CN112779778B - Coating composition and application thereof - Google Patents

Coating composition and application thereof Download PDF

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Publication number
CN112779778B
CN112779778B CN201911091893.4A CN201911091893A CN112779778B CN 112779778 B CN112779778 B CN 112779778B CN 201911091893 A CN201911091893 A CN 201911091893A CN 112779778 B CN112779778 B CN 112779778B
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Prior art keywords
coating composition
wax
fibrous
present
composition
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CN201911091893.4A
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CN112779778A (en
Inventor
尹延征
刘月文
刘续峰
李军
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Honeywell Performance Materials and Technologies China Co Ltd
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Honeywell Performance Materials and Technologies China Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a coating composition and application thereof. The coating composition is prepared from formulation raw materials comprising a wax emulsion, a resin binder, optionally a film-forming aid, and optionally other additives. The coating composition provided by the invention has the advantages of simple preparation process, convenience in application and the like. The coating composition according to the present invention can be applied to a fibrous substrate or a fibrous article to enhance the abrasion resistance between fibrous substrates or between fibrous articles and the breaking strength of the fibrous substrate or fibrous article.

Description

Coating composition and application thereof
Technical Field
The invention relates to the field of paint. In particular, the present invention relates to a coating composition and its use.
Background
Fibrous articles for specific applications often require high strength and high abrasion resistance. The inclusion of high strength fibers in such fibrous articles is well known. Commonly used high strength fibers include Ultra High Molecular Weight Polyethylene (UHMWPE) fibers, aramid fibers (e.g., poly (terephthalamide)), graphite fibers, nylon fibers, glass fibers, and the like.
Coating techniques have been widely employed to further improve the overall properties, particularly abrasion resistance, of such fibrous articles. The general procedure involves coating a fiber, yarn or fabric with a coating composition having a specific composition, air drying or drying in an oven to obtain a coated fibrous article.
CN102016151B discloses a fibrous substrate having a multilayer coating thereon. The fibrous substrate comprises one or more fibers having a tenacity of about 7 g/denier or greater and a tensile modulus of about 150 g/denier or greater, the fibrous substrate is treated with a polymeric binder material, after which a wax is applied over the binder layer, passed through a press, melted and dispersed on the surface of the fibrous substrate at elevated temperature and pressure or penetrating deep into the fibrous substrate.
A composite material comprising a bimodal adhesive is disclosed in CN107635763 a. The binder comprising a crystalline component having a melting temperature and an amorphous component having a softening temperature, coating the first plurality of fibers and the second plurality of fibers with the binder, and positioning the first plurality of fibers at an angle of 90 ° to the second plurality of fibers; the first and second pluralities of fibers are then heated to the melting temperature of the crystalline component and pressed through a flat bed laminator to form a composite.
The above methods all involve high temperature and/or high pressure conditions and are difficult to use in rope and fishing net applications and do not mention the effect of the coating on the strength of the fibrous substrate.
Accordingly, there is a need for a coating composition that is simple in preparation process and capable of treating various fibrous substrates or fibrous articles at normal temperature, so that the fibrous substrates or fibrous articles can exhibit improved wear resistance between the fibrous substrates or between the fibrous articles and breaking strength of the fibrous substrates or fibrous articles after coating the coating composition.
Disclosure of Invention
In view of the foregoing, the present invention provides a coating composition, a method of treating a fibrous substrate or fibrous article using the same, and the use thereof for improving the abrasion resistance between fibrous substrates or between fibrous articles and the breaking strength of the fibrous substrate or fibrous article, thereby effectively solving or at least alleviating one or more of the problems of the prior art.
According to a first aspect of the present invention there is provided a coating composition comprising, based on the total weight of the composition, the following formulation materials:
20 to 90% by weight of a wax emulsion,
10 To 80% by weight of a resin binder,
0 To 30% by weight of a film-forming auxiliary, and
0 To 10% by weight of other additives selected from wetting agents, leveling agents, defoamers, light stabilizers and combinations thereof.
In some embodiments, the wax emulsion comprises 10 to 50 weight percent of a wax selected from the group consisting of carnauba wax, polyethylene homopolymer wax, oxidized polyethylene wax, polypropylene wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer wax, ethylene-maleic anhydride graft copolymer wax, propylene-maleic anhydride graft copolymer wax, paraffin wax, fischer-tropsch wax, montan wax, microcrystalline wax, and combinations thereof, based on the total weight of the wax emulsion.
In some embodiments, the resin binder is selected from the group consisting of aqueous polyurethanes, aqueous acrylic resins, aqueous polyester resins, aqueous silicon-containing, fluorine-containing resins, aqueous amino resins, aqueous alkyd resins, aqueous epoxy resins, aqueous phenolic resins, aqueous oils and aqueous polybutadiene, aqueous hyperbranched polymers, and combinations thereof.
In some embodiments, the coalescent is selected from alcohols having 1 to 20 carbon atoms, alcohol ethers, ketones, and combinations thereof.
In some embodiments, the wax is selected from oxidized polyethylene waxes having a density of at least 0.95g/cm 3, an acid number in the range of 1 to 100mg KOH/g.
According to a second aspect of the present invention there is provided a method of treating a fibrous substrate or fibrous article comprising applying to the substrate or article a coating composition according to the first aspect of the present invention.
In some embodiments, the coating composition has a size of 4 to 33g per 100g of substrate or article.
According to a third aspect of the present invention there is provided the use of a coating composition according to the first aspect of the present invention for improving the abrasion resistance between fibrous substrates or between fibrous articles.
According to a fourth aspect of the present invention there is provided the use of a coating composition according to the first aspect of the present invention for improving the breaking strength of a fibrous substrate or fibrous article.
According to a fifth aspect of the present invention there is provided a fibrous product having applied thereto a coating composition according to the first aspect of the present invention.
According to a sixth aspect of the present invention there is provided a downstream product prepared from a fibrous product according to the fifth aspect of the present invention.
The coating composition according to the present invention can be used to improve the abrasion resistance between fibrous substrates or between fibrous products and the breaking strength of the fibrous substrates or fibrous products, and various fibrous substrates or fibrous products can be conveniently treated at normal temperature and pressure using the coating composition according to the present invention, compared to a method of preparing a fibrous material having good abrasion resistance using high temperature and/or high pressure.
Detailed Description
In order for those skilled in the art to further understand the present invention, specific embodiments of the present invention are described in detail below. It should be understood that the described embodiments of the invention are merely exemplary and that the invention is not limited to these embodiments.
According to a first aspect of the present invention there is provided a coating composition comprising, based on the total weight of the composition, the following formulation materials:
20 to 90% by weight of a wax emulsion,
10 To 80% by weight of a resin binder,
0 To 30% by weight of a film-forming auxiliary, and
0 To 10% by weight of other additives selected from wetting agents, leveling agents, defoamers, light stabilizers and combinations thereof.
In some embodiments, the wax emulsion comprises 10 to 50 wt% wax, based on the total weight of the wax emulsion.
The term "wax" as used herein is generally defined as a material that is solid at room temperature, but melts or softens at temperatures in excess of 40 ℃ without decomposing. They are generally organic and insoluble in water at room temperature, but can form pastes and gels in certain non-polar organic solvents.
Preferably, the waxes useful in the coating compositions of the present invention have a molecular weight in the range of 400 to 25,000g/mol and have a melting point in the range of 40 ℃ to 150 ℃.
Suitable waxes for use in the present invention include natural waxes and synthetic waxes including, but not limited to: animal waxes such as beeswax, chinese wax, spermaceti and wool wax; vegetable waxes such as wood wax, bayberry wax, candelilla wax, carnauba wax, castor wax, cogongrass wax, japan wax, jojoba oil wax, rice bran wax, and soybean wax; mineral waxes such as ceresin, montan, ozokerite and peat waxes; petroleum waxes such as paraffin wax and microcrystalline wax; and synthetic waxes such as Fischer-Tropsch waxes, polyolefin waxes (including polyethylene homopolymer waxes, oxidized polyethylene waxes, polypropylene waxes), stearamide waxes, substituted amide waxes, ethylene-acrylic acid copolymer waxes, ethylene-vinyl acetate copolymer waxes, ethylene oxide-vinyl acetate copolymer waxes, ethylene-maleic anhydride graft copolymer waxes, propylene-maleic anhydride graft copolymer waxes, and other chemically modified waxes.
In some embodiments, the wax is selected from the group consisting of carnauba wax, polyethylene homopolymer wax, oxidized polyethylene wax, polypropylene wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer wax, oxidized ethylene-vinyl acetate copolymer wax, ethylene-maleic anhydride graft copolymer wax, propylene-maleic anhydride graft copolymer wax, paraffin wax, fischer-tropsch wax, montan wax, microcrystalline wax, and combinations thereof.
Preferably, the wax is selected from the group consisting of propylene-maleic anhydride graft copolymer waxes, oxidized polyethylene waxes, and combinations thereof.
More preferably, the wax is selected from oxidized polyethylene waxes.
In some embodiments, the wax is selected from oxidized polyethylene waxes having a melting point in the range of 40 to 150 ℃, preferably 120 to 150 ℃, a number average molecular weight in the range of 500 to 10,000g/mol, preferably 2000 to 5000g/mol, and an acid number in the range of 1 to 100mg KOH/g, preferably 5 to 50mg KOH/g.
In some embodiments, the wax is selected from high density oxidized polyethylene waxes.
Preferably, the high density oxidized polyethylene wax has a density of at least 0.95g/cm 3, preferably at least 0.98g/cm 3.
Preferably, the high density oxidized polyethylene wax has an acid number in the range of 1 to 100mg KOH/g, preferably 5 to 50mg KOH/g, more preferably 7 to 35mg KOH/g.
In a preferred embodiment, the wax is selected from oxidized polyethylene waxes having a density of at least 0.98g/cm 3, an acid number in the range of 7 to 35mg KOH/g.
As examples of suitable propylene-maleic anhydride graft copolymer waxes, mention may be made of propylene-maleic anhydride graft copolymer waxes A-C950P from Honival.
As examples of suitable oxidized polyethylene waxes, mention may be made of the A-C series of oxidized polyethylene waxes from Honival, inc., such as A-C629, A-C307, A-C316, A-C325 and A-C330.
Conventional methods and materials well known to those skilled in the art may be used to prepare the wax emulsions of the present invention.
For example, the wax emulsion of the present invention may be prepared by the steps of:
(a) Heating a mixture of wax, an emulsifying agent, an optional emulsifying aid, an optional salt additive, an optional alkaline agent and a part of deionized water (for example, 40-90% of the total weight of the deionized water) in a certain weight ratio to 120-160 ℃ in a closed environment, and keeping for a period of time;
(b) Adding the rest deionized water into the mixture, maintaining a closed environment, maintaining the temperature at 120-160 ℃, and maintaining for a period of time to obtain an emulsion;
(c) The resulting emulsion was rapidly cooled to room temperature to give a wax emulsion.
The wax emulsion of the present invention may also be prepared by the steps of:
(a) Heating a mixture of wax, an emulsifying agent, an optional emulsifying auxiliary agent, an optional salt additive, an optional alkaline agent and deionized water according to a certain weight ratio to 120-160 ℃ in a closed environment, and keeping for a period of time to obtain an emulsion;
(b) The resulting emulsion was rapidly cooled to room temperature to give a wax emulsion.
In some embodiments, the emulsifier is used in an amount of 0.5 to 20 wt.%. The emulsifier useful in the present invention may be any suitable emulsifier known to those skilled in the art including, but not limited to, fatty alcohol polyoxyethylene ethers, polyethylene glycol fatty acid esters, alkyl amine oxides, or combinations thereof.
Preferably, the emulsifier used in the present invention is selected from the group consisting of C 10-18 fatty alcohol polyoxyethylene ethers. For example, a suitable emulsifier may be the Foryl series from kemel fine chemical (Shanghai) Inc.
In some embodiments, the emulsifying aid is present in an amount of 0.01 to 2.0% by weight. Emulsifying aids useful in the present invention include, but are not limited to, dihydroxyc 1-4 alkylamines, such as dimethylethanolamine.
In some embodiments, the salt additive is used in an amount of 0.01 to 0.5 wt.%. Salt additives useful in the present invention include, but are not limited to sodium metabisulfite.
In some embodiments, the alkaline agent is used in an amount of 0.1 to 2 weight percent. Alkaline agents useful in the present invention include, but are not limited to, sodium hydroxide, potassium hydroxide, dimethylethanolamine, or combinations thereof.
The wax emulsion is present in the coating composition in an amount of 20 to 90 wt%, preferably 25 to 85 wt%, more preferably 35 to 75 wt%, still more preferably 40 to 65 wt%, based on the total weight of the coating composition.
In some embodiments, the wax emulsion is present in the coating composition in an amount of 30 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80wt%, based on the total weight of the coating composition.
The coating composition of the present invention includes a resin binder. In general, any resin binder that has good film forming properties and is compatible with the wax emulsion system of the present invention can be used to formulate the coating composition of the present invention.
Suitable resin binders include, but are not limited to, aqueous polyurethanes, aqueous acrylics, aqueous polyester resins, aqueous silicones, fluorine-containing resins, aqueous amino resins, aqueous alkyds, aqueous epoxies, aqueous phenolic resins, aqueous oils and aqueous polybutadiene, aqueous hyperbranched polymers, and combinations thereof.
Preferably, the resin binder is selected from the group consisting of aqueous polyurethane, aqueous acrylic resin, and combinations thereof.
More preferably, the resin binder is selected from aqueous polyurethanes. The aqueous polyurethanes useful in the present invention are commercially available, for example, IMPRANIL DL1537, IMPRANIL DLH aqueous polyurethanes available from kesi corporation; ICO-THANE, ICO-THANE aqueous polyurethane available from Belgium I-Coat; XL-901, XL-902 waterborne polyurethane available from Jiangsu Xinglong photoelectric Co.
The resin binder is present in the coating composition in an amount of 10 to 80 wt%, preferably 20 to 75 wt%, more preferably 25 to 70 wt%, still more preferably 30 to 65 wt%, based on the total weight of the coating composition.
In a preferred embodiment, the wax is selected from high density oxidized polyethylene waxes and the resin binder is selected from aqueous polyurethanes, each in the amounts as defined above.
Film forming aids may optionally be included in the coating compositions of the present invention. The film forming aid is preferably selected from alcohols having 1 to 20 carbon atoms (including, but not limited to, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol, and the like), alcohol ethers (including, but not limited to, propylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diethylene glycol hexyl ether, triethylene glycol butyl ether, tripropylene glycol butyl ether), ketones (including, but not limited to, acetone, butanone), and combinations thereof.
When present, the coalescent is present in the coating composition in an amount of 1 to 30 wt.%, preferably 2 to 20 wt.%, more preferably 5 to 15 wt.%, based on the total weight of the coating composition.
Other additives may optionally be included in the coating compositions of the present invention, including, but not limited to, wetting agents, leveling agents, defoamers, light stabilizers, and the like. The type and amount of the appropriate additives can be selected by those skilled in the art according to actual needs.
When present, the other additives are present in the coating composition in an amount of 0.5 to 9 wt%, preferably 1 to 7 wt%, based on the total weight of the coating composition.
The coating compositions of the present invention may be formulated using any suitable method known to those skilled in the art.
For example, the coating composition of the present invention can be prepared by mixing together the wax emulsion obtained as described above and the resin binder in a certain ratio at ordinary temperature with stirring until uniform.
In some preferred embodiments, the dry weight ratio of wax emulsion to resin binder is from 1:4 to 4:1, preferably from 1:2 to 2:1, more preferably from 2:3 to 3:2.
If desired, a film forming aid may be added with stirring.
If necessary, a pH adjustor can be added with stirring to adjust the pH of the mixture to 7.5 to 10.0. The pH regulator is selected from but not limited to dimethylethanolamine, potassium hydroxide, sodium hydroxide.
Any of the other additives described above may be added with stirring, if desired.
In a preferred embodiment, the coating composition of the present invention is prepared, for example, by the steps of: stirring and mixing the resin adhesive and the film forming additive together at normal temperature until the mixture is uniform; then optionally adding a pH regulator to adjust the pH of the mixture to 7.5-10.0; then, optionally adding any other additives, and continuously stirring and mixing until the mixture is uniform; finally, the wax emulsion obtained as described above was added while continuing to stir and mix until uniform, to obtain the coating composition of the present invention.
Deionized water may be added as appropriate to adjust the viscosity of the mixture, if desired, in one or more of the above-described steps of the process.
According to a second aspect of the present invention there is provided a method of treating a fibrous substrate or fibrous article comprising applying to the fibrous substrate or fibrous article a coating composition according to the first aspect of the present invention.
The term "fibrous substrate" as used herein may be a single fiber or a plurality of fibers, such as yarns. Preferably, the fibrous substrate is a yarn.
The fibrous substrate of the present invention may be selected from any type of polymeric fiber, preferably selected from high strength, high modulus fibers, such as polyolefin fibers (including, but not limited to, ultra high molecular weight polyethylene fibers and ultra high molecular weight polypropylene fibers), aramid fibers, graphite fibers, nylon fibers, glass fibers, and the like.
Particularly preferred fiber types for use in the present invention include those sold under the trademark Horniwell IncPolyethylene fibers sold and "lycra" sold by chinese petrochemical instrumentation. Also preferably included are those sold under the trademark/>, by Kolon Industries, inc. of KolonAramid fibers are sold. These fiber types are known in the art and are commercially available.
The term "fibrous article" as used herein means articles that may be further obtained from fibrous substrates as defined herein, including but not limited to ropes, webs or other wovens and nonwovens.
The coating compositions of the present invention can be applied to a fibrous substrate or fibrous article by a variety of suitable processes known in the art including, but not limited to, dip coating, spray coating, spin coating, flow coating, curtain coating, roll coating, knife coating, and combinations thereof.
In a preferred embodiment, the coating composition of the present invention is applied to a fibrous substrate or fibrous article by dip coating.
In some embodiments, the treatment process further comprises drying the coated fibrous substrate or fibrous article after the application of the coating composition according to the present invention. The coated fibrous substrate or fibrous article may be dried using oven drying, air drying, vacuum drying, or a combination thereof for a suitable period of time.
In a preferred embodiment, the coating composition of the present invention is poured into a coating tank, and the fibrous substrate or fibrous article is passed through the coating tank for dipping, extruding and drying to obtain a coated fibrous substrate or fibrous article.
The choice of the different coating process parameters is known to the person skilled in the art, depending on the manner of coating.
In some embodiments, the coating composition has a size of 4 to 33g/100g, preferably 5 to 30g/100g of fibrous substrate or fibrous article. In the context of the present invention, the term "sizing amount" means the dry coverage of the coating composition according to the invention on the treated fibrous substrate or fibrous article.
According to a third aspect of the present invention there is provided the use of a coating composition according to the first aspect of the present invention for improving the abrasion resistance between fibrous substrates or between fibrous articles.
In some embodiments, the yarn products to which the coating compositions of the present invention are applied exhibit up to 5 times greater yarn-to-yarn abrasion resistance than the original yarn without the coating (YOY).
According to a fourth aspect of the present invention there is provided the use of a coating composition according to the first aspect of the present invention for improving the breaking strength of a fibrous substrate or fibrous article.
In some embodiments, yarn products to which the coating compositions of the present invention are applied exhibit up to 9.2% improvement in breaking strength over yarns to which only the resin binder is applied.
In some embodiments, the rope products to which the coating compositions of the present invention are applied exhibit up to 11.8% improved breaking strength over ropes to which only the resin binder is applied.
According to a fifth aspect of the present invention there is provided a fibrous product having applied thereto a coating composition according to the first aspect of the present invention.
In the present application, the fibrous product is a product obtained from a fibrous substrate or fibrous article as defined herein after application of a coating composition according to the present application.
In some embodiments, the coating composition has a size of 4 to 33g/100g, preferably 5 to 30g/100g of fibrous substrate or fibrous article.
According to a sixth aspect of the present invention there is provided a downstream product prepared from a fibrous product according to the fifth aspect of the present invention.
In some embodiments, the downstream products include, but are not limited to, downstream products obtained from the fibrous products of the fifth aspect of the present invention further via woven or nonwoven processes known to those of skill in the art. For example, the downstream product may be a rope, web or other woven and nonwoven formed further from a yarn product obtained after application of a coating composition according to the invention.
The coating composition provided by the invention can be manufactured by a simple preparation process and can be conveniently applied to various fiber substrates or fiber products. The fibrous substrate or fibrous article after treatment with the coating composition of the present invention exhibits significantly improved abrasion resistance between fibrous substrates or between fibrous articles and breaking strength of the fibrous substrate or fibrous article.
In the present description and claims, all numbers expressing temperatures, amounts, concentrations, densities, percentages and so forth, are to be understood as being modified in all instances by the term "about".
As used herein, "comprising" and "including" include both the case of consisting of only the contained elements and the case of containing other elements in addition to the contained elements.
The conception and technical effects of the present invention will be further described with reference to examples so that those skilled in the art can fully understand the objects, features, and effects of the present invention. However, the scope of the present invention is not limited by the following examples.
Examples
The main raw materials in the examples are illustrated:
a-C316: high density oxidized polyethylene wax available from hopweil corporation;
a-C325: high density oxidized polyethylene wax available from hopweil corporation;
a-C629: oxidized polyethylene wax available from hopweil corporation;
a-C950P: propylene-maleic anhydride graft copolymer waxes available from hopweil corporation;
Nonionic emulsifiers Foryl, foryl 2403: ethoxylated fatty alcohols having 9EO and 3EO respectively, commercially available from kekii fine chemical (Shanghai) limited;
IMPRANIL DL1537: aqueous polyurethane adhesive available from kesi corporation with a solids content of 59%;
ICO-THANE: aqueous polyurethane adhesive available from belgium I-Coat company with a solids content of 34%;
wetting agent Surfynol 104BC: purchasing from Yingchuang China;
UV additives Tinuvin292, tinuvin400: purchased from basf (china) limited;
leveling agent BYK333: purchased from pick chemistry;
defoamer Foamstar ST2454: purchased from basf (china) limited;
ultra-high molecular weight polyethylene fiber 1: spectra S980 (1600D) available from Honiweil corporation;
Aramid fiber 2: heracron (1000D) available from Kolon Industries, inc;
ultra-high molecular weight polyethylene fiber 3: lilon (1600D) purchased from China petrochemical instrumentation chemical fiber;
Ultra-high molecular weight polyethylene fiber 4: lilun (1500D) purchased from China petrochemical instrumentation chemical fiber;
ultra-high molecular weight polyethylene fiber 5: lilon (1000D) purchased from China petrochemical instrumentation chemical industry.
Description of the apparatus used in the examples:
Yarn wear tester: purchased from FIROCON, yarn-on-Yarn Abrasion Tester, germany;
industrial twisting machine: available from Twist technology, model TW-5/250;
Breaking strength tester: INSTRON universal tester.
Preparation of wax emulsion
High density oxidized polyethylene wax: a-C316 (100 g), emulsifying agent: foryl 2409 (16.25 g) and Foryl 2403 (6.25 g), alkaline agent: potassium hydroxide (1.75 g), salt additives: sodium metabisulfite (1 g) and part of deionized water (175 g) are added into a reaction vessel and are sealed, heated to 155-160 ℃ and kept for 30 minutes; injecting the rest deionized water (125 g) into a container, sealing, maintaining the temperature at 155-160 ℃ for 30 minutes; the resulting emulsion was then cooled to room temperature as soon as possible to obtain wax emulsion 1.
The wax emulsions 2 to 6 were prepared under the same conditions as those for the preparation of the wax emulsion described above, with varying kinds of wax. The proportions of the raw materials are shown in the following table 1.
Table 1 raw materials and proportions used for preparing wax emulsions 1 to 6
EXAMPLE 2 preparation of coating composition comprising resin Binder
Resin binder IMPRANIL DL1537 aqueous polyurethane (34 g) was added to the reaction vessel while stirring; deionized water (18 g) is added, and the mixing speed is regulated at proper time to ensure that the materials flow along the container wall; DMEA (0.02 g) was added to adjust pH to 8.0-9.5; deionized water (22.04 g) is added, and the mixing speed is regulated in time; adding a film forming auxiliary agent to include ethanol (5 g), 1-methoxy-2-propanol (5 g) and 2-butoxyethanol (10 g), and adjusting the mixing speed at a proper time; deionized water (2 g) was added to flush the tubing; slowly adding a wetting agent Surfynol 104BC (1 g), a UV additive Tinuvin292 (0.2 g) and Tinuvin400 (0.4 g), and adjusting the mixing speed at proper time; slowly adding a leveling agent BYK333 (0.04 g) and a defoaming agent Foamstar ST2454 (0.3 g), and timely adjusting the mixing speed; deionized water (2 g) was added to flush the pipe and viscosity adjust and obtain a base coating composition other than the wax emulsion; finally, wax emulsions 1 to 6 prepared as described above were added to prepare final coating compositions by selecting different dry weight ratios of wax to resin binder.
Examples 3-8 preparation of coated fibrous substrates
3 Ultra high molecular weight polyethylene fibers 1 were twisted at 30 twists/m using a Twist technology TW-5/250 industrial twisting machine and wound into yarn I. The coating compositions prepared by using wax emulsions 1 to 3 and 5 in example 2 were poured into a coating tank, and the yarn was wound into a yarn product having the coating of the present invention after dipping in the coating tank, extruding the gel, and drying.
The yarn-to-yarn abrasion resistance (YOY) of the above coated fibrous substrates was tested according to CI 1503-09 TEST METHOD FOR YARN-ON-YARN ABRASION WET AND DRY, wherein the yarn was spun for 1 week under a load of 1.4kg and the test results are shown in Table 2 below.
Comparative example 1
Referring to example 3, a control yarn was obtained using only polyurethane dip-coated yarn I and subjected to YOY test, the test results being shown in table 2 below.
Table 2 abrasion resistance of yarn to yarn
Example 9
Referring to example 3, yarn II was similarly prepared using aramid fiber 2, and then a yarn product having a coating of the invention was prepared and tested using the coating composition formulated with wax emulsion 4 in example 2, with the test results shown in table 3 below.
Comparative example 2
Referring to example 3, a control yarn was obtained using only polyurethane dip-coated yarn II and subjected to YOY test, the test results being shown in table 3 below.
TABLE 3 abrasion resistance of yarn to yarn
As can be seen from tables 2 and 3, the yarn products to which the coating compositions of the present invention were applied exhibited significantly improved yarn-to-yarn abrasion resistance compared to the original yarn and the yarn to which the resin binder alone was applied. For example, as shown in table 2, yarn products treated with the coating composition of the present invention (examples 3-8) showed YOY performance that could be improved up to 7.3 times as compared to the uncoated raw yarn I and the yarn obtained using only the polyurethane dip coating treatment (comparative example 1). As shown in table 3, the yarn product treated with the coating composition of the invention (example 9) showed YOY performance that could be improved up to 13.8 times compared to the uncoated raw yarn II and the yarn obtained using only the polyurethane dip coating treatment (comparative example 2).
The coating compositions referred to in examples 3-5 were formulated using wax emulsions prepared from A-C316, A-C629 and a mixture of A-C316 and A-C629 in a weight ratio of 7:1, respectively. By comparing the YOY values of the treated yarns, it was found that the use of high density oxidized polyethylene wax was more effective in improving YOY performance than the use of low density oxidized polyethylene wax.
From the data of comparative examples 1 and 2, it was found that the application of the resin binder alone did not only improve the yarn-to-yarn abrasion resistance, but rather deteriorated the performance. This phenomenon can also be verified from the data of example 7: the YOY value increases when the resin binder amount is reduced (i.e., the dry weight ratio of resin binder: wax is reduced) compared to example 3, which also uses wax emulsion 1. Thus, the addition of a proportion of wax emulsion to the coating composition of the present invention serves to significantly improve the abrasion resistance of the fibrous substrate.
Examples 10 to 11
Yarn III was prepared with reference to example 3 using 20 ultra high molecular weight polyethylene fibers 3, and then a yarn product with the coating of the present invention was prepared using the coating composition formulated with wax emulsion 6 in example 2.
The yarn breaking strength was tested on an INSTRON universal tester and the test results are shown in table 4 below as an average of at least three measurements.
Comparative example 3
Referring to example 3, a control yarn was obtained using only polyurethane dip-coated yarn III and tested, and the test results are shown in table 4 below.
TABLE 4 breaking strength of yarns
As can be seen from table 4, the break strength of the yarn product to which the coating composition of the present invention was applied was improved by at least 5.3% compared to the break strength of the yarn to which the polyurethane adhesive alone was applied.
Example 12
Yarn IV was prepared at 25 turns/meter using 24 ultra high molecular weight polyethylene fibers 4 and 1 ultra high molecular weight polyethylene fiber 5, as described in example 3, and then a coating composition formulated with wax emulsion 6 in example 2 was used to prepare a yarn product having a coating according to the present invention.
The yarn breaking strength was tested on an INSTRON universal tester and the test results are shown in table 5 below as an average of at least three measurements.
Comparative example 4
Referring to example 3, a control yarn was obtained using only polyurethane dip-coated yarn IV and tested, and the test results are shown in table 5 below.
TABLE 5 yarn break Strength
As can be seen from table 5, the break strength of the yarn product to which the coating composition of the present invention was applied was improved by 9.2% compared to the break strength of the yarn to which the polyurethane adhesive alone was applied.
Example 13
A rope product with a coating according to the invention was prepared using the coating composition formulated with wax emulsion 6 in example 2 after a 12-strand rope with a diameter of 10mm and a linear density of 52g/m was produced using the yarn IV in example 12 by a braiding machine.
The breaking strength of the rope was tested on an INSTRON universal tester and the test results are shown in table 6 below as an average of at least three measurements.
Comparative example 5
Referring to example 3, the control rope was obtained by dip-coating the rope of example 13 using only polyurethane and tested, and the test results are shown in table 6 below.
Table 6 rope breaking strength
As can be seen from table 6, the breaking strength of the rope products to which the coating composition of the present invention was applied was improved by at least 11.8% compared to the breaking strength of the ropes to which the polyurethane adhesive alone was applied.
The foregoing description is only of the preferred embodiments of the present application, and is not intended to limit the scope of the present application. The essential technical aspects of the application are broadly defined in the scope of the claims, and any person skilled in the art will recognize that all changes may be made in the form and detail of the application as defined in the claims.

Claims (26)

1. A coating composition characterized in that it is formulated from the following materials, based on the total weight of the composition:
20 to 90% by weight of a wax emulsion,
10 To 80% by weight of a resin binder,
0 To 30% by weight of a film-forming auxiliary, and
0 To 10% by weight of other additives selected from wetting agents, leveling agents, defoamers, light stabilizers and combinations thereof,
The wax is selected from oxidized polyethylene wax having a density of at least 0.95g/cm 3, propylene-maleic anhydride graft copolymer wax, and combinations thereof, and the resin binder is selected from the group consisting of aqueous polyurethane, aqueous acrylic resin, aqueous polyester resin, aqueous silicon-containing, fluorine-containing resin, aqueous amino resin, aqueous alkyd resin, aqueous epoxy resin, aqueous phenolic resin, aqueous oil and aqueous polybutadiene, aqueous hyperbranched polymer, and combinations thereof.
2. The coating composition of claim 1, wherein the wax emulsion comprises 10 to 50 wt% wax, based on the total weight of the wax emulsion.
3. The coating composition according to claim 1 or 2, characterized in that the wax emulsion is present in the composition in an amount of 25 to 85 wt. -%, based on the total weight of the composition.
4. The coating composition according to claim 1 or 2, characterized in that the wax emulsion is present in the composition in an amount of 35 to 75 wt. -%, based on the total weight of the composition.
5. The coating composition according to claim 1 or 2, characterized in that the wax emulsion is present in the composition in an amount of 40-65 wt. -%, based on the total weight of the composition.
6. The coating composition according to claim 1 or 2, characterized in that the resin binder is present in the composition in an amount of 20 to 75 wt. -%, based on the total weight of the composition.
7. The coating composition according to claim 1 or 2, characterized in that the resin binder is present in the composition in an amount of 25 to 70 wt. -%, based on the total weight of the composition.
8. The coating composition according to claim 1 or 2, characterized in that the resin binder is present in the composition in an amount of 30-65 wt. -%, based on the total weight of the composition.
9. The coating composition according to claim 1 or 2, characterized in that the film forming aid is present in the composition in an amount of 1 to 30 wt. -%, based on the total weight of the composition.
10. The coating composition according to claim 1 or 2, characterized in that the film forming aid is present in the composition in an amount of 2 to 20 wt. -%, based on the total weight of the composition.
11. The coating composition according to claim 1 or 2, characterized in that the film forming aid is present in the composition in an amount of 5 to 15 wt. -%, based on the total weight of the composition.
12. The coating composition of claim 9 wherein the film forming aid is selected from the group consisting of alcohols having 1 to 20 carbon atoms, alcohol ethers, ketones, and combinations thereof.
13. The coating composition according to claim 1 or 2, characterized in that the further additive is present in the composition in an amount of 0.5 to 9 wt. -%, based on the total weight of the composition.
14. The coating composition according to claim 1 or 2, wherein the resin binder is selected from aqueous polyurethanes.
15. The coating composition of claim 1 wherein the wax is selected from oxidized polyethylene waxes having a density of at least 0.98g/cm 3.
16. The coating composition of claim 1 wherein the wax is selected from oxidized polyethylene waxes having an acid number in the range of 1 to 100mg KOH/g.
17. The coating composition of claim 1 wherein the wax is selected from oxidized polyethylene waxes having an acid number in the range of 5 to 50mg KOH/g.
18. The coating composition according to claim 1 or 2, characterized in that the dry weight ratio of the resin binder to the wax emulsion is 1:4 to 4:1.
19. The coating composition according to claim 1 or 2, characterized in that the dry weight ratio of the resin binder to the wax emulsion is 1:2 to 2:1.
20. A method of treating a fibrous substrate or fibrous article, characterized in that it comprises applying the coating composition according to any one of claims 1-19 to the fibrous substrate or fibrous article.
21. The method of claim 20, wherein the sizing amount of the coating composition is 4 to 33g/100g of the fibrous substrate or fibrous article.
22. The method of claim 20, wherein the sizing amount of the coating composition is from 5 to 30g/100g of the fibrous substrate or fibrous article.
23. Use of the coating composition of any one of claims 1-19 for improving the abrasion resistance between fibrous substrates or between fibrous articles.
24. Use of the coating composition of any one of claims 1-19 for improving the breaking strength of a fibrous substrate or fibrous article.
25. A fibrous product having applied thereto the coating composition of any one of claims 1-19.
26. A downstream product prepared from the fibrous product of claim 25.
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