Carbodiimide Crosslinking Agents for Textile Treatment

Abstract

To provide a carbodiimide crosslinking agent for fiber treatment that achieves improved friction fastness in printing at a relatively low temperature.SOLUTION: The present invention provides a carbodiimide crosslinking agent for fiber treatment, comprising a polycarbodiimide composition which is obtained by carbodiimidizing a reaction product of a linear aliphatic diisocyanate and an alcohol, and which is configured such that: the alcohol contains a polyol and a monool; and the carbodiimide equivalent of the polycarbodiimide composition is less than 550 g / mol.SELECTED DRAWING: None

Description

[Technology Field]

[0001] This invention relates to a carbodiimide crosslinking agent for fiber processing. [Background technology]

[0002] Conventionally, a known textile processing method involves preparing an ink by mixing a pigment, a water-dispersible resin, and a crosslinking agent, printing the ink onto the fabric, and then curing the ink to form an image on the fabric. Furthermore, the use of a carbodiimide composition as a crosslinking agent in textile processing has been proposed.

[0003] As an example of a carbodiimide composition, a polycarbodiimide composition has been proposed, which is obtained by reacting dicyclohexylmethane-4,4-diisocyanate with a carbodiimide reaction, and then reacting the resulting reaction product with polyoxyethylene glycol of molecular weight 1000 and polyoxyethylene glycol (see, for example, Patent Document 1 (Synthesis Example 5)). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-104605 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Crosslinking agents for textile printing are required to produce fibers with excellent friction fastness (abrasion resistance) even when the printing process is performed at relatively low temperatures (for example, below 120°C).

[0006] However, when the carbodiimide composition described in Patent Document 1 is used as a crosslinking agent for textile printing, there is a problem in that the friction fastness of the textile printing process is not sufficient.

[0007] The present invention relates to a carbodiimide crosslinking agent for textile processing that can improve friction fastness when textile printing is performed at relatively low temperatures. [Means for solving the problem]

[0008] The present invention [1] comprises a polycarbodiimide composition comprising a carbodiimide modified product of a reaction between a linear aliphatic diisocyanate and alcohols, wherein the alcohols include polyols and monools, and the carbodiimide equivalent of the polycarbodiimide composition is less than 550 g / mol, comprising a carbodiimide crosslinking agent for fiber treatment.

[0009] The present invention [2] contains the fiber treatment carbodiimide crosslinking agent described in [1] above, wherein the molecular weight of the polyol is 120 or more and 1000 or less.

[0010] The present invention [3] comprises the fiber treatment carbodiimide crosslinking agent described in [1] or [2] above, wherein the average number of functional groups of the polyol is 2.

[0011] The present invention [4] comprises a carbodiimide crosslinking agent for fiber treatment according to any one of the above [1] to [3], wherein the linear aliphatic diisocyanate is 1,5-pentanediisocyanate.

[0012] The present invention [5] includes a carbodiimide crosslinking agent for fiber treatment described in any one of the above [1] to [4], wherein, in the chromatogram obtained by gel permeation chromatography of the polycarbodiimide composition, the area ratio of the peak area with a polystyrene equivalent molecular weight of 500 or less to the total peak area is 6.5% or less, and the area ratio of the peak area with a polystyrene equivalent molecular weight of 1000 or less to the total peak area is 10.0% or less. [Effects of the Invention]

[0013] In the present invention, a carbodiimide crosslinking agent for fiber treatment is obtained by the reaction of a linear aliphatic diisocyanate with alcohols containing polyols. This prepolymer is then carbodiimidized to obtain a relatively high molecular weight carbodiimide modified product. As a result, by using this carbodiimide crosslinking agent for fiber treatment, it is possible to improve the friction fastness when printing is performed at relatively low temperatures (120°C or below). [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 shows the GPC chromatogram of the polycarbodiimide composition obtained in Example 1. [Modes for carrying out the invention]

[0015] The carbodiimide crosslinking agent for fiber treatment of the present invention is a crosslinking agent (crosslinking agent for printing) used for printing on fibers or leather. In the following, the carbodiimide crosslinking agent for fiber treatment may be simply referred to as a crosslinking agent.

[0016] The crosslinking agent contains a polycarbodiimide composition, and preferably the crosslinking agent consists of a polycarbodiimide composition.

[0017] The polycarbodiimide composition contains, as a main component (for example, in a proportion of 90% by mass or more relative to the polycarbodiimide composition), a carbodiimide modified product of the reaction between a linear aliphatic diisocyanate and alcohols.

[0018] Carbodiimide-modified compounds can be obtained by carbodiimide-forming the reaction products of linear aliphatic diisocyanates and alcohols.

[0019] Examples of linear aliphatic diisocyanates include linear aliphatic diisocyanates with 1 to 20 carbon atoms, such as ethylene diisocyanate, 1,3-propane diisocyanate, 1,4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 1,8-octanediisocyanate (octamethylene diisocyanate), and 1,12-dodecane diisocyanate (dodecamethylene diisocyanate).

[0020] These linear aliphatic diisocyanates can be used alone or in combination of two or more types.

[0021] By using a linear aliphatic diisocyanate, it is possible to improve low-temperature curability and friction fastness.

[0022] As the linear aliphatic diisocyanate, from the viewpoint of improving low-temperature curability and friction fastness, preferably, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI) can be mentioned, and more preferably, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI) can be mentioned.

[0023] In particular, 1,5-pentane diisocyanate has fewer carbon atoms and a smaller molecular weight than 1,6-hexane diisocyanate. Therefore, when producing a polycarbodiimide composition with the same molecular weight, when using 1,5-pentane diisocyanate, compared with the case of using 1,6-hexane diisocyanate, the carbodiimide group concentration in the polycarbodiimide composition can be increased. In addition, 1,5-pentane diisocyanate with an odd number of carbon atoms has lower crystallinity due to the amorphous structure derived from the odd number of carbon atoms than 1,6-hexane diisocyanate with an even number of carbon atoms, and thus has excellent fluidity and dispersibility. As a result, it is possible to improve low-temperature curability and friction fastness.

[0024] Furthermore, when using 1,5-pentamethylene diisocyanate, compared with the case of using 1,6-hexamethylene diisocyanate, the thermal decomposition of the uretonimine group described later is likely to occur. Therefore, a polycarbodiimide composition can be obtained in a good yield. In addition, since it can be handled even at a low temperature, the high molecular weight of uretonimine can be suppressed.

[0025] Alcohols contain polyols and monools, and preferably consist of polyols and monools.

[0026] A polyol is an organic compound having two or more hydroxyl groups in the molecule, and examples include monomer polyols and polymer polyols.

[0027] Monomeric polyols are organic monomers (single compounds (hereinafter the same)) having two or more hydroxyl groups in their molecule, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 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-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C2-20)diols, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1, Examples include 3- or 1,4-cyclohexanediols and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octen-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, and other dihydric alcohols; trihydric alcohols such as glycerin, trimethylolpropane, and triisopropanolamine; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, allitol, isitol, dalcitol, althritol, inositol, and dipentaerythritol; heptahydric alcohols such as perceitol; and octahydric alcohols such as sucrose.

[0028] These monomeric polyols can be used individually or in combination of two or more types.

[0029] Preferably, the monomer polyol is a dihydric alcohol, and more preferably, 1,6-hexanediol or 1,10-decanediol.

[0030] Polymer polyols are organic polymers (polymerized compounds (hereinafter the same)) having two or more hydroxyl groups in their molecules. Examples include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. Preferably, polyether polyols, polyester polyols, and polycarbonate polyols are used.

[0031] Examples of polyether polyols include polyoxyalkylene (2-3 carbon atoms) polyols and polytetramethylene ether polyols.

[0032] Examples of polyoxyalkylene (C2-C3) polyols include monomeric polyols and addition polymers of C2-C3 alkylene oxides initiated from known monomeric (low molecular weight) polyamines.

[0033] Examples of monomeric polyols include the monomeric polyols described above, preferably dihydric alcohols and trihydric alcohols, and more preferably dihydric alcohols.

[0034] Examples of alkylene oxides having 2 to 3 carbon atoms include propylene oxide (1,2-propylene oxide) and ethylene oxide. These alkylene oxides can be used individually or in combination of two or more types.

[0035] Examples of polyoxyalkylene (C2-C3) polyols include, for example, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene-polyoxypropylene glycol (random and / or block copolymers of propylene oxide and ethylene oxide).

[0036] Furthermore, polyoxyalkylene (2-3 carbon atoms) polyols also include polytrimethylene glycol, among others.

[0037] Examples of polytrimethylene ether glycols include glycols obtained by the polycondensation reaction of 1,3-propanediol derived from plant components.

[0038] Examples of polytetramethylene ether polyols include ring-opening polymers obtained by cationic polymerization of tetrahydrofuran (polytetramethylene ether glycol (crystalline)), and amorphous (non-crystalline) polytetramethylene ether glycols obtained by copolymerizing alkyl-substituted tetrahydrofuran or the aforementioned dihydric alcohols with polymerization units such as tetrahydrofuran.

[0039] Examples of polyester polyols include polycondensates obtained by reacting monomeric polyols with polybasic acids under known conditions.

[0040] Examples of monomeric polyols include the monomeric polyols mentioned above, and preferably, dihydric alcohols.

[0041] Examples of polybasic acids include saturated aliphatic dicarboxylic acids (C11-C13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, and sebacic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, and naphthalenedicarboxylic acid; and hexahydro Examples include alicyclic dicarboxylic acids such as phthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, and het acid, and acid anhydrides derived from these carboxylic acids, such as oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic acid anhydride, 2-alkyl(C12-C18) succinic anhydride, tetrahydrophthalic anhydride, and trimellitic anhydride, as well as acid halides derived from these carboxylic acids, such as oxalic acid dichloride, adipic acid dichloride, and sebacate acid dichloride.

[0042] These polybasic acids can be used individually or in combination of two or more types.

[0043] Preferred polybasic acids include saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and acid anhydrides.

[0044] Furthermore, examples of polyester polyols include plant-derived polyester polyols, specifically, plant oil-based polyester polyols obtained by condensing a hydroxycarboxylic acid such as a hydroxyl group-containing vegetable oil fatty acid (e.g., castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) with a monomer polyol as an initiator under known conditions.

[0045] Furthermore, examples of polyester polyols include lactone-based polyester polyols such as polycaprolactone polyol and polyvalerolactone polyol, which are obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, or lactides such as L-lactide and D-lactide, using the above-mentioned monomer polyol (preferably a dihydric alcohol) as an initiator. In addition, alcohol-modified lactone polyols obtained by copolymerizing these with the above-mentioned dihydric alcohol are also included.

[0046] Examples of polycarbonate polyols include ring-opening polymers of ethylene carbonate (crystalline polycarbonate polyols) initiated by the monomer polyols described above (preferably the dihydric alcohols), and amorphous polycarbonate polyols obtained by copolymerizing a ring-opening polymer with a dihydric alcohol having 4 to 6 carbon atoms (such as 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, or 1,6-hexanediol). Also, plant-derived polycarbonate polyols derived from plant-derived raw materials such as isosorbide are also examples. Amorphous indicates that the substance is liquid at room temperature (25°C). Crystalline indicates that the substance is solid at room temperature (25°C).

[0047] These polymer polyols can be used individually or in combination of two or more types.

[0048] From the viewpoint of improving low-temperature curability and frictional fastness, the polymer polyols preferably include polyether polyols and polyester polyols (preferably lactone-based polyester polyols), more preferably polyether polyols, and even more preferably polytetramethylene ether polyols.

[0049] These polyols can be used individually or in combination of two or more types.

[0050] Preferably, polyols are polyols that have been used for a long time.

[0051] The molecular weight of the polyol (or the average molecular weight of the polyols when multiple polyols are used in combination) is, from the viewpoint of low-temperature curability and frictional fastness, for example, 60 or more, preferably 100 or more, more preferably 120 or more, even more preferably 150 or more, even more preferably 200 or more, and particularly preferably 300 or more. For example, it is 5000 or less, preferably 3000 or less, more preferably 2000 or less, even more preferably 1500 or less, and particularly preferably 1000 or less.

[0052] If the molecular weight of the polyol is within the above range, excellent low-temperature curability and frictional fastness can be obtained.

[0053] The molecular weight of monomeric polyols can be calculated from their molecular skeleton and number of atoms. The molecular weight of polymeric polyols is determined as a number-average molecular weight, calculated as the molecular weight equivalent to standard polystyrene using gel permeation chromatography. The molecular weight of a polyol is then calculated as the average value of the molecular weights of its components.

[0054] Furthermore, the average number of functional groups in the polyol is, for example, 2 or more, preferably 8 or less, more preferably 6 or less, more preferably 4 or less, even more preferably 3 or less, and particularly preferably 2, from the viewpoint of low-temperature curability and frictional fastness.

[0055] A monool is an organic compound having one hydroxyl group in its molecule, and examples include monomeric monools and polymeric monools.

[0056] Monomeric monools are organic monomers having one hydroxyl group in their molecule, and examples include aliphatic monools such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol (10 carbon atoms), lauryl alcohol (12 carbon atoms), cetyl alcohol (14 carbon atoms), stearyl alcohol (18 carbon atoms), oleyl alcohol (18 carbon atoms), and eicosanol (20 carbon atoms); ether monools such as 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol monomethyl ether (also known as methyl cellosolve), and diethylene glycol monoethyl ether (also known as ethyl carbitol); and aromatic alcohols such as phenol and its derivatives, benzyl alcohol and its derivatives, phenethyl alcohol and its derivatives, and naphthol and its derivatives.

[0057] These monomeric monools can be used individually or in combination of two or more types.

[0058] Preferably, the monomeric monool is an aliphatic monool, more preferably an aliphatic monool having 2 to 6 carbon atoms, and even more preferably isobutanol.

[0059] A polymer monool is an organic polymer having one hydroxyl group in its molecule, for example, a encapsulated polymer polyol in which the ends are sealed with alkyl groups except for one end. These are some examples.

[0060] More specifically, examples include encapsulated polymers (sometimes referred to as single-end encapsulated polymer diols) in which one end of a bifunctional polymer polyol (polymer diol) is encapsulated by an alkyl group or the like.

[0061] Examples of end-capping polymer diols include end-capping polyether diols, end-capping polyester diols, end-capping polycarbonate diols, end-capping polyurethane diols, end-capping epoxy diols, end-capping vegetable oil diols, end-capping polyolefin diols, end-capping acrylic diols, and end-capping vinyl monomer-modified diols, with end-capping polyether diols being preferred.

[0062] Examples of end-capped polyetherdiols include, more preferably, end-capped polyoxyethylene glycol and end-capped polyoxyethylene-polyoxypropylene glycol.

[0063] Single-ended polyoxyethylene glycol is a polyethylene glycol monoalkyl ether in which one of the terminal hydroxyl groups of polyoxyethylene glycol is encapsulated with an alkyl group (i.e., the hydroxyl group is replaced with an oxyalkylene group).

[0064] End-capped polyoxyethylene-polyoxypropylene glycol can be obtained by known methods, without any particular limitations.

[0065] In polyethylene glycol monoalkyl ethers, the number of carbon atoms in the alkyl group is 1 or more, for example, 20 or less, preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 2 or less. That is, examples of alkyl groups for sealing one end include a methyl group and an ethyl group.

[0066] Examples of such polyethylene glycol monoalkyl ethers include polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.

[0067] One-ended polyoxyethylene-polyoxypropylene glycol is a polyoxyethylene-polyoxypropylene glycol monoalkyl ether in which one of the terminal hydroxyl groups of polyoxyethylene-polyoxypropylene glycol is encapsulated with an alkyl group (i.e., the hydroxyl group is replaced with an oxyalkylene group).

[0068] One-ended polyoxyethylene-polyoxypropylene glycol is not particularly limited and can be obtained by known methods. Specifically, for example, it can be obtained by adding ethylene oxide and propylene oxide using a monohydric alcohol (such as a monoalkyl ether of dipropylene glycol) in which one of the terminal hydroxyl groups of the dihydric alcohol described above is encapsulated with an alkyl group as an initiator.

[0069] In polyoxyethylene-polyoxypropylene glycol monoalkyl ethers, the number of carbon atoms in the alkyl group is 1 or more, for example, 20 or less, preferably 8 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 2 or less. That is, preferred alkyl groups for encapsulating one end include methyl groups and ethyl groups.

[0070] Examples of such polyoxyethylene-polyoxypropylene glycol monoalkyl ethers include polyoxyethylene-polyoxypropylene glycol monomethyl ether and polyoxyethylene-polyoxypropylene glycol monoethyl ether.

[0071] Furthermore, in polyoxyethylene-polyoxypropylene glycol monoalkyl ether, the ratio of oxyethylene groups to the total mass of oxyethylene groups and oxypropylene groups is, from the viewpoint of low-temperature curability and frictional fastness, for example, 1% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0072] These polymer monools can be used individually or in combination of two or more types.

[0073] As a polymer monool, from the viewpoint of low-temperature curability and frictional fastness, one-end capped polyoxyethylene-polyoxypropylene glycol is preferred.

[0074] These monoalls can be used individually or in combination of two or more types.

[0075] Preferably, the monool is either a polymer monool used alone or a polymer monool and a monomer monool used in combination. More preferably, the polymer monool is used alone.

[0076] When polymer monools and monomer monools are used in combination, the ratio of their use, from the viewpoint of low-temperature curability and frictional resistance, is such that the polymer monool is, for example, 50 mol% or more, preferably 70 mol% or more, and for example, 90 mol% or less, preferably 80 mol% or less, relative to the total moles of the polymer monools. Also, the monomer 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.

[0077] The molecular weight of the monool (or the average molecular weight of the monools when multiple monools are used in combination) is, from the viewpoint of low-temperature curability and frictional resistance, for example, 50 or more, preferably 100 or more, more preferably 200 or more, and even more preferably 400 or more, and from the viewpoint of low-temperature curability and frictional resistance, for example, 5000 or less, preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0078] If the molecular weight of the monool is within the above range, excellent low-temperature curability and frictional fastness can be obtained.

[0079] The molecular weight of monomeric monools can be calculated from their molecular skeleton and number of atoms. The molecular weight of polymeric monools is determined as a number-average molecular weight, calculated as the polystyrene-equivalent molecular weight by gel permeation chromatography. The molecular weight of the monool is then calculated as the average of the molecular weights of its components.

[0080] In the case of alcohols, the ratio of polyols and monools used together is determined based on the molar ratio of the number of hydroxyl groups derived from the polyol to the number of hydroxyl groups derived from the monool.

[0081] Specifically, from the viewpoint of low-temperature curability and frictional fastness, the molar ratio of hydroxyl groups derived from polyol to hydroxyl groups derived from monool (hydroxyl groups derived from polyol / hydroxyl groups derived from monool) is, for example, 0.1 or more, preferably 0.5 or more, more preferably 0.8 or more, and for example, less than 2.0, preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.2 or less.

[0082] In other words, a polycarbodiimide composition containing a carbodiimide modified product can be obtained by first reacting a linear aliphatic diisocyanate as a raw material component with the above-mentioned alcohols (monools and polyols) under predetermined conditions to obtain an isocyanate-terminated prepolymer as a reaction product, and then further subjecting the isocyanate-terminated prepolymer to a carbodiimide reaction.

[0083] In such cases, if the combined ratio of polyol and monool is within the above range, a moderately high molecular weight prepolymer is obtained by the reaction of linear aliphatic diisocyanate with alcohols (described later), and this prepolymer is then carbodiimide-modified. As a result, the carbodiimide-modified product has a relatively high molecular weight, and compared to cases with relatively low molecular weights, excellent low-temperature curability and frictional fastness can be obtained.

[0084] The method for producing the polycarbodiimide composition will be described in detail below.

[0085] In this method, first, the linear aliphatic diisocyanate and the alcohols mentioned above are subjected to a urethane reaction (urethane reaction step).

[0086] In the urethane formation process, the reaction ratio between linear aliphatic diisocyanate and alcohols is set according to the types (molecular weight, etc.) of linear aliphatic diisocyanate and alcohols, such that the equivalent ratio (NCO / OH) of isocyanate groups of linear aliphatic diisocyanate to hydroxyl groups of alcohols is within the range described later, and the carbodiimide equivalent (g / mol) of the polycarbodiimide composition is set accordingly.

[0087] More specifically, although it depends on the type of linear aliphatic diisocyanate and alcohol, the reaction ratio between the linear aliphatic diisocyanate and the alcohol is such that the equivalent ratio of isocyanate groups of the linear aliphatic diisocyanate to the hydroxyl groups of the alcohol (NCO / OH) is, for example, greater than 2, preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, for example, 16 or less, preferably 10 or less, more preferably less than 8, and even more preferably 6 or less. In other words, in the urethane formation step, the reaction is preferably carried out in a ratio in which there is an excess of isocyanate groups relative to the hydroxyl groups.

[0088] If the reaction ratio between linear aliphatic diisocyanate and alcohols is within the above range, excellent low-temperature curability and frictional fastness can be obtained.

[0089] Furthermore, in this reaction, known urethane catalysts, such as amines or organometallic compounds, may be added as needed.

[0090] Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, and N-methylmorpholine; quaternary ammonium salts such as tetraethylhydroxylammonium; and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.

[0091] Examples of organometallic compounds include organotin compounds such as tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin(IV) dilaurate), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, and dibutyltin dichloride; organolead compounds such as lead octanoate and lead naphthenate; organonickel compounds such as nickel naphthenate; organocaltyl compounds such as cobalt naphthenate; organocupend compounds such as copper octate; and organobismuth compounds such as bismuth octoate and bismuth neodecanoate.

[0092] Furthermore, examples of potassium salts such as potassium carbonate, potassium acetate, and potassium octylate can be used as urethane catalysts.

[0093] These urethane catalysts can be used individually or in combination of two or more types.

[0094] The blending ratio of the urethane catalyst is not particularly limited and can be set as appropriate depending on the purpose and application.

[0095] Furthermore, the reaction conditions in the urethane formation process are set according to the types of linear aliphatic diisocyanates and alcohols, as well as the equivalent ratio (NCO / OH) mentioned above, so that the carbodiimide equivalent (g / mol) of the polycarbodiimide composition falls within the range described later.

[0096] More specifically, the reaction conditions in the urethane formation process are, for example, under atmospheric pressure and an inert gas (e.g., nitrogen gas) atmosphere, with a reaction temperature of, for example, 30°C or higher, preferably 60°C or higher, and for example, 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.

[0097] This allows for the acquisition of a prepolymer as a reaction product between a linear aliphatic diisocyanate and alcohols. The prepolymer has isocyanate groups at its molecular ends (i.e., it is an isocyanate-terminated prepolymer).

[0098] Next, in this method, the reaction solution containing the reaction product from the urethane formation step is heated in the presence of a carbodiimide catalyst to carry out the carbodiimide reaction (carbodiimide step).

[0099] The carbodiimide catalyst is not particularly limited, but examples include trialkyl phosphate ester compounds, phosphone oxide compounds, phosphone sulfide compounds, phosphine oxide compounds, and phosphine compounds.

[0100] Examples of trialkyl phosphate esters include trimethyl phosphate, triethyl phosphate, and trioctyl phosphate, which are trialkyl phosphate ester compounds having 3 to 24 carbon atoms.

[0101] Examples of phospholen oxide compounds include 3-methyl-1-phenyl-2-phosphoren-1-oxide (MPPO), 1-ethyl-3-methyl-2-phosphoren-1-oxide (EMPO), 1-butyl-3-methyl-2-phosphoren-1-oxide, 1-benzyl-3-methyl-2-phosphoren-1-oxide, 1,3-dimethyl-2-phosphoren-1-oxide, 1-phenyl-2-phosphoren-1-oxide, 1-methyl-2-phosphoren-1-oxide, 1-ethyl-2-phosphoren-1-oxide, and their double bond isomers, as well as other phosphoren oxide compounds having 4 to 18 carbon atoms.

[0102] Examples of phospholensulfide compounds include phospholensulfide compounds with 4 to 18 carbon atoms, such as 1-phenyl-2-phosphoren-1-sulfide.

[0103] Examples of phosphine oxide compounds include triphenylphosphine oxide and tritlylphosphine oxide, which are phosphine oxide compounds with 3 to 21 carbon atoms.

[0104] Examples of phosphine compounds include phosphine compounds with 3 to 30 carbon atoms, such as bis(oxadiphenylphosphino)ethane.

[0105] These carbodiimide catalysts can be used individually or in combination of two or more types.

[0106] Preferred carbodiimide catalysts include phospholene oxide compounds, more preferably 3-methyl-1-phenyl-2-phospholene-1-oxide and 1-ethyl-3-methyl-2-phospholene-1-oxide.

[0107] By using the above-mentioned carbodiimide catalyst, the activity of carbodiimide can be improved, the reaction temperature can be lowered, and side reactions such as uretonimination can be suppressed, allowing for the production of polycarbodiimide compositions in good yield and increasing the content of carbodiimide groups.

[0108] As a carbodiimide catalyst, 3-methyl-1-phenyl-2-phosphoren-1-oxide is particularly preferred from the viewpoint of obtaining excellent low-temperature curability and frictional robustness.

[0109] The proportion of the carbodiimide catalyst is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of linear aliphatic diisocyanate (linear aliphatic diisocyanate used in the urethane formation process).

[0110] Furthermore, the reaction conditions in the carbodiimide conversion step are set so that the proportion of carbodiimide groups (carbodiimide equivalents) in the resulting polycarbodiimide composition falls within a specific range described later. More specifically, from the viewpoint of promoting the progress of the carbodiimide conversion reaction and reducing uretonimine, the reaction temperature is, for example, 125°C or higher, preferably 130°C or higher, more preferably 135°C or higher, and for example, 180°C or lower, preferably 170°C or lower, and more preferably 160°C or lower, under normal pressure and an inert gas (such as nitrogen gas) atmosphere. 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.

[0111] By carrying out the reaction under these conditions, the reaction product obtained in the urethane formation process (isocyanate-terminated prepolymer) can undergo decarboxylation condensation via the isocyanate group, efficiently generating carbodiimide groups.

[0112] More specifically, if the reaction temperature is above the lower limit mentioned above, the carbodiimide reaction can proceed while promoting the decomposition reaction of the generated uretonimine into carbodiimide and isocyanate groups. Below the lower limit, this thermal decomposition reaction becomes very unlikely to occur, the uretonimine content increases, and the carbodiimide group content decreases. In addition, the molecular weight increases due to the increase in uretonimine, which may cause the reaction solution to solidify. On the other hand, if the reaction temperature is below the upper limit mentioned above, polymerization loss can be reduced. If the temperature exceeds the upper limit, polymerization reactions other than carbodiimide and uretonimine are promoted, which not only reduces the carbodiimide group content but also makes the reaction solution more likely to solidify due to the increase in molecular weight.

[0113] Furthermore, in the carbodiimide step, from the viewpoint of ensuring a smooth carbodiimide reaction and promoting decarboxylation condensation, the reaction mixture is preferably refluxed in the presence of an organic solvent. That is, the carbodiimide reaction is carried out under reflux.

[0114] Examples of organic solvents 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; aliphatic hydrocarbons such as n-hexane, n-heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; 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), and 3-methyl- Examples of organic solvents include glycol ether esters such as 3-methoxybutyl acetate and ethyl-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, and ethylene glycol diethyl ether 1,2-diethoxyethane; halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, and dichloroethane; and polar aprotons such as N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphonylamide. These organic solvents can be used individually or in combination of two or more types.

[0115] Preferably, the organic solvent is one in which the reflux temperature is within the range of the reaction temperature described above.

[0116] Examples of such organic solvents include xylene, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate.

[0117] The proportion of the organic solvent is not particularly limited, but from the viewpoint of obtaining excellent low-temperature curability and frictional resistance, it is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, and for example, 2000 parts by mass or less, preferably 500 parts by mass or less, per 100 parts by mass of linear aliphatic diisocyanate (linear aliphatic diisocyanate used in the urethane formation process).

[0118] By refluxing the reaction mixture in the presence of an organic solvent, the decomposition reaction of uretonimine can be promoted while the carbodiimide reaction can proceed smoothly. Furthermore, carbon dioxide generated during the carbodiimide conversion of the isocyanate group can be removed, thereby accelerating the carbodiimide conversion.

[0119] By this method, a carbodiimide modified product containing a urethane group and a carbodiimide group, and optionally a uretonimine group, can be obtained.

[0120] More specifically, in the urethane formation process, urethane groups derived from the isocyanate groups of the linear aliphatic diisocyanate are generated.

[0121] Next, when the reaction product obtained in the urethane formation process (isocyanate-terminated prepolymer) is heated in the carbodiimide formation process, carbodiimide groups derived from the isocyanate groups at the molecular ends are generated. In some cases, a portion of the generated carbodiimide groups reacts with the isocyanate groups at the molecular ends to form uretonimine groups. The uretonimine groups are then thermally decomposed by continued heating in the carbodiimide formation process, regenerating carbodiimide groups and isocyanate groups at the molecular ends, and further generating carbodiimide groups derived from the isocyanate groups at the molecular ends.

[0122] In this way, the isocyanate group of the linear aliphatic diisocyanate is converted to a urethane group and a carbodiimide group (and possibly a uretonimine group).

[0123] As a result, a carbodiimide modified product is obtained that contains urethane groups and carbodiimide groups, and optionally uretonimine groups.

[0124] Furthermore, this yields a polycarbodiimide composition containing a modified carbodiimide as the main component. The polycarbodiimide composition may also contain unreacted linear aliphatic diisocyanate as a minor component. The content ratio of linear aliphatic diisocyanate is appropriately set within a range that does not impair the excellent effects of the present invention.

[0125] Furthermore, in this method, if necessary, the polycarbodiimide composition obtained in the carbodiimide conversion step described above may be further reacted with alcohols. In the following, the urethane conversion step before the carbodiimide conversion step may be referred to as the first urethane conversion step, and the urethane conversion step after the carbodiimide conversion step may be referred to as the second urethane conversion step.

[0126] Specifically, if the polycarbodiimide composition obtained in the carbodiimide process further has isocyanate groups at the molecular termini, the isocyanate groups at the molecular termini can be urethane-converted by reacting the polycarbodiimide composition with alcohols.

[0127] Furthermore, when the second urethane formation step is carried out, the amount of by-products derived from alcohols increases, the molecular weight increases rapidly, fluidity decreases, and workability may be reduced. Also, the dispersibility in the aqueous dispersion composition may decrease. For this reason, it is preferable to carry out only the first urethane formation step and the carbodiimide formation step without performing the second urethane formation step.

[0128] The method for producing the polycarbodiimide composition is not limited to the above; for example, a linear aliphatic diisocyanate, a carbodiimide catalyst, and alcohols can be combined and heated together.

[0129] Furthermore, if necessary, unreacted linear aliphatic diisocyanates, unreacted alcohols, low molecular weight compounds (by-products), organic solvents, carbodiimide catalysts, urethane catalysts, etc., can be removed from the polycarbodiimide composition by known methods such as distillation, extraction, and filtration.

[0130] Furthermore, the polycarbodiimide composition may optionally contain known additives, such as storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), plasticizers, anti-blocking agents, heat stabilizers, light stabilizers, antioxidants, mold release agents, catalysts, pigments, surface modifiers, dispersants, dyes, lubricants, fillers, and hydrolysis inhibitors, at appropriate timings. The proportion of additives to be added is not particularly limited and can be set appropriately according to the purpose and application.

[0131] Furthermore, polycarbodiimide compositions can be used alone or in combination of two or more types.

[0132] The carbodiimide equivalent (g / mol) of the polycarbodiimide composition obtained in this way is, for example, 300 or more, preferably 350 or more, more preferably 400 or more, even more preferably 410 or more, particularly preferably 430 or more, and 550 or less, preferably 530 or less, more preferably 500 or less, even more preferably 480 or less, particularly preferably 460 or less.

[0133] The carbodiimide equivalent (g / mol) is determined according to the examples described later. 13 It is measured by 13C-NMR.

[0134] In other words, the carbodiimide equivalent (g / mol) can be calculated from the charging ratio, 13 The measured values ​​obtained by 13C-NMR are used.

[0135] Furthermore, because such polycarbodiimide compositions use alcohols containing polyols and monools in predetermined proportions, they have a higher molecular weight and a reduced amount of low molecular weight components compared to polycarbodiimide compositions that use only monools.

[0136] Specifically, in the chromatogram obtained by gel permeation chromatography of a polycarbodiimide composition, the area ratio of the peak area of ​​polystyrene-equivalent molecular weights of 500 or less to the total peak area is From the viewpoint of obtaining excellent frictional durability, for example, the amount is 10.0% or less, preferably 8.0% or less, more preferably 7.0% or less, even more preferably 6.5% or less, even more preferably 6.0% or less, even more preferably 5.0% or less, and particularly preferably 4.5% or less.

[0137] Furthermore, in the chromatogram obtained by gel permeation chromatography of a polycarbodiimide composition, the area ratio of the peak area of ​​polystyrene-equivalent molecular weights of 1000 or less to the total peak area is From the viewpoint of obtaining excellent frictional durability, for example, the amount is 15.0% or less, preferably 12.0% or less, more preferably 10.0% or less, even more preferably 9.0% or less, even more preferably 8.0% or less, and particularly preferably 7.0% or less.

[0138] The area ratio can be calculated by measuring the molecular weight distribution of the isocyanurate derivative of pentamethylene diisocyanate using a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), in accordance with the examples described later, and obtaining the area ratio in the resulting chromatogram (chart). The area ratios for peak areas with molecular weights of 500 or less, and for peak areas with molecular weights of 1000 or less, are based on the calibration curve for standard polystyrene.

[0139] Furthermore, if the area ratio of peak areas with a molecular weight of 500 or less is within the above range, and the area ratio of peak areas with a molecular weight of 1000 or less is within the above range, then improvements in low-temperature curability and frictional resistance can be achieved.

[0140] The carbodiimide crosslinking agent for fiber processing is not particularly limited as long as it contains a polycarbodiimide composition, but it is prepared, for example, as an aqueous dispersion in which the polycarbodiimide composition is dispersed in water (hereinafter referred to as the aqueous dispersion composition) or as a solution in which the polycarbodiimide composition is dissolved in an organic solvent (hereinafter referred to as the solution composition).

[0141] The aqueous dispersion composition contains a polycarbodiimide composition and water.

[0142] There are no particular limitations on the method for dispersing the polycarbodiimide composition in water, and examples include adding water to the polycarbodiimide composition and stirring, or adding the polycarbodiimide composition to water and stirring. Preferably, water is added to the polycarbodiimide composition.

[0143] The ratio of the polycarbodiimide composition to water is not particularly limited, but the concentration of the polycarbodiimide composition (resin component) in the water-dispersed composition (i.e., the solid content concentration) is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less.

[0144] If the curing agent is a water-dispersible composition, compatibility with water-based resins (main component) can be improved, resulting in excellent low-temperature curing properties and frictional resistance.

[0145] The solution composition contains a polycarbodiimide composition and an organic solvent.

[0146] Examples of organic solvents include the organic solvents listed above, and preferably include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.

[0147] Furthermore, the solvent used in the carbodiimide step may also be used as the organic solvent in the solution composition. For example, the solvent used after the carbodiimide step can be used as the organic solvent in the solution composition without being removed by distillation.

[0148] There are no particular limitations on the method for dissolving the polycarbodiimide composition in an organic solvent. Examples include adding the organic solvent to the polycarbodiimide composition and stirring, or adding the polycarbodiimide composition to the organic solvent and stirring. Preferably, the organic solvent is added to the polycarbodiimide composition.

[0149] The ratio of the polycarbodiimide composition to the organic solvent is not particularly limited, but the concentration of the polycarbodiimide composition (resin component) in the solution composition (i.e., the solid content concentration) is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less.

[0150] If the curing agent is a solution composition, compatibility with oil-based resins (main component) can be improved, and excellent low-temperature curing properties and frictional resistance can be obtained.

[0151] Preferably, a carbodiimide crosslinking agent for fiber processing is an aqueous dispersion of a polycarbodiimide composition.

[0152] Furthermore, in the above-mentioned carbodiimide crosslinking agent for fiber treatment, a prepolymer is obtained by the reaction of a linear aliphatic diisocyanate with alcohols containing polyols, and this prepolymer is then carbodiimidized to obtain a relatively high molecular weight carbodiimide modified product. As a result, by using the carbodiimide crosslinking agent for fiber treatment, it is possible to improve the friction fastness when printing is performed at relatively low temperatures (below 120°C).

[0153] More specifically, the carbodiimide crosslinking agent for fiber processing is suitably used as a raw material for printing inks for printing fiber materials.

[0154] The raw material for textile printing ink comprises the above-mentioned crosslinking agent as a polyisocyanate component and a main component having a carboxyl group.

[0155] Examples of main components containing carboxyl groups include aqueous resins containing carboxyl groups and oil-based resins containing carboxyl groups.

[0156] Examples of aqueous resins containing carboxyl groups include hydrophilic polymers containing carboxyl groups, specifically hydrophilic polyester resins containing carboxyl groups, hydrophilic polyamide resins containing carboxyl groups, hydrophilic polyurethane resins (hydrophilic polyurethane polyols) containing carboxyl groups, hydrophilic acrylic resins (hydrophilic acrylic polyols) containing carboxyl groups, and hydrophilic polyolefin resins containing carboxyl groups (e.g., polypropylene, polyethylene, polypropylene-polyethylene (random block) copolymers, and other polyolefins with 4 or more carbon atoms in the repeating units). These aqueous resins containing carboxyl groups can be used individually or in combination of two or more types.

[0157] Preferred examples of aqueous resins having carboxyl groups include hydrophilic polyurethane resins (hydrophilic polyurethane polyols) and hydrophilic acrylic resins (hydrophilic acrylic polyols) having carboxyl groups.

[0158] Examples of oil-based resins containing carboxyl groups include hydrophobic polymers containing carboxyl groups, specifically hydrophobic polyester resins containing carboxyl groups, hydrophobic polyamide resins containing carboxyl groups, hydrophobic polyurethane resins (hydrophobic polyurethane polyols) containing carboxyl groups, hydrophobic acrylic resins (hydrophobic acrylic polyols) containing carboxyl groups, and hydrophobic polyolefin resins containing carboxyl groups (e.g., polypropylene, polyethylene, polypropylene-polyethylene (random block) copolymers, and other polyolefins with 4 or more carbon atoms in the repeating units). These oil-based resins containing carboxyl groups can be used individually or in combination of two or more types.

[0159] Preferred examples of oil-based resins having carboxyl groups include hydrophobic polyurethane resins (hydrophobic polyurethane polyols) and hydrophobic acrylic resins (hydrophobic acrylic polyols) having carboxyl groups.

[0160] These can be used individually or in combination of two or more types.

[0161] Preferably, the main component and crosslinking agent are a combination in which the main component is an aqueous resin and the crosslinking agent is an aqueous dispersion composition. Also preferably, the main component is an oil-based resin and the crosslinking agent is a solution composition.

[0162] From the viewpoint of reducing organic solvents and protecting the global environment, a combination of an aqueous main component and an aqueous dispersion composition is preferred.

[0163] Then, a textile printing ink is prepared from such a two-component system of ink raw materials (main component and crosslinking agent).

[0164] Such ink raw materials for textile printing are not particularly limited as long as they contain the main component and the crosslinking agent described above. They may be a two-component type in which the main component and crosslinking agent are prepared separately and mixed at the time of use, or they may be a one-component type in which the main component and crosslinking agent are pre-mixed.

[0165] Preferably, a two-component type ink raw material for textile printing is used.

[0166] The content ratio of the main component and the crosslinking agent is such that, on a solid content basis, the main component 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 95.0 parts by mass or less, per 100 parts by mass of their total amount. The crosslinking 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.

[0167] Furthermore, the molar ratio of carbodiimide groups in the crosslinking agent to carboxyl groups in the main component is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more, and for example, 2.5 or less, preferably 2.0 or less, more preferably 1.5 or less.

[0168] Furthermore, a pigment is preferably incorporated into either the crosslinking agent or the main component, or both. The pigment is not particularly limited and examples include blue pigments, white pigments, black pigments, and so on.

[0169] The proportion of pigment added 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, relative to the total sum of the crosslinking agent, main component and pigment.

[0170] Furthermore, the crosslinking agent and / or the main component may contain, as needed, additives such as epoxy resins, catalysts (e.g., urethane catalysts), coating modifiers, leveling agents, viscosity modifiers, defoamers, stabilizers such as antioxidants and UV absorbers, plasticizers, surfactants, surface modifiers, dispersants, fillers, organic or inorganic fine particles, fungicides, and silane coupling agents. The amount of these additives is determined appropriately depending on the purpose and application.

[0171] Furthermore, the above-mentioned aqueous resin having a carboxyl group and / or the above-mentioned oil-based resin having a carboxyl group can be used in combination with other resins (for example, hydroxyl group-containing polyurethane resin, hydroxyl group-containing acrylic resin, hydroxyl group-containing polyester resin, etc.) as the main component.

[0172] Furthermore, the polycarbodiimide composition described above can be used in combination with other crosslinking agents (for example, polyisocyanate resins (such as blocked polyisocyanate), epoxy resins, melamine resins, etc.) as crosslinking agents.

[0173] The printing ink is then printed onto the object to be printed using a known printing device (for example, an inkjet device), and subsequently heated and cured as needed.

[0174] Examples of materials that can be printed include textiles, and more specifically, fabrics and leather.

[0175] The fibers of the fabric are not particularly limited and include, for example, natural fibers (e.g., silk, cotton, linen, etc.) and synthetic fibers (e.g., nylon, polyester, rayon, etc.). The form of the fabric is not particularly limited and includes, for example, woven fabrics, knitted fabrics, and nonwoven fabrics. The leather is not particularly limited and includes, for example, natural leather and artificial leather.

[0176] 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. Typically, it is 5°C or higher, more preferably 20°C or higher.

[0177] This process forms an ink-cured product (cured coating film, polyurethane resin). Since the resulting ink-cured product is formed from the above-mentioned printing ink, it exhibits excellent low-temperature curing properties and abrasion resistance. [Examples]

[0178] Next, the present invention will be described based on manufacturing examples, embodiments, and comparative examples, but the present invention is not limited to the embodiments described below. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, specific numerical values ​​such as blending ratios (content percentages), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the blending ratios (content percentages), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0179] <IRスペクトル> The completion of the carbodiimide reaction in the method for producing the polycarbodiimide composition was confirmed by measuring the IR spectrum using the following apparatus and conditions.

[0180] IR measurement device: Perkin Elmer Frontier FT-IR Measurement method: ATR (reflection method) Wavenumber range: 4000-400cm -1 Resolution 4cm -1 <Carbodiimide equivalent (g / mol) of polycarbodiimide composition> The carbodiimide equivalent of the polycarbodiimide composition is 13 The measured values ​​were determined from the results of 1C-NMR. Additionally, the calculated carbodiimide equivalent from the initial charge was obtained as a reference value.

[0181] In other words, with the following equipment and conditions 13 1C-NMR was measured, and the percentage of uretonimine groups relative to the total of 1 mole of carbodiimide groups, uretonimine groups, allophanate groups, and urethane groups was calculated using the following formula. Tetramethylsilane in CDCL3 solvent (0 ppm) was used as the standard for chemical shift ppm. Equipment; ECA-500 model (manufactured by JEOL) Conditions: Measurement frequency: 125 MHz, Solvent: CDCL3, Solute concentration: 50% by mass Measurement temperature: Room temperature, Number of scans: 8500 Repetition time: 3.0 seconds, pulse width: 30° (3.70 μs) Carbon assignment peak of the carbodiimide group (N=C=N group within the carbodiimide group) :139ppm Assignment peaks of carbon atoms in the uretonimine group (C=O and C=N groups within the uretonimine group) : 159 ppm, 145 ppm Carbon assignment peak of the allophanate group (C=O group within the allophanate group) :154ppm (Assignment peak of carbon in the urethane group (C=O group within the urethane group)) :156ppm (Carbodiimide equivalent) = {(Weight of solids added) - (Molar ratio of carbon dioxide generated to urethane groups) × (Total moles of alcohol added) × 44.01} / {(Molar ratio of carbodiimide groups to urethane groups) × (Total moles of alcohol added)} The molar ratio of generated carbon dioxide to urethane groups and the molar ratio of carbodiimide groups to urethane groups are calculated as follows.

[0182] (Molar ratio of carbon dioxide generated relative to urethane group) = {(integral value of carbodiimide group) + (integral value of uretonimine group)} / {(integral value of urethane group) + (integral value of allophanate group)} (Molar ratio of carbodiimide groups to urethane groups) = (Integral value of carbodiimide groups) / {(Integral value of urethane groups) + (Integral value of allophanate groups)} <Area ratio> Using a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), the ratio of peak areas with a polystyrene-equivalent molecular weight of 500 or less to the total peak area, and the ratio of peak areas with a polystyrene-equivalent molecular weight of 1000 or less to the total peak area were determined from the chromatograms obtained under the following GPC measurement conditions.

[0183] Figure 1 shows the GPC chromatogram of the polycarbodiimide composition obtained in Example 1, which will be described later. In the figure, the peak number, retention time, and molecular weight of the peak top are also shown.

[0184] Equipment: HLC-8320GPC (manufactured by Tosoh Corporation) Three LF-804 columns (Shodex brand name) connected in series. Column temperature: 40°C Eluent; tetrahydrofuran Flow rate: 1.0mL / min Detection method; differential refractive index Standard material; standard polyconducting compound Manufacturing Example 1 (Manufacturing of pentane diisocyanate) 99.9% by mass of 1,5-pentanediisocyanate (hereinafter sometimes abbreviated as PDI) was obtained by the same procedure as in Example 1 of the specification in the international publication pamphlet WO2012 / 121291.

[0185] Manufacturing Example 2 (Production of polyoxyethylene-polyoxypropylene monomethyl ether) Using dipropylene glycol monomethyl ether as an initiator and potassium hydroxide (hereinafter referred to as KOH) as a catalyst, these alkylene oxides (ethylene oxide and propylene oxide) were randomly added and polymerized at a temperature of 110°C and a maximum reaction pressure of 0.4 MPa gauge (G) until the hydroxyl value (hereinafter referred to as OHV) reached 102 mg KOH / g, so that the mass ratio of ethylene oxide to propylene oxide in the polyol was 50:50, thereby preparing a crude polyol.

[0186] Next, to the crude polyol heated to 80°C under a nitrogen atmosphere, deionized water and 1.05 equivalents of phosphoric acid (in the form of a 75.2% by weight aqueous solution) relative to KOH were added, and the mixture was neutralized at 80°C for 2 hours.

[0187] Next, dehydration under reduced pressure was initiated while increasing the temperature, and an adsorbent was added when the pressure reached 40 kPa. Finally, the mixture was heated and subjected to reduced pressure for 3 hours at 105°C and a pressure of 1.33 kPa or less.

[0188] Subsequently, polyoxyethylene-polyoxypropylene monomethyl ether was obtained by filtration.

[0189] The ratio of oxyethylene groups to the total amount of oxyethylene and oxypropylene groups in polyoxyethylene-polyoxypropylene monomethyl ether (hereinafter referred to as the EO ratio) was 50% by mass. Furthermore, the number-average molecular weight, measured by gel permeation chromatography, was 550.

[0190] This polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) was designated as monool A.

[0191] Example 1 • Production of polycarbodiimide compositions In a four-necked flask equipped with a stirrer, thermometer, reflux tubing, and nitrogen inlet tube, 100.0 parts by mass of pentamethylene diisocyanate (PDI) obtained in Production Example 1, 16.2 parts by mass of PTG-250 (polytetramethylene ether glycol, molecular weight 250), and 71.4 parts by mass of monool A (polyoxyethylene-polyoxypropylene monomethyl ether obtained in Production Example 2 (EO ratio 50% by mass, molecular weight 550)) were charged at room temperature. The mixture was heated to 80°C under atmospheric pressure while introducing nitrogen and stirred for 4 hours (urethane formation process).

[0192] Next, 758.3 parts by mass of propylene glycol monomethyl ether acetate (PMA) and 2.0 parts by mass of 3-methyl-1-phenyl-2-phosphoren-1-oxide (MPPO) were added, and the mixture was stirred under reflux (150°C) (carbodiimide step). The completion of the reaction was confirmed by infrared absorption (IR) spectroscopy, which showed a reading of 2260 cm⁻¹, originating from the stretching vibration of the isocyanate group. -1 This was confirmed by the near-complete disappearance of the absorption peak in the vicinity.

[0193] After the reaction was complete, the mixture was cooled to 80°C, and the PMA was removed under reduced pressure until the remaining PMA content was 2% or less, to obtain a polycarbodiimide composition. 13 ¹³C-NMR measurements revealed that the carbodiimide equivalent was 450 g / mol (calculated value: 317 g / mol).

[0194] Furthermore, a portion of the obtained polycarbodiimide composition was extracted, and its E-type viscosity at 25°C was measured to be 4000 mPa·s.

[0195] Preparation of aqueous dispersions (aqueous dispersions) of polycarbodiimide compositions. A polycarbodiimide composition was placed in a flask, and distilled water was gradually added until the resin solids content reached 40%, and the mixture was stirred to obtain an aqueous dispersion of the polycarbodiimide composition.

[0196] Preparation of aqueous resin compositions The obtained aqueous dispersion of polycarbodiimide composition was used as a curing agent. A polyurethane dispersion (30% by mass solids, 1122 g / mol of carboxyl groups in the solids) was used as the main component, and the mixture was prepared by mixing the curing agent and the main component so that the equivalent ratio of carbodiimide groups to carboxyl groups was 0.5.

[0197] 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.

[0198] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0199] Example 3 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 9.5 parts by mass of PTG-250, 83.9 parts by mass of monool A, and 781.9 parts by mass of PMA were used. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0200] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0201] Example 4 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 35.1 parts by mass of PTG-650 (polytetramethylene ether glycol, molecular weight 650) was used instead of PTG-250, 59.5 parts by mass of monool A, and 786.4 parts by mass of PMA. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0202] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0203] Example 5 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 45.9 parts by mass of PTG-850 (polytetramethylene ether glycol, molecular weight 850) was used instead of PTG-250, 59.5 parts by mass of monool A, and 829.6 parts by mass of PMA. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0204] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0205] 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. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0206] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0207] Example 7 Monoall A (polyoxyethylene-polyoxypropylene monomethyl ether obtained in Production Example 2 (EO ratio 50% by mass, molecular weight 550)) and isobutanol were mixed in a molar ratio of 3:1. This solution was designated as Monoall B.

[0208] Then, a polycarbodiimide composition was obtained in the same manner 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 (in the table, a solution in which polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) and isobutanol are mixed in a molar ratio of 3:1 is denoted as monool B).

[0209] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0210] Example 8 A polycarbodiimide composition was obtained in the same manner as in Example 1, 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. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0211] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0212] Example 9 A polycarbodiimide composition was obtained 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. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0213] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0214] Example 10 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 69.5 parts by mass of PTG-1500 (polytetramethylene ether glycol, molecular weight 1500) was used instead of PTG-250, 51.0 parts by mass of monool A, and 889.9 parts by mass of PMA. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0215] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0216] Example 11 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 13.0 parts by mass of PCL 303 (Plaxel 303, polycaprolactone triol, molecular weight 300, manufactured by Daicel Corporation) and 745.3 parts by mass of PMA were used instead of PTG-250. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0217] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0218] Example 12 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 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 were used instead of PDI. The analytical values ​​of the obtained polycarbodiimide composition are shown in Table 1.

[0219] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0220] 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.

[0221] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0222] 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.

[0223] Furthermore, an aqueous dispersion of the polycarbodiimide composition was prepared using the same method as in Example 1, and a resin composition was prepared.

[0224] Comparative Example 2 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.

[0225] Also, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared to obtain a resin composition.

[0226] Comparative Example 3 · Production of polycarbodiimide composition Into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 200.0 parts by mass of 4,4-dicyclohexylmethane diisocyanate (H 12 MDI) and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) were enclosed. 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).

[0227] Next, 100.0 parts by mass of the obtained carbodiimide, 13.6 parts by mass of PTG-250, and 60.0 parts by mass of Uniox M550 (polyoxyethylene monomethyl ether, molecular weight 550, manufactured by NOF Corporation) were enclosed in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, and the reaction was carried out at 120 ° C while introducing nitrogen (urethane formation step). The completion of the reaction was confirmed by the almost disappearance of the absorption peak around 2260 cm -1 derived from the stretching vibration of the isocyanate group by infrared absorption (IR) spectrum measurement.

[0228] · Preparation of an aqueous dispersion (aqueous dispersion composition) of the polycarbodiimide composition The obtained polycarbodiimide composition derived from H 12 MDI was put into a flask, and distilled water was gradually added while heating to 80 ° C so that the resin solid content became 40%. After stirring for 5 minutes and then cooling, an aqueous dispersion of the polycarbodiimide composition was obtained.

[0229] · Preparation of an aqueous resin composition The resulting aqueous dispersion of polycarbodiimide composition was used as a curing agent. A hydrophilic polyurethane having carboxyl groups (polyurethane dispersion, solid content 30% by mass, carboxyl group equivalent of solid content 1122 g / mol) was used as the main component, and the mixture was prepared by mixing the curing agent and the carboxyl groups in the main component so that the equivalent ratio of carbodiimide groups in the curing agent to carboxyl groups in the main component was 0.5.

[0230] Comparative Example 4 A polycarbodiimide composition was synthesized according to the method described in Synthesis Example 5 of Japanese Patent Application Publication No. 2018-104605, and an aqueous dispersion of the polycarbodiimide composition was prepared in the same manner as in each example.

[0231] That is, in a four-necked flask equipped with a stirrer, thermometer, reflux tube and nitrogen inlet tube, 4,4-dicyclohexylmethane diisocyanate (H) is added at room temperature. 12 100.0 parts by mass of MDI and 0.5 parts by mass of 3-methyl-1-phenyl-2-phosphoren-1-oxide (MPPO) were sealed in. The mixture was reacted at 180°C for 7 hours while introducing nitrogen to obtain a carbodiimide having isocyanate groups at both ends (carbodiimide step).

[0232] Next, in a four-necked flask equipped with a stirrer, thermometer, reflux tubing, and nitrogen inlet tube, 86 parts by mass of Uniox M550 (polyoxyethylene monomethyl ether, molecular weight 550, manufactured by Nippon Oil & Fats Co., Ltd.) (0.5 equivalents relative to the isocyanates at both ends of the carbodiimide) were sealed in the obtained carbodiimide and reacted at 150°C for 1 hour. Then, 77 parts by mass of PEG-1000 (polyoxyethylene glycol, weight-average molecular weight 1000) were added and reacted for another 1 hour (urethane formation step). The completion of the reaction was confirmed by infrared absorption (IR) spectroscopy, which showed a reading of 2260 cm⁻¹, originating from the stretching vibration of the isocyanate group. -1 This was confirmed by the near-complete disappearance of the absorption peak in the vicinity.

[0233] Preparation of aqueous dispersions (aqueous dispersions) of polycarbodiimide compositions. The obtained H 12A polycarbodiimide composition derived from MDI was placed in a flask, and distilled water was gradually added while heating to 80°C until the resin solids content reached 40%. After stirring for 5 minutes, the mixture was cooled to obtain an aqueous dispersion of the polycarbodiimide composition.

[0234] Preparation of aqueous resin compositions The resulting aqueous dispersion of polycarbodiimide composition was used as a curing agent. A hydrophilic polyurethane having carboxyl groups (polyurethane dispersion, solid content 30% by mass, carboxyl group equivalent of solid content 1122 g / mol) was used as the main component, and the mixture was prepared by mixing the curing agent and the carboxyl groups in the main component so that the equivalent ratio of carbodiimide groups in the curing agent to carboxyl groups in the main component was 0.5.

[0235] <Rating> • Friction fastness test (wet) The aqueous dispersions of the polycarbodiimide compositions obtained in each example and comparative example were evaluated by a friction fastness test simulating JIS L 0849 (2013).

[0236] More specifically, first, a compound solution with the following formulation was prepared.

[0237] Main ingredient: Takelac W-6110 (product name, manufactured by Mitsui Chemicals): 100 parts by mass Crosslinking agent: Aqueous dispersion of polycarbodiimide composition: 2 parts by mass Pigment: AF Blue E-2B (product name, manufactured by Dainichi Seika Kogyo): 23 parts by mass Distilled water: 75 parts by mass Next, a piece of white cloth attached for testing, used in JIS L 0849 (2013) (compliant with JIS L 0803 (2011), Kanakin No. 3), was cut to approximately 220 mm in length and 30 mm in width. The cloth was soaked in the above-mentioned solution, dried overnight at room temperature, and then dried at 80°C for 5 minutes to obtain a test specimen.

[0238] On the other hand, the attached white cloth for testing (compliant with JIS L 0803 (2011), Kanakin No. 3) was cut to approximately 50 mm in length and 50 mm in width, and moistened with distilled water to obtain a white cloth for friction.

[0239] Then, the above-mentioned test specimen and friction cloth were attached to the No. 428 Gakushin-type abrasion testing machine (Yasuda Seiki Seisakusho Co., Ltd., Friction Testing Machine Type II), and rubbed under the conditions of a load of 200g, a swing amplitude of 100mm, and 100 reciprocating cycles (30 cycles / min).

[0240] The L value of the friction cloth after friction was measured using a spectrocolor meter (Spectro Color Meter 2000, Nippon Denshoku Industries Co., Ltd.).

[0241] The L value indicates that a higher value means whiter the material is and the less it is contaminated. The L value of the white friction cloth before the test was 92.

[0242] [Table 1]

[0243] [Table 2]

[0244] [Table 3]

[0245] [Table 4]

Claims

1. The polycarbodiimide composition includes a carbodiimide-modified product of a reaction product of a linear aliphatic diisocyanate and an alcohol, The alcohols include polyols and monools, The polycarbodiimide composition has a carbodiimide equivalent weight of less than 550 g / mol. A carbodiimide crosslinking agent for treating fibers, characterized in that:

2. The molecular weight of the polyol is 120 or more and 1000 or less.

2. The carbodiimide crosslinking agent for fiber treatment according to claim 1.

3. The average functionality of the polyol is 2.

3. The carbodiimide crosslinking agent for fiber treatment according to claim 1 or 2.

4. The linear aliphatic diisocyanate is 1,5-pentane diisocyanate.

4. The carbodiimide crosslinking agent for fiber treatment according to claim 1, wherein the carbodiimide crosslinking agent is a hydroxybenzoate.

5. In the chromatogram obtained by measuring the polycarbodiimide composition by gel permeation chromatography, 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 area ratio of the peak area with a polystyrene equivalent molecular weight of 1000 or less to the total peak area is 10.0% or less 5. The carbodiimide crosslinking agent for fiber treatment according to claim 1, wherein the carbodiimide crosslinking agent is a hydroxybenzoate.

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