Title of the invention: Polycarbodiimide composition, method for producing a polycarbodiimide composition, aqueous dispersion composition, solution composition, resin composition, cured resin, and carbodiimide cross-linking agent for fiber treatment.
Technical field
[0001]
　The present invention relates to a polycarbodiimide composition, a method for producing a polycarbodiimide composition, an aqueous dispersion composition, a solution composition, a resin composition, a cured resin product, and a carbodiimide cross-linking agent for fiber treatment.
Background technology
[0002]
　Conventionally, in the fields of adhesives, coating agents and the like, resin compositions containing a main agent and a curing agent are known, and as a curing agent, for example, a carbodiimide-based curing agent is known.
[0003]
　More specifically, pentamethylene diisocyanate and polyethylene glycol monomethyl ether having a molecular weight of 550 and 1-methoxy-2-propanol (both monool) are subjected to a urethanization reaction, followed by a carbodiimidization reaction, and further, 1-. A polycarbodiimide composition obtained by adding methoxy-2-propanol to a urethanization reaction has been proposed (see, for example, Patent Document 1 (Example 1)).
[0004]
　Then, by drying and curing the resin composition composed of such a polycarbodiimide composition (curing agent) and the main agent, a cured resin product such as a coating film can be obtained.
[0005]
　The polycarbodiimide composition and the resin composition are excellent in low-temperature quick-curing property, and the obtained resin cured product is excellent in various physical properties such as water resistance and chemical resistance.
Prior art literature
Patent documents
[0006]
Patent Document 1: International Publication WO2017 / 119443
Outline of the invention
Problems to be solved by the invention
[0007]
　On the other hand, the polycarbodiimide composition may be required to have thermal stability depending on the application, and the cured resin product may be required to have further chemical resistance depending on the application. In particular, for example, in fiber processing applications, frictional fastness is required when printing is performed at a relatively low temperature.
[0008]
　INDUSTRIAL APPLICABILITY According to the present invention, a cured product having excellent chemical resistance can be obtained, a polycarbodiimide composition having excellent thermal stability, a method for producing the polycarbodiimide composition, an aqueous dispersion composition containing the polycarbodiimide composition, and an aqueous dispersion composition containing the polycarbodiimide composition. A solution composition, a resin composition containing a polycarbodiimide composition, a cured resin product obtained by curing the resin composition, and an attempt to improve friction fastness when printing at a relatively low temperature. It is a carbodiimide cross-linking agent for fiber treatment that can be used.
Means to solve problems
[0009]
　The present invention [1] is a polycarbodiimide composition containing a carbodiimide modified product of a reaction product of a linear aliphatic diisocyanate and alcohols, wherein the alcohols contain a polyol and a monool, and in the alcohols. The molar ratio of the number of hydroxyl groups derived from the polyol (hydroxyl group derived from polyol / hydroxyl group derived from monool) to the number of hydroxyl groups derived from monool is less than 2.0, and the carbodiimide equivalent of the polycarbodiimide composition is 300 g / g. It contains a polycarbodiimide composition of mol or more and less than 550 g / mol.
[0010]
　The present invention [2] includes the polycarbodiimide composition according to the above [1], wherein the polyol has a molecular weight of 120 or more and 1000 or less.
[0011]
　The present invention [3] includes the polycarbodiimide composition according to the above [1] or [2], wherein the polyol has an average number of functional groups of 2.
[0012]
　The present invention [4] contains the polycarbodiimide composition according to any one of the above [1] to [3], wherein the linear aliphatic diisocyanate is 1,5-pentanediisocyanate.
[0013]
　In the present invention [5], in the chromatogram when the polycarbodiimide composition is measured by gel permeation chromatograph, the area ratio of the peak area having a polystyrene-equivalent molecular weight of 500 or less to the total peak area is 6.5% or less. The polycarbodiimide composition according to any one of the above [1] to [4], wherein the area ratio of the peak area having a polystyrene-equivalent molecular weight of 1000 or less to the total peak area is 10.0% or less. I'm out.
[0014]
　In the present invention [6], a urethanization step in which a linear aliphatic diisocyanate and alcohols are urethanized, and a reaction product in the urethanization step is heated in the presence of a carbodiimidization catalyst to cause a carbodiimidation reaction. The alcohols include a polyol and monool, and the alcohols include a molar ratio of the number of hydroxyl groups derived from the polyol to the number of hydroxyl groups derived from the monool (hydroxyl derived from polyol / derived from monool). The equivalent ratio (NCO / OH) of the isocyanate group of the linear aliphatic diisocyanate to the total amount of the hydroxyl group of the monool and the hydroxyl group of the polyol in the urethanization step. Includes a method for producing a polycarbodiimide composition of 3 or more and less than 8.
[0015]
　In the present invention [7], the polycarbodiimide composition according to any one of the above [1] to [5] is dispersed in water at a solid content concentration of 5% by mass or more and 90% by mass or less. Contains an aqueous dispersion composition that is a liquid.
[0016]
　The present invention [8] is a solution in which the polycarbodiimide composition according to any one of the above [1] to [5] is dissolved in an organic solvent at a solid content concentration of 5% by mass or more and 90% by mass or less. Contains a solution composition.
[0017]
　The present invention [9] includes a resin composition containing a main agent having a carboxyl group and a curing agent containing the polycarbodiimide composition according to any one of the above [1] to [5]. ..
[0018]
　The present invention [10] includes a cured resin product, which is a cured product of the resin composition according to the above [9].
[0019]
　The present invention [11] contains a carbodiimide cross-linking agent for fiber treatment, which comprises the polycarbodiimide composition according to the above [1].
Effect of the invention
[0020]
　In the polycarbodiimide composition of the present invention, since the alcohols as the raw material components contain the polyol and monool in a predetermined ratio, the carbodiimide modified product has a higher molecular weight than the case where the alcohols do not contain the polyol. .. Specifically, a prepolymer is obtained by reacting a linear aliphatic diisocyanate with an alcohol containing a polyol, and the prepolymer is carbodiimided, so that a relatively high molecular weight carbodiimide modified product can be obtained. As a result, a cured film having excellent chemical resistance can be obtained from the polycarbodiimide composition.
[0021]
　On the other hand, if the carbodiimide modified product has an excessively high molecular weight, it tends to thicken and may be inferior in thermal stability. On the other hand, in the polycarbodiimide composition of the present invention, since the ratio of the polyol and the monool is adjusted in the carbodiimide modified product, the molecular weight is only appropriately increased and the heat stability is also excellent.
[0022]
　Further, in the polycarbodiimide composition of the present invention, since the carbodiimide equivalent is adjusted to a predetermined ratio, a cured film having excellent appearance and chemical resistance can be obtained.
[0023]
　Therefore, the polycarbodiimide composition of the present invention, the aqueous dispersion composition of the present invention containing the polycarbodiimide composition, the solution composition of the present invention, and the resin composition of the present invention containing the polycarbodiimide composition are thermally stable. A cured product having excellent properties and further excellent appearance and chemical resistance can be obtained.
[0024]
　Further, the cured resin product of the present invention is excellent in appearance and chemical resistance.
[0025]
　Further, since the carbodiimide cross-linking agent for fiber treatment of the present invention contains the above-mentioned polycarbodiimide composition, it is possible to improve the friction fastness when the printing treatment is performed at a relatively low temperature (120 ° C. or lower).
A brief description of the drawing
[0026]
FIG. 1 shows a GPC chromatogram of the polycarbodiimide composition obtained in Example 1.
Mode for carrying out the invention
[0027]
　The polycarbodiimide composition of the present invention contains, as a main component (for example, at a ratio of 90% by mass or more with respect to the polycarbodiimide composition), a carbodiimide modified product of a reaction product of a linear aliphatic diisocyanate and alcohols. To do.
[0028]
　The carbodiimide modified product can be obtained by subjecting a reaction product of a linear aliphatic diisocyanate to an alcohol to a carbodiimideization reaction.
[0029]
　Examples of the linear aliphatic diisocyanis include ethylene diisocyanis, 1,3-propanediisocyanis, 1,4-butane diisocyanis, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), and 1,6-hexane diisocyanate (hexamethylene). Diisocyanis, HDI) 1,8-octane diisocyanate (octamethylene diisocyanate), 1,12-dodecane diisocyanis (dodecamethylene diisocyanate) and other linear aliphatic diisocyanates having 1 to 20 carbon atoms can be mentioned.
[0030]
　These linear aliphatic diisocyanates can be used alone or in combination of two or more.
[0031]
　By using a linear aliphatic diisocyanate, a polycarbodiimide composition having excellent thermal stability can be obtained, and a cured resin product (described later) having excellent appearance and chemical resistance can be obtained. In addition, fibers can be obtained. It is possible to improve low temperature curability and friction fastness in applications of carbodiimide curing agents for treatment (described later).
[0032]
　As a linear aliphatic diisocyanate, 1,5- is preferable from the viewpoint of thermal stability, appearance and chemical resistance, as well as low temperature curability and friction fastness in the use of a carbodiimide hardener for fiber treatment (described later). Pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI) can be mentioned, and 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI) can be mentioned more preferably.
[0033]
　In particular, 1,5-pentane diisocyanate has a smaller number of carbon atoms and a smaller molecular weight than 1,6-hexane diisocyanate. Therefore, when producing a polycarbodiimide composition having the same molecular weight, 1,5-pentane diisocyanate is used. , The carbodiimide group concentration in the polycarbodiimide composition can be increased as compared with the case of using 1,6-hexane diisocyanate. As a result, a polycarbodiimide composition excellent in low-temperature quick-curing property can be obtained, and further, a resin cured product (described later) excellent in various physical properties (appearance, chemical resistance, etc.) can be obtained. Further, 1,5-pentanediisocyanate having an odd number of carbon atoms has lower crystallinity due to an amorphous structure derived from an odd number of carbon atoms than 1,6-hexanediisocyanate having an even number of carbon atoms. It is excellent in dispersibility, and the physical properties of the obtained cured resin product (described later) are improved. In addition, the low temperature curability and friction fastness in the use of the carboniimide curing agent for fiber treatment (described later) are improved.
[0034]
　Furthermore, when 1,5-pentamethylene diisocyanate is used, thermal decomposition of the uretonimine group, which will be described later, is more likely to occur than when 1,6-hexamethylene diisocyanate is used, so that a polycarbodiimide composition can be obtained in good yield. it can. Moreover, since it can be handled even at a low temperature, it is possible to suppress the increase in the molecular weight of uretonimine.
[0035]
　Alcohols include polyols and monools, preferably consisting of polyols and monools.
[0036]
　The polyol is an organic compound having two or more hydroxyl groups in the molecule, and examples thereof include a monomer polyol and a polymer polyol.
[0037]
　The monomeric polyol is an organic monomer (single compound (same below)) having two or more hydroxyl groups in the molecule, and is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butane. Diol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol , 1,14-, Tetradecanediol, 1,16-Hexadecandiol, 1,18-Octadecanediol, 1,20-Eicosandiol, Neopentyl glycol, 3-Methyl-1,5-Pentanediol, 2,2 2-trimethylpentanediol, 3,3-dimethylolheptan, alkane (C2-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol And their mixtures, bisphenol hydride A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, etc. Dihydric alcohols such as trivalent alcohols such as glycerin, trimethylolpropane, triisopropanolamine, eg tetravalent alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, eg pentavalent alcohols such as xylitol, eg Hexic alcohols such as sorbitol, mannitol, aritol, iditol, darsitol, altritor, inositol and dipentaerythritol, for example, heptavalent alcohols such as persetol, for example, octavalent alcohols such as sucrose and the like can be mentioned.
[0038]
　These monomeric polyols can be used alone or in combination of two or more.
[0039]
　As the monomeric polyol, a dihydric alcohol is preferably used, and 1,6-hexanediol and 1,10-decanediol are more preferable.
[0040]
　The polymer polyol is an organic polymer having two or more hydroxyl groups in the molecule (polymerized compound (the same applies hereinafter)), for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyurethane polyol, an epoxy polyol, a vegetable oil polyol, and a polyolefin. Examples thereof include polyols, acrylic polyols and vinyl monomer-modified polyols, and preferred examples include polyether polyols, polyester polyols and polycarbonate polyols.
[0041]
　Examples of the polyether polyol include a polyoxyalkylene (2 to 3 carbon atoms) polyol and a polytetramethylene ether polyol.
[0042]
　Examples of the polyoxyalkylene (2 to 3 carbon atoms) polyol include addition polymerization of an alkylene oxide having 2 to 3 carbon atoms using a monomer polyol or a known monomer (low molecular weight) polyamine as an initiator. Things can be mentioned.
[0043]
　Examples of the monomeric polyol include the above-mentioned monomeric polyols, preferably dihydric alcohols and trihydric alcohols, and more preferably dihydric alcohols.
[0044]
　Examples of the alkylene oxide having 2 to 3 carbon atoms include propylene oxide (1,2-propylene oxide) and ethylene oxide. In addition, these alkylene oxides can be used alone or in combination of two or more.
[0045]
　Specific examples of the polyoxyalkylene (2 to 3 carbon atoms) polyol include polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene-polyoxypropylene glycol (random and / or ethylene oxide of propylene oxide and ethylene oxide). Block copolymer) and the like.
[0046]
　Further, as the polyoxyalkylene (2 to 3 carbon atoms) polyol, polytrimethylene glycol and the like are also included.
[0047]
　Examples of the polytrimethylene ether glycol include glycols obtained by a polycondensation reaction of 1,3-propanediol derived from a plant component.
[0048]
　Examples of the polytetramethylene ether polyol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (polytetramethylene ether glycol (crystalline)), alkyl-substituted tetrahydrofuran in a polymerization unit such as tetrahydrofuran, and the above-mentioned divalent. Examples thereof include amorphous (non-crystalline) polytetramethylene ether glycol obtained by copolymerizing alcohol.
[0049]
　Examples of the polyester polyol include a polycondensate obtained by reacting a monomeric polyol with a polybasic acid under known conditions.
[0050]
　Examples of the monomeric polyol include the above-mentioned monomeric polyol, and preferably a dihydric alcohol.
[0051]
　Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Saturated aliphatic dicarboxylic acids (C11-13) such as azelaic acid, sebacic acid, eg unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, eg phthalic acid, isophthalic acid, terephthalic acid, toluene Aromatic dicarboxylic acids such as dicarboxylic acids and naphthalenedicarboxylic acids, such as alicyclic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, het acid, and their carboxylic acids. Acid anhydrides derived from acids such as oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (C12-C18) succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and further. Examples include acid halides derived from these carboxylic acids and the like, such as oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.
[0052]
　These polybasic acids can be used alone or in combination of two or more.
[0053]
　Preferred examples of the polybasic acid include saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and acid anhydrides.
[0054]
　Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, the above-mentioned monomer polyol is used as an initiator, and a hydroxyl group-containing vegetable oil fatty acid (for example, a castor oil fatty acid containing ricinoleic acid, 12-hydroxysteare). Examples thereof include a vegetable oil-based polyester polyol obtained by subjecting a hydroxycarboxylic acid such as an acid-containing hydrogenated castor oil fatty acid) to a condensation reaction under known conditions.
[0055]
　Further, as the polyester polyol, for example, lactones such as ε-caprolactone and γ-valerolactone, for example, L-lactide, using the above-mentioned monomer polyol (preferably 2-trivalent alcohol) as an initiator. , D-lactide and the like obtained by ring-opening polymerization of lactides and the like, lactone-based polyester polyols such as polycaprolactone polyols and polyvalerolactone polyols, and further, alcohols obtained by copolymerizing the above dihydric alcohols with them. Examples include modified lactone polyols.
[0056]
　Examples of the polycarbonate polyol include a ring-opening polymer (crystalline polycarbonate polyol) of ethylene carbonate using the above-mentioned monomer polyol (preferably the above-mentioned dihydric alcohol) as an initiator, and for example, a polycarbonate polyol having 4 to 6 carbon atoms. Acyclic in which a dihydric alcohol (1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc.) and a ring-opening polymer are copolymerized. Sexual polycarbonate polyol and the like can be mentioned. In addition, a plant-derived polycarbonate polyol derived from a plant-derived raw material such as isosorbide can be mentioned. Amorphous means that it is liquid at room temperature (25 ° C.). Further, crystallinity indicates that it is solid at room temperature (25 ° C.).
[0057]
　These polymer polyols can be used alone or in combination of two or more.
[0058]
　As the polymer polyol, from the viewpoint of improving the thermal stability of the polycarbodiimide composition and improving the low temperature curability and friction fastness in the use of the carbodiimide curing agent for fiber treatment (described later), the polyether polyol is preferable. , Polyester polyol (preferably lactone-based polyester polyol), more preferably a polyether polyol, and further preferably a polytetramethylene ether polyol.
[0059]
　These polyols can be used alone or in combination of two or more.
[0060]
　Preferred examples of the polyol include polymer polyols.
[0061]
　The molecular weight of the polyol (the average molecular weight of the polyol when used in combination) is the thermal stability of the polycarbodiimide composition, as well as the low temperature curability and friction fastness in the use of carbodiimide curing agents for fiber treatment (described later). From the viewpoint of improving the above, for example, it is 60 or more, preferably 100 or more, more preferably 120 or more, still more preferably 150 or more, particularly preferably 200 or more, and the chemical resistance of the cured resin product (described later). From the viewpoint of, for example, 5000 or less, preferably 2000 or less, more preferably 1000 or less, still more preferably 800 or less, and particularly preferably 500 or less.
[0062]
　When the molecular weight of the polyol is in the above range, the polycarbodiimide composition can obtain excellent thermal stability, and a cured resin product (described later) having excellent chemical resistance can be obtained. In addition, the fiber Excellent low temperature curability and friction fastness in applications of carbodiimide curing agents for treatment (described later) can be obtained.
[0063]
　The molecular weight of the monomeric polyol can be calculated from the molecular skeleton and the number of atoms. Further, the molecular weight of the polymer polyol is determined as a number average molecular weight as a standard polystyrene-equivalent molecular weight measured by gel permeation chromatograph measurement. Then, the molecular weight of the polyol is calculated as an average value of the molecular weights of each component.
[0064]
　The average number of functional groups of the polyol is, for example, 2 or more from the viewpoint of improving the thermal stability of the polycarbodiimide composition, as well as the low temperature curability and frictional fastness in the use of the carbodiimide curing agent for fiber treatment (described later). For example, 8 or less, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, and particularly preferably 2.
[0065]
　The monool is an organic compound having one hydroxyl group in the molecule, and examples thereof include monomer monool and polymer monool.
[0066]
　The monomeric monool is an organic monomer having one hydroxyl group in the molecule, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol, hexanol, cyclohexanol, heptanol. , Octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol (10 carbons), lauryl alcohol (12 carbons), cetyl alcohol (14 carbons), stearyl alcohol (18 carbons), oleyl alcohol (carbons) Number 18), aliphatic monools such as eikosanol (20 carbon atoms), for example, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol monomethyl ether (also known as methyl cellosolve), diethylene glycol monoethyl ether ( Ether monools such as (also known as ethyl carbitol), such as phenol and its derivatives, benzyl alcohol and its derivatives, phenethyl alcohol and its derivatives, aromatic alcohols such as naphthol and its derivatives, and the like.
[0067]
　These monomeric monools can be used alone or in combination of two or more.
[0068]
　The monomeric monool preferably includes an aliphatic monool, more preferably an aliphatic monool having 2 to 6 carbon atoms, and further preferably isobutanol.
[0069]
　The polymer monool is an organic polymer having one hydroxyl group in the molecule, and
examples thereof include a sealant in which the end of the polymer polyol is sealed with an alkyl group or the like except for one end. ..
[0070]
　More specifically, for example, a sealant in which one end of a bifunctional polymer polyol (polymer diol) is sealed with an alkyl group or the like (hereinafter, may be referred to as a one-end sealed polymer diol). And so on.
[0071]
　Examples of the one-ended sealed polymer diol include one-ended sealed polyether diol, one-ended sealed polyester diol, one-ended sealed polycarbonate diol, one-ended sealed polyurethane diol, one-ended sealed epoxy diol, and one-ended sealed polymer diol. Examples thereof include sealed vegetable oil diols, one-ended sealed polyolefin diols, one-ended sealed acrylic diols, one-ended sealed vinyl monomer modified diols, and preferably one-ended sealed polyether diols.
[0072]
　More preferably, the one-ended sealed polyether diol includes one-ended sealed polyoxyethylene glycol, one-ended sealed polyoxyethylene-polyoxypropylene glycol, and the like.
[0073]
　The one-terminal sealed polyoxyethylene glycol is a polyethylene glycol monoalkyl ether in which one terminal hydroxyl group of the polyoxyethylene glycol is sealed with an alkyl group (that is, the hydroxyl group is replaced with an oxyalkylene group).
[0074]
　The one-ended sealed polyoxyethylene-polyoxypropylene glycol is not particularly limited and can be obtained by a known method.
[0075]
　In polyethylene glycol monoalkyl ether, the number of carbon atoms of the alkyl group is 1 or more, for example, 20 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. Is. That is, examples of the alkyl group for sealing one end include a methyl group and an ethyl group.
[0076]
　Specific examples of such polyethylene glycol monoalkyl ether include polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.
[0077]
　One-ended sealed polyoxyethylene-polyoxypropylene glycol is a polyoxyethylene-poly in which one terminal hydroxyl group of polyoxyethylene-polyoxypropylene glycol is sealed with an alkyl group (that is, the hydroxyl group is replaced with an oxyalkylene group). Oxypropylene glycol monoalkyl ether.
[0078]
　The one-ended sealed polyoxyethylene-polyoxypropylene glycol is not particularly limited and can be obtained by a known method. Specifically, for example, ethylene oxide and propylene oxide are added using a monohydric alcohol (such as monoalkyl ether of dipropylene glycol) in which one terminal hydroxyl group of the above-mentioned dihydric alcohol is sealed with an alkyl group as an initiator. It can be obtained by reacting.
[0079]
　In the polyoxyethylene-polyoxypropylene glycol monoalkyl ether, the number of carbon atoms of the alkyl group is 1 or more, for example, 20 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less. Particularly preferably, it is 2 or less. That is, as the alkyl group for sealing one end, preferably, a methyl group and an ethyl group can be mentioned.
[0080]
　Specific examples of such polyoxyethylene-polyoxypropylene glycol monoalkyl ether include polyoxyethylene-polyoxypropylene glycol monomethyl ether and polyoxyethylene-polyoxypropylene glycol monoethyl ether.
[0081]
　Further, in the polyoxyethylene-polyoxypropylene glycol monoalkyl ether, the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group is, for example, 1% by mass from the viewpoint of the balance between water dispersibility and water resistance. The above is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less. It is mass% or less, more preferably 70 mass% or less.
[0082]
　These polymer monools can be used alone or in combination of two or more.
[0083]
　As the polymer monool, it is preferably one-ended sealed from the viewpoint of improving thermal stability, appearance and chemical resistance, as well as low temperature curability and friction fastness in applications of carbodiimide curing agents for fiber treatment (described later). Anti-polyoxyethylene-polyoxypropylene glycol can be mentioned.
[0084]
　These monools can be used alone or in combination of two or more.
[0085]
　As the monool, preferably, the polymer monool is used alone, or the polymer monool and the monomer monool are used in combination. More preferably, the polymer monool is used alone.
[0086]
　When polymer monool and monomeric monool are used in combination, the combined ratios are thermal stability, appearance and chemical resistance, as well as low temperature curability and low temperature curability in the application of carbodiimide curing agents for fiber treatment (described later). From the viewpoint of improving frictional fastness, the polymer monool is, for example, 50 mol% or more, preferably 70 mol% or more, and for example, 90 mol% or less, preferably 90 mol% or less, based on the total moles thereof. It is 80 mol% or less. The monomeric monool is, for example, 10 mol% or more, preferably 20 mol% or more, and for example, 50 mol% or less, preferably 30 mol% or less.
[0087]
　The molecular weight of monool (the average molecular weight of monool when used in combination) is the thermal stability of the polycarbodiimide composition, as well as the low temperature curability and friction in the application of carbodiimide curing agents for fiber treatment (described later). From the viewpoint of improving the toughness, for example, it is 50 or more, preferably 100 or more, more preferably 200 or more, still more preferably 400 or more, and the chemical resistance of the cured resin product (described later), in addition, the fiber. From the viewpoint of improving low temperature curability and friction fastness in the use of the carbodiimide curing agent for treatment (described later), it is, for example, 5000 or less, preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less. ..
[0088]
　When the molecular weight of monool is in the above range, the polycarbodiimide composition can obtain excellent thermal stability, and a cured resin product (described later) having excellent chemical resistance can be obtained. Excellent low temperature curability and friction fastness in applications of carbodiimide curing agents for fiber treatment (described later) can be obtained.
[0089]
　The molecular weight of the monomeric monool can be calculated from the molecular skeleton and the number of atoms. Further, the molecular weight of the polymer monool is determined as a number average molecular weight as a polystyrene-equivalent molecular weight measured by gel permeation chromatograph measurement. Then, the molecular weight of monool is calculated as an average value of the molecular weights of each component.
[0090]
　In alcohols, the combined ratio of polyol and monool is set based on the molar ratio of the number of hydroxyl groups derived from polyol to the number of hydroxyl groups derived from monool.
[0091]
　Specifically, from the viewpoint of improving low-temperature curability and friction fastness in applications of carbodiimide curing agents for fiber treatment (described later), in addition to thermal stability, appearance and chemical resistance, the number of hydroxyl groups derived from monool The molar ratio of the number of hydroxyl groups derived from the polyol (hydroxyl group derived from the polyol / hydroxyl group derived from monool) is, for example, 0.1 or more, preferably 0.5 or more, more preferably 0.8 or more. It is less than 0, preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.2 or less.
[0092]
　That is, in the polycarbodiimide composition containing a modified carbodiimide, first, a linear aliphatic diisocyanate as a raw material component and the above alcohols (monool and polyol) are reacted under predetermined conditions, and an isocyanate group is used as a reaction product. After obtaining the terminal prepolymer, it can be further obtained by subjecting the isocyanate group-terminal prepolymer to a carbodiimidization reaction.
[0093]
　In such a case, if the combined ratio of the polyol and monool is within the above range, a prepolymer having an appropriately high molecular weight can be obtained by the reaction of the linear aliphatic diisocyanate with alcohols (described later). The prepolymer is carbodiimidized. Therefore, the modified carbodiimide has a relatively high molecular weight, and excellent thermal stability, appearance, and chemical resistance can be obtained as compared with the case where the modified carbodiimide has a relatively low molecular weight.
[0094]
　The method for producing the polycarbodiimide composition will be described in detail below.
[0095]
　In this method, first, the above-mentioned linear aliphatic diisocyanate and the above-mentioned alcohols are subjected to a urethanization reaction (urethaneization step).
[0096]
　In the urethanization step, the reaction ratio of the linear aliphatic diisocyanate to the alcohols is the carbodiimide equivalent of the polycarbodiimide composition as the equivalent ratio (NCO / OH) of the isocyanate groups of the linear aliphatic diisocyanate to the hydroxyl group of the alcohols. It is set according to the type (molecular weight, etc.) of the linear aliphatic diisocyanate and alcohols so that (g / mol) is in the range described later.
[0097]
　More specifically, although it depends on the type of the linear aliphatic diisocyanate and the alcohols, the reaction ratio of the linear aliphatic diisocyanate to the alcohols is the isocyanate group of the linear aliphatic diisocyanate with respect to the hydroxyl group of the alcohols. The equivalent ratio (NCO / OH) is, for example, more than 2, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, for example, 16 or less, preferably 10 or less. It is preferably less than 8, more preferably 6 or less. That is, in the urethanization step, the reaction is preferably carried out at a ratio in which the isocyanate group is excessive with respect to the hydroxyl group.
[0098]
　When the reaction ratio of the linear aliphatic diisocyanate and the alcohols is within the above range, a cured resin product (described later) having excellent chemical resistance can be obtained.
[0099]
　Further, in this reaction, for example, a known urethanization catalyst such as amines or an organometallic compound may be added, if necessary.
[0100]
　Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.
[0101]
　Examples of the organic metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, and dibutyltin dilaurate (dilauric acid). Organic tin compounds such as dibutyltin (IV)), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, eg organic lead compounds such as lead octanoate, lead naphthenate, eg Examples thereof include organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octeneate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.
[0102]
　Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.
[0103]
　These urethanization catalysts can be used alone or in combination of two or more.
[0104]
　The blending ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.
[0105]
　The reaction conditions in the urethanization step include the types of linear aliphatic diisocyanates and alcohols and the above equivalent ratio (NCO /) so that the carbodiimide equivalent (g / mol) of the polycarbodiimide composition is within the range described later. It is set according to OH) and the like.
[0106]
　More specifically, the reaction conditions in the urethanization step are, for example, under normal pressure and an atmosphere of an inert gas (for example, nitrogen gas), the reaction temperature is, for example, 30 ° C. or higher, preferably 60 ° C. or higher. For example, the temperature is 150 ° C. or lower, preferably 120 ° C. or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and for example, 50 hours or less, preferably 40 hours or less.
[0107]
　As a result, a prepolymer can be obtained as a reaction product of the linear aliphatic diisocyanate and alcohols. The prepolymer has an isocyanate group at the molecular end (that is, it is an isocyanate group-terminated prepolymer).
[0108]
　Then, in this method, the reaction solution containing the reaction product in the above-mentioned urethanization step is heated in the presence of a carbodiimidization catalyst to cause a carbodiimidization reaction (carbodiimidization step).
[0109]
　The carbodiimidization catalyst is not particularly limited, and examples thereof include a trialkyl phosphate-based compound, a phosphorene oxide-based compound, a phosphoren sulfide-based compound, a phosphine oxide-based compound, and a phosphine-based compound.
[0110]
　Examples of the trialkyl phosphate ester include trialkyl phosphate-based compounds having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate, and trioctyl phosphate.
[0111]
　Examples of the phosphorene oxide-based compound include 3-methyl-1-phenyl-2-phospholen-1-oxide (MPPO), 1-ethyl-3-methyl-2-phospholen-1-oxide (EMPO), and 1, -Butyl-3-methyl-2-phospholen-1-oxide, 1-benzyl-3-methyl-2-phospholen-1-oxide, 1,3-dimethyl-2-phospholen-1-oxide, 1-phenyl-2 -Phosphorene oxides having 4 to 18 carbon atoms such as phospholen-1-oxide, 1-methyl-2-phosphoren-1-oxide, 1-ethyl-2-phosphoren-1-oxide and their double-bonded isomers. Examples include system compounds.
[0112]
　Examples of the phosphoren sulfide compound include a phospholen sulfide compound having 4 to 18 carbon atoms such as 1-phenyl-2-phosphorene-1-sulfide.
[0113]
　Examples of the phosphine oxide-based compound include phosphine oxide-based compounds having 3 to 21 carbon atoms such as triphenylphosphine oxide and tritrylphosphine oxide.
[0114]
　Examples of the phosphine-based compound include phosphine-based compounds having 3 to 30 carbon atoms such as bis (oxadiphenylphosphino) ethane.
[0115]
　These carbodiimidization catalysts can be used alone or in combination of two or more.
[0116]
　Examples of the carbodiimidization catalyst preferably include phosphoren oxide-based compounds, and more preferably 3-methyl-1-phenyl-2-phosphorene-1-oxide and 1-ethyl-3-methyl-2-phosphoren-. 1-Oxide is mentioned.
[0117]
　By using the above-mentioned carbodiimidization catalyst, the activity of carbodiimideization can be improved and the reaction temperature can be lowered, and side reactions such as uretonimization can be suppressed to obtain a polycarbodiimide composition in good yield. In addition, the content of the carbodiimide group can be improved.
[0118]
　As a carbodiimided catalyst, it is particularly preferable from the viewpoint of obtaining a cured resin product (described later) having excellent water resistance, and from the viewpoint of improving low temperature curability and friction fastness in the use of a carbodiimide curing agent for fiber treatment (described later). Examples include 3-methyl-1-phenyl-2-phospholen-1-oxide.
[0119]
　The blending ratio of the carbodiimidization catalyst is, for example, 0.01 part by mass or more, preferably 0.05 part by mass with respect to 100 parts by mass of the linear aliphatic diisocyanate (linear aliphatic diisocyanate used in the urethanization step). It is 20 parts by mass or less, preferably 10 parts by mass or less.
[0120]
　Further, the reaction conditions in the carbodiimideization step are set so that the content ratio (carbodiimide equivalent) of the carbodiimide group of the obtained polycarbodiimide composition is within a specific range described later. More specifically, from the viewpoint of advancing the carbodiimidization reaction and reducing uretonimine, the reaction temperature is, for example, 125 ° C. or higher, preferably 125 ° C. or higher, under normal pressure and an atmosphere of an inert gas (nitrogen gas, etc.). It is 130 ° C. or higher, more preferably 135 ° C. or higher, and for example, 180 ° C. or lower, preferably 170 ° C. or lower, more preferably 160 ° C. or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and for example, 50 hours or less, preferably 40 hours or less.
[0121]
　By reacting under such conditions, the reaction product (isocyanate group-terminated prepolymer) obtained in the urethanization step can be decarbonated and condensed via the isocyanate group to efficiently generate a carbodiimide group.
[0122]
　More specifically, when the reaction temperature is equal to or higher than the above lower limit, the carbodiimideization reaction can proceed while promoting the reaction in which the produced uretonimine decomposes into carbodiimide and isocyanate groups. If the temperature is lower than the above lower limit, this thermal decomposition reaction is very unlikely to occur, the content of uretonimine increases, and the content of carbodiimide groups decreases. In addition, the molecular weight may increase due to the increase in uretonimine, and the reaction solution may solidify. On the other hand, if the reaction temperature is not more than the above upper limit, the polymerization loss can be reduced. When the above upper limit temperature is exceeded, polymerization reactions other than carbodiimidization and uretonimination are promoted, not only the content of carbodiimide groups decreases, but also the reaction solution tends to solidify due to the increase in molecular weight.
[0123]
　Further, in the carbodiimidization step, the reaction solution is preferably refluxed in the presence of an organic solvent from the viewpoint of smoothing the carbodiimidization reaction and promoting decarboxylation condensation. That is, the carbodiimidization reaction is carried out under reflux.
[0124]
　Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate and amyl acetate, for example. , N-Hexane, n-heptane, octane and other aliphatic hydrocarbons, such as cyclohexane, methylcyclohexane and other alicyclic hydrocarbons, such as toluene, xylene, ethylbenzene and other aromatic hydrocarbons, 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 monomethyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl Glycol ether esters such as -3-ethoxypropionate, 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, ethylene glycol Ethers such as diethyl ether 1,2-diethoxyethane, for example, halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, for example, N. Examples thereof include polar aprotons such as -methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide. These organic solvents can be used alone or in combination of two or more.
[0125]
　As the organic solvent, preferably, an organic solvent in which the temperature at reflux is within the above-mentioned reaction temperature range can be mentioned.
[0126]
　Specific examples of such an organic solvent include xylene, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate.
[0127]
　The blending ratio of the organic solvent is not particularly limited, but from the viewpoint of obtaining a cured resin product (described later) having an excellent appearance, in addition, improvement of low temperature curability and friction fastness in the application of a carbodiimide curing agent for fiber treatment (described later). From the viewpoint of, for example, 50 parts by mass or more, preferably 100 parts by mass or more, for example, 2000 parts by mass with respect to 100 parts by mass of the linear aliphatic diisocyanate (linear aliphatic diisocyanate used in the urethanization step). It is less than or equal to parts by mass, preferably less than or less than 500 parts by mass.
[0128]
　By refluxing the reaction solution in the presence of an organic solvent, the carbodiimidization reaction can be smoothly carried out while promoting the decomposition reaction of uretonimine, and the carbon dioxide gas generated by the carbodiimidization of the isocyanate group is eliminated. Therefore, carbodiimidization can be promoted.
[0129]
　Then, by such a method, a carbodiimide modified product containing a urethane group and a carbodiimide group and, in some cases, a uretonimine group can be obtained.
[0130]
　More specifically, first, in the urethanization step, a urethane group derived from the isocyanate group of the linear aliphatic diisocyanate is generated.
[0131]
　Next, when the reaction product (isocyanate group-terminated prepolymer) obtained in the urethanization step is heated in the carbodiimidization step, a carbodiimide group derived from the isocyanate group at the molecular terminal is formed, and in some cases, it is formed. A part of the carbodiimide group reacts with the isocyanate group at the end of the molecule to generate a uretonimine group. The uretonimine group is thermally decomposed by continuing heating in the carbodiimideization step, the carbodiimide group and the isocyanate group at the molecular terminal are regenerated, and further, the carbodiimide group derived from the isocyanate group at the molecular end is generated. ..
[0132]
　In this way, the isocyanate group of the linear aliphatic diisocyanate is converted to a urethane group and a carbodiimide group (and optionally a uretonimine group).
[0133]
　As a result, a modified carbodiimide containing a urethane group and a carbodiimide group and, in some cases, a uretonimine group is obtained.
[0134]
　Further, as a result, a polycarbodiimide composition containing a modified carbodiimide as a main component can be obtained. The polycarbodiimide composition can also contain an unreacted linear aliphatic diisocyanate as an accessory component. The content ratio of the linear aliphatic diisocyanate is appropriately set as long as the excellent effects of the present invention are not impaired.
[0135]
　Further, in this method, if necessary, the polycarbodiimide composition obtained in the above-mentioned carbodiimideization step can be further reacted with alcohols. In the following, the urethanization step before the carbodiimidization step may be referred to as a first urethanization step, and the urethanization step after the carbodiimidization step may be referred to as a second urethanization step.
[0136]
　Specifically, when the polycarbodiimide composition obtained in the carbodiimideization step further has an isocyanate group at the molecular terminal, the polycarbodiimide composition is reacted with alcohols to cause isocyanate at the molecular end. The group can be urethaneized.
[0137]
　When the second urethanization step is carried out, the amount of by-products derived from alcohols increases, the molecular weight rapidly increases, the fluidity decreases, and the workability decreases, or the aqueous dispersion composition. Dispersibility in objects may decrease. Therefore, preferably, the second urethanization step is not carried out, and only the first urethanization step and the carbodiimidization step are carried out.
[0138]
　The method for producing the polycarbodiimide composition is not limited to the above, and for example, a linear aliphatic diisocyanate, a carbodiimidization catalyst, and alcohols can be collectively mixed and heated.
[0139]
　Further, if necessary, from the polycarbodiimide composition, for example, unreacted linear aliphatic diisocyanate, unreacted alcohols, low molecular weight compound (by-product), organic solvent, carbodiimide catalyst, urethanization catalyst, etc. Can also be removed by known methods such as distillation, extraction and filtration.
[0140]
　Further, if necessary, the polycarbodiimide composition further includes known additives such as storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), plasticizers, blocking inhibitors, and heat-resistant stables. Agents, light-resistant stabilizers, antioxidants, mold release agents, catalysts, pigments, surface conditioners, dispersants, dyes, lubricants, fillers, hydrolysis inhibitors and the like can be added at appropriate timings. The addition ratio of the additive is not particularly limited, and is appropriately set according to the purpose and application.
[0141]
　In addition, the polycarbodiimide composition can be used alone or in combination of two or more.
[0142]
　The carbodiimide equivalent (g / mol) of the polycarbodiimide composition thus obtained is 300 or more, preferably 350 or more, more preferably 400 or more, still more preferably 410 or more, and particularly preferably 430 or more. Yes, 550 or less, preferably 530 or less, more preferably 500 or less, still more preferably 480 or less, and particularly preferably 460 or less.
[0143]
　The carbodiimide equivalent (g / mol) is measured by 13 C-NMR in accordance with Examples described later .
[0144]
　That is, the carbodiimide equivalent (g / mol) can be calculated from the charging ratio, but the measured value by 13 C-NMR is adopted.
[0145]
　Further, since such a polycarbodiimide composition uses alcohols containing a polyol and monool in a predetermined ratio, it has a higher molecular weight and a lower molecular weight than a polycarbodiimide composition using only monool. It has been reduced.
[0146]
　Specifically, in the chromatogram when the polycarbodiimide composition is measured by gel permeation chromatograph, the area ratio of the peak area having a polystyrene-equivalent molecular weight of 500 or less to the total peak area is the thermal stability, chemical resistance and appearance. From the viewpoint of improving the friction fastness in the application of the carbodiimide curing agent for fiber treatment (described later), for example, 7.0% or less, preferably 6.5% or less, and more. It is preferably 6.0% or less, more preferably 5.0% or less, and particularly preferably 4.5% or less.
[0147]
　Further, in the chromatogram when the polycarbodiimide composition was measured by gel permeation chromatograph, the area ratio of the peak area having a polystyrene-equivalent molecular weight of 1000 or less to the total peak area improved the thermal stability, chemical resistance and appearance. From the viewpoint of improving the excellent frictional fastness in the application of the carbodiimide curing agent for fiber treatment (described later), for example, 12.0% or less, preferably 10.0% or less, more preferably. It is 9.0% or less, more preferably 8.0% or less, and particularly preferably 7.0% or less.
[0148]
　The area ratio was measured by measuring the molecular weight distribution of the isocyanurate derivative of pentamethylene diisocyanate by a gel permeation chromatograph (GPC) equipped with a differential refractometer (RID) in accordance with an example described later. It can be calculated as an area ratio in the obtained chromatogram (chart). The area ratio of the peak area having a molecular weight of 500 or less and the area ratio of the peak area having a molecular weight of 1000 or less are based on the calibration curve of standard polystyrene.
[0149]
　When the area ratio of the peak area having a molecular weight of 500 or less is in the above range and the area ratio of the peak area having a molecular weight of 1000 or less is in the above range, the appearance, chemical resistance and thermal stability can be improved. In particular, the appearance of the cured resin product (described later) can be improved, and in addition, the low temperature curability and friction fastness in the application of the carbodiimide curing agent for fiber treatment (described later) can be improved.
[0150]
　In such a polycarbodiimide composition, since the alcohols as the raw material components contain the polyol and the monool in a predetermined ratio, the carbodiimide modified product has a higher molecular weight than the case where the alcohols do not contain the polyol. Will be done. Specifically, a prepolymer is obtained by reacting a linear aliphatic diisocyanate with an alcohol containing a polyol, and the prepolymer is carbodiimided, so that a relatively high molecular weight carbodiimide modified product can be obtained. As a result, a cured resin product (described later) having excellent chemical resistance can be obtained from the polycarbodiimide composition.
[0151]
　On the other hand, if the carbodiimide modified product has an excessively high molecular weight, it tends to thicken and may be inferior in thermal stability. On the other hand, in the polycarbodiimide composition of the present invention, since the ratio of the polyol and the monool is adjusted in the carbodiimide modified product, the molecular weight is only appropriately increased and the heat stability is also excellent.
[0152]
　Further, in the above-mentioned polycarbodiimide composition, since the carbodiimide equivalent is adjusted to a predetermined ratio, a cured resin product (described later) having excellent appearance and chemical resistance can be obtained.
[0153]
　That is, the above-mentioned polycarbodiimide composition is excellent in thermal stability, and a cured resin product (described later) having excellent appearance and chemical resistance can be obtained.
[0154]
　Further, according to the above-mentioned method for producing a polycarbodiimide composition, the polycarbodiimide composition can be efficiently produced.
[0155]
　The polycarbodiimide composition is excellent in thermal stability, and a cured resin product having excellent appearance and chemical resistance can be obtained. Therefore, the polycarbodiimide composition is suitably used as a curing agent in the resin composition.
[0156]
　The resin composition contains a curing agent containing a polycarbodiimide composition and a main agent having a carboxyl group.
[0157]
　The curing agent is not particularly limited as long as it contains a polycarbodiimide composition, but for example, an aqueous dispersion in which the polycarbodiimide composition is dispersed in water (hereinafter, referred to as an aqueous dispersion composition) or a polycarbodiimide composition. The product is prepared as a solution in which the product is dissolved in an organic solvent (hereinafter, referred to as a solution composition) or the like.
[0158]
　The aqueous dispersion composition contains a polycarbodiimide composition and water.
[0159]
　The method for dispersing the polycarbodiimide composition in water is not particularly limited, and examples thereof include a method in which water is added to the polycarbodiimide composition and stirred, and a method in which the polycarbodiimide composition is added to water and stirred. .. Preferably, water is added to the polycarbodiimide composition.
[0160]
　The ratio of the polycarbodiimide composition to water is not particularly limited, but the concentration (that is, solid content concentration) of the polycarbodiimide composition (resin component) in the aqueous dispersion composition is, for example, 5% by mass or more, preferably 5% by mass or more. It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.
[0161]
　If the curing agent is an aqueous dispersion composition, the compatibility with the aqueous resin (main agent) can be improved, and a cured product having excellent appearance and chemical resistance can be obtained. Moreover, since such an aqueous dispersion composition contains the above-mentioned polycarbodiimide composition, it is excellent in thermal stability.
[0162]
　The solution composition contains a polycarbodiimide composition and an organic solvent.
[0163]
　Examples of the organic solvent include the above-mentioned organic solvents, and preferred examples thereof include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.
[0164]
　Further, the solvent used in the carbodiimidization step may be used as the organic solvent of the solution composition. For example, the solvent used after the carbodiimidization step can be used as it is as an organic solvent in the solution composition without distilling off.
[0165]
　The method for dissolving the polycarbodiimide composition in an organic solvent is not particularly limited, and a method of adding an organic solvent to the polycarbodiimide composition and stirring, a method of adding the polycarbodiimide composition to the organic solvent and stirring, etc. Can be mentioned. Preferably, an organic solvent is added to the polycarbodiimide composition.
[0166]
　The ratio of the polycarbodiimide composition to the organic solvent is not particularly limited, but the concentration (that is, solid content concentration) of the polycarbodiimide composition (resin component) in the solution composition is, for example, 5% by mass or more, preferably 5% by mass or more. It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.
[0167]
　If the curing agent is a solution composition, the compatibility with the oil-based resin (main agent) can be improved, and a cured product having excellent appearance and chemical resistance can be obtained. Moreover, such a solution composition is excellent in thermal stability.
[0168]
　Examples of the main agent having a carboxyl group include an aqueous resin having a carboxyl group and an oil-based resin having a carboxyl group.
[0169]
　Examples of the aqueous resin having a carboxyl group include a hydrophilic polymer having a carboxyl group, and specifically, a hydrophilic polyester resin having a carboxyl group, a hydrophilic polyamide resin having a carboxyl group, and a carboxyl group. Hydrophilic polyurethane resin (hydrophilic polyurethane polyol), hydrophilic acrylic resin having a carboxyl group (hydrophilic acrylic polyol), hydrophilic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block) co-weight Examples thereof include a copolymer (polyolefin) resin having 4 or more carbon atoms as a repeating unit. These aqueous resins having a carboxyl group can be used alone or in combination of two or more.
[0170]
　Preferred examples of the aqueous resin having a carboxyl group include a hydrophilic polyurethane resin having a carboxyl group (hydrophilic polyurethane polyol) and a hydrophilic acrylic resin having a carboxyl group (hydrophilic acrylic polyol).
[0171]
　Examples of the oil-based resin having a carboxyl group include a hydrophobic polymer having a carboxyl group, and specifically, a hydrophobic polyester resin having a carboxyl group, a hydrophobic polyamide resin having a carboxyl group, and a carboxyl group. Hydrophobic polyurethane resin (hydrophobic polyurethane polyol), hydrophobic acrylic resin having a carboxyl group (hydrophobic acrylic polyol), hydrophobic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block)) Examples thereof include polymers (polyolefins) resins having 4 or more carbon atoms as a repeating unit. These oil-based resins having a carboxyl group can be used alone or in combination of two or more.
[0172]
　Examples of the oil-based resin having a carboxyl group include a hydrophobic polyurethane resin having a carboxyl group (hydrophobic polyurethane polyol) and a hydrophobic acrylic resin having a carboxyl group (hydrophobic acrylic polyol).
[0173]
　These can be used alone or in combination of two or more.
[0174]
　The main agent and the curing agent are preferably a combination in which the main agent is an aqueous resin and the curing agent is an aqueous dispersion composition. Further, preferably, a combination in which the main agent is an oil-based resin and the curing agent is a solution composition can be mentioned.
[0175]
　As the resin composition, from the viewpoint of reducing the organic solvent and protecting the global environment, a combination of an aqueous main agent and an aqueous dispersion composition is preferable.
[0176]
　Further, the resin composition is not particularly limited as long as it contains the above-mentioned main agent and the above-mentioned curing agent, and may be a two-component type in which the main agent and the curing agent are separately prepared and mixed at the time of use. It may be a one-component type in which a main agent and a curing agent are mixed in advance.
[0177]
　As the resin composition, a two-component type resin composition is preferable.
[0178]
　The content ratio of the main agent and the curing agent is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, and for example, 99.5 parts by mass or less, preferably 99.5 parts by mass or more, based on 100 parts by mass of the total amount of the main agent. , 95.0 parts by mass or less. The curing agent is, for example, 0.5 parts by mass or more, preferably 5 parts by mass or more, and for example, 90 parts by mass or less, preferably 70 parts by mass or less.
[0179]
　Further, the molar ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, for example, 2. It is 5 or less, preferably 2.0 or less, and more preferably 1.5 or less.
[0180]
　In addition, as necessary, the main agent and the curing agent may be one or both of them, for example, an epoxy resin, a catalyst (such as a urethanization catalyst), a coating improver, a leveling agent, a viscosity modifier, and a defoamer. Additives such as agents, stabilizers such as antioxidants and UV absorbers, plasticizers, surfactants, pigments, surface conditioners, dispersants, fillers, organic or inorganic fine particles, fungicides, silane coupling agents, etc. May be blended. The blending amount of these additives is appropriately determined depending on the purpose and use thereof.
[0181]
　Further, as the main agent, the above-mentioned aqueous resin having a carboxyl group and / or the above-mentioned oil-based resin having a carboxyl group and other resins (for example, a hydroxyl group-containing polyurethane resin, a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, etc.) ) Can also be used together.
[0182]
　Further, as the curing agent, the above-mentioned polycarbodiimide composition and other curing agents (for example, polyisocyanate resin (block polyisocyanate or the like), epoxy resin, melamine resin or the like) can be used in combination.
[0183]
　Since the above-mentioned polycarbodiimide composition is used as the curing agent in such a resin composition, it is possible to obtain a cured resin composition having excellent thermal stability and excellent appearance and chemical resistance.
[0184]
　The method for producing the cured resin product is not particularly limited. For example, when the resin composition is a one-component type, the resin composition is directly applied to the object to be coated or the adherend. In the case of the two-component resin composition type, the main agent and the curing agent are mixed, and the obtained mixture is applied to the object to be coated or the adherend. Then, the resin composition is heat-cured to obtain a cured resin product.
[0185]
　In the above resin composition, the curing temperature is relatively low, specifically, for example, 100 ° C. or lower, preferably 80 ° C. or lower. Further, for example, it is 20 ° C. or higher, preferably 30 ° C. or higher.
[0186]
　Further, the curing time is relatively short, specifically, for example, 1 hour or less, preferably 30 minutes or less. Further, for example, it is 1 minute or longer, preferably 5 minutes or longer.
[0187]
　Further, if necessary, the heat-cured resin cured product can be further dried.
[0188]
　In such a case, the drying temperature may be room temperature, for example, 10 ° C. or higher, preferably 15 ° C. or higher, and for example, 40 ° C. or lower, preferably 30 ° C. or lower.
[0189]
　The drying time is, for example, 1 minute or more, preferably 5 minutes or more, and for example, 2 hours or less, preferably 1 hour or less.
[0190]
　Since the obtained cured resin product is a cured product of a resin composition having excellent thermal stability, it is excellent in productivity, and is also excellent in appearance and chemical resistance.
[0191]
　Further, since the polycarbodiimide composition is obtained by using a linear aliphatic diisocyanate, the cured resin product obtained by using the polycarbodiimide composition is also excellent in light resistance (weather resistance).
[0192]
　Therefore, resin compositions and cured resin products include coating materials, adhesive materials (adhesives), adhesive materials (adhesive materials), inks, sealants, molding materials, foams and optical materials, as well as polyesters, polylactic acids, and polyamides. It is suitably used in various fields such as resin modifiers for modifying resins such as polyimide and polyvinyl alcohol, printing treatment agents, and fiber treatment agents.
[0193]
　When used as a coating material, for example, plastic paint, automobile exterior paint, automobile interior paint, electrical / electronic material paint, optical material (lens, etc.) paint, building material paint, glass coat paint, woodwork Examples thereof include paints, film coating paints, ink paints, artificial and synthetic leather paints (coating agents), can paints (coating agents), paper coating paints, and heat-sensitive paper coating paints.
[0194]
　Examples of the paint for plastics include paints for molded products in which plastic materials (for example, various polymer materials such as polyolefins, ABS, polycarbonates, polyamides, polyesters and composites thereof) are used. Is a paint for housings (mobile phones, smartphones, personal computers, tablets, etc.), paints for automobile parts (automobile interior materials, headlamps, etc.), paints for household electrical appliances, paints for robot materials, paints for furniture, and stationery. Examples thereof include paints, paints for flexible materials such as rubber, elastomers and gels, paints for eyewear materials (lenses, etc.), paints for optical lenses of electronic devices (surface coating agents), and the like.
[0195]
　Examples of the film coating paint include paints for optical members (optical films, optical sheets, etc.), optical coating materials, textile paints, electronic electrical material paints, food packaging paints, medical film paints, and the like. Examples thereof include paints for cosmetic packages, paints for decorative films, and paints for release films.
[0196]
　Examples of the adhesive include a packaging material adhesive, an electric device adhesive, a liquid crystal display (LCD) adhesive, an organic EL display adhesive, an organic EL lighting adhesive, and a display device (electronic paper or plasma display). Adhesives for), LED adhesives, interior / exterior adhesives for automobiles, home appliances adhesives, building material adhesives, solar cell backsheet adhesives, adhesives for various batteries (lithium ion batteries, etc.), etc. Can be mentioned.
[0197]
　Examples of the ink paint include vehicles of various inks (plate ink, screen ink, flexographic ink, gravure ink, jet ink, printing ink, etc.).
[0198]
　Further, in the field of fiber treatment agents, the above-mentioned polycarbodiimide composition is used as, for example, a carbodiimide cross-linking agent for fiber treatment.
[0199]
　The carbodiimide cross-linking agent for fiber treatment is a cross-linking agent (cross-linking agent for printing) used for printing on fibers or leather. In the following, the carbodiimide cross-linking agent for fiber treatment may be simply referred to as a cross-linking agent.
[0200]
　The cross-linking agent contains the above-mentioned polycarbodiimide composition, and preferably, the cross-linking agent comprises the above-mentioned polycarbodiimide composition.
[0201]
　The carbodiimide cross-linking agent for fiber treatment is not particularly limited as long as it contains a polycarbodiimide composition, and for example, an aqueous dispersion in which the polycarbodiimide composition is dispersed in water (the above-mentioned aqueous dispersion composition) or polycarbodiimide The composition is prepared as a solution in which the composition is dissolved in an organic solvent (the above-mentioned solution composition) or the like. As the carbodiimide cross-linking agent for fiber treatment, an aqueous dispersion composition of a polycarbodiimide composition is preferable.
[0202]
　Since such a carbodiimide cross-linking agent for fiber treatment contains the above-mentioned polycarbodiimide composition, it is possible to improve the friction fastness when the printing treatment is performed at a relatively low temperature (120 ° C. or lower).
[0203]
　More specifically, the carbodiimide cross-linking agent for fiber treatment is preferably used as a raw material for printing ink for printing fibers.
[0204]
　The printing ink raw material includes the above-mentioned cross-linking agent as a polyisocyanate component and a main agent having a carboxyl group.
[0205]
　Examples of the main agent having a carboxyl group include the above-mentioned aqueous resin having a carboxyl group, the above-mentioned oil-based resin having a carboxyl group, and the like.
[0206]
　The main agent and the cross-linking agent are preferably a combination in which the main agent is an aqueous resin and the cross-linking agent is an aqueous dispersion composition. Further, preferably, a combination in which the main agent is an oil-based resin and the cross-linking agent is a solution composition can be mentioned.
[0207]
　From the viewpoint of reducing the amount of organic solvent and protecting the global environment, a combination of an aqueous base material and an aqueous dispersion composition is preferable.
[0208]
　Then, the printing ink is prepared from such a two-component printing ink raw material (main agent and cross-linking agent).
[0209]
　Such a printing ink raw material is not particularly limited as long as it contains the above-mentioned main agent and the above-mentioned cross-linking agent, and is a two-component type in which the main agent and the cross-linking agent are separately prepared and mixed at the time of use. It may be a one-component type in which the main agent and the cross-linking agent are mixed in advance.
[0210]
　As the printing ink raw material, a two-component type printing ink raw material is preferable.
[0211]
　The content ratio of the main agent and the cross-linking agent is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, and for example, 99.5 parts by mass, based on 100 parts by mass of the total amount thereof in terms of solid content. Parts or less, preferably 95.0 parts by mass or less. The cross-linking agent is, for example, 0.5 parts by mass or more, preferably 5 parts by mass or more, and for example, 90 parts by mass or less, preferably 70 parts by mass or less.
[0212]
　Further, the molar ratio of the carbodiimide group in the cross-linking agent to the carboxyl group in the main agent is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, for example, 2. It is 5 or less, preferably 2.0 or less, and more preferably 1.5 or less.
[0213]
　In addition, a pigment is preferably blended in either one or both of the cross-linking agent and the main agent. The pigment is not particularly limited, and examples thereof include a blue pigment, a white pigment, and a black pigment.
[0214]
　The blending ratio of the pigment is, for example, 1% by mass or more, preferably 10% by mass or more, for example, 40% by mass or less, preferably 30% by mass or less, based on the total amount of the cross-linking agent, the main agent and the pigment.
[0215]
　In addition, for either one or both of the cross-linking agent and the main agent, for example, an epoxy resin, a catalyst (such as a urethanization catalyst), a coating improver, a leveling agent, a viscosity modifier, a defoaming agent, etc. Contains stabilizers such as antioxidants and UV absorbers, plasticizers, surfactants, surface conditioners, dispersants, fillers, organic or inorganic fine particles, fungicides, silane coupling agents and other additives. May be good. The blending amount of these additives is appropriately determined depending on the purpose and use thereof.
[0216]
　Further, as the main agent, the above-mentioned aqueous resin having a carboxyl group and / or the above-mentioned oil-based resin having a carboxyl group and other resins (for example, a hydroxyl group-containing polyurethane resin, a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, etc.) ) Can also be used together.
[0217]
　Further, as the cross-linking agent, the above-mentioned polycarbodiimide composition and other cross-linking agents (for example, polyisocyanate resin (block polyisocyanate or the like), epoxy resin, melamine resin or the like) can be used in combination.
[0218]
　Then, the printing ink is printed on the printing target by a known printing device (for example, an inkjet device), and then heat-treated and cured as necessary.
[0219]
　Examples of the printing target include fibers, and more specifically, fabrics, leathers, and the like.
[0220]
　The fibers of the fabric are not particularly limited, and examples thereof include natural fibers (for example, silk, cotton, linen, etc.) and synthetic fibers (for example, nylon, polyester, rayon, etc.). The form of the fabric is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, and non-woven fabrics. The leather is not particularly limited, and examples thereof include natural leather and artificial leather.
[0221]
　The heating temperature is relatively low, more specifically 120 ° C. or lower, preferably 100 ° C. or lower, and even more preferably 80 ° C. or lower. Usually, it is 5 ° C. or higher, more preferably 20 ° C. or higher.
[0222]
　As a result, an ink cured product (cured coating film, polyurethane resin) is formed. Since the obtained ink-cured product is formed from the above-mentioned printing ink, it is excellent in low-temperature curability and friction fastness.
[0223]
　The use of the polycarbodiimide composition is not limited to the above, and for example, a solid hydrolysis resistance inhibitor for polyester resins, polyamide resins, polylactic acid, etc., for example, a liquid hydrolysis resistance inhibitor for polyester polyols, etc. For example, convergence of composite materials for acid-modified polyolefins (maleic acid-modified polyolefins, etc.), polyolefin-based emulsions in which acid-modified polyolefins are water-dispersed, acrylic emulsions containing acid moieties, for example, various fibers (carbon fibers, glass fibers, etc.). It can be suitably used as a reinforcing material for a material, for example, a fiber reinforced plastic (CFRP, FRP, etc.), and further as a sizing agent, a curing agent, and the like.
Example
[0224]
　Next, the present invention will be described with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values ​​such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to.
[0225]
　
　The completion of the carbodiimidization reaction in the method for producing the polycarbodiimide composition was confirmed by measuring the IR spectrum with the following equipment and conditions.
[0226]
　IR measuring device: Fourier FT-IR
　measuring method manufactured by Perkin Elmer : ATR (reflection method)　　
　Wave frequency range: 4000 to 400 cm -1　　
　Resolution 4 cm -1　　
　
　Polycarbodiimide composition The carbodiimide equivalent of 13 was determined from the measured result of 13 C-NMR. Moreover, as a reference value, the calculated value of the carbodiimide equivalent from the charged amount was obtained.
[0227]
　That is, 13 C-NMR was measured under the following equipment and conditions, and the content ratio of the uretonimine group to a total of 1 mol of the carbodiimide group, the uretonimine group, the allophanate group, and the urethane group was calculated by the following formula. As a reference for the chemical shift ppm, tetramethylsilane (0 ppm) in the CDCL 3 solvent was used.
Equipment; ECA-500 type (manufactured by Nippon Denshi)
Conditions; Measurement frequency: 125 MHz, Solvent: CDCL 3 , Solute concentration: 50 mass%
Measurement temperature: Room temperature, Number of scans 8500 Repeat
time: 3.0 seconds, Pulse width: 30 ° (3.70 μsec)
Carbon attribution peak of carbodiimide group (N = C = N group in carbodiimide group)
: 139ppm Carbon attribution peak of
uretonimine group (C = O group in uretonimine group, C = N group)
159ppm, 145ppm
Carbon attribution peak of allophanate group (C = O group in allophanate group)
: 154ppm Carbon attribution peak of
urethane group (C = O group in urethane group)
: 156ppm
　(Carbodiimide equivalent) = {(Mole weight of carbodiimide group charged)-(Mole ratio of carbon dioxide generated to urethane group) x (Total number of moles charged with alcohol) x 44.01}} / {(Mole ratio of carbodiimide group to urethane group) ) × (Total number of moles charged with alcohol)
　The molar ratio of carbon dioxide generated to the urethane group and the molar ratio of the carbodiimide group to the urethane group are calculated as follows.
[0228]
　(Mole ratio of carbon dioxide generated to urethane group) = {(Integral value of carbodiimide group) + (Integral value of uretonimine group)} / {(Integral value of urethane group) + (Integral value of allophanate group)}
(Urethane Molar ratio of carbodiimide group to group) = (integral value of carbodiimide group) / {(integral value of urethane group) + (integral value of allophanate group)}
　
　Gel equipped with differential refractometer (RID) According to the chromatogram obtained by the permeation chromatograph (GPC) under the following GPC measurement conditions, the ratio of the peak area having a polystyrene-equivalent molecular weight of 500 or less to the total peak area and the peak area having a polystyrene-equivalent molecular weight of 1000 or less to the total peak area. The ratio of each was calculated.
[0229]
　The GPC chromatogram of the polycarbodiimide composition obtained in Example 1 described later is shown in FIG. In addition, in the figure, the peak number / retention time / molecular weight of the peak top are also shown.
[0230]
　　Equipment; HLC-8320GPC (manufactured by Tosoh)
　　column; LF-804 (trade name manufactured by Shodex) connected in series
　　Column temperature; 40 ° C.
　　eluent; tetrahydrofuran
　　flow rate; 1.0 mL / min
　　Detection method; differential refractometer
　　Standard substance; Standard polystyrene
　Production Example 1 (Production of pentane diisocyanate)
　99.9% by mass of 1,5-pentane diisocyanate (hereinafter referred to as PDI) by the same operation as in Example 1 in the specification of International Publication Pamphlet WO2012 / 121291. It may be abbreviated.)
[0231]
　Production Example 2 (Production of polyoxyethylene-polyoxypropylene monomethyl ether) Using
　dipropylene glycol monomethyl ether as an initiator and potassium hydroxide (hereinafter, KOH) as a catalyst, the temperature is 110 ° C. and the maximum reaction pressure is 0.4 MPa. In the gauge (G), these alkylene oxides (ethylene oxide and propylene oxide) are used up to a hydroxyl value (hereinafter, OHV) of 102 mgKOH / g so that the mass ratio of ethylene oxide and propylene oxide in the polyol is 50:50. A crude polyol was prepared by random addition polymerization.
[0232]
　Next, ion-exchanged water and 1.05 equivalents of phosphoric acid (in the form of a 75.2 wt% aqueous solution) with respect to KOH were added to the crude polyol heated to 80 ° C. under a nitrogen atmosphere, and the temperature was 80 ° C. In, the neutralization reaction was carried out for 2 hours.
[0233]
　Then, while raising the temperature, dehydration under reduced pressure was started, and when the pressure was 40 kPa, an adsorbent was added. Finally, it was heated and reduced pressure for 3 hours under the conditions of 105 ° C. and 1.33 kPa or less.
[0234]
　Then, it was filtered to obtain polyoxyethylene-polyoxypropylene monomethyl ether.
[0235]
　The ratio of the oxyethylene group to the total amount of the oxyethylene group and the oxypropylene group (hereinafter referred to as the EO ratio) of the polyoxyethylene-polyoxypropylene monomethyl ether was 50% by mass. The number average molecular weight measured by the gel permeation chromatograph was 550.
[0236]
　This polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) was designated as monool A.
[0237]
　Example 1
　-Production of polycarbodiimide composition The
　pentamethylene diisocyanate (PDI) obtained in Production Example 1 was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube at room temperature. 100.0 parts by mass, PTG-250 (polytetramethylene ether glycol, molecular weight 250) 16.2 parts by mass, Monool A (polyoxyethylene-polyoxypropylene monomethyl ether obtained in Production Example 2 (EO ratio 50) 71.4 parts by mass of mass%, molecular weight 550)) was charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 4 hours (urethaneization step).
[0238]
　Subsequently, 758.3 parts by mass of propylene glycol monomethyl ether acetate (PMA) and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholen-1-oxide (MPPO) were charged, and the mixture was refluxed (150). Stirred at (° C.) (carbodiimidization step). The completion of the reaction was confirmed by infrared absorption (IR) spectrum measurement by the fact that the absorption peak near 2260 cm -1 derived from the expansion and contraction vibration of the isocyanate group almost disappeared.
[0239]
　After completion of the reaction, the mixture was cooled to 80 ° C., and PMA was distilled off under reduced pressure until the residual ratio of PMA became 2% or less to obtain a polycarbodiimide composition. As a result of measuring the obtained polycarbodiimide composition by 13 C-NMR, the carbodiimide equivalent was 450 g / mol (calculated value was 317 g / mol).
[0240]
　Further, a part of the obtained polycarbodiimide composition was taken out and the E-type viscosity at 25 ° C. was measured and found to be 4000 mPa · s.
[0241]
　-Preparation of an aqueous dispersion (aqueous dispersion composition) of the
　polycarbodiimide composition Put the polycarbodiimide composition in a flask, gradually add distilled water so that the resin solid content becomes 40%, and stir to make the polycarbodiimide. An aqueous dispersion of the composition was obtained.
[0242]
　-Preparation of water-based resin composition
　The aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. Polyurethane dispersion (solid content 30% by mass, solid content carboxyl group equivalent 1122 g / mol) was used as the main agent, and mixed so that the equivalent ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent was 0.5. , A resin composition was prepared.
[0243]
　Example 2
　A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 21.2 parts by mass of PTG-250, 62.0 parts by mass of monool A, and 740.8 parts by mass of PMA were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0244]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0245]
　Example 3
　A polycarbodiimide composition was obtained in the same manner as in Example 1 except that PTG-250 was used in an amount of 9.5 parts by mass, monool A was used in an amount of 83.9 parts by mass, and PMA was used in an amount of 781.9 parts by mass. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0246]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0247]
　Example 4
　Except for using 35.1 parts by mass of PTG-650 (polytetramethylene ether glycol, molecular weight 650), 59.5 parts by mass of monool A, and 786.4 parts by mass of PMA instead of PTG-250. A polycarbodiimide composition was obtained in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0248]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0249]
　Example 5
　PTG-850 (polytetramethylene ether glycol, molecular weight 850) was used in place of PTG-250 by 45.9 parts by mass, monool A by 59.5 parts by mass, and PMA by 829.6 parts by mass. A polycarbodiimide composition was obtained in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0250]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0251]
　Example 6 A
　polycarbodiimide composition was obtained in the same manner as in Example 1 except that 18.2 parts by mass of PPG-280 (polypropylene glycol, molecular weight 280) and 766.1 parts by mass of PMA were used instead of PTG-250. It was. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0252]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0253]
　Example 7
　Monool A (polyoxyethylene-polyoxypropylene monomethyl ether obtained in Production Example 2 (EO ratio 50% by mass, molecular weight 550)) and isobutanol were mixed at a molar ratio of 3: 1. This solution was designated as Monool B.
[0254]
　Then, a polycarbodiimide composition was obtained by the same method as in Example 1 except that 55.9 parts by mass of monool B and 696.6 parts by mass of PMA were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1 (a solution in which polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) and isobutanol are mixed at a molar ratio of 3: 1 is shown. (Indicated as monool B).
[0255]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0256]
　Example 8
　Except that 11.3 parts by mass of 1,10-DD (1,10-decanediol), 71.4 parts by mass of monool A, and 738.6 parts by mass of PMA were used instead of PTG-250. A polycarbodiimide composition was obtained in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0257]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0258]
　Example 9
　Polycarbodiimide composition in the same manner as in Example 1 except that 7.7 parts by mass of 1,6-HD (1,6-hexanediol) and 724.1 parts by mass of PMA were used instead of PTG-250. I got something. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0259]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0260]
　Example 10
　Except that 69.5 parts by mass of PTG-1500 (polytetramethylene ether glycol, molecular weight 1500), 51.0 parts by mass of monool A, and 889.9 parts by mass of PMA were used instead of PTG-250. A polycarbodiimide composition was obtained in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0261]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0262]
　Example 11 The
　same method as in Example 1 except that 13.0 parts by mass of PCL 303 (Placel 303, polycaprolactone triol, molecular weight 300, manufactured by Daicel) was used instead of PTG-250, and 745.3 parts by mass of PMA was used. The polycarbodiimide composition was obtained in. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0263]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0264]
　Example 12
　Other than using 100.0 parts by mass of HDI (hexamethylene diisocyanate), 14.9 parts by mass of PTG-250, 65.4 parts by mass of monool A, and 729.1 parts by mass of PMA instead of PDI. Obtained a polycarbodiimide composition in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0265]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0266]
　Example 13 A
　polycarbodiimide composition was obtained in the same manner as in Example 1 except that 1724.1 parts by mass of PMA and 4.0 parts by mass of MPPO were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0267]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0268]
　Example 14
　-Production of polycarbodiimide composition
　Implemented except that 20.3 parts by mass of PTG-250, 12.0 parts by mass of isobutanol (iBA) instead of monool A, and 537.2 parts by mass of PMA were used. A polycarbodiimide composition was obtained in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0269]
　-Preparation of a solution (solution composition) of the
　polycarbodiimide composition The polycarbodiimide composition is placed in a flask, butyl acetate is gradually added so that the resin solid content becomes 40%, and the mixture is stirred to prepare the polycarbodiimide composition. A solution was obtained.
[0270]
　-Preparation of solvent-based resin composition
　The solution of the obtained polycarbodiimide composition was used as a curing agent. Acrylic resin (solid content 50% by mass, solid content carboxyl group equivalent 2004 g / mol) was used as the main agent, and the mixture was mixed so that the equivalent ratio of the carbodiimide group in the curing agent and the carboxyl group in the main agent was 0.5. A resin composition was prepared.
[0271]
　Comparative Example 1
　A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 0.0 part by mass of PTG-250, 101.9 parts by mass of monool A and 815.7 parts by mass of PMA were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0272]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0273]
　Comparative Example 2
　A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 24.9 parts by mass of PTG-250, 54.9 parts by mass of monool A, and 727.35 parts by mass of PMA were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0274]
　Further, an aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, but a uniform aqueous dispersion could not be obtained.
[0275]
　Comparative Example 3
　A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 27.0 parts by mass of PTG-250, 118.9 parts by mass of monool A, and 991.8 parts by mass of PMA were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0276]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0277]
　Comparative Example 4
　Conducted except that 8.1 parts by mass of PTG-250, 35.7 parts by mass of Uniox M550 (polyoxyethylene monomethyl ether, molecular weight 550, manufactured by NOF CORPORATION), and 583.1 parts by mass of PMA were used. A polycarbodiimide composition was obtained in the same manner as in Example 1. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.
[0278]
　Moreover, the aqueous dispersion of the polycarbodiimide composition was prepared by the same method as in Example 1, and the resin composition was prepared.
[0279]
　Comparative Example 5
　-Production of polycarbodiimide composition In
　a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube , 200 of 4,4-dicyclohexylmethane diisocyanate (H 12 MDI) was added at room temperature. .0 parts by mass, 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholen-1-oxide (MPPO) was encapsulated. While introducing nitrogen, the reaction was carried out at 170 ° C. for 7 hours to obtain a carbodiimide having three carbodiimide groups in one molecule and isocyanate groups at both ends (carbodiimidization step).
[0280]
　Next, in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of the obtained carbodiimide, 13.6 parts by mass of PTG-250, and Uniox M550 ( Polyoxyethylene monomethyl ether, molecular weight 550, manufactured by Nippon Oil & Fats Co., Ltd.) was sealed in 60.0 parts by mass and reacted at 120 ° C. while introducing nitrogen (urethaneization step). The completion of the reaction was confirmed by infrared absorption (IR) spectrum measurement by the fact that the absorption peak near 2260 cm -1 derived from the expansion and contraction vibration of the isocyanate group almost disappeared.
[0281]
　-Preparation of an aqueous dispersion of a polycarbodiimide composition (aqueous dispersion composition) The
　obtained polycarbodiimide composition derived from H 12 MDI is placed in a flask and heated to 80 ° C. to increase the resin solid content to 40%. Distilled water was gradually added as described above. The mixture was stirred for 5 minutes and then cooled to obtain an aqueous dispersion of the polycarbodiimide composition.
[0282]
　-Preparation of water-based resin composition
　The aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. Hydrophilic polyurethane having a carboxyl group (polyurethane dispersion, solid content 30% by mass, solid content carboxyl group equivalent 1122 g / mol) is used as the main agent, and the equivalent ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent is 0. A resin composition was prepared by mixing so as to be .5.
[0283]
　Comparative Example 6 A
　polycarbodiimide composition was synthesized according to the method described in Synthesis Example 5 of JP-A-2018-104605, and an aqueous dispersion of the polycarbodiimide composition was prepared in the same manner as in each example.
[0284]
　That is, in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen introduction tube, at room temperature , 100.0 parts by mass of 4,4-dicyclohexylmethane diisocyanate (H 12 MDI), 3-methyl-. 0.5 parts by mass of 1-phenyl-2-phospholen-1-oxide (MPPO) was encapsulated. While introducing nitrogen, the reaction was carried out at 180 ° C. for 7 hours to obtain a carbodiimide having an isocyanate group at both ends (carbodiimideization step).
[0285]
　Next, in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, uniox M550 (polyoxyethylene monomethyl ether, molecular weight 550, manufactured by Nippon Oil & Fats Co., Ltd.) was added to the obtained carbodiimide. After encapsulating 86 parts by mass (0.5 equivalent with respect to both terminal isocyanates of carbodiimide) and reacting at 150 ° C. for 1 hour, 77 parts by mass of PEG-1000 (polyoxyethylene glycol, weight average molecular weight 1000) was added. Then, the reaction was carried out for another 1 hour (urethaneization step). The completion of the reaction was confirmed by infrared absorption (IR) spectrum measurement by the fact that the absorption peak near 2260 cm -1 derived from the expansion and contraction vibration of the isocyanate group almost disappeared.
[0286]
　-Preparation of an aqueous dispersion of a polycarbodiimide composition (aqueous dispersion composition) The
　obtained polycarbodiimide composition derived from H 12 MDI is placed in a flask and heated to 80 ° C. to increase the resin solid content to 40%. Distilled water was gradually added as described above. The mixture was stirred for 5 minutes and then cooled to obtain an aqueous dispersion of the polycarbodiimide composition.
[0287]
　-Preparation of water-based resin composition
　The aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. Hydrophilic polyurethane having a carboxyl group (polyurethane dispersion, solid content 30% by mass, solid content carboxyl group equivalent 1122 g / mol) is used as the main agent, and the equivalent ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent is 0. A resin composition was prepared by mixing so as to be .5.
[0288]
　
　　
　-Thermal stability test
　1.0 g of the obtained polycarbodiimide composition is placed in a 10 mL screw bottle, blown with nitrogen, covered with a screw cap, and stored at 40 ° C. And observed the liquidity. The evaluation criteria are as follows.
Liquidity did not disappear in less than 3: 2 weeks.
2: It disappeared in 1 week or more and less than 2 weeks.
Liquidity disappeared in less than 1: 1 week.
[0289]
　　 The
　resin composition is applied to a standard test plate (JIS-G-3303 SPTE) using a 250 mil doctor blade, dried at 80 ° C. for 5 minutes and 10 minutes, and further dried at room temperature for 1 minute. It was dried for a time to obtain a coating film made of a cured resin product. The obtained coating film was evaluated by the following method. In addition, Comparative Example 2 was not evaluated because an aqueous dispersion could not be obtained.
[0290]
　Appearance of coating film The appearance of the
　coating film (coating film dried at 80 ° C. for 5 minutes) was visually evaluated. The evaluation criteria are as follows.
5: Almost no wrinkles were seen.
4: Wrinkles were seen in some parts.
3: Many wrinkles were seen.
2: Wrinkles and cracks were seen.
1: There were many wrinkles and cracks, and the solvent resistance described later could not be evaluated.
[0291]
　-Solvent resistant (chemical resistant)
　coating film (80 ° C. 5 minutes dry coating film and 80 ° C. 10 minutes dry coating film), in the case of an aqueous resin composition, methyl ethyl ketone, solvent-based resin composition In the case of, the gauze impregnated with a 50% ethanol aqueous solution was rubbed while being pressed with a load of 50 g, and the number of times until the coating film cracked was measured. The evaluation criteria are as follows.
The coating film was cracked at 5: 350 times or more, and the coating film was cracked at
4: 300 times or more and less than 350 times.
3: The coating film cracked after 250 times or more and less than 300 times.
2: The coating film cracked after 100 times or more and less than 250 times.
The coating film cracked less than 1: 100 times.
[0292]
　　
　The aqueous dispersions of the polycarbodiimide compositions obtained in Examples 1 to 13, Comparative Example 1, Comparative Example 3 and Comparative Examples 5 to 6 were subjected to JIS L 0849 (2013). It was evaluated by a simulated friction fastness test.
[0293]
　More specifically, first, a compounding solution having the following formulation was prepared.
[0294]
　Main agent: Takelac W-6110 (trade name, manufactured by Mitsui Chemicals): 100 parts by mass
　Cross-linking agent: Aqueous dispersion of polycarbodiimide composition: 2 parts by mass
　Pigment: AF Blue E-2B (trade name, manufactured by Dainichiseika Kogyo) : 23 parts by mass
　Distilled water: 75 parts by mass
　Next, the test attachment white cloth (JIS L 0803 (2011) compliant, Kanakin No. 3) used in JIS L 0849 (2013) is about 220 mm in length and about 220 mm in width. It was cut to 30 mm, soaked with the above-mentioned compounding solution, dried overnight at room temperature, and dried at 80 ° C. for 5 minutes to obtain a test piece.
[0295]
　On the other hand, a white cloth attached to the test (JIS L 0803 (2011) compliant, Kanakin No. 3) was cut into a length of about 50 mm and a width of about 50 mm and moistened with distilled water to obtain a white cloth for friction.
[0296]
　Then, the above-mentioned test piece and the white cloth for friction were put into No. 428 Gakushin type wear tester (manufactured by Yasuda Seiki Seisakusho, friction tester type II) was attached and rubbed under the conditions of a load of 200 g, a runout width of 100 mm, and a number of reciprocations of 100 times (30 times / minute).
[0297]
　The L value of the white cloth for friction after rubbing was measured using a spectrocolor meter 2000 (Nippon Denshoku Industries Co., Ltd.).
[0298]
　The higher the L value, the whiter the color, indicating that the degree of contamination is small, and the L value of the friction white cloth before the test is 92.
[0299]
[table 1]

[0300]
[Table 2]

[0301]
[Table 3]

[0302]
[Table 4]

[0303]
　Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be construed in a limited manner. Modifications of the present invention that will be apparent to those skilled in the art are included in the claims below.
Industrial availability
[0304]
　The polycarbodiimide composition of the present invention, the method for producing a polycarbodiimide composition, the aqueous dispersion composition, the solution composition, the resin composition and the cured resin are the coating material, the adhesive material (adhesive), the adhesive material (adhesive material). , Ink, sealant, molding material, foam and optical material, resin modifier, printing treatment agent, fiber treatment agent (carbodiimide cross-linking agent for fiber treatment) and the like.
The scope of the claims
[Claim 1]
　A polycarbodiimide composition containing a carbodiimide modified product of a reaction product of a linear aliphatic diisocyanate and alcohols,
　wherein the alcohols contain a polyol and a monool, and in the
　alcohols, a hydroxyl group derived from the monool. The molar ratio of the number of hydroxyl groups derived from the polyol (hydroxyl group derived from the polyol / hydroxyl group derived from monool) to the number is less than 2.0, and
　the carbodiimide equivalent of the polycarbodiimide composition is 300 g / mol or more and less than 550 g / mol. A
polycarbodiimide composition, characterized in that it is present.
[Claim 2]

The polycarbodiimide composition according to claim 1, 　wherein the polyol has a molecular weight of 120 or more and 1000 or less .
[Claim 3]

The polycarbodiimide composition according to claim 1, 　wherein the polyol has an average number of functional groups of 2 .
[Claim 4]

The polycarbodiimide composition according to claim 1, 　wherein the linear aliphatic diisocyanate is 1,5-pentane diisocyanate .
[Claim 5]
　In the chromatogram when the polycarbodiimide composition was measured by gel permeation chromatograph, the
　area ratio of the peak area having a polystyrene-equivalent molecular weight of 500 or less to the total peak area was 6.5% or less, and the
　polystyrene-equivalent molecular weight was 1000 or less. The
polycarbodiimide composition according to claim 1, wherein the area ratio of the peak area of ​​the above to the total peak area is 10.0% or less .
[Claim 6]
　It
　comprises a urethanization step in which a linear aliphatic diisocyanate and alcohols are urethanized, and a carbodiimidization step in which the reaction product in the urethanization step is heated in the presence of a carbodiimidization catalyst to cause a carbodiimidization reaction
.
　The alcohols include a polyol and monool, and in the
　alcohols, the molar ratio of the number of hydroxyl groups derived from the polyol (the hydroxyl group derived from the polyol / the hydroxyl group derived from monool) to the number of hydroxyl groups derived from the monool is 2.0. In the
　urethanization step, the equivalent ratio (NCO / OH) of the isocyanate group of the linear aliphatic diisocyanate to the total amount of the hydroxyl group of the monool and the hydroxyl group of the polyol is 3 or more and less than 8. A
method for producing a polycarbodiimide composition.
[Claim 7]

　An aqueous dispersion 　composition according to claim 1, wherein the polycarbodiimide composition is an aqueous dispersion liquid dispersed in water at a solid content concentration of 5% by mass or more and 90% by mass or less
.
[Claim 8]

　A solution 　composition according to claim 1, wherein the polycarbodiimide composition is a solution dissolved in an organic solvent at a solid content concentration of 5% by mass or more and 90% by mass or less
.
[Claim 9]
　A resin composition
　comprising a main agent having a carboxyl group and a curing agent containing the polycarbodiimide composition according to claim 1
.
[Claim 10]
　A cured resin product, which is a cured product of the resin composition according to claim 9.
[Claim 11]
　A
carbodiimide cross-linking agent for fiber treatment, which comprises the polycarbodiimide composition according to claim 1 .