Dyeable compositions, fibers, and processes

Abstract

A dyeable composition comprising polyurethane and carbodiimide, a fiber prepared from the dyeable composition, and a process for preparing the dyeable composition are disclosed.

Description

Technical Field

[0001] The present disclosure generally relates to a dyeable composition, a fiber prepared from the dyeable composition, and a process for preparing the dyeable composition.

Background Art

[0002] Dyeable polymer compositions are widely used in various applications such as fibers and fabrics.

[0003] Polyurethane-urea-based dyeable compositions for dry spinning and wet spinning, as well as thermoplastic polyurethane compositions for melt spinning, are known. The resulting fibers are widely used in clothing, bags, packages, and other consumer products. Two main problems associated with polyurethane-based synthetic fibers are their insufficient dyeability and their color fastness after fading or washing.

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a need for a dyeable composition with improved dyeability and color fastness after dyeing with dye chemicals and even after washing.

Means for Solving the Problems

[0005] According to a first aspect of the present disclosure, polyurethane, and Formula (I):

Chemical Formula

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0006] According to a second aspect of the present disclosure, there is provided a fiber prepared from the dyeable composition.

[0007] According to a third aspect of the present disclosure, a) preparing a polyurethane; and b) adding to the polyurethane a compound of formula (I): [Chemical formula] Formula (I) [Wherein, n is an integer of 1 or more and 10 or less; R1 and R2 are each independently selected from unsubstituted or substituted alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, or arylene, and any combination thereof; X1 and X2 are each independently selected from formulas (II) to (X): [Chemical formula] <00001ll>Formula (II) [Chemical formula] [ Formula (III) <00ooo118>[Chemical formula] [ Formula (IV) [Chemical formula] Formula (V) [Chemical formula] Formula (VI) [Chemical formula] Formula (VII) <00ooo138>[Chemical formula] Formula (VIII) [ka] Formula (IX) [ka] Formula (X) A divalent base that can be independently represented by either of the following; Q1-Q6, R3, and R4 are independent of each other. A) Unsubstituted or substituted monovalent hydrocarbon groups, B) A monovalent group containing one or more oxygen, nitrogen, sulfur, phosphorus, or silicon atoms, and C) A monovalent group containing one or more repeating units selected from ethers, esters, thioethers, amides, imides, siloxanes, urethanes, ureas, allophanates, or any combination thereof. [A monovalent organic group selected from] A process for preparing a dyeable composition is provided, comprising the step of adding a carbodiimide represented by . [Modes for carrying out the invention]

[0008] It should be understood that the above summary and the following detailed description are illustrative and descriptive only and do not limit any subject matter claimed. In this disclosure, unless otherwise specifically stated, the use of the singular includes the plural. It should be noted that, as used herein and in the appended claims, the singular forms "a," "an," and "the" include multiple references unless the context makes it clear otherwise. In this application, the use of "or" means "and / or" unless otherwise specified. Furthermore, the use of the term "including" and its alternative forms, such as "include," "includes," and "included," is not limiting.

[0009] Unless otherwise defined, all technical and scientific terms used herein have the meanings generally understood by those skilled in the art in which this disclosure pertains. Where used herein, the following terms have the meanings given below unless otherwise specified.

[0010] Unless otherwise specified, all percentages (%) refer to "mass percentages".

[0011] A carbodiimide group refers to a divalent group with the formula -N=C=N-.

[0012] An alkyl group is a monovalent hydrocarbon group derived from an alkane by removing one hydrogen atom from any carbon atom. Typical alkyl groups include, but are not limited to, methyl-CH3, ethyl-C2H5, n-propyl-CH2CH2CH3, and isopropyl-CH(CH3)2.

[0013] A cycloalkyl group is a monovalent hydrocarbon group derived from cycloalkanes by removing one hydrogen atom from a ring carbon atom. Typical cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, and cyclohexyl.

[0014] An alkenyl group is a monovalent hydrocarbon group derived from an alkene by removing one hydrogen atom from an unsaturated carbon atom. A typical cycloalkyl group is the ethenyl group -CH=CH2 (commonly known as vinyl), but it is not limited to this group.

[0015] A cycloalkenyl group is a monovalent hydrocarbon group derived from cycloalkenes by removing one hydrogen atom from an unsaturated carbon atom. A typical cycloalkyl group is the 3-cyclohexenyl group. [ka] ) are some examples, but are not limited to these.

[0016] An alkynyl group is a monovalent group derived from an alkyne by removing one hydrogen atom from a triple-bonded carbon atom. A typical alkynyl group is ethynyl HC≡C- (commonly known as the acetylene group), but it is not limited to this.

[0017] A cycloalkynyl group is a monovalent group derived from an alkyne by removing one hydrogen atom from a triple bond carbon atom. A typical cycloalkynyl group is the 3-cyclooctinyl group. [ka] ) are some examples, but are not limited to these.

[0018] An aryl group is a monovalent group derived from an arene by removing one hydrogen atom from an aromatic carbon atom. Typical aryl groups include phenyl-C6H5 and naphthalenyl-C6H5. 10 H7 is one example, but it is not limited to these.

[0019] An alkylene group is a divalent hydrocarbon group derived from an alkane by removing two hydrogen atoms from the alkane. Typical alkylene groups include, but are not limited to, the methylene group (-CH2-), the ethylene group (-CH2CH2-), and the hexamethylene group (-CH2CH2CH2CH2CH2CH2-).

[0020] A cycloalkylene group is a divalent hydrocarbon group derived from a cycloalkane by removing two hydrogen atoms from it. A typical cycloalkylene group is the 1,4-cyclohexylene group. [ka] ) are some examples, but are not limited to these.

[0021] An alkenylene group is a divalent hydrocarbon group derived from an alkene by removing two hydrogen atoms from it. A typical example of an alkylene group is the ethenylene group (-CH=CH-), but it is not limited to this.

[0022] A cycloalkenylene group is a divalent hydrocarbon group derived from a cycloalkene by removing two hydrogen atoms from it. A typical cycloalkylene group is the 3,6-cyclohexenylene group. [ka] ) are some examples, but are not limited to these.

[0023] An alkylylene group is a divalent hydrocarbon group derived from an alkyne by removing two hydrogen atoms from the alkyne. A typical alkylylene group is the ethynylene group (-C≡C-), but it is not limited to this group.

[0024] A cycloalkylynylene group is a divalent hydrocarbon group derived from a cycloalkyne by removing two hydrogen atoms from the cycloalkyne. A typical cycloalkylynylene group is the 3,7-cyclooctynylene group. [ka] ) are some examples, but are not limited to these.

[0025] An arylene group is a divalent hydrocarbon group derived from an arene by removing two hydrogen atoms from two carbon atoms. A typical arylene group is the 1,4-phenylene group. [ka] ) are some examples, but are not limited to these.

[0026] Polyurethane, abbreviated as "PU," refers to a polymer that is an addition product of a diisocyanate or polyisocyanate with one or more isocyanate-reactive compounds (preferably compounds having two or more isocyanate-reactive functional groups). Examples of isocyanate-reactive compounds include polyethers, polyesters, polycarbonates, polyamines, diols, triols, diamines, and triamines. In this specification, polyurethane includes thermoplastic polyurethanes formed from diisocyanates, polyols, and low molecular weight diols; polyurethane-ureas formed from diisocyanates or polyisocyanates, polyols, and low molecular weight diamines or triamines; and / or other addition products of diisocyanates or polyisocyanates and polyols or polyamines.

[0027] Polyurethane-urea, also known as poly(urethane-urea), refers to a polymer containing urethane bonds (-OC(=O)-NH-) and urea bonds (-NH-C(=O)-NH-) as repeating units. Polyurethane-urea can be an addition product of diisocyanate or polyisocyanate, polyol, and diamine or triamine as a chain extender.

[0028] Unless otherwise specified, temperature is room temperature and pressure is ambient pressure.

[0029] This disclosure provides a dyeable composition. This dyeable composition comprises polyurethane and Equation (I): [ka] Equation (I) [In the formula, n is greater than or equal to 1 and less than or equal to 10; R1 and R2 are divalent groups independently selected from unsubstituted or substituted alkylenes, cycloalkylenes, alkenylenes, cycloalkenylenes, alkynylenes, cycloalkylenes, or arylenes, and any combination thereof; X1 and X2 are given by equations (II) to (X): [ka] Formula (II) [ka] Formula (III) [ka] Formula (IV) [ka] Formula (V) [ka] Equation (VI) [ka] Formula (VII) [ka] Formula (VIII) [ka] Formula (IX) [ka] Formula (X) A divalent base that can be independently represented by either of the following; Q1-Q6, R3, and R4 are independent of each other. A) Unsubstituted or substituted monovalent hydrocarbon groups, B) A monovalent group containing one or more oxygen, nitrogen, sulfur, phosphorus, or silicon atoms, and C) A monovalent group containing one or more repeating units selected from ethers, esters, thioethers, amides, imides, siloxanes, urethanes, ureas, allophanates, or any combination thereof. [A monovalent organic group selected from] Carbodiimide represented by and Includes.

[0030] In category (A), the monovalent hydrocarbon group can be any alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl group. The monovalent hydrocarbon group may be linear or branched. Substitutions may be one or more halogen atoms, alkoxy groups, dialkylamino groups, alkylthio groups, nitro groups, nitroso groups, nitrile groups, etc. Substitutions may occur once or multiple times.

[0031] Category (B) includes, as an example, any monovalent hydrocarbon group interrupted by at least one oxygen atom (-O-), one alkyl group nitrogen atom (-NR-), a sulfur atom (-S-), a phosphorus-containing bond (e.g., -O-PO(OR)-O-), a silicon-containing bond (e.g., -O-Si(CH3)2-O-), etc.

[0032] Examples of Category (C) include methoxy-terminated polyoxyethylene, ethoxy-terminated polycaprolactone, or methoxy-terminated polydimethylsiloxane.

[0033] Please note that "n" is the average number of repeating units in the carbodiimide, and can be an integer or a fraction.

[0034] Preferably, R1 is the same as R2, X1 is the same as X2, and R3 is the same as R4.

[0035] Preferably, n is 1 or more and 5 or less, and more preferably, n is 1 or more and 3 or less.

[0036] Preferably, at least one of X1 and X2 is represented by formula (II) or formula (IX).

[0037] Preferably, R1 and R2 are independently given by equations (XI) to (XVII): [ka] Formula (XI) [ka] Equation (XII) [ka] Equation (XIII) [ka] Formula (XIV) [ka] Formula (XV) [ka] Formula (XVI) [ka] Formula (XVII) It is a divalent group represented by either of the following.

[0038] In the above equation, the line connecting the substituent to the center of the ring indicates that the substituent can be located at any possible position on the ring.

[0039] Preferably, at least one of R1 and R2 is represented by formula (XII), formula (XV), formula (XVI), or formula (XVII).

[0040] Preferably, R3 and R4 are ethyl, isopropyl, n-butyl, cyclohexyl, benzyl, 2-ethoxyethyl, 2-(dimethylamino)ethyl, methoxy-terminated polyoxyethylene, or any combination thereof.

[0041] In this dyeable composition, carbodiimide can function as a dye enhancer, which is particularly useful in spinning for preparing dyeable fibers or fabrics based on thermoplastic polyurethane and / or polyurethane-urea.

[0042] Preferably, the carbodiimide content is 0.1% to 12% by mass, more preferably 0.3% to 7% by mass, and even more preferably 0.5% to 4% by mass, relative to the mass of polyurethane.

[0043] Preferably, the polyurethane is polyurethane-urea obtained as a reaction product of an isocyanate-terminated prepolymer with a diamine or polyamine. More preferably, the isocyanate-terminated prepolymer is an adduct of a polyol with a diisocyanate or polyisocyanate. The diamine or polyisocyanate is in excess; that is, not all isocyanate functional groups are neutralized by the hydroxyl functional groups in the polyol. More preferably, the dyeable composition comprises a solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and any combination thereof. The isocyanate-terminated prepolymer and / or the diamine or polyamine may be dissolved in the solvent. The dyeable composition may be used in a dry spinning process in which the solvent is evaporated and the dissolved polyurethane-urea coagulates to form fibers.

[0044] Alternatively, the polyurethane in the dyeable composition is preferably a thermoplastic polyurethane obtained as a reaction product of a diisocyanate, a chain extender, and a polymer diol. The chain extender is preferably a diol having a molecular weight of less than 300 g / mol, such as 1,3-propanediol, 1,4-butanediol, or 1,6-hexanediol. Preferably, the dyeable composition does not contain a solvent. The dyeable composition can be used in a melt spinning process in which the thermoplastic polyurethane is melted and extruded to form fibers.

[0045] Preferably, the dyeable composition further comprises an auxiliary agent selected from antioxidants, UV absorbers, anti-yellowing agents, matting agents, and lubricants. The auxiliary agent can introduce performance or properties to the final product, such as textiles, including good dyeability, oxidation resistance, UV resistance, yellowing resistance, desirable appearance, feel, and high processability.

[0046] The preparation of carbodiimides is well known and is taught, for example, in U.S. Patent No. 6,730,807 (B1). In this process, isocyanates often undergo a carbodiimide formation reaction, which is then capped at the ends with a capping agent.

[0047] End-capping agents are monofunctional isocyanate-reactive compounds that can react with terminal isocyanate functional groups (e.g., those within carbodiimides) to form chemical bonds. Exemplary end-capping agents include, but are not limited to, primary amines, secondary amines, ureas, urethanes, isocyanates, thiocarbamates, alcohols, phenols, thiols, or thiophenols. The chemical bonds formed during end-capping may be divalent bonds of ureas, biuret, uretonimine, uredione, substituted 2,4-diamino-1,3-diazetidine, allophanates, thioallophanates, urethanes, or thiourethanes.

[0048] In addition to isocyanate-reactive functional groups, the end-capturing agent may also contain monovalent groups that are inert to isocyanate functional groups.

[0049] The end-capturing agent may be one of the following compounds:

[0050] (A) Compounds consisting of an isocyanate-reactive functional group and an unsubstituted or substituted monovalent hydrocarbon group.

[0051] The monovalent hydrocarbon group may be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl group. The monovalent hydrocarbon group may be linear or branched. Substitutions may include one or more halogen atoms, alkoxy groups, dialkylamino groups, alkylthio groups, nitro groups, nitroso groups, nitrile groups, etc. Examples include low molecular weight alcohols, amines, or thiols.

[0052] (B) A compound comprising an isocyanate-reactive functional group and a monovalent group containing one or more oxygen, nitrogen, sulfur, phosphorus, or silicon atoms.

[0053] As a specific example, end-capturing agents can be reaction products of a hydrosiloxane containing a Si-H bond with a monoalcohol or monoamine having a carbon-carbon double bond.

[0054] (C) A compound comprising an isocyanate-reactive functional group and a monovalent group containing one or more repeating units selected from ethers, esters, thioethers, amides, imides, siloxanes, or any combination thereof.

[0055] For example, this compound may be a polyether monoalcohol or polyether monoamine. Oligomerous / polymeric diols or diamines may be based on polyethers, polyesters, polythioethers, polyamides, polyimides, polysiloxanes, or other repeating units. Examples include monohydroxy-terminated polypropylenes, monohydroxy-terminated polycaprolactones, monoamine-terminated polyamides, or monohydroxy-terminated polydimethylsiloxanes.

[0056] Preferably, the end-capping agent is a monoalcohol, monoamine, tertiary amino monoalcohol (e.g., N,N-dimethylaminoethanol), alkoxy monoamine or aryloxy monoamine (e.g., 3-methoxypropylamine), diol monoether (e.g., ethylene glycol monomethyl ether), monohydroxy-terminated polystyrene, monohydroxy-terminated polyether (e.g., reaction product of ethylene oxide and monoalcohol), monoamine-terminated polyether (e.g., monoamines commercially available as Jeffamine® M series monoamines), monohydroxy-terminated polyester (e.g., ring-opening polymerization product of caprolactone and monoalcohol), monoamine-terminated polyester (e.g., ring-opening polymerization product of caprolactone and monoamine), monohydroxy-terminated siloxane, etc.

[0057] Specific examples of end-captives include, but are not limited to, ethanol, isopropyl alcohol, n-butanol, 1-octanol, benzyl alcohol, 2-ethoxyethanol, 2-(dimethylamino)ethanol, methoxypolyethylene glycol, or any combination thereof. However, anyone skilled in the art can select any other similar monofunctional isocyanate-reactive compound or any combination thereof as an end-captive.

[0058] This dyeable composition, a) Steps to prepare polyurethane, b) Add the following formula to the polyurethane: [ka] Equation (I) [In the formula, n is greater than or equal to 1 and less than or equal to 10; R1 and R2 are divalent groups independently selected from unsubstituted or substituted alkylenes, cycloalkylenes, alkenylenes, cycloalkenylenes, alkynylenes, cycloalkylenes, or arylenes, and any combination thereof; X1 and X2 are given by equations (II) to (X): [ka] Formula (II) [ka] Formula (III) [ka] Formula (IV) [ka] Formula (V) [ka] Equation (VI) [ka] Formula (VII) [ka] Formula (VIII) [ka] Formula (IX) [ka] Formula (X) A divalent base that can be independently represented by either of the following; Q1-Q6, R3, and R4 are independent of each other. A) Unsubstituted or substituted monovalent hydrocarbon groups, B) A monovalent group containing one or more oxygen, nitrogen, sulfur, phosphorus, or silicon atoms, and C) A monovalent group containing one or more repeating units selected from ethers, esters, thioethers, amides, imides, siloxanes, urethanes, ureas, allophanates, or any combination thereof. [A monovalent organic group selected from] It can be prepared by a process that includes the step of adding a carbodiimide represented by [formula].

[0059] This dyeable composition may be used in: 1) various spinning processes, including dry spinning, wet spinning, and melt spinning for the manufacture of fibers and fabrics; 2) molding processes, including injection molding and extrusion molding for the manufacture of profiles, laminates, sheets, or pipes, for example; and 3) other shaping processes that can be used for the manufacture of articles.

[0060] Solution spinning (wet spinning and dry spinning) is a method of producing fibers from a spinning solution (sometimes called "dope") containing the final fiber material, particularly a polymer material including polyurethane-urea or polyvinyl chloride, and a volatile solvent. A volatile solvent is a solvent that can dissolve polymer materials.

[0061] Dry spinning refers to a special type of solution spinning in which the spinning solution is pushed through a spinneret into an evaporation chamber. A flow of hot air collides with the jet of spinning solution coming out of the spinneret, evaporating the solvent and solidifying the filament.

[0062] Wet spinning is a process similar to dry spinning, but in this case, the spinning solution is extruded into a hot water bath, where the filaments solidify.

[0063] Melt spinning refers to a fiber manufacturing process in which a thermoplastic polymer, such as thermoplastic polyurethane, is melted into a viscous molten material. This molten material is then continuously pushed into multiple spinnerets by a spinning pump, and the fiber flow is discharged through the pores of the spinnerets. After cooling in air or water, solidified fibers are formed.

[0064] According to this disclosure, fibers are prepared from the dyeable composition. This preparation may follow a wet spinning process, a dry spinning process, or a melt spinning process.

[0065] This disclosure further provides fabrics containing fibers prepared from the dyeable composition. Because carbodiimide is present in the dyeable composition, fibers and fabrics prepared from the dyeable composition exhibit good dyeability, color fastness, and maintenance, or even improvement, of mechanical properties compared to fibers / fabrics before dyeing or fibers / fabrics dyed with other dye enhancers. These fabrics may find applications in clothing, furniture, or car interiors.

[0066] The following materials were used in this example.

[0067] Stain enhancer:

[0068] CDE 001, manufactured by BASF, is a carbodiimide with approximately 2.0 carbodiimide functional groups per molecule.

[0069] SAM, poly(N,N-diethyl-2-aminoethyl methacrylate), is commercially available from Penglai Spark Chemicals as a 35% by mass solution in N,N-dimethylacetamide.

[0070] XHTS 011 is a polymer of aminoalkyl alcohol and diisocyanate dissolved in N,N-dimethylacetamide, an anti-yellowing agent and dye enhancer, commercially available from Penglai Spark Chemicals.

[0071] Raw materials for polyurethane-urea synthesis:

[0072] Methylenediphenyl diisocyanate, manufactured by BASF;

[0073] Oligomer polyol: PolyTHF(registered trademark) 1800, average molecular weight 1,800 g / mol, manufactured by BASF;

[0074] Amines: Ethylenediamine and diethylamine, both manufactured by BASF;

[0075] Solvent: N,N-dimethylacetamide, manufactured by BASF;

[0076] Auxiliary drugs:

[0077] Antioxidant: IRGANOX® 245, manufactured by BASF;

[0078] UV absorber: TINUVIN (registered trademark) 1130, manufactured by BASF;

[0079] Anti-yellowing agent: HN-150, manufactured by Tokyo Chemical Industry Co., Ltd.

[0080] A polyurethane-urea solution for preparing a thin film was prepared according to the following steps:

[0081] 1) In an N2-purged reactor, 100 parts by mass of PolyTHF 1800 and 23.07 parts by mass of methylenediphenyl diisocyanate were reacted to form an isocyanate-terminated prepolymer with an isocyanate content of 2.50% by mass. After cooling the prepolymer to 40°C, 150.41 parts by mass of N,N-dimethylacetamide was added as a solvent to form a prepolymer solution;

[0082] 2) To the diluted prepolymer solution, a solution of 2.08 parts by mass of ethylenediamine and 0.46 parts by mass of diethylamine in 116.49 parts by mass of N,N-dimethylacetamide was added under high-speed mixing. Finally, a homogeneous polyurethane-urea solution was obtained; and

[0083] 3) To the polyurethane-urea solution, 1.25 parts by mass of antioxidant, 0.63 parts by mass of UV absorber, and 1.25 parts by mass of anti-yellowing agent were added, and the system was then thoroughly mixed to form a dope.

[0084] Thin film preparation A polyurethane-urea thin film was prepared by the following steps: First, a dope and a stain enhancer were mixed together to form a mixture; second, the mixture was poured onto a precisely horizontally aligned glass plate to form a thin layer; third, the mold was placed in an oven at 50°C under a nitrogen atmosphere to evaporate the solvent for 3 days; and finally, the obtained thin film was removed from the mold. The thin film had an average thickness of 200-260 μm.

[0085] Staining process The dyeing process was carried out using a Mathis Labomat beaker dyeing system. A polyurethane-urea thin film was placed in a dyeing bath (2% by mass of Telon® Red M-R01 acid dye relative to the fabric in 10% by mass of acetate buffer) at room temperature. The mass ratio of the dyeing bath to the thin film was 10. The pH of the dyeing bath was adjusted to 4-5. The dyeing bath in which the thin film was immersed was heated to 98°C at a rate of 2°C / min. The dyeing bath was maintained at 98°C for 1 hour, and then cooled to 60°C at a rate of 3°C / min. Finally, the thin film was thoroughly rinsed and dried to obtain a dried thin film.

[0086] Cleaning process The rinsed, dyed thin film was attached to a piece of multifiber. This combination was placed in a soaping solution (5 g / L ISO soap, 2 g / L Na2CO3, and the remainder water, according to ISO standard 105-C10) at room temperature. The washing system was heated to 60°C and maintained at that temperature for 40 minutes. It was then cooled to 40°C. Finally, the thin film was thoroughly rinsed and dried.

[0087] To evaluate the color depth of dyed thin films before and after washing, the K / S value at a wavelength of 520 nm was measured for each sample. K represents the color absorption coefficient, and S represents the color scattering coefficient. The color depth value (K / S) was calculated using the Kubelka-Munk theory (ISO 9416). These values ​​represent the color intensity at a specific wavelength λ compared to a blank sample. The blank sample was fabric made from each fiber that was not immersed in the dye bath. A higher K / S value indicates a deeper color. A Datacolor SF600 colorimeter was used with a D65 light source and a measurement angle of 10°. The measurement was repeated four times, and the average value was obtained.

[0088] The polyurethane-urea thin film exhibited dyeing and mechanical properties as tested in accordance with the standards listed in Table 1. In the tensile test, the tensile modulus was measured starting with strain intervals of 0.05% to 0.25% and a crosshead speed of 1 mm / min. In subsequent tensile tests, the cross-speed was set to 200 mm / min. For the hysteresis test, the polyurethane-urea thin film was stretched (loaded) and released (load removed) five times consecutively up to a strain of 300%. The residual elongation values ​​after the first and fifth cycles were measured, and the "E" value was determined accordingly. res-1 " and "E res-5 It is represented as ".

[0089] [Table 1]

[0090] A series of polyurethane-urea thin films PF1 to PF9 were prepared by using different dye enhancers on a polyurethane-urea dyeable composition and varying the dosage of the dye enhancer. Their properties, including the dosage and performance of the dye enhancer, are shown in Table 2.

[0091] [Table 2]

[0092] Table 2 suggests that, due to its low molecular weight, this carbodiimide resulted in polyurethane-urea products with higher color intensity compared to polymer-type dye enhancers. Even at low doses of carbodiimide, the dyeable composition exhibited good color intensity both before and after washing. In addition to improved dyeing performance, thin films prepared from the dyeable composition containing this carbodiimide maintained or even improved mechanical properties such as elongation at break and tensile strength. The impact of the introduction of carbodiimide on the hysteresis properties of polyurethane-urea thin films was also limited, as shown by the comparison between PF1 and one of PF2-PF7.

Claims

1. Polyurethane and Equation (I): 【Chemistry 1】 Equation (I) [In the formula, n is greater than or equal to 1 and less than or equal to 10; R １ and R ２ is a divalent group independently selected from unsubstituted or substituted alkylenes, cycloalkylenes, alkenylenes, cycloalkenylenes, alkylylenes, cycloalkylylenes, or arylenes, and any combination thereof; X １ and X ２ Equations (II) to (X): 【Chemistry 2】 Formula (II) 【Transformation 3】 Formula (III) 【Chemistry 4】 Formula (IV) 【Transformation 5】 Formula (V) 【Transformation 6】 Equation (VI) 【Transformation 7】 Formula (VII) 【Transformation 8】 Formula (VIII) 【Chemistry 9】 Formula (IX) 【Chemistry 10】 Formula (X) A divalent base that can be independently represented by either of the following: Q １ ~Q ６ , R ３ , and R ４ Independently, A) Unsubstituted or substituted monovalent hydrocarbon groups, B) A monovalent group containing one or more oxygen, nitrogen, sulfur, phosphorus, or silicon atoms, and C) A monovalent group containing one or more repeating units selected from ethers, esters, thioethers, amides, imides, siloxanes, urethanes, ureas, allophanates, or any combination thereof. [A monovalent organic group selected from the following] Carbodiimide represented by and A dyeable composition containing [a specific substance].

2. R １ is R ２ and is identical to, X １ is X ２ and is identical to, R ３ is R ４ and is identical to, the dyeable composition according to claim 1.

3. The dyeable composition according to claim 1, wherein n is 1 or more and 5 or less, preferably n is 1 or more and 3 or less.

4. X １ and X ２ The dyeable composition according to claim 1, wherein at least one of the is represented by formula (II) or formula (IX).

5. R １ and R ２ However, independently, equations (XI) to (XVII): 【Chemistry 11】 Formula (XI) 【Chemistry 12】 Equation (XII) 【Chemistry 13】 Equation (XIII) 【Chemistry 14】 Formula (XIV) 【Chemistry 15】 Formula (XV) 【Chemistry 16】 Formula (XVI) 【Chemistry 17】 Formula (XVII) The dyeable composition according to claim 1, wherein the divalent group is represented by any of the following.

6. R １ and R ２ The dyeable composition according to claim 5, wherein at least one of the is represented by formula (XII), formula (XV), formula (XVI), or formula (XVII).

7. R ３ and R ４ The dyeable composition according to claim 1, wherein is ethyl, isopropyl, n-butyl, cyclohexyl, benzyl, 2-ethoxyethyl, 2-(dimethylamino)ethyl, methoxy-terminated polyoxyethylene, or any combination thereof.

8. The dyeable composition according to claim 1, wherein the content of the carbodiimide is 0.1% to 12% by mass, preferably 0.3% to 7% by mass, and more preferably 0.5% to 4% by mass, relative to the mass of the polyurethane.

9. The dyeable composition according to claim 1, wherein the polyurethane is a polyurethane-urea obtained as a reaction product of an isocyanate-terminated prepolymer and a diamine or polyamine.

10. The dyeable composition according to claim 9, wherein the isocyanate-terminated prepolymer is an adduct of a polyol with a diisocyanate or polyisocyanate.

11. The dyeable composition according to claim 9, further comprising a solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and any combination thereof.

12. The dyeable composition according to claim 1, wherein the polyurethane is a thermoplastic polyurethane obtained as a reaction product of a diisocyanate, a chain extender, and a polymer diol.

13. The dyeable composition according to claim 1, further comprising an auxiliary agent selected from antioxidants, UV absorbers, anti-yellowing agents, matting agents, and lubricants.

14. A fiber prepared from the dyeable composition according to any one of claims 1 to 13.

15. (a) A step of preparing polyurethane, (b) The polyurethane is given formula (I): [Chemistry 18] Equation (I) [In the formula, n is greater than or equal to 1 and less than or equal to 10; R １ and R ２ is a divalent group independently selected from unsubstituted or substituted alkylenes, cycloalkylenes, alkenylenes, cycloalkenylenes, alkylylenes, cycloalkylylenes, or arylenes, and any combination thereof; X １ and X ２ Equations (II) to (X): 【Chemistry 19】 Formula (II) 【Chemistry 20】 Formula (III) 【Chemistry 21】 Formula (IV) 【Chemistry 22】 Formula (V) 【Chemistry 23】 Equation (VI) 【Chemistry 24】 Formula (VII) 【Chemistry 25】 Formula (VIII) 【Chemistry 26】 Formula (IX) 【Chemistry 27】 Formula (X) A divalent base that can be independently represented by either of the following: Q １ ~Q ６ , R ３ , and R ４ Independently, A) Unsubstituted or substituted monovalent hydrocarbon groups, B) A monovalent group containing one or more oxygen, nitrogen, sulfur, phosphorus, or silicon atoms, and C) A monovalent group containing one or more repeating units selected from ethers, esters, thioethers, amides, imides, siloxanes, urethanes, ureas, allophanates, or any combination thereof. [A monovalent organic group selected from the following] The step of adding carbodiimide represented by and A process for preparing a dyeable composition, including [a specific substance].

Images