TWI503464B - Surface coated polyester-based fibrous substrate - Google Patents

Description

Surface coated polyester-based fibrous substrate

The present invention relates to a polyester-based fibrous substrate having a surface coated at least partially with a composition comprising certain perfluoropolyethers, and a method of providing the same. The polyester-based fibrous substrate has improved resistance to wear or abrasion after surface coating as compared to an untreated fibrous substrate.

A class of polymers containing an ester functional group on the main chain of the polyester. The most widely known polyesters are polyalkylene terephthalates, including polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate ( PBT). Polyester fibers have certain known properties such as high tenacity, low water absorption, mold resistance, crease resistance, and extremely small shrinkage compared to other synthetic fibers. The main applications of polyester fibers include clothing and home furnishings such as carpets, curtains, fabrics, wall coverings and upholstery. Other applications for polyester fibers include hoses, conveyor belts, tire cords, and filler fibers, covers, and upholstery fillers for cushioning and insulation materials in pillows.

The use of polyester in industrial fabrics, sportswear, ropes or carpets is continually seeking ways to improve the resistance or wear resistance of polyester. Methods of improving the resistance or abrasion resistance of the polyester fiber include, for example, increasing the basic thickness of the fiber, changing the cross-sectional shape of the fiber, or changing the conditions of the fiber during the spinning/drawing process. Further, the addition of an inorganic filler to the polyester prior to melt spinning has been disclosed in JP 4228113, in which a woven fabric is made of a PET yarn containing 2% TiO ₂ and exhibiting high tear strength.

However, there is still a need to provide a simple surface treatment with a suitable coating or spray composition to further improve the resistance or wear resistance of polyester based fibrous substrates (eg, fabrics, yarns, carpets).

It is known that coating or spraying a composition of a fluoropolymer can change its physical/chemical properties on a fibrous substrate. For example, US 2003/0139521 (US 6,737,498) discloses a fluorochemical composition which provides an oil-repellent and/or water-repellent fluorochemical composition to a fibrous substrate. U.S. Patent No. 4,929,471 discloses the use of a polymer based on a vinyl ether having a perfluoroalkyl group to treat a polyester fabric during the manufacturing process to produce a physics similar to that found in silk or rayon. Characteristic polyester fabric.

Therefore, it is necessary to find a surface treatment composition suitable for a polyester-based fiber substrate to improve its resistance to wear or abrasion.

Provided herein is a coated substrate comprising a fibrous substrate comprising a polyester, wherein the fibrous substrate is at least partially coated with a coating composition, wherein the coating composition comprises Formula I Perfluoropolyether:

F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I)

Wherein n is an integer from 5 to 100.

Provided herein is a method of improving the abrasion resistance of a fibrous substrate comprising a polyester comprising the steps of:

(i) applying a coating composition to at least a portion of the surface of the fibrous substrate, the coating composition comprising a perfluoropolyether of formula I:

F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I)

Wherein n is an integer from 5 to 100;

(ii) drying the coated fibrous substrate;

(iii) selectively washing the coated fibrous substrate from step (ii) with water; and drying the rinsed fibrous substrate.

All publications, patent applications, patents, and other references mentioned herein are hereby expressly incorporated by reference in their entirety in their entirety in their entirety herein

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In the event of a conflict, the present specification and the definitions contained therein shall prevail.

Trademarks are indicated in capital letters unless otherwise stated.

All percentages, parts, ratios, etc., are by weight unless otherwise indicated.

When a quantity, a concentration, or other value or parameter has a specified range, a preferred range, or a table listing the upper and lower ideal values, this should be understood to specifically disclose all ranges consisting of any number of upper and lower limits or ideal values, regardless of Whether to disclose these ranges separately. If a range of values is recited herein, the range is intended to include the endpoints of the range and all integers and fractions thereof. The scope of the invention is not intended to be limited to the specific values described in the context of defining a range.

When the term "about" is used to describe a numerical value or a range of endpoints, it is understood that the disclosure includes the particular value or endpoint.

As used herein, the terms "including", "comprising", "having", "comprising" or "comprising" or any other variation are intended to mean a non-exclusive inclusion. For example, a set of compounds, processes, methods, articles, or devices containing the plural elements listed in the list are not necessarily limited to the elements listed in the list, but may include, but not explicitly listed, Process, method, article or other element inherent in the device. In addition, unless expressly stated otherwise, “or” means an inclusive “or” rather than an exclusive “or”. For example, a condition A "or" B is satisfied with any of the following: A is true (or exists) and B is pseudo (or non-existent), A is pseudo (or non-existent), and B is true (or Exist) and both A and B are true (or exist).

In addition, the indefinite articles "a" and "an", "the" The word "a" or "an" is intended to include the singular and the s

The materials, methods, and examples are merely illustrative, and are not intended to be limiting. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

The following is a detailed description of the invention.

Polyester based fiber substrate

Polyester polymers are well known to those of ordinary skill in the art and may comprise any condensation polymerization product derived from the esterification or transesterification of a monoalcohol with a dicarboxylic acid comprising the ester thereof.

The alcohols include diols having from 2 to about 10 carbon atoms, such as ethylene glycol, propylene glycol, butylene glycol, methoxy polyalkylene glycol, neopentyl glycol, 1,3-propanediol, butylene glycol, A composition of hexanediol, diethylene glycol, polyethylene glycol, cyclohexanedimethanol or a combination of two or more thereof. Other suitable diols include ethylene glycol, 1,4-butanediol, 1,2-propanediol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,5-pentane Long chain made of diol, 1,6-hexanediol, 1,2-, 1,3-, and 1,4 cyclohexanedimethanol, a reaction product of a diol or a polyol and an alkylene oxide A diol and a polyol or a combination of two or more thereof.

The dicarboxylic acid comprises terephthalic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, glutaric acid, isophthalic acid, 1,10-sebacic acid, phthalic acid, dodecane The diacid, ester forms an equivalent (for example: a diester such as dimethyl terephthalate) or a combination of two or more thereof. Other diacids which can be used to form the polyester include isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, hydrazine Acid, 1,12-dodecanedioic acid and derivatives thereof, such as dimethyl, diethyl, dipropyl esters of these dicarboxylic acids or a combination of two or more thereof.

Polyethylene terephthalate (PET) is a polyester prepared by condensation polymerization of ethylene glycol with terephthalic acid (or dimethyl terephthalate). The PET may be a PET homopolymer or copolymer of polyethylene terephthalate preferably having 70 wt% or more, or a blend thereof. It can be modified by up to 30% by weight of a polyester made from other diols or diacids.

Polytrimethylene terephthalate (PTT) is a polyester which can be prepared by condensation polymerization of 1,3-propanediol with terephthalic acid (or dimethyl terephthalate). The 1,3-propanediol used to make the PTT is preferably derived from a renewable source ("bio-derived" 1,3-propanediol) by biochemical means. The PTT may be a homopolymer or copolymer of PTT preferably containing 70 wt% or more, or a blend thereof. It can be modified by up to 30% by weight of a polyester made of other diol or diacid. The most preferred resin is a PTT homopolymer.

Polybutylene terephthalate (PBT) is a polyester which can be prepared by condensation polymerization of 1,4-butanediol with terephthalic acid (or dimethyl terephthalate). The PBT may be a homopolymer or copolymer of PBT preferably containing 70% by weight or more, or a blend thereof. It can be modified with up to 30% by weight of polyester made from other diols or diacids. The most preferred resin is a PBT homopolymer.

Polyesters and methods for their manufacture are well known to those of ordinary skill in the art.

In one embodiment, the fibrous substrate consisting of a polyester is selected from the group consisting of PET, PTT, PBT, and blends thereof. In another embodiment, the fibrous substrate is comprised of a polyester selected from the group consisting of a PTT homopolymer or a PTT copolymer containing 70 wt% or more of PTT.

There is no particular limitation on the term "fibrous substrate". For the purposes of the present invention, the term "fibrous substrate" includes fibers, yarns, fabrics, textiles or finished products that can be used in clothing, home furnishings, carpets, and other consumer products. The fibrous substrate of the present invention may be a "knit", "woven" or "non-woven" substrate. The nonwoven substrate can include a substrate in which the fibers are mesh or cotton-like fibers joined by heat, entanglement, and/or pressure. A particularly preferred fibrous substrate of the present invention is selected from the group consisting of fibers, fabrics, yarns, and carpets.

Coating composition

High molecular weight hexafluoropropylene oxide polymers, including their blocked and chain extended derivatives, are used as high performance elastomers, dispersants or lubricants depending on their molecular weight and different physical properties. Surprisingly, surface treatment of the polyester-based fibrous substrate with a coating composition comprising a perfluoropolyether of the formula I provides unexpectedly beneficial results in terms of damage/wear resistance.

The coating composition of the present invention comprises a perfluoropolyether of the formula I:

F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I)

Wherein n is an integer from 5 to 100.

Preferred coating compositions of the present invention comprise a perfluoropolyether of formula I wherein n is an integer from 10 to 60; more preferably from 15 to 40.

Preferred coating compositions of the present invention comprise a perfluoropolyether of the formula I having a molecular weight in the range of from 1000 to 16,000; more preferably in the range of from 1,800 to 10,000; optimally, in the range of from 2,600 to 7,000. In the range.

The coating composition of the present invention further comprises at least one solvent. Suitable solvents include (per)fluorinated solvents having a boiling point below 100 °C. For example, perfluoropolyethers such as Galde HT55 (bp 55 ° C.) Solvay Plastics; perfluoroalkanes, such as perfluorooctane, perfluorohexane; hydrofluoroalkanes, such as 2H, 3H-decafluoropentane (EI du Pont de Nemours and Company (Wilmington) ,Del,USA),Vertrel XF, bp 55 ° C); (per) fluorocycloalkanes, such as 1H, IH, 2H-heptafluorocyclopentane (Zeorora -H, bp 82.5 ° C); purchased from 3M company, the trade name is Novec Hydrofluoroethers, including methoxy nonafluorobutane (HFE-7100, bp 61 ° C), ethoxy nonafluorobutane (HFE-7200, bp 76 ° C), 2-trifluoromethyl-3- Ethoxy decafluorohexane (HFE-7300, bp 98 ° C); hydrofluoropolyethers, such as H-Galden ZV60 (bp 60 ° C.). Preferred solvents include 2H, 3H-decafluoropentane and methoxy nonafluorobutane. In another embodiment, the coating composition of the present invention may further comprise a thickening agent to achieve and maintain the desired viscosity, a fragrance, a dye; or a mixture of two or more such ingredients. Perfumes used include natural and synthetic fragrances, perfumes, fragrances, essential oils, and any other simple substance that releases aroma and a mixture of liquid or powdered compounds. In the case of natural flavors, there are animal-derived perfumes such as musk, civet, castor, ambergris or the like, and plant-derived perfumes such as lemon oil, rose oil, and citronella oil. , sandalwood oil, peppermint oil, cinnamon oil or the like. Further, in the case of a synthetic fragrance, for example, a mixed fragrance of, for example, ava-pinene, limonene, geraniol, linalool, lavanol, nerolidol or the like is present.

The coating compositions of the present invention may also contain other ingredients to provide additional benefits to the polyester-based fibrous substrate, and/or to improve efficacy and formulation.

The coating composition of the present invention can be applied to the fibrous substrate in the form of a solution, a gel, a spray or a foam.

Depending on the method of application of the coating composition, the amount of perfluoropolyether of the formula I or a mixture thereof (in % by weight) in the coating composition is present, typically from about 0.1, based on the total weight of the coating composition. % varies to about 50%, preferably from about 1% to about 40% and more preferably from about 5% to about 20%.

The amount of solvent (in % by weight) contained in the coating composition may vary from about 50% to about 99.9%, preferably from about 60% to about 99.0%, and more, depending on the total weight of the coating composition. Preferably, it is from about 80% to about 95%.

The amount of the thickener (in % by weight) contained in the coating composition may vary from 0% to about 10%, preferably from about 0.1% to about 5%, based on the total weight of the coating composition. More preferably, it is from about 0.2% to about 1%.

The amount of perfume (in % by weight) contained in the coating composition may vary from 0% to about 15%, preferably from about 0.1% to about 10%, and more preferably, based on the total weight of the coating composition. It is from about 0.2% to about 5%.

Some examples of particularly suitable perfluoropolyethers of formula I are commercially available and are selected from Krytox GPL-104, Krytox GPL-105 or Krytox GPL-106 fluorinated oil (having an average molecular weight of about 3000, 4800, and 6000, respectively, and was obtained from EI du Pont de Nemours and Company, respectively, Wilmington, Del, USA).

U.S. Patent No. 4,356,291 (DuPont) discloses a perfluoropolyether ending in various end groups and a process for its manufacture, which are incorporated herein by reference.

The coating composition of the present invention may be in the form of a solution, gel, paste, spray or foam. The coating composition of the present invention can be applied to the fibrous substrate (e.g., a fabric, yarn, a garment, a carpet, or other substance) via a dipping, soaking, spraying or spraying process followed by a drying step.

The coating composition of the present invention is preferably present in the form of a clear liquid which is used as an impregnation solution or a spray, and any of the foregoing forms are stable and maintain their liquid state under environmental conditions for a long time without gelation. .

An example of a general composition of an impregnation solution and a spray formulation can be found in Table 1 below.

For the spray composition, the coating composition according to the present invention preferably has a viscosity in the range of from about 0.3 cp to about 5 cp; and in the form of a liquid regulator formulation of from about 100 cp to about 450 cp. . One particular advantage of the present invention is that the viscosity within this range can be achieved without the addition of a viscosity control agent as is conventional.

Surface treatment method

The invention further relates to a method of improving the resistance and/or abrasion resistance of a fibrous substrate consisting of a polyester as described below.

The coating composition of the present invention is applied to a fibrous substrate in various conventional procedures. To be applied to a washable garment textile, the coating composition can be applied from an organic solution, for example, by brushing, dipping, spraying, filling, rolling, foaming or the like. It can be applied to dyed or undyed textile substrates. For carpets, the coating composition of the present invention can be applied to one side of the carpet by dipping into a solution or spraying with a spray and/or foam application.

The coating composition solution of the present invention can be diluted to suit a particular application method and/or device. When the coating composition is applied to the surface of the fibrous substrate, an effective amount of the coating composition is applied to at least a portion of the surface of the fibrous substrate to achieve the desired improvement in abrasion resistance. If the fibrous substrate is a woven fabric, yarn or textile, the coating composition of the present invention is preferably applied at a concentration of from about 0.1 g/L to about 50 g/L, more preferably from about 0.5 g/L to About 25 g/L.

A dispersion or solution of the coating composition is typically applied to the fibrous substrate by immersing the substrate in a solution of the coating composition for a sufficient period of time (from a few seconds to a few minutes) The coating composition is sufficiently absorbed, or by spraying a solution of the coating composition onto the surface of the fibrous substrate.

Once the surface of the fibrous substrate is at least partially coated by the coating composition, the substrate is dried at a temperature ranging from room temperature to about 60 °C. In one embodiment, a large fibrous substrate, such as a carpet, is air dried at room temperature. After drying, the surface coated fibrous substrate is optionally rinsed with water and dried in the same manner as described above. Additionally, the coating composition can be applied multiple times to improve abrasion resistance.

Further depending on the particular method of application, the perfluoropolyether of formula I may be applied not only to the surface of the fibrous substrate but also to the fibrous substrate to different depths. In one embodiment, it can be found throughout the entire fibrous substrate. In another embodiment, it can be found that it is at least partially above and below the surface.

For coated fibrous substrates, such as dried fabrics, textiles or carpets, the applied amount of coating composition is sufficient to provide from about 0.1 to 50 wt%, relative to the total weight of the coated fibrous substrate. A perfluoropolyether of formula I; provided that the treatment does not substantially affect the appearance and feel of the fibrous substrate. More preferably, the coated fibrous substrate contains from about 1 to 35 wt% of a perfluoropolyether of formula I relative to the total weight of the coated fibrous substrate. Most preferably, the coated fibrous substrate contains from about 5 to 20% by weight of a perfluoropolyether of formula I relative to the total weight of the coated fibrous substrate.

Accordingly, one embodiment of the present invention is directed to a method of improving the abrasion resistance of a fibrous substrate comprising a polyester comprising the steps of:

(i) immersing at least a portion of the surface of the fibrous substrate in a coating composition comprising a perfluoropolyether of the formula I:

F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I)

Wherein n is an integer from 5 to 100;

(ii) the fibrous substrate to which the dried surface is coated;

(iii) selectively washing the fibrous substrate from step (ii) with water; and drying the washed fibrous substrate.

According to another aspect, the present invention provides a method of improving the abrasion resistance of a fibrous substrate comprising a polyester comprising the steps of:

(i) spraying at least a portion of the surface of the fibrous substrate with a coating composition comprising a perfluoropolyether of formula I,

F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I)

Wherein n is an integer from 5 to 100;

(ii) the fibrous substrate to which the dried surface is coated;

(iii) selectively washing the fibrous substrate from step (ii) with water; and drying the washed fibrous substrate.

Even without further elaboration, it is believed that one of ordinary skill in the art in the <RTIgt; Therefore, the following examples are for illustrative purposes only and are not intended to limit the disclosure of the invention. Percentages are by weight unless otherwise indicated.

The abbreviation "Ex" stands for "example" and "Comp." stands for "comparative", followed by a number representing an example of the preparation of the compound.

Instance material

The polyester-based fiber substrate in the example is a fabric composed of PTT (plain weave), also known as SORONA. Also available from EI du Pont de Nemours and Company (Wilmington, DE, USA).

The perfluoropolyether of formula I used in the examples includes Krytox GPL104 (molecular weight about 3000), Krytox GPL105 (molecular weight about 4800) and Krytox GPL 106 (molecular weight about 6000) was obtained from EI du Pont de Nemours and Company (Wilmington, DE, USA).

The prepared coating composition is as follows:

1) Coating solution A: Krytox with 2H, 3H-decafluoropentane (CAS No. 138495-42-8) GPL104 was diluted to a 10 wt% solution.

2) Coating solution B: Krytox with 2H, 3H-decafluoropentane (CAS No. 138495-42-8) GPL105 is diluted to a 10 wt% solution.

3) Coating solution C: with HFE-7100 (methoxy hexafluorobutane and methoxy nonafluoroisobutane (3M company Novec ) a mixture of solvents) will Krytox GPL106 is diluted to a 10 wt% solution.

Sample preparation

For Ex. 1-6: The fabric sample was cut into strips 10 cm wide and 10 cm long and the initial weight (W0) was recorded. The fabric sample was dipped into the coating composition for 30 seconds; it was dried at ambient temperature until the weight was constant; and the weight (W1) of the surface treated fabric sample was recorded. The dried fabric sample was immersed in 1000 mL of water and gently stirred for 1 hour. The fabric sample was picked up, dried flat in a vacuum oven at ambient temperature until the weight was constant, and the final weight (W2) was recorded.

For Ex. 7-12: The fabric sample was cut into strips 10 cm wide and 10 cm long and the initial weight (W0) was recorded. The fabric sample was sprayed with the coating composition to cover most of the surface; it was dried at ambient temperature until the weight was constant; and the weight (W1) of the surface treated fabric sample was recorded. The dried fabric sample was immersed in 1000 mL of water and gently stirred for 1 hour. The fabric sample was picked up, dried flat in a vacuum oven at ambient temperature until the weight was constant, and the final weight (W2) was recorded.

Preparation of comparative samples

A comparative fabric sample was prepared in the same manner as the test sample, and the fabric was immersed in 1000 mL of water containing no perfluoropolyether of Formula I (for Comp. Ex. 1-3) or sprayed with perfluoropolyether without Formula I. Water (for Comp. Ex. 4-5).

Wear test & results

A Taber abrasion test was used to evaluate the wear properties of fabric samples according to ASTM Standard D3884-07. The machine model is a Taber with a CS-10 grinding wheel. 5131 grinder with a load of 1000 grams. Its wheel speed is 60 rpm. After each abrasion test, the grinding wheel was polished again with a polishing paper for 25 revolutions. The wear resistance is evaluated by the number of wear revolutions required to cause a yarn to break.

Table 2 lists the coating results of Examples 1 to 6 and Comparative Examples 1 to 3 and their wear properties.

Table 2. Dip Coating and Wear Results & Wear Properties

Table 3 lists the coating results of Examples 7 to 12 and Comparative Examples 4 to 5 and their wear properties.

The data in Tables 2 and 3 demonstrate that a polyester-based fibrous substrate (i.e., a SORONA) is surface treated with a coating composition comprising a perfluoropolyether of formula I as compared to Comparative Examples 1 through 5. Fabrics) can produce significant improvements in wear resistance.

Claims (8)

A coated substrate comprising a fibrous substrate comprising a polyester, wherein the fibrous substrate is at least partially coated with a coating composition, wherein the coating composition comprises a perfluoropolyether of the formula I: F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I) wherein n is an integer from 5 to 100, and the total weight of the coated substrate comprises 0.1-50% by weight of Formula I Perfluoropolyether. The coated substrate of claim 1, wherein n is an integer from 10 to 60. The coated substrate of claim 1, wherein the polyester is selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate or a blend thereof . The coated substrate of claim 1, wherein the polyester is a polytrimethylene terephthalate homopolymer or a poly(p-phenylene terephthalate) comprising at least 70% by weight of polytrimethylene terephthalate. Propylene acrylate copolymer. The coated substrate of claim 1, wherein the fibrous substrate is selected from the group consisting of fibers, fabrics, yarns, or carpets. The coated substrate of claim 1, wherein the coating composition comprises from about 0.1 to 50% by weight of a perfluoropolyether of formula I, based on the total composition. A method for improving the abrasion resistance of a fibrous substrate comprising a polyester comprising the steps of: (i) applying a coating composition to at least a portion of a surface of the fibrous substrate, the coating composition Including a perfluoropolyether of the formula I: F-[CF(CF ₃ )-CF ₂ O] _n -CF ₂ CF ₃ (I) wherein n is an integer from 5 to 100; (ii) dry coated a fibrous substrate; and (iii) selectively rinsing the coated fibrous substrate from step (ii) with water; and drying the rinsed fibrous substrate; wherein the coating from step (ii) The total weight of the fibrous substrate covered comprises from 0.1 to 50% by weight of a perfluoropolyether of formula I. The method of claim 7, wherein the step of applying is selected from the group consisting of brushing, dipping, spraying, filling, rolling, or foaming.