream, two hours reaction solution was passed has solidified (hardened product was rubbery.).
[0286]
　Thereafter, tried the preparation of aqueous dispersions and solutions of similarly polycarbodiimide composition as in Example 1, polycarbodiimide composition ends up settling, the aqueous dispersion and solution was not obtained.
[0287]
　　

　stability test at · 40 ° C.
　Put 1.0 part by weight polycarbodiimide obtained composition in a screw bottle 10 mL, after the nitrogen blow, was capped with a screw cap, 40 stored at ° C., (in the upside down bottle until polycarbodiimide does not flow) until fluidity is lost was observed. Was also similarly tested solution prepared polycarbodiimide composition.
4 took one month or more to liquidity disappears.
3 was less than 1 month or more 2 weeks until fluidity is lost.
Until 2 fluidity disappeared was less than 2 weeks a week or more.
Was less than 1 week to 1 fluidity is lost.

　Evaluation of Coating film
　with 250 mil doctor blade, after applying the resin composition to a standard test plate (JIS-G-3303 SPTE) , dried for 10 minutes and 30 minutes at 80 ° C., further at room temperature in dried 1 hour to obtain a coating film made of the cured resin. The resulting coating film was evaluated by the following methods.
[0288]
　
　was evaluated the appearance of the coating film (80 ° C. 10 min) visually. The criteria for evaluation described below.
Smooth coating film has been confirmed in good clear.
Bad thingy has been confirmed.
[0289]
　
　on the coating film (80 ° C. 10 min), distilled water and spots were visually observed the change of the coating film appearance after 23 ° C. 24 hours. The criteria for evaluation described below.
Favorable change was not confirmed.
Failure whitening has been confirmed.
[0290]
　
　the overcoat (80 ° C. 10 minutes and 30 minutes), in the case of water-based resin composition, methyl ethyl ketone, 50% ethanol aqueous solution in the case of the resin composition of the solvent system a gauze impregnated with, rubbing while pressing with a load of 50g, was measured the number of times until the crack coating film. The criteria for evaluation described below.
4 300 times more in the coating film was cracked
coating was cracked in less than 3 250 times more than 300 times.
Coating was cracked at less than 250 times more than 100 times.
Coating was cracked at less than 1 100 times.
[0291]
[Table 1]

[0292]
[Table 2]

[0293]
[table 3]

[0294]
[Table 4]

[0295]
　The above invention has been provided as illustrative embodiments of the present invention, this is merely illustrative and should not be construed restrictively. Modification of the present invention that will be obvious to those skilled in the art will be covered by the following claims.
Industrial Applicability
[0296]
　Polycarbodiimide composition of the present invention, a method of manufacturing a polycarbodiimide composition, aqueous dispersion composition, solution composition, the resin composition and the cured resin, coating material, adhesive material (adhesive), adhesive material (adhesive) , inks, sealants, molding materials, foams and optical materials, resin modifiers, textile treating agents, in various fields such as fiber treatment agent, is preferably used.

The scope of the claims
[Requested item 1]
A polyisocyanate having a primary isocyanate groups, the reaction product of an alcohol,
the alcohol is
at least one oxyethylene-containing alcohol containing oxyethylene groups,
　at least one not containing an oxyethylene group oxyethylene-free alcohol
wherein the
　solubility parameter of at least one of said oxyethylene-free alcohol, 11.20 (cal / cm 3 ) 1/2 or less
and wherein the polycarbodiimide composition .
[Requested item 2]
　The content of oxyethylene groups, wherein the relative polycarbodiimide composition is 35 mass% to 10 mass%
, wherein the polycarbodiimide composition of claim 1.
[Requested item 3]
　Solubility parameter of 11.20 (cal / cm 3 ) 1/2 the polyoxyethylene-free alcohol is less,
　primary alcohols and / or secondary alcohol
, characterized in that, according to claim 1 polycarbodiimide composition.
[Requested item 4]
　Solubility parameter of 11.20 (cal / cm 3 ) 1/2 the polyoxyethylene-free alcohol or less is
　a monovalent alcohol containing less 12 or 4 or more carbon atoms
and wherein the claim polycarbodiimide composition according to 1.
[Requested item 5]
　Solubility parameter of 11.20 (cal / cm 3 ) 1/2 or less the polyoxyethylene-free alcohol,
　isobutanol, 2-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol , 3-methoxy-1-butanol, 1-octanol, is at least one selected from the group consisting of 2-ethyl-1-hexanol and 1-dodecanol
, wherein the polycarbodiimide of claim 1 Composition.
[Requested item 6]
　The polyisocyanate is an aliphatic polyisocyanate
, characterized in that, polycarbodiimide composition of claim 1.
[Requested item 7]
　The polyisocyanate is a pentamethylene diisocyanate
, wherein the polycarbodiimide composition of claim 1.
[Requested item 8]
　A polyisocyanate having a primary isocyanate group, and urethanization step of reacting urethanization and alcohols,
　the reaction product in the urethanization step, by heating in the presence of a carbodiimidization catalyst, carbodiimidization step of carbodiimidization DOO
equipped with,
　the alcohols,
　and at least one oxyethylene-containing alcohol containing oxyethylene groups,
　and at least one polyoxyethylene-free alcohol not containing an oxyethylene group
comprises,
　at least one of said oxy solubility parameter of the ethylene-free alcohol, 11.20 (cal / cm 3 ) 1/2 or less
and wherein the method for producing a polycarbodiimide composition.
[Requested item 9]
　To the hydroxyl group of the alcohol, the equivalent ratio of the isocyanate groups of the polyisocyanate (NCO / OH), characterized in that exceed 2 is 10 or less,
the production method of the polycarbodiimide composition according to claim 8 .
[Requested item 10]
　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.
[Requested item 11]
　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.
[Requested item 12]
　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.
[Requested item 13]
　Characterized in that it is a cured product of the resin composition according to claim 12, cured resin.