Anti-pilling merino wool fabric, garments containing same, and methods for manufacturing same

Abstract

To provide an anti-pilling wool fabric with a coating having pilling resistance and resistance to fiber loss from fabric surface.SOLUTION: The coating is formed by a coating formulation including at least two diisocyanates, at least two catalyst, a water dispersing agent, a buffer and water. The coating provides a polycarbodiimide crosslinker reactive to the relative less reactive groups on polypeptide of the wool fabric and promotes crosslinking between polypeptides of the wool fabric under relatively mild processing conditions so as to enhance mechanical strength of the wool fabric whilst no significant effect of the original finish merino wool fabric and / or garment and fiber loss from fabric surface are observed, compared to conventional treatment methods on wool fabric. There is also provided a corresponding coating formulation and method of fabricating the anti-pilling wool fabric.SELECTED DRAWING: Figure 3A

Description

[Technical field]

[0001] The present invention provides an anti-pilling merino wool fabric. In particular, the present invention provides an anti-pilling merino wool fabric having a pilling resistance of 4 or more according to the JIS L1076 ICI method and a fiber loss of less than 0.2% w / w after 15 cycles of home washing without a laundry net. Related manufacturing methods and garments including the same are also provided. [Background technology]

[0002] Animal fibers such as merino wool have relatively weak tensile strength compared to synthetic fibers such as polyester, and are prone to fiber breakage. Fabrics containing wool fibers are prone to fiber loss from the fabric surface during wear or washing to form fuzz. In addition, the presence of cuticle scales on the merino wool fiber surface further leads to differences in the coefficient of friction between fibers. The presence of mechanical actions, including washing, rubbing and abrasion, on the wool fabric surface creates directional movement of the fibers, allowing the fuzz to entangle into pills, and the aggregated pills are eventually worn off from the merino wool fabric surface.

[0003] To reduce fiber loss and pilling from the surface of merino wool fabrics, conventional solutions mainly include reducing fiber loss and fuzz entanglement and pill agglomeration, reducing inter-fiber friction and increasing the mechanical strength of the fiber. In particular, these methods include enzyme treatment to remove small and short loose fibers from the fabric surface, plasma treatment to reduce inter-fiber friction, and the use of polyacrylate-based coatings on wool fibers to increase the mechanical strength of wool fibers to reduce fiber loss from the surface. However, these methods often have drawbacks. For example, the use of polyacrylate-based coatings cannot be applied to the finished merino wool fabric or garment, and can result in significant discoloration of the original finish. Enzyme treatments are not selective to only the loose fibers on the fabric surface, and can potentially result in more fiber loss. Plasma treatments have been found to have obstacles in industrialization.

[0004] Therefore, there is a need for new merino wool fabrics containing coated fibers that have improved mechanical properties while avoiding pilling and loss of fiber from the surface. Summary of the Invention

[0005] Thus, one aspect of the present invention provides an anti-pilling merino wool fabric having a pilling resistance of 4 or greater with less than 0.2% w / w fiber loss in 15 cycles of domestic washing without a laundry bag, the anti-pilling merino wool fabric being coated with a formulation comprising: about 8-30% w / w polymeric binder in water; and about 70-92% w / w buffer in water, the polymeric binder comprising at least two diisocyanates, at least two catalysts, and a water dispersant.

[0006] In a preferred embodiment, the pilling resistance of the wool fabric is determined according to the JIS L1076 ICI method.

[0007] In an embodiment according to the first aspect of the present invention, the at least two diisocyanates include isophorone diisocyanate and 1,6-hexamethylene diisocyanate.

[0008] In a particular embodiment, the isophorone diisocyanate and 1,6-hexamethylene diisocyanate are in a molar ratio of 4:1.

[0009] In an embodiment according to the first aspect of the present invention, the at least two catalysts include 3-methyl-1-phenyl-2-phospholene-1 oxide and dibutyltin(IV) dilaurate.

[0010] In certain embodiments, the 3-methyl-1-phenyl-2-phospholene-1 oxide is in a molar concentration of about 0.2 to 1.0% relative to the at least two diisocyanates.

[0011] In another particular embodiment, the dibutyltin(IV) dilaurate is at a concentration of about 0.01% w / w relative to the water dispersant.

[0012] In one embodiment, the water dispersant is one or both of polyethylene glycol monomethyl ether 350 and polyethylene glycol monomethyl ether 550.

[0013] In one embodiment, the buffer is selected from phosphate or borate; the buffer is adjusted to a pH of about 8.0.

[0014] The formulation introduces a polycarbodiimide crosslinker to the less reactive carboxyl groups present on the fibers of merino wool fabric. The polycarbodiimide polymer chains of the crosslinker can also be tuned by adjusting the ratio of different monomers, added catalysts, and / or reaction conditions, which increases the flexibility of the formulation. The formulation can be fully cured within 48 hours at room temperature, making it easy to form a coating on existing merino wool fabric.

[0015] A second aspect of the present invention provides a method of producing a merino wool fabric according to the first aspect, the method comprising: providing a merino wool fabric; preparing a coating formulation comprising mixing a first diisocyanate and a second diisocyanate in a first molar ratio and a first catalyst in a second molar ratio relative to the first and second diisocyanates to form a first solution; adding a first weight percent of a water dispersant and a second weight percent of a second catalyst, relative to the total weight of the first and second diisocyanates, to the first solution to form a second solution; adding water to the second solution and mixing until a homogenous solution is formed to form a third solution of a polymer binder in water; preparing a fourth solution comprising a buffer in water at pH 8.0; adding the fourth solution to the third solution and mixing until a homogenous solution is formed to obtain the coating formulation; applying the coating formulation to the merino wool fabric; and removing excess of the coating formulation from the merino wool fabric and then drying.

[0016] In one embodiment, the first diisocyanate is selected from isophorone diisocyanate and the second diisocyanate is selected from 1,6-hexamethylene diisocyanate.

[0017] In certain embodiments, the first molar ratio between the first diisocyanate and the second diisocyanate is 4:1.

[0018] In another particular embodiment, the first catalyst is selected from 3-methyl-1-phenyl-2-phospholene-1 oxide.

[0019] More specifically, the second molar ratio of the first catalyst to the first and second diisocyanates is about 0.2% to 1%.

[0020] In one embodiment, the water dispersant is one or both of polyethylene glycol monomethyl ether 350 and polyethylene glycol monomethyl ether 550.

[0021] In certain embodiments, the first weight percent of the water dispersant is about 126% based on the total weight of the first and second diisocyanates.

[0022] In one embodiment, the second catalyst is selected from dibutyltin(IV) dilaurate.

[0023] In certain embodiments, the second weight percent of the second catalyst is about 0.01% based on the weight of the water dispersant.

[0024] In one embodiment, the buffer is selected from phosphate or borate.

[0025] In one embodiment, the first and second diisocyanates are mixed by stirring until a clear solution is obtained, and then the mixture is heated to 160° C. for about 35-50 minutes, and then the mixture is cooled to about 120° C. to obtain the first solution.

[0026] In one embodiment, the second solution is obtained by first mixing the second catalyst and the water dispersant until a homogeneous solution is formed, and then adding the homogeneous solution to the first solution and stirring at about 120° C. for about 2 hours.

[0027] In one embodiment, after the second solution is cooled to 80° C., water is added dropwise to the second solution with stirring until a clear homogenous solution is obtained and the water content in the polymer binder reaches about 63% w / w.

[0028] In one embodiment, the fourth solution, comprising at least about 70% w / w buffer in water relative to the third solution, is added to the third solution and then mixed until a homogenous solution is formed as the coating formulation.

[0029] In one or more aspects of the invention, the wool fabrics described herein that are coated with the coating formulations described herein and / or produced according to the methods described herein may be finished wool fabrics that have already been dyed with colorants, and / or dyes, and / or reactive dyes.

[0030] Also provided are garments comprising the merino wool fabric described in any of the aspects of the invention and / or prepared by the method according to any of the aspects of the invention, including, but not limited to, rib knits, shirts, dresses, sweaters, and the like. [Brief description of the drawings]

[0031] The present disclosure will become more fully understood from the detailed description that follows, which is given by way of example only and not by way of limitation.

[0032] [Figure 1A] FIG. 1A shows a schematic of the technical challenge of cross-linking wool fibers when reactive dyes are present on the finished merino wool fabric and / or garment.

[0033] [Figure 1B] FIG. 1B illustrates in schematic form how the present invention addresses the technical problem in the prior art illustrated in FIG. 1A.

[0034] [Figure 1C] FIG. 1C illustrates generally how the present invention provides for crosslinking reactive groups on wool fabric with reactive dyes, according to one embodiment of the present invention.

[0035] [Diagram 2]FIG. 2 shows a schematic of the preparation of the coating formulation.

[0036] [Figure 3A] Figure 3A shows the anti-pilling performance of the present invention on single jersey knits with respect to their surface morphology according to the JIS L1076 ICI method. The enlarged view in the upper right corner shows a series of reference photos of the surface morphology of the corresponding fabrics graded (1.0-5.0) according to the JIS L1076 ICI method.

[0037] [Figure 3B] FIG. 3B shows the anti-pilling performance of the present invention for a 2×2 milling cutter in terms of surface morphology according to the JIS L1076 ICI method. The enlarged view in the upper right corner shows a series of reference photos of the surface morphology of the corresponding fabrics graded (1.0-5.0) according to the JIS L1076 ICI method. Definition

[0038] The terms "a" or "an" are used to mean one or more, and the term "or" is used to refer to a non-exclusive "or" unless otherwise specified. In addition, terms used herein and not otherwise defined are to be understood as being for purposes of description only, not limitation. Furthermore, all publications, patents, and patent documents referred to herein are incorporated by reference in their entirety as if individually incorporated by reference. In the event of a conflict between the usage of this specification and a document so incorporated by reference, the usage in the incorporated reference shall be considered as supplementary to the usage of this specification. In the event of irreconcilable discrepancies, the usage in this specification shall prevail.

[0039] In the manufacturing methods described herein, steps may be performed in any order without departing from the principles of the invention, unless a temporal or operational sequence is explicitly recited. A statement in a claim that a first step is performed and then several other steps are subsequently performed shall mean that the first step is performed before any of the other steps, but the other steps may be performed in any suitable order unless further recited within the other steps. For example, a claim element reciting "steps A, B, C, D, and E" shall be interpreted to mean that step A is performed first and step E is performed last, and steps B, C, and D may be performed in any order between steps A and E, and that order still falls within the scope of the claimed process language. A particular step or subset of steps may also be repeated. Furthermore, certain steps may be performed simultaneously, unless explicit claim language recites that they are performed separately. For example, a step claimed to perform X and a step claimed to perform Y may be performed simultaneously in a single operation, and the resulting process falls within the scope of the claimed process language.

[0040] "Association" or variations thereof as described herein with respect to interactions between different compounds, molecules and / or substances, where such expressions or terms are applied, can refer to any physical, chemical and / or other possible bonds between the compounds, molecules and / or substances.

[0041] As used herein, a "water dispersant" refers to an agent that aids in dispersing the polycarbodiimide polymer in water. In particular, the agent reacts with the polycarbodiimide polymer to form "caps" on both ends of the polymer to produce a homogenous solution of the polycarbodiimide polymer in water.

[0042] In this disclosure, "polycarbodiimide polymer" and "polycarbodiimide crosslinker" are used interchangeably to refer to polymers that react with less reactive groups on animal fibers, such as, for example, finished wool fabrics or garments, such as merino wool fabrics or garments.

[0043] The anti-pilling performance of the wool fabrics or garments described herein is tested and graded according to JIS L1076 ICI method, where grade 5 indicates excellent anti-pilling property and grade 1 indicates poor anti-pilling property.

[0044] The "color fade" of the finished wool fabric or garment described herein is rated on a gray scale grading according to ISO 105-A02 against the original finished wool fabric or garment, with grade 5 indicating minimal color fade impact against the original finish of the fabric and grade 1 indicating significant color fade impact against the original finish of the fabric. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. Specific embodiments are provided for illustrative purposes only and should not be construed in a limiting manner.

[0046] With reference to FIG. 1A, typical polypeptides of wool fibers on fabrics, such as polypeptides of merino wool fibers, have reactive functional groups, among which amino groups (NH2) are usually reacted with one or more reactive dyes to provide the finish and / or coloring of the wool fabric. Therefore, it is very difficult to perform crosslinking of wool fibers, a method to increase the mechanical strength of wool fibers to reduce fiber loss from the surface. The surface lacks reactive functional groups to react and / or crosslink with the polymers of the protective polymer coating to improve the mechanical strength of said fibers and reduce fiber loss and pilling from the fabric surface. To address this technical challenge, the present invention provides polymers for crosslinking with the polypeptides of wool fabrics with less reactive functional groups, but with relatively mild processing / reaction conditions and can be performed in water. The covalent bond between the reactive dye and the amino groups on the polypeptides of wool fibers remains intact, reducing the possibility of fading of the original finish of the wool fabric and / or garment (FIG. 1B). In a preferred embodiment, a polycarbodiimide crosslinker is provided as a crosslinker that interacts with carboxylic acid groups on the polypeptides of the wool fiber to form first O-acylisourea groups and subsequently N-acylurea groups when one polypeptide is crosslinked to another polypeptide via a polycarbodiimide polymer (Figure 1C).

[0047] Referring to Figure 2, the polycarbodiimide crosslinker in the present invention is obtained by reacting at least two monomers, such as two diisocyanates, isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI), with a first catalyst, such as 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), for a first time (t1) to form a first reaction product (200), i.e., a polycarbodiimide polymer. After cooling, the polycarbodiimide polymer is further reacted with a water dispersant, such as polyethylene glycol monomethyl ether 550 (MPEG550), and a second catalyst, such as dibutyltin (IV) dilaurate, for a second time (t2) to form a polymer binder, which is then cooled. Water is added dropwise into the polymer binder and heated to a temperature (T1) with stirring until a homogeneous solution (210) of the polymer binder is obtained in the water. The homogenous solution (210) is further mixed with a pH 8.0 buffer solution before being coated onto the wool fabric.

[0048] In a preferred embodiment, t1 is about 50 minutes and the first reaction between the two diisocyanates and the first catalyst is carried out at about 155-160°C, more preferably at 160°C.

[0049] In another preferred embodiment, t2 is about 2 hours and the second reaction between the polycarbodiimide polymer, MPEG 550, and dibutyltin(IV) dilaurate is carried out at about 120°C.

[0050] In yet another preferred embodiment, T1 is about 80° C. and the homogenous solution obtained after adding water dropwise to the polymer binder has a final water content of about 63% w / w.

[0051] In another preferred embodiment, the homogenous solution, i.e., polymer binder in water, is mixed with a phosphate or borate buffer in water at pH 8.0, where the solution is at least 8% of the total solution mass.

[0052] Working Example

[0053] Example 1: Preparation of Merino wool fabric coating compound:

[0054] Table 1 below summarizes the composition of the polymer binder (I) in water according to one embodiment of the present invention.

[0055] [Table 1]

[0056] Preparation procedure: 3-Methyl-1-phenyl-2-phospholene-1-oxide (MPPO) (0.5 mol % relative to the total amount of the two diisocyanates), isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI) (25 mol % relative to the amount of isophorone diisocyanate; i.e., molar ratio of IPDI to HDI=4:1) were placed in a 500 mL flask with stirring until a clear solution was obtained. The solution was then heated to 160° C. for 50 minutes (t1). 1) After 50 minutes, the solution was cooled to 120° C. Dibutyltin(IV) dilaurate (0.01% by weight relative to MPEG 550) was added to MPEG 550 (126% by weight relative to the total weight of the two diisocyanates) with stirring until a homogeneous solution was obtained. The homogeneous solution was added to the above cooled solution with stirring. The reaction mixture was kept stirring at 120° C. for 2 hours (t2). 2) After stirring for 2 hours, the reaction mixture from (2) was cooled to 80° C. (T1). Water (170% by weight relative to the total weight of the added reagents) was added dropwise with stirring until a clear homogeneous solution was obtained. Final water content: 63% w / w.

[0057] Example 2 - Variations in polymer binder composition and / or preparation conditions:

[0058] Table 2 below summarizes, apart from the composition (I) of the polymer binder in water described in Example 1, three other examples, namely compositions (II), (III) and (IV) of the polymer binder in water:

[0059] [Table 2]

[0060] Example 3 - Other variations in the preparation of polymer binders

[0061] Table 3 below summarizes other variations in the preparation of polymer binders containing polyethylene glycol monomethyl ether 350 (MPEG 350).

[0062] [Table 3]

[0063] Example 4 – Pilling resistance of Merino wool fabrics with different coating formulations

[0064] In this example, about 8% w / w of the polymer binder composition in water (I)-(IV) from Examples 1 and 2 was added with about 92% w / w of phosphate or borate buffer at pH 8.0 and then a 2×2 milled merino wool fabric was immersed in each coating formulation.

[0065] Under laboratory conditions, the merino wool fabrics were immersed in 350 mL of the coating formulation for 30 minutes at room temperature or 25° C. with agitation in a wash fastness tester. Each fabric was then squeezed with a laboratory wringer (approximately 10 lbs) to remove excess solution and then tumble dried for 30 minutes at 80° C. Each fabric was then line dried at ambient conditions for 48 hours and ironed before testing.

[0066] Table 4 below summarizes the pilling resistance results according to the JIS L1076 ICI method.

[0067] [Table 4]

[0068] From Table 4, it can be seen that the pilling resistance results of the 2x2 milled coated merino wool fabrics having coating formulations comprising any of the compositions of polymeric binders (I), (II), (III) and (IV) in water and a pH 8 buffer of phosphate or borate are superior compared to the uncoated merino wool fabric.

[0069] Example 5 - Variations in the ratio of polymer binder in water to buffer in water:

[0070] Table 5 below provides two different ratios of polymer binder in water to buffer solution (phosphate or borate) (Table 1) and their pilling resistance of coated merino wool fabrics on 2x2 milling. The conditions and procedures for coating on black 2x2 milling are as described in Example 4.

[0071] [Table 5]

[0072] From Table 5, the 2x2 milled black merino wool fabrics coated with coating formulations having a higher polymer binder ratio had lower pilling resistance than those coated with coating formulations having a lower polymer binder ratio (or higher buffer portion).

[0073] Example 6 - Effect of different fabric structures and / or colors on pilling prevention, fading of original finish, and fiber loss during 15 home wash cycles without a laundry bag

[0074] Table 6 below summarizes the pilling resistance according to JIS L1076 ICI method of single jersey knit for 2x2 milling of different colors (white, black, green, blue, red) coated with the coating formulation according to item 1 of Example 5. The fade grey scale grading results for the original finish of Merino wool fabric were evaluated according to ISO105-A02.

[0075] For the fiber loss evaluation for home washing cycles according to JIS L0217 method 103, Merino wool garments were washed for 5 minutes in a washing machine specified according to the above test standard using ECE standard detergent, without using a laundry net, rinsed for 2 minutes, and then rinsed for another 2 minutes. The above cycle was repeated 15 times. The washed garments were then laid flat to dry. All fibers discharged from the washing machine hose and those remaining in the wash mashing were collected. They were dried and adjusted to standard humidity before being weighed. The fiber loss percentage is defined as the amount of fiber loss (g) divided by the weight of the garment before the test (g).

[0076] [Table 6]

[0077] 3A and 3B show the results of pilling resistance ratings for single jersey knits and 2×2 milled knits of different colors, respectively, coated with the coating formulation according to item 1 of Example 5, compared to uncoated knits.

[0078] From Table 6, as described above, both single jersey knits and 2x2 milled knits coated with the coating formulation of Example 5, item 1, provide excellent pilling resistance (rating of 4.0 or higher) regardless of color, with minimal color loss to the original finish (according to the grayscale rating of the original finish of merino wool fabrics according to ISO 105-A02). The coating formation on both single jersey and 2x2 milled knits does not significantly affect the fiber loss of coated and finished merino wool garments in 15 cycles of home washing without a laundry net. Merino wool fabrics coated with the coating formulation of the present invention, regardless of their construction method or color, have excellent pilling resistance, minimal color loss to the original finish, and no significant fiber loss in 15 cycles of home washing without a laundry net.

[0079] Example 7 - Comparative Example of the Composition of Polymer Binder in Water (V)

[0080] Table 7 below summarizes the comparative compositions of the polymer binder (V) in water with respect to (I) described in Example 1.

[0081] [Table 7]

[0082] The main difference between compositions (V) and (I) is in the selection of the water dispersant. Triethylene glycol monomethyl ether was used in composition (V) instead of polyethylene glycol monomethyl ether (MPEG) used in composition (I). The remaining ingredients and reaction conditions of composition (V) are substantially the same as those used in (I). This composition does not form a homogeneous solution of the polymer binder in water and therefore is not applicable as a component of a coating formulation to provide anti-pilling merino wool fabric.

[0083] Example 8 - Comparative Example of the Composition of Polymer Binder in Water (VI) Table 8 below summarizes the comparative compositions of the polymer binder (VI) in water with respect to (I) described in Example 1.

[0084] [Table 8] Polyethylene glycol monomethyl ether 1000 (MPEG 1000) was used in composition (VI) instead of polyethylene glycol monomethyl ether 550 (MPEG 550) used in composition (I). The remaining ingredients and reaction conditions of composition (VI) are substantially the same as those used in (I). This composition is not applicable as a component of a coating formulation to provide anti-pilling merino wool fabrics since it does not form a homogenous solution of the polymer binder in water. [Industrial Applicability]

[0085] The present invention is applicable to merino wool fabrics, particularly wool fabrics including finished wool fabrics or finished garments, and provides pilling resistance of at least 4 according to certain standards while preventing color fading and fiber loss during washing.

Claims

1. An anti-pilling merino wool fabric, The anti-pilling merino wool fabric has a polycarbodiimide crosslinker coated on the merino wool fabric; the polycarbodiimide crosslinker is configured to interact with carboxyl groups on a polypeptide of the merino wool fabric; The polycarbodiimide crosslinker is formed from a coating formulation; The coating formulation comprises: a polymeric binder, 8-30% w / w in water, said polymeric binder being a reaction product formed by reacting isophorone diisocyanate and 1,6-hexamethylene diisocyanate with 3-methyl-1-phenyl-2-phospholene-oxide and dibutyltin (IV) dilaurate and glycol monomethyl ether; 70-92% w / w buffer in water; Including, the coating formulation is applied to the merino wool fabric, excess of the coating formulation is removed, and the coated merino wool fabric is dried, thereby leaving the polycarbodiimide crosslinker on the merino wool fabric. Anti-pilling merino wool fabric.

2. The anti-pilling merino wool fabric according to claim 1, having a pilling resistance of 4 or more according to JIS L1076 ICI method and suffering from a fiber loss of less than 0.2% w / w after 15 cycles of domestic washing without using a laundry net.

3. 2. The anti-pilling merino wool fabric of claim 1, wherein the glycol monomethyl ether is one or both of polyethylene glycol monomethyl ether 350 and polyethylene glycol monomethyl ether 550.

4. 2. The anti-pilling merino wool fabric of claim 1, wherein the buffer is selected from phosphates or borates and has a pH adjusted to 8.

0.

5. The anti-pilling merino wool fabric of claim 1, wherein the molar ratio of isophorone diisocyanate and 1,6-hexamethylene diisocyanate is 4:

1.

6. The anti-pilling merino wool fabric of claim 1, wherein 3-methyl-1-phenyl-2-phospholene-1 oxide is in a molar concentration of 0.2 to 1.0% relative to said isophorone diisocyanate and 1,6-hexamethylene diisocyanate.

7. 2. The anti-pilling merino wool fabric according to claim 1, wherein the dibutyltin (IV) dilaurate is at a concentration of 0.01% w / w relative to the glycol monomethyl ether.

8. A garment comprising the anti-pilling merino wool fabric of claim 1.

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