WO2021000918A1 - 一种用于纤维表面处理的组合物和纤维的处理方法 - Google Patents

一种用于纤维表面处理的组合物和纤维的处理方法 Download PDF

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WO2021000918A1
WO2021000918A1 PCT/CN2020/099939 CN2020099939W WO2021000918A1 WO 2021000918 A1 WO2021000918 A1 WO 2021000918A1 CN 2020099939 W CN2020099939 W CN 2020099939W WO 2021000918 A1 WO2021000918 A1 WO 2021000918A1
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Prior art keywords
fiber
anhydride
latex
epoxy resin
nano
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PCT/CN2020/099939
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English (en)
French (fr)
Inventor
宁南英
黄伟
田明
王文才
张立群
于冰
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北京化工大学
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Application filed by 北京化工大学 filed Critical 北京化工大学
Priority to JP2021578203A priority Critical patent/JP7333106B2/ja
Priority to EP20834615.5A priority patent/EP3992357A4/en
Priority to US17/624,499 priority patent/US20220275571A1/en
Priority to CN202080060962.XA priority patent/CN114341424B/zh
Priority to KR1020227003755A priority patent/KR20220052914A/ko
Publication of WO2021000918A1 publication Critical patent/WO2021000918A1/zh

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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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/692—Polymers of conjugated dienes containing carboxylic acid groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8074—Lactams
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10—Latex
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
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    • 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
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    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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    • 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
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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    • 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

Definitions

  • the invention relates to the technical field of fiber dipping, in particular to a fiber surface treatment composition and a fiber treatment method.
  • Fiber cords and cord fabrics as rubber reinforcing materials, are widely used in products such as tires, hoses and conveyor belts.
  • the good elasticity of the rubber matrix is used to withstand the large deformation of the composite material when it is stressed, and the fiber skeleton material is used to resist the damage of the composite material due to its higher strength and rigidity.
  • the interface adhesion between the fiber and the rubber matrix determines the stress transmission efficiency and fatigue life of the composite material.
  • the interface interaction between the fiber and the rubber is weak.
  • the resorcinol-formaldehyde-latex (RFL) impregnation method has become the most effective method to improve the adhesion between fiber and rubber.
  • the mechanism of RFL impregnation treatment is that the resorcinol-formaldehyde thermosetting resin phase interacts with the polar groups on the fiber surface due to its hydroxyl groups.
  • the rubber latex phase can be cross-linked with the rubber matrix through a co-vulcanization process, thereby enhancing the bonding effect between the fiber and the rubber.
  • resorcinol and formaldehyde are extremely harmful to human health and the environment.
  • US20120041113, US5565507A, and US20150314644 disclose non-RFL environmentally friendly dipping liquids with epoxy resin as the main body.
  • US20120041113 discloses a dipping liquid composed of epoxy resin, blocked isocyanate, amino curing agent, and latex, which is used for one-bath treatment of polyester and nylon fibers.
  • US5565507A discloses a dipping liquid composed of epoxy resin with more than trifunctionality and latex containing carboxyl group, pyridine or amino group, which is used to enhance the adhesion between fiber fabric and rubber.
  • US20150314644 discloses an dipping liquid composed of epoxy resin, polyamine with a molecular weight greater than 190 Daltons, and rubber latex, which is used to improve the adhesion between cord and rubber, and its adhesion effect is equivalent to RFL.
  • US20150259560 and US20150315410 disclose non-RFL environmentally friendly dipping liquids with acrylic resin and epoxy resin as the main body.
  • US20150259560 discloses a dipping liquid composed of acrylic resin, epoxy compound, isocyanate, and rubber latex, which is used to improve the bonding effect between fibers and cords and rubber.
  • US20150315410 discloses a dipping solution composed of acrylic resin with carboxyl group, epoxy resin, blocked isocyanate, styrene butadiene latex or styrene butadiene vinyl pyridine latex, and its adhesive effect is slightly better than RFL.
  • US7256235, US7482290, and US20040249053 disclose non-RFL environmental protection dipping liquids mainly composed of maleic anhydride polymers.
  • US20040249053 discloses a dipping liquid composed of maleic anhydride grafted polymer, latex with carboxyl group and pyridine, which is used to treat epoxy-activated polyester fiber.
  • US7482290 discloses a dipping liquid composed of maleic anhydride imide polymer, ethylenically unsaturated carboxylic acid metal salt, and latex, which is used to improve the adhesion between fiber fabric and rubber.
  • US7256235 discloses a dipping liquid composed of half-esterified maleic anhydride polybutadiene, chlorosulfonated polyethylene or its mixture, carbon black, and latex, which is used to improve the adhesion of fiber fabric and EPDM rubber. It is suitable for high temperature resistant conveyor belt.
  • KR2018110986A discloses a two-bath dipping system.
  • the one-bath dipping liquid is composed of epoxy resin and isocyanate
  • the two-bath dipping liquid is composed of epoxy resin, isocyanate, polyurethane dispersion PUD resin, amine compound, and latex.
  • the bonding effect of the fiber after this method is slightly better than that of RFL treatment.
  • CN110284326A reports an impregnation treatment system containing special amino resin, blocked isocyanate, auxiliary agent, and latex.
  • the adhesion effect of the nylon fiber treated by this method can reach the treatment effect of RFL.
  • CN106120350A reports an impregnation treatment system containing tannins, polyamines and latex.
  • the adhesion effect of the polyester cord treated by this method is equivalent to RFL, and the adhesion effect at high temperature is better than RFL.
  • the present invention provides a composition for fiber surface treatment.
  • the composition has excellent adhesive strength and does not contain resorcinol-formaldehyde.
  • composition for fiber surface treatment includes the following components: maleic anhydride polymer, epoxy resin, blocked isocyanate, curing agent, rubber latex, solvent and optional fillers.
  • the parts by weight of each component are as follows:
  • the maleic anhydride polymer is selected from maleic anhydride grafted polybutadiene, maleic anhydride grafted polyisoprene and maleic anhydride grafted styrene-butadiene At least one of the ene binary copolymers; preferably maleic anhydride grafted polybutadiene.
  • the grafting rate of maleic anhydride is 10-50%.
  • the molecular weight (number average) of the maleic anhydride polymer is 3000-10000.
  • the epoxy resin can be dissolved in water or latex emulsion, preferably selected from bisphenol A epoxy resin, epoxidized novolac resin, ethylene glycol diglycidyl ether, poly Ethylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ether, glycerol glycidyl ether, three Hydroxymethylpropane glycidyl ether, tetraphenol ethane tetraglycidyl ether epoxy resin, sorbitol glycidyl ether, resorcinol bisglycidyl ether type epoxy resin and bisresorcinol formal tetraglycidol
  • the curing agent is selected from one or more of imidazole curing agents, amine curing agents and acid anhydride curing agents.
  • the imidazole curing agent is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2 -Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and 1-cyanoethyl
  • -2-undecylimidazole is preferably 1-cyanoethyl-2-ethyl-4methylimidazole.
  • the amine curing agent is selected from one or more of hyperbranched polyamide, hyperbranched polyethyleneimine, supramolecular polyoxyethylene amine, polyoxyethylene diamine and polyamide , Preferably hyperbranched polyethyleneimine.
  • the acid anhydride curing agent is selected from phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride glyceride, methylhexahydrophthalic anhydride
  • phthalic anhydride methylnadic anhydride, pyromellitic anhydride, ethylene glycol bistrimellitic anhydride, methylcyclohexenetetracarboxylic dianhydride, trimellitic anhydride and polyazelaic anhydride or There are many kinds, preferably trimellitic anhydride.
  • the blocked isocyanate is a blocked isocyanate formed by an isocyanate and a blocking agent, preferably the isocyanate is selected from trimethyl-1,6-hexamethylene diisocyanate, tetramethylene Diisocyanate, tetramethyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-benzene diisocyanate, 1,4-benzene diisocyanate, isophorone diisocyanate, and One or more of phenylmethane diisocyanates, the blocking agent is selected from one or more of ⁇ -caprolactam, methyl ethyl ketoxime and phenol; the blocked isocyanate is preferably caprolactam-terminated diphenylmethane Diisocyanate.
  • the solvent is an aqueous solvent, preferably water, more preferably deionized water.
  • the filler is selected from nano silica, carbon black, nano titanium dioxide, nano zinc oxide, nano iron oxide, nano calcium oxide, nano calcium carbonate, carbon nanotubes, attapulgite, nanofibers
  • nano silica carbon black
  • nano titanium dioxide nano zinc oxide
  • nano iron oxide nano calcium oxide
  • nano calcium carbonate carbon nanotubes
  • attapulgite nanofibers
  • sodium sulfate, halloysite, nano-aramid fiber, basalt fiber, nano-whisker, graphene oxide, montmorillonite, mica, kaolin and hydrotalcite preferably nano-cellulose, nano-silica, At least one of montmorillonite and carbon nanotubes.
  • the filler is a filler treated with a filler surface modifier.
  • the filler surface modifier is selected from amino silane coupling agents, epoxy silane coupling agents, alkyl silane coupling agents, isocyanate-based silane coupling agents, and polyether silane coupling agents One or more agents; preferably from ⁇ -aminopropyl triethoxysilane (KH550), ⁇ -glycidoxypropyl trimethoxysilane (KH560), ⁇ -methacryloxypropyl Trimethoxysilane (KH570), ⁇ -mercaptopropyltriethoxysilane (KH580), bis-[ ⁇ -(triethoxysilyl)propyl]tetrasulfide (Si69) and vinyl triethoxy At least one of silane (A151).
  • the rubber latex is selected from the group consisting of styrene-butadiene latex, styrene-butadiene latex, styrene-butadiene latex, neoprene latex, nitrile latex, chlorosulfonated polyethylene latex, natural rubber latex, and epoxidized natural rubber latex At least one of them.
  • the styrene butadiene latex is preferably carboxyl styrene butadiene latex; the nitrile butadiene latex is preferably carboxyl nitrile butadiene latex; and the natural latex is preferably epoxidized natural latex.
  • the solid content of the rubber latex is 20-60 wt%.
  • the present invention also provides a fiber surface treatment method, which includes:
  • Step 1) immersing the fibers in a dipping solution, wherein the dipping solution is prepared from the composition according to the first aspect of the present invention
  • Step 2 drying and curing the impregnated fiber obtained in step 1).
  • the dipping solution described in step 1) includes: maleic anhydride polymer; epoxy resin; blocked isocyanate; curing agent; rubber latex; solvent; and optional component filler Prepared.
  • the dipping liquid described in step 1) includes:
  • the temperature for implementing the impregnation is 15-40°C, and the time is 2-60s.
  • the drying temperature is 100-150°C and the time is 1-10 min; the curing temperature is 180-260°C and the time is 1-10 min.
  • the pH of the dipping solution is adjusted to alkaline before dipping, for example, the pH is 8.0-11.0.
  • the pH of the dipping solution is adjusted to be alkaline by using an alkaline solution such as potassium hydroxide solution or aqueous ammonia solution, for example, the pH is 8.0-11.0.
  • the present invention also provides a fiber surface treatment method, which includes the following steps:
  • Step C) Place the fiber treated in step B) in a second dipping solution for dipping, where the second dipping solution contains a maleic anhydride polymer, a second epoxy resin, a curing agent, rubber latex, and a solvent And optional fillers;
  • Step D drying and curing the fiber treated in step C).
  • the impregnation temperature is 15-40°C, and the time is 2-30s.
  • the drying temperature is 100-150° C.
  • the time is 1-10 min.
  • the curing temperature is 180-260° C.
  • the time is 1-10 min.
  • the impregnation temperature is 15-40°C, and the time is 2-60s.
  • step D the drying temperature is 100-150° C., and the time is 1-10 min.
  • the curing temperature is 180-260° C.
  • the time is 1-10 min.
  • the pH of the second dipping solution is adjusted to be alkaline before use, preferably 8.0-11.0.
  • the raw materials for preparing the first dipping liquid include:
  • the first epoxy resin 0.5-4 parts; preferably 0.5-2.5 parts;
  • the raw materials for preparing the second dipping liquid include:
  • the types and amounts of maleic anhydride polymer, blocked isocyanate, curing agent, rubber latex, solvent, and filler are the same as those mentioned above, and will not be repeated here.
  • the first epoxy resin may be the same or different, and both the first epoxy resin and the second epoxy resin may be dissolved in water or latex emulsion, preferably selected from bisphenol A type Epoxy resin, epoxidized novolac resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butane Glycol diglycidyl ether, diglycidyl ether, glycerol glycidyl ether, trimethylolpropane glycidyl ether, tetraphenol ethane tetraglycidyl ether epoxy resin, sorbitol glycidyl ether, resorcinol One or more of phenol bisglycidyl ether type epoxy resin and bisresorcinol formal tetraglycidyl ether;
  • the fiber is rayon, nylon 6, nylon 66, meta or para aramid fiber, polyethylene terephthalate (PET), polyethylene naphthalate Ester (PEN), polyimide, carbon fiber, or mixed twisted cord of the above fibers.
  • the form of the fiber is selected from monofilament, bundle yarn, twisted cord, canvas, cord fabric or a combination thereof.
  • the present invention proposes a new type of composition for fiber surface treatment.
  • single-bath dipping treatment for example, the treatment method according to the second aspect of the present invention
  • two-bath dipping treatment for example, the treatment method according to the third aspect of the present invention
  • the composition of the present invention does not contain toxic and harmful components such as resorcinol and formaldehyde, and will not cause harm to the human body and the environment.
  • the fiber processed by the invention has excellent bonding effect and can replace the traditional RFL technology. At the same time, the treatment composition will not damage the strength of the fiber and will not affect its use.
  • the fiber surface treatment method is simple and easy to operate, and can be mass-produced.
  • the double-bath method has a better effect.
  • the isocyanate and epoxy resin in the one-bath formula can react with the amide group on the surface of the aramid fiber at high temperature, greatly improving its surface activity.
  • the epoxy resin and maleic anhydride polymer in the two-bath formulation can react with the activated fiber surface groups and form a resin network under the action of the curing agent, which can significantly improve the adhesion between the fiber and the rubber. ⁇ effect.
  • Fillers are added to the composition of the present invention to further improve the bonding effect between the fiber and the rubber.
  • composition for fiber surface treatment of the present invention is environmentally friendly, harmless to the human body and the environment, low in raw material prices, greatly improved in bonding performance, and can replace RFL.
  • the epoxy resin added in the present invention is water-soluble, the added filler has better dispersibility after modification, the composition of the dipping solution is relatively stable, and the viscosity will not increase significantly when placed at room temperature for a long time, which is beneficial to the glue solution Long-term storage and transportation.
  • the preparation of dipping liquid and fiber treatment process are simple, which is beneficial to industrialized production.
  • the cord fabric treated by the present invention is light yellow, and the addition of different fillers will affect the color, which provides the possibility to produce cord fabrics of different colors.
  • Glycerol glycidyl ether CAS 13236-02-7, purchased from Beijing Hanlongda Technology Development Co., Ltd.
  • Ethylene glycol diglycidyl ether CAS 2224-15-9, purchased from Beijing Hanlongda Technology Development Co., Ltd.
  • Sorbitol glycidyl ether CAS 68412-01-1, purchased from Nanya Epoxy Resin Co., Ltd.
  • Hyperbranched polyethyleneimine CAS 9002-98-6, purchased from Beijing Huawei Ruike Chemical Co., Ltd., with a weight average molecular weight of 1200.
  • Maleic anhydride grafted polybutadiene purchased from Crayville (Guangzhou) Chemical Co., Ltd., the number average molecular weight is about 5000, the grafting rate of maleic anhydride is 20-50%, and its molecular structure:
  • ⁇ -Caprolactam-terminated diphenylmethane diisocyanate CAS 5101-68-8, grade CBI 50, purchased from Changzhou Keying Chemical Co., Ltd.
  • VP latex Styrene-butadiene-vinylpyridine latex (VP latex): brand VP-15, purchased from Jiangsu Yatai Chemical Co., Ltd., with a solid content of 40% by weight.
  • Concentrated natural rubber latex purchased from Hainan Natural Rubber Industry Group Co., Ltd., with a solid content of 60wt%.
  • Nano titanium dioxide (Shanghai Minrell Chemical Technology Co., Ltd., particle size 40nm); Montmorillonite (Nanocor company production, G105); Attapulgite (Jiangsu Shengyi Nano Technology Co., Ltd., purification type 601); Graphene oxide (Shandong Oubo New Materials Co., Ltd., OBO-GO-P2); Carbon Nanotubes (Beijing Deke Island Gold Technology Co., Ltd., CNT107).
  • ⁇ -Aminopropyltriethoxysilane (KH550): CAS 919-30-2, purchased from Beijing Hanlongda Technology Development Co., Ltd., branded as Johnlong.
  • Resorcinol CAS 108-46-3, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., purity ⁇ 99wt%.
  • Formaldehyde CAS 50-00-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., purity 37wt%.
  • the standard rubber (refer to GBT9101-2017 for the standard rubber formula) is completely covered on the dipping cord, and the extraction pattern is prepared, and finally it is put on a flat vulcanizing machine for vulcanization, and the vulcanization temperature is 136 °C, curing pressure is 15MPa, curing time is 50min.
  • the preparation method of the peel force test strip is as follows:
  • the peeling method of Shenma Industrial Co., Ltd. to determine the adhesion of a single cord of nylon 66 dipping.
  • the standard rubber is completely covered on the dipping cord to prepare a peeling sample, and finally it is placed on a flat vulcanizing machine Carry out vulcanization, the vulcanization temperature is 160°C, the vulcanization pressure is 2.354MPa, and the vulcanization time is 20min.
  • the preparation method of cord breaking strength sample is as follows:
  • the cord breaking strength test is tested according to GB/T32108-2015; the H draw-out force is tested according to GB/T2942-2009; the method of peeling test is as follows:
  • the film cavity is 2mm deep, 250mm long, 170mm wide, each sample is 20mm wide, and the distance between the pieces is 6mm, and the two sides of the mold are kept 10mm.
  • the thickness of the cover and the bottom of the mold is not less than 10mm.
  • Vulcanization process 1) After preheating the mold at 136°C for 15-20 minutes, put a single cord into the groove to make the cord vertical tension; 2) Put a long cord at the bottom of the mold near the frame 20mm, 160mm wide and 0.5mm thick film with cellophane slightly larger than the film; 3) Put a 240mm long, 160mm wide, and 1.7mm thick film on the cellophane, and attach the same size interlining cloth on the cellophane. After the gland is closed, vulcanization is carried out. After vulcanization, cool for at least 2h, then trim the sample to test the peel force (each sample contains 5 cords).
  • Test process The part separated by cellophane is clamped into the upper and lower chucks of the tensile machine at an angle of 180°, and then stretched and peeled.
  • the speed of the tensile machine is set to 300mm/min, and the peeling length is (150 ⁇ 10)mm.
  • the average adhesive force (N) is read from the peel curve, and the peel adhesive force of a single cord is calculated.
  • the weight average molecular weight of the hyperbranched polymer was determined by static light scattering method, and the relative number average molecular weight of other linear polymers was determined by GPC.
  • the preparation method of the dipping solution Dissolve all the components (except latex) in deionized water at a predetermined weight ratio, and stir the solution vigorously at 500 rpm with an electric stirrer at 25° C. for 1.5 hours. Subsequently, styrene-butadiene-vinylpyridine latex was added to the solution, and the device was kept at 25° C. and stirred vigorously for 2 hours. During the stirring, potassium hydroxide was added to adjust the pH of the solution to 8.7.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 3 minutes
  • the curing temperature is 210°C
  • the curing time is 3 minutes.
  • the preparation method of the dipping liquid is the same as in Example 1.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 3 minutes
  • the curing temperature is 210°C
  • the curing time is 3 minutes.
  • the preparation method of the dipping liquid is the same as in Example 1.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 1.5min
  • the curing temperature is 225°C
  • the curing time is 1.5min.
  • the preparation method of the dipping solution Add nano-titanium dioxide and deionized water into a beaker, and perform ultrasonic stirring.
  • the power of the ultrasonic device is 400W and the ultrasonic stirring time is 1h to obtain dispersed fillers.
  • all components except latex were added to deionized water in a predetermined weight ratio, and the solution was vigorously stirred at 25° C. with an electric stirrer at 500 rpm for 2 hours.
  • the styrene-butadiene-vinylpyridine latex was added to the mixed solution, and the device was kept at 25° C. and stirred vigorously at 500 rpm with an electric stirrer for 2.5 hours.
  • potassium hydroxide was added to adjust the pH of the solution to 9.0.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 1.5min
  • the curing temperature is 225°C
  • the curing time is 1.5min.
  • the preparation method of the dipping solution add nano titanium dioxide and deionized water into a beaker, add modifier KH550/ethanol (KH550/ethanol volume ratio 2:1, ethanol (purity ⁇ 95wt%)) (the amount of KH550 is the amount of filler 10wt%) was slowly added to the mixed solution of nano-titanium dioxide and deionized water, and ultrasonically stirred, the power of the ultrasonic device was 400W, and the time of ultrasonic stirring was 1h to obtain dispersed modified nano-titanium dioxide. Then, all components (except latex) were added to deionized water in a predetermined weight ratio, and the solution was vigorously stirred at 25° C. with an electric stirrer at 500 rpm for 2 hours.
  • the styrene-butadiene-vinylpyridine latex was added to the mixed solution, and the device was kept at 25° C. and stirred vigorously at 500 rpm with an electric stirrer for 2.5 hours. During the stirring, potassium hydroxide was added to adjust the pH of the solution to 9.0.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 1.5min
  • the curing temperature is 225°C
  • the curing time is 1.5min.
  • the preparation method of the dipping liquid is the same as in Example 4.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 1.5min
  • the curing temperature is 230°C
  • the curing time is 1.5min.
  • the preparation method of the dipping liquid is the same as in Example 5.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 1.5min
  • the curing temperature is 230°C
  • the curing time is 1.5min.
  • the preparation method of the dipping liquid is the same as in Example 4.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 3 minutes
  • the curing temperature is 210°C
  • the curing temperature is 3 minutes.
  • the preparation method of the dipping liquid is the same as in Example 5.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 3 minutes
  • the curing temperature is 210°C
  • the curing temperature is 3 minutes.
  • the preparation method of the dipping liquid is the same as in Example 5.
  • Dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 2min
  • the curing temperature is 220°C
  • the curing time is 2min.
  • Comparative example 1 is traditional RFL dipping treatment, and the RFL formula is as follows:
  • RFL dipping treatment method immerse the fiber cord in the dipping solution for 3 seconds, then dry and solidify in an oven.
  • the drying temperature is 150°C
  • the drying time is 2min
  • the curing temperature is 225°C
  • the curing time is 2min.
  • Examples 1-10 used a single-bath method to treat fiber cords.
  • the cords used in Examples 1 and 2 were nylon 6 cords (1170dtex/2), and the cords used in Examples 3, 4, and 5 were nylon 66 cords. (1400dtex/2), the cords used in Examples 6-10 are nylon 66 cords (1870dtex/2).
  • the cords used in Comparative Examples 1-3 were RFL single-bath treated fiber cords, the cords used in Comparative Example 1 were nylon 6 cords (1170dtex/2), and the cords used in Comparative Example 2 were nylon 66 cords (1400dtex/ 2)
  • the cord used in Comparative Example 3 is nylon 66 cord (1870dtex/2).
  • EP refers to epoxy resin and PBMA refers to maleic anhydride grafted polymer.
  • the strength of the fiber treated by this method will not be significantly reduced, and will not affect its use. It can be seen from Examples 4-10 that the addition of fillers can further improve the H extraction force and the peeling force, and the adhesion effect of the environmentally friendly impregnation system has been further improved. At the same time, the modification of the filler is beneficial to improve its dispersibility in the dipping solution, and is more beneficial to the improvement of the bonding effect. It can be seen from Examples 5, 7, 9, and 10 that the addition of fillers of different shapes, including granular fillers, rod-shaped fillers, and flaky fillers, all have good effects. The results of the experiment are in line with expectations.
  • the effect of improving the interface adhesion can be achieved.
  • the coating rate on the surface of the fibers reached 100%, which shows that the dipping system has a stable bonding effect and can meet the application requirements.
  • Examples 11-15 are fiber cords treated by a double bath method.
  • the cords used in Examples 11 and 14 are aramid cords (1670dtex/2), and the cords used in Examples 12 and 15 are polyester cords (1440dtex/ 2)
  • the cord used in Example 13 is aramid/nylon 66 double-twisted cord (A1670dtex/1+N1400dtex/1).
  • the cords used in Comparative Examples 4, 5, and 6 were RFL double-bath treated fiber cords, the cords used in Comparative Example 4 were aramid cords (1670dtex/2), and the cords used in Comparative Example 5 were polyester cords (1440dtex/ 2)
  • the cord used in Comparative Example 6 is an aramid/nylon 66 double-twisted cord (A1670dtex/1+N1400dtex/1).
  • the preparation method of the first bath dipping liquid add sorbitol glycidyl ether, ⁇ -caprolactam-terminated diphenylmethane diisocyanate and deionized water into the beaker according to the experimental formula, and use an electric stirrer at 25°C at 500rpm strong Stir for 1h.
  • the preparation method of the second bath dipping liquid maleic anhydride grafted polybutadiene, glycerol glycidyl ether, 1-cyanoethyl-2-ethyl-4methylimidazole according to the predetermined feeding ratio Add deionized water and stir vigorously at 500 rpm with an electric stirrer for 1 hour at 25°C. Then the styrene-butadiene-vinylpyridine latex was slowly added to the solution and stirring continued for 2h. During the stirring, the pH of the solution was adjusted to 9.0 by adding an aqueous ammonia solution.
  • Dipping treatment method first put the fiber in the first bath dipping solution, immerse at room temperature for 3s, dry at 150°C for 1.5min, and cure at 230°C for 1.5min; then put the fiber in the second bath dipping solution In, after immersing at room temperature for 3s, drying at 150°C for 1.5 min, and curing at 250°C for 1.5 min.
  • the preparation method of the first bath dipping liquid Add sorbitol glycidyl ether, ⁇ -caprolactam-terminated diphenylmethane diisocyanate, and phenol-terminated isophorone diisocyanate into deionized water according to the experimental formula, and at 25°C Stir vigorously for 1.5 hours at 500 rpm with an electric stirrer.
  • the preparation method of the second bath dipping solution add nano-titanium dioxide and deionized water into a beaker, add a mixed solution of modifier KH550/ethanol (KH550/ethanol volume ratio 2:1, ethanol (purity ⁇ 95wt%))
  • KH550/ethanol volume ratio 2:1, ethanol (purity ⁇ 95wt%) The amount of KH550 is 10wt% of the amount of filler) slowly added to the mixed solution of nano-titanium dioxide and deionized water, and ultrasonically stirred, the power of the ultrasonic device is 400W, and the time of ultrasonic stirring is 1h to obtain dispersed modified nano-filler.
  • all components except latex were added to deionized water in a predetermined weight ratio, and the solution was vigorously stirred at 25° C.
  • Dipping treatment method first put the fiber in the first bath dipping solution, immerse at room temperature for 3 seconds, dry at 150°C for 1.5min, and cure at 230°C for 1.5min; then put the fiber in the second bath for dipping After being immersed in the liquid for 3 seconds at room temperature, it was dried at 150°C for 1.5 minutes and cured at 240°C for 2 minutes.
  • the preparation method of the dipping liquid is the same as in Example 12.
  • Dipping treatment method first put the fiber in the first bath dipping solution, immerse at room temperature for 3s, dry at 150°C for 1.5min, and react at 220°C for 1.5min; then put the fiber in the second bath dipping solution In, after immersing for 3 seconds at room temperature, drying at 150°C for 1.5 min, and curing at 230°C for 2 min.
  • the preparation method of the dipping liquid is the same as in Example 12.
  • Dipping treatment method first put the fiber in the first bath dipping solution, immerse at room temperature for 3s, dry at 150°C for 1.5min, and cure at 230°C for 1.5min; then put the fiber in the second bath dipping solution After immersing for 3 seconds at room temperature, drying at 150°C for 1.5 min, and curing at 250°C for 2 min.
  • the preparation method of the dipping liquid is the same as in Example 12.
  • Dipping treatment method first put the fiber in the first bath dipping solution, immerse at room temperature for 3s, dry at 150°C for 1.5min, and cure at 230°C for 1.5min; then put the fiber in the second bath dipping solution After immersing for 3 seconds at room temperature, drying at 150°C for 1.5 min, and curing at 240°C for 2 min.
  • Comparative Example 4 is the traditional RFL two-bath method to treat aramid fiber.
  • Preparation of the pretreatment liquid Add sorbitol glycidyl ether and ⁇ -caprolactam-terminated diphenylmethane diisocyanate to deionized water according to the experimental formula, and use an electric stirrer to vigorously stir for 1.5h at 500rpm at 25°C.
  • RFL dipping solution In the first step, add 0.1 part of sodium hydroxide and 100 parts of deionized water to the beaker, stir vigorously for 10 minutes at 500 rpm with an electric stirrer, then add 3.7 parts of resorcinol and stir for 10 minutes, and finally add formaldehyde Stir 5.4 parts of the aqueous solution (37wt%) for 6h at room temperature to obtain a uniform reaction liquid; add 80 parts of VP latex (solid content 40wt%) in the second step, stir at room temperature for 20h, add 1 part of ammonia before the end of the stirring, Finally, the RFL dipping liquid is obtained.
  • Dipping treatment method first put the fiber in a prepreg solution, immerse at room temperature for 3s, dry at 150°C for 1.5min, and cure at 230°C for 1.5min; then place the fiber in RFL dipping solution at room temperature After immersing for 3s, dry at 150°C for 1.5min, and cure at 250°C for 1.5min.
  • the dipping liquid formula and treatment process of Comparative Examples 5 and 6 are the same as those of Comparative Example 4, except that the treated fibers are different.
  • the cords used in Comparative Example 4 are aramid cords (1670dtex/2), and those used in Comparative Example 5
  • the cord is a polyester cord (1440dtex/2)
  • the cord used in Comparative Example 6 is an aramid/nylon 66 double-twisted cord (A1670dtex/1+N1400dtex/1).
  • the fiber cords of Examples 11-15 and Comparative Examples 4-6 after immersion treatment were prepared according to the above method to prepare test samples, and the H extraction test, peel test and cord strength test were performed. The test results are shown in Table 2.
  • EP refers to epoxy resin and PBMA refers to maleic anhydride grafted polymer.

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Abstract

本发明公开了一种用于纤维表面处理的组合物及纤维表面处理方法。本发明的纤维表面处理组合物包括马来酸酐化的聚合物、环氧树脂、封闭型异氰酸酯、固化剂、橡胶胶乳、溶剂以及任选组分填料。采用本发明处理的纤维具有优异的粘合性能，可以达到或者优于RFL的粘合效果。

Description

一种用于纤维表面处理的组合物和纤维的处理方法 技术领域
本发明涉及纤维浸胶技术领域，具体地说，是涉及一种纤维表面处理的组合物和纤维的处理方法。
背景技术
纤维帘线、帘子布作为橡胶的增强材料，在轮胎、胶管以及输送带等产品中有着广泛的应用。橡胶基体良好的弹性用来承受复合材料受力时产生的大变形，而纤维骨架材料因其较高的强度和刚度用来抵抗应力对复合材料产生的破坏。纤维与橡胶基体之间的界面粘合力决定了复合材料的应力传递效率和疲劳寿命。然而，由于原始纤维的高结晶度和化学惰性，导致纤维与橡胶之间的界面相互作用较弱。
自1935年以来，间苯二酚-甲醛-胶乳(RFL)浸渍方法成为提高纤维与橡胶之间粘合力的最有效方法。RFL浸渍处理的机理是间苯二酚-甲醛热固性树脂相由于其羟基而与纤维表面的极性基团相互作用。同时，橡胶胶乳相可通过共硫化过程与橡胶基体交联，从而增强纤维与橡胶之间的粘合效果。但是，间苯二酚和甲醛对人体健康和环境具有极大的危害。但该方法使用的间苯二酚和甲醛已被国际癌症研究机构(IARC)列为致癌物质，越来越多国家正开始禁止在轮胎生产中使用间苯二酚和甲醛。因此，迫切需要开发新型环保的纤维浸渍处理体系来代替传统的RFL处理方法。
US20120041113、US5565507A、US20150314644公开了以环氧树脂为主体的非RFL环保浸胶液。其中，US20120041113公开了一种由环氧树脂、封端的异氰酸酯、氨基固化剂、胶乳组成的浸胶液，用于一浴法处理聚酯、尼龙纤维。US5565507A公开了一种由三官能度以上的环氧树脂、含有羧基、吡啶或氨基基团的胶乳组成的浸胶液，用于增强纤维织布与橡胶之间的粘合性能。US20150314644公开了一种由环氧树脂、分子量大于190道尔顿的多胺、橡胶胶乳组成的浸胶液，用于提高帘线和橡胶间的粘合性能，其粘合效果与RFL相当。
US20150259560、US20150315410公开了以丙烯酸树脂、环氧树脂为主体的非RFL环保浸胶液。其中，US20150259560公开了一种由丙烯酸树脂、环氧化合物、异氰酸酯、橡胶胶乳组成的浸胶液，用于提高纤维以及帘布和橡胶间的粘合效果。US20150315410公开了一种由带羧基的丙烯酸树脂、环氧树脂、封闭异氰酸酯、苯乙烯丁二烯胶乳或苯乙烯丁二烯乙烯基吡啶胶乳组成的浸胶液，其粘合效果要略优于RFL。
US7256235、US7482290、US20040249053公开了马来酸酐化聚合物为主体的非RFL环 保浸胶液。其中，US20040249053公开了一种由马来酸酐接枝聚合物、带羧基和吡啶的胶乳组成的浸胶液，用于处理环氧活化过的聚酯纤维。US7482290公开了一种由马来酸酐化酰亚胺聚合物、乙烯基不饱和羧酸金属盐、胶乳组成的浸胶液，用于改善纤维织物与橡胶的粘合性能。US7256235公开了一种由半酯化马来酸酐化聚丁二烯、氯磺化聚乙烯或其混合物、炭黑、胶乳组成的浸胶液，用于提高纤维织物与三元乙丙橡胶的粘合性能，适用于耐高温传送带。
KR2018110986A公开了一种二浴法浸胶体系，一浴浸胶液由环氧树脂、异氰酸酯组成，二浴浸胶液由环氧树脂、异氰酸酯、聚氨酯分散体PUD树脂、胺类化合物、胶乳组成，该方法处理后纤维的粘合效果要稍优于RFL处理。
CN110284326A报道了一种包含特种氨基树脂、封闭异氰酸酯、助剂、胶乳的浸渍处理体系，该方法处理尼龙纤维的粘合效果可以达到RFL的处理效果。
CN106120350A报道了一种包含单宁酸、多元胺、胶乳的浸渍处理体系，该方法处理的聚酯帘布的粘合效果与RFL相当，高温下的粘合效果要优于RFL。
尽管以上对比文件公开了一些非RFL的浸渍处理方法，但目前仍没有商业化的非RFL浸渍处理的纤维产品。
发明内容
在第一个方面，本发明提供了一种用于纤维表面处理的组合物。该组合物具有优异的粘合强度，并且不含间苯二酚-甲醛。
本发明提供的用于纤维表面处理的组合物包括以下组分：马来酸酐化的聚合物、环氧树脂、封闭型异氰酸酯、固化剂、橡胶胶乳、溶剂以及任选组分填料。
根据本发明的一些实施方式，所述组合物中，各组分的重量份数如下：
Figure PCTCN2020099939-appb-000001
根据本发明的一些实施方式，所述马来酸酐化的聚合物选自马来酸酐接枝聚丁二烯、马来酸酐接枝聚异戊二烯和马来酸酐接枝苯乙烯-丁二烯二元共聚物中的至少一种；优选为马来 酸酐接枝聚丁二烯。
根据本发明的一些实施方式，马来酸酐的接枝率为10-50％。
根据本发明的一些实施方式，马来酸酐化的聚合物的分子量(数均)为3000-10000。
根据本发明的一些实施方式，所述环氧树脂均可以溶解在水中或胶乳乳液中，优选选自双酚A型环氧树脂、环氧化线性酚醛树脂、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、1,2-丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、1，4-丁二醇二缩水甘油醚、二缩水甘油醚、丙三醇缩水甘油醚、三羟甲基丙烷缩水甘油醚、四酚基乙烷四缩水甘油醚环氧树脂、山梨醇缩水甘油醚、间苯二酚双缩水甘油醚型环氧树脂和双间苯二酚缩甲醛四缩水甘油醚中的一种或多种；进一步优选为水溶性好的丙三醇缩水甘油醚、乙二醇二缩水甘油醚和山梨醇缩水甘油醚中的一种或多种。
根据本发明的一些实施方式，所述固化剂选自咪唑类固化剂、胺类固化剂和酸酐类固化剂中的一种或多种。
根据本发明的一些实施方式，所述咪唑类固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑和1-氰乙基-2-十一烷基咪唑中的一种或多种，优选为1-氰基乙基-2-乙基-4甲基咪唑。
根据本发明的一些实施方式，所述胺类固化剂选自超支化聚酰胺、超支化聚乙烯亚胺、超分子聚氧乙烯胺、聚氧乙烯双胺和聚酰胺中的一种或多种，优选为超支化聚乙烯亚胺。
根据本发明的一些实施方式，所述酸酐类固化剂选自邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、偏苯三甲酸酐甘油酯、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐、均苯四甲酸酐、乙二醇双偏苯三甲酸酐、甲基环己烯四酸二酐、偏苯三甲酸酐和聚壬二酸酐中的一种或多种，优选为偏苯三甲酸酐。
根据本发明的一些实施方式，所述封闭型异氰酸酯为由异氰酸酯和封端剂形成的封闭型异氰酸酯，优选所述异氰酸酯选自三甲基-1,6-六亚甲基二异氰酸酯、四亚甲基二异氰酸酯、四甲基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-苯二异氰酸酯、1,4-苯二异氰酸酯、异佛尔酮二异氰酸酯和二苯基甲烷二异氰酸酯中的一种或多种，所述封端剂选自ε-己内酰胺、丁酮肟和苯酚中一种或多种；所述封闭型异氰酸酯优选为己内酰胺封端的二苯基甲烷二异氰酸酯。
根据本发明的一些实施方式，所述溶剂为水性溶剂，优选为水，更优选为去离子水。
根据本发明的一些实施方式，所述填料选自纳米二氧化硅、炭黑、纳米二氧化钛，纳米氧化锌、纳米氧化铁、纳米氧化钙、纳米碳酸钙、碳纳米管、凹凸棒石、纳米纤维素、埃洛 石、纳米芳纶纤维、玄武岩纤维、纳米晶须、氧化石墨烯、蒙脱石、云母、高岭土和水滑石的一种或多种；优选为纳米纤维素、纳米二氧化硅、蒙脱石和碳纳米管中的至少一种。
根据本发明的一些实施方式，所述填料为经填料表面改性剂处理后的填料。
根据本发明的一些实施方式，所述填料表面改性剂选自氨基硅烷偶联剂、环氧基硅烷偶联剂、烷基硅烷偶联剂、异氰酸酯基硅烷偶联剂和聚醚硅烷偶联剂的一种或多种；优选自γ―氨丙基三乙氧基硅烷(KH550)、γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、γ-巯丙基三乙氧基硅烷(KH580)、双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)和乙烯基三乙氧基硅烷(A151)中的至少一种。
根据本发明的一些实施方式，所述橡胶胶乳选自丁吡胶乳、丁苯胶乳、丁苯吡胶乳、氯丁胶乳、丁腈胶乳、氯磺化聚乙烯胶乳、天然胶乳和环氧化天然胶乳中的至少一种。所述丁苯胶乳优选为羧基丁苯胶乳；所述丁腈胶乳优选为羧基丁腈胶乳；所述天然胶乳优选为环氧化天然胶乳。
根据本发明的一些实施方式，所述橡胶胶乳的固含量为20～60wt％。
在第二个方面，本发明还提供了一种纤维表面的处理方法，其包括：
步骤1)将纤维置于浸胶液中进行浸渍，其中所述浸胶液由根据本发明第一个方面所述的组合物制备而成；
步骤2)将步骤1)得到的浸渍后的纤维进行干燥和固化。
根据本发明的一些实施方式，步骤1)中所述的浸胶液包括：马来酸酐化的聚合物；环氧树脂；封闭型异氰酸酯；固化剂；橡胶胶乳；溶剂；以及任选组分填料制备而成。
根据本发明的一些实施方式，步骤1)中所述的浸胶液包括：
Figure PCTCN2020099939-appb-000002
根据本发明的一些实施方式，实施所述浸渍的温度为15-40℃，时间为2-60s。
根据本发明的一些实施方式，实施所述干燥的温度为100～150℃，时间为1～10min；实施所述固化的温度为180～260℃，时间为1～10min。
根据本发明的一些实施方式，步骤1)中，浸渍前先将所述浸胶液的pH调节为碱性，例如pH为8.0-11.0。在一些实施例中，通过用碱性溶液例如氢氧化钾溶液或氨水溶液将浸胶液的pH调节为碱性，例如pH为8.0-11.0。
在第三个方面，本发明还提供了一种纤维表面的处理方法，其包括以下步骤：
步骤A)将纤维置于第一浸胶液中进行浸渍，其中第一浸胶液包含第一环氧树脂、封闭型异氰酸酯和溶剂；
步骤B)将步骤A)处理后的纤维进行干燥，然后进行固化；
步骤C)将步骤B)处理后的纤维置于第二浸胶液中进行浸渍，其中第二浸胶液含马来酸酐化的聚合物、第二环氧树脂、固化剂、橡胶胶乳、溶剂以及任选组分填料；
步骤D)将步骤C)处理后的纤维进行干燥和固化。
根据本发明的一些实施方式，步骤A)中，实施所述浸渍的温度为15-40℃，时间为2-30s。
根据本发明的一些实施方式，步骤B)中，实施所述干燥的温度为100-150℃，时间为1-10min。
根据本发明的一些实施方式，步骤B)中，实施所述固化的温度为180-260℃，时间为1-10min。
根据本发明的一些实施方式，步骤C)中，实施所述浸渍的温度为15-40℃，时间为2-60s。
根据本发明的一些实施方式，步骤D)中，实施所述干燥的温度为100-150℃，时间为1-10min。
根据本发明的一些实施方式，步骤D)中，实施所述固化的温度为180-260℃，时间为1-10min。
根据本发明的一些实施方式，使用前将所述第二浸胶液的pH调节碱性，优选为8.0-11.0。
根据本发明的一些实施方式，第一浸胶液的制备原料包括：
溶剂                                100份；
第一环氧树脂                        0.5～4份；优选0.5～2.5份；
封闭型异氰酸酯                      2～10份；优选4～8份；
根据本发明的一些实施方式，第二浸胶液的制备原料包括：
Figure PCTCN2020099939-appb-000003
Figure PCTCN2020099939-appb-000004
根据本发明的处理方法，其中马来酸酐化的聚合物、封闭型异氰酸酯、固化剂、橡胶胶乳、溶剂以及填料的种类及用量与前述相同，在此不再赘述。
根据本发明的一些实施方式，所述第一环氧树脂可以相同或者不同，所述第一环氧树脂和第二环氧树脂均可以溶解在水中或胶乳乳液中，优选选自双酚A型环氧树脂、环氧化线性酚醛树脂、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、1，2-丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、二缩水甘油醚、丙三醇缩水甘油醚、三羟甲基丙烷缩水甘油醚、四酚基乙烷四缩水甘油醚环氧树脂、山梨醇缩水甘油醚、间苯二酚双缩水甘油醚型环氧树脂和双间苯二酚缩甲醛四缩水甘油醚中的一种或多种；优选为进一步优选为水溶性好的丙三醇缩水甘油醚、乙二醇二缩水甘油醚和山梨醇缩水甘油醚中的一种或多种。在一种实施方式中，第一环氧树脂为山梨醇缩水甘油醚；第二环氧树脂为乙二醇二缩水甘油醚和/或丙三醇缩水甘油醚。
根据本发明的一些实施方式，所述纤维为人造丝、尼龙6、尼龙66、间位或对位芳纶纤维、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺、碳纤维或上述纤维的混编加捻帘线。
根据本发明的一些实施方式，所述纤维的形式选自单丝、束丝、加捻帘线、帆布、帘子布或其组合。
本发明提出了一种新型的用于纤维表面处理的组合物。根据不同的纤维种类、用途可以选择采用单浴浸渍处理(例如根据本发明第二个方面所述的处理方法)或者双浴浸渍处理(例如根据本发明第三个方面所述的处理方法)，可以选择添加或不添加水溶性纳米填料。可以选择纳米填料是否进行表面改性。该方法处理纤维具有很好的粘合效果，可以达到替代RFL的目的。
本发明的组合物不含有间苯二酚、甲醛等有毒有害成分，不会对人体和环境造成危害。采用本发明处理后的纤维具有优异的粘合效果，可以替代传统的RFL技术。同时，该处理组合物不会损坏纤维的强度，不会对其使用造成影响。
本发明组合物中，所有原料均为工业化的产品，容易获得。纤维表面的处理方法简单易操作，且能够进行大规模的生产。例如处理芳纶纤维等表面惰性的纤维时，采用双浴法具有更好的效果。一浴配方中的异氰酸酯以及环氧树脂在高温下可与芳纶表面的酰胺基团反应，大大提高其表面活性。而二浴配方中的环氧树脂和马来酸酐化的聚合物可与活化后的纤维表面基团反应，并在固化剂的作用下形成树脂网络，这可以显著提高纤维与橡胶之间的粘合效果。
本发明的组合物中加入了填料，进一步提高了纤维与橡胶的粘合效果。
本发明的优势和特点：
1.本发明的用于纤维表面处理的组合物绿色环保，对人体、环境无害，原材料价格低廉，粘合性能提高较大，能够替代RFL。
2.本发明所添加的环氧树脂为水溶性，添加的填料改性后有较好分散性，浸胶液的组份较为稳定，在室温条件下长期放置粘度不会大幅增加，利于胶液的长期储存及运输。
3.本发明中，浸胶液制备和纤维处理工艺简单，有利于工业化的生产。
4.本发明处理后的帘子布为淡黄色，不同填料的加入会对颜色产生影响，为生产所需不同颜色的帘子布提供了可能。
具体实施方式
以下实施例和对比例中使用的材料均可商购获得，其中：
丙三醇缩水甘油醚：CAS 13236-02-7，购自北京翰隆达科技发展有限公司。
乙二醇二缩水甘油醚：CAS 2224-15-9，购自北京翰隆达科技发展有限公司。
山梨醇缩水甘油醚：CAS 68412-01-1，购自南亚环氧树脂有限公司。
超支化聚乙烯亚胺：CAS 9002-98-6，购自北京华威锐科化工有限公司，重均分子量为1200。
马来酸酐接枝聚丁二烯：购自克雷威利(广州)化工有限公司，数均分子量为5000左右，马来酸酐的接枝率为20-50％，其分子结构式：
Figure PCTCN2020099939-appb-000005
1-氰基乙基-2-乙基-4甲基咪唑：CAS 23996-25-0，购自上海迈瑞尔化学技术有限公司。
ε-己内酰胺封端的二苯基甲烷二异氰酸酯：CAS 5101-68-8，牌号CBI 50，购自常州市科英化工有限公司。
苯乙烯-丁二烯-乙烯基吡啶胶乳(VP胶乳)：牌号VP-15，购自江苏亚泰化工有限公司，固含量40wt％。
浓缩天然胶乳：购自海南天然橡胶产业集团股份有限公司，固含量60wt％。
填料：纳米二氧化钛(上海迈瑞尔化学技术有限公司，粒径为40nm)；蒙脱石(NANOCOR公司生产，G105)；凹凸棒石(江苏圣一纳米科技有限公司，提纯601型)；氧化石墨烯(山东欧铂新材料有限公司，OBO-GO-P2)；碳纳米管(北京德科岛金科技有限公司，CNT107)。
γ―氨丙基三乙氧基硅烷(KH550)：CAS 919-30-2，购自北京翰隆达科技发展有限公司，品牌Johnlong。
间苯二酚：CAS 108-46-3，购自上海阿拉丁生化科技股份有限公司，纯度≥99wt％。
甲醛：CAS 50-00-0，购自上海阿拉丁生化科技股份有限公司，纯度37wt％。
以下实施例和对比例中的H抽出力试验样条制备方法如下：
参考标准GB/T2942-2009，将标准胶(标准胶橡胶配方参照GBT9101-2017)完全包覆在浸胶帘线上，制备抽出式样，最后将其放在平板硫化机上进行硫化，硫化温度为136℃，硫化压力为15MPa，硫化时间为50min。
剥离力试验样条制备方法如下：
参考神马实业股份有限公司的剥离法测定锦纶66浸胶单根帘线粘合力标准，将标准胶完全包覆在浸胶帘线上，制备剥离试样，最后将其放在平板硫化机上进行硫化，硫化温度为160℃，硫化压力为2.354MPa，硫化时间为20min。
帘线拉断强度试样制备方法如下：
参考标准GB/T32108-2015，将浸胶帘线夹持在拉力试验机下进行测试，拉伸速度为300±5mm/min。
以下实施例和对比例中，帘线拉断强度测试按照GB/T32108-2015测试；H抽出力按照按照GB/T2942-2009测试；剥离测试的方法如下：
(1)硫化模具尺寸：膜腔深2mm，长250mm，宽170mm，每片试样宽20mm，片与片间隔6mm，模具两边各保留10mm，盖板与模具底板厚度均不小于10mm。(2)硫化所用橡胶胶料配方与H抽出力测试相同。
(3)硫化工艺：160℃×20min，压力2.354Mpa。
(4)硫化过程：1)将模具在136℃下预热15～20min后，将单根帘线装入凹槽内，使帘线垂直张紧；2)在模具下端靠近边框处放入长20mm、宽160mm、厚0.5mm的胶片并在上面附上稍大于胶片的玻璃纸；3)在玻璃纸上放上长240mm、宽160mm、厚1.7mm的胶片，同时在上面附上相同尺寸的衬布。压盖合模后进行硫化。硫化后至少冷却2h，再修剪试样测试剥离力(每片试样含有5根帘线)。
(5)测试过程：将用玻璃纸分离的部分以180°角夹入拉力机上、下夹头，进行拉伸剥离。拉力机速度设置为300mm/min，剥离长度为(150±10)mm。根据剥离曲线读取平均粘合力(N)，计算得到单根帘线的剥离粘合力。
实施例和对比例中，超支化聚合物采用静态光散法，测定重均分子量，其他线性聚合物，采用GPC，测定相对数均分子量。
实施例1
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000006
浸胶液的制备方法：将所有组分(胶乳除外)以预定的重量比溶于去离子水中，在25℃下用电动搅拌器在500rpm强力搅拌溶液1.5h。随后，将苯乙烯-丁二烯-乙烯基吡啶胶乳添加到该溶液中，并将该装置保持在25℃下强力搅拌2h。在搅拌期间，添加氢氧化钾以将溶液的pH调节至8.7。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为3min，固化温度为210℃，固化时间为3min。
实施例2
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000007
浸胶液的制备方法同实施例1。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为3min，固化温度为210℃，固化时间为3min。
实施例3
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000008
浸胶液的制备方法同实施例1。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为1.5min，固化温度为225℃，固化时间为1.5min。
实施例4
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000009
浸胶液的制备方法：将纳米二氧化钛和去离子水加入烧杯中，进行超声搅拌，超声设备的功率为400W，超声搅拌的时间为1h，得到分散的填料。然后，将所有组分(胶乳除外)以预定的重量比加入去离子水中，并将溶液在25℃下用电动搅拌器在500rpm强力搅拌2h。最后，将苯乙烯-丁二烯-乙烯基吡啶胶乳添加到混合溶液中，并将该装置保持在25℃下用电动搅拌器在500rpm强力搅拌2.5h。在搅拌期间，添加氢氧化钾以将溶液的pH调节至9.0。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为1.5min，固化温度为225℃，固化时间为1.5min。
实施例5
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000010
浸胶液的制备方法：将纳米二氧化钛和去离子水加入烧杯中，将改性剂KH550/乙醇(KH550/乙醇体积比2:1，乙醇(纯度≥95wt％))(KH550用量为填料用量的10wt％)的混合溶液缓慢加入纳米二氧化钛和去离子水的混合溶液中，进行超声搅拌，超声设备的功率为400W，超声搅拌的时间为1h，得到分散的改性纳米二氧化钛。然后，将所有组分(胶乳除外)以预定的重量比加入去离子水中，并将溶液在25℃下用电动搅拌器在500rpm强力搅拌2h。最后，将苯乙烯-丁二烯-乙烯基吡啶胶乳添加到混合溶液中，并将该装置保持在25℃下用电动搅拌器在500rpm强力搅拌2.5h。在搅拌期间，添加氢氧化钾以将溶液的pH调节至9.0。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为1.5min，固化温度为225℃，固化时间为1.5min。
实施例6
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000011
浸胶液的制备方法同实施例4。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温 度为150℃，干燥时间为1.5min，固化温度为230℃，固化时间为1.5min。
实施例7
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000012
浸胶液的制备方法同实施例5。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为1.5min，固化温度为230℃，固化时间为1.5min。
实施例8
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000013
浸胶液的制备方法同实施例4。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为3min，固化温度为210℃，固化温度为3min。
实施例9
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000014
浸胶液的制备方法同实施例5。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为3min，固化温度为210℃，固化温度为3min。
实施例10
一种纤维表面环保浸渍处理体系，单浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000015
浸胶液的制备方法同实施例5。
浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为2min，固化温度为220℃，固化时间为2min。
对比例1
对比例1为传统RFL浸胶处理，RFL配方如下表：
原料 份数
去离子水 100
间苯二酚 3.7
甲醛(37wt％) 5.4
氢氧化钠(100wt％) 0.1
VP胶乳(40wt％固含量) 80.0
氨水 1.0
RFL的制备：0.1份氢氧化钠和100份去离子水加入烧杯中，用电动搅拌器在500rpm强力搅拌10min，再加入间苯二酚3.7份搅拌10min，最后加入甲醛水溶液(37wt％)5.4份在常温下搅拌6h，得到均匀的反应液；
加入VP胶乳(固含量40wt％)80份，在常温下搅拌20h，搅拌快结束前，加入氨水1份，最终得到RFL浸胶液。
RFL浸渍处理方法：将纤维帘线在浸渍液中浸渍3秒钟，然后在烘箱中干燥并固化。干燥温度为150℃，干燥时间为2min，固化温度为225℃，固化时间为2min。
实施例1-10采用单浴法处理纤维帘线，实施例1、2中所用帘线为尼龙6帘线(1170dtex/2)，实施例3、4、5中所用帘线为尼龙66帘线(1400dtex/2)，实施例6-10所用帘线为尼龙66帘线(1870dtex/2)。对比例1-3中所用帘线为RFL单浴处理纤维帘线，对比例1所用帘线为尼龙6帘线(1170dtex/2)，对比例2中所用帘线为尼龙66帘线(1400dtex/2)，对比例3所用帘线为尼龙66帘线(1870dtex/2)。
将实施例1-10以及对比例1-3浸渍处理后的纤维帘线，按照以上方法制备测试样品，进行H抽出测试、剥离测试以及帘线强度测试，测试得到的结果如表1所示。
表1单浴法处理纤维帘线数据
Figure PCTCN2020099939-appb-000016
Figure PCTCN2020099939-appb-000017
备注：EP指代环氧树脂，PBMA指代马来酸酐接枝的聚合物。
从上表的数据可以看出，实施例2、3(未添加填料)的H抽出性能与对比例RFL处理效果相当，而剥离力要略高于RFL。实施例4、6、8(添加未改性填料)的H抽出力比对比例RFL高出了10％左右，剥离力也高于RFL。实施例5、7、9、10(添加改性填料)的H抽出力比对比例RFL高了15-20％，剥离力较RFL也有明显提高。这说明了该新型纤维表面环保浸渍体系具有优异的粘合效果，达到乃至超过了RFL处理的粘合水平。并且从帘线强度的测试结果看，该方法处理纤维的强度不会明显降低，不会对其使用造成影响。从实施例4-10可以看出，填料的加入可以进一步提升H抽出力和剥离力，该环保浸渍体系的粘合效果得到了进一步提升。同时，对填料的改性有利于提高其在浸胶液中分散性，更加有利于粘合效果 的提升。从实施例5、7、9、10可以看出，不同形状填料的加入，包括颗粒填料、棒状填料、片状填料，均具有良好的效果。实验的结果符合预期，通过在浸胶液加入填料来调控浸胶层的模量，在纤维与橡胶之间构筑模量过渡层，可以达到提升界面粘合的效果。实施例2-10的纤维在剥离后，其表面的覆胶率达到了100％，这说明了该浸渍体系粘合效果稳定，能够达到应用的要求。
实施例11-15为采用双浴法处理纤维帘线，实施例11、14所用帘线为芳纶帘线(1670dtex/2)，实施例12、15所用帘线为聚酯帘线(1440dtex/2),实施例13所用帘线为芳纶/尼龙66复捻帘线(A1670dtex/1+N1400dtex/1)。对比例4、5、6所用帘线为RFL双浴处理纤维帘线，对比例4所用帘线为芳纶帘线(1670dtex/2)，对比例5所用帘线为聚酯帘线(1440dtex/2)，对比例6所用帘线为芳纶/尼龙66复捻帘线(A1670dtex/1+N1400dtex/1)。
实施例11
一种纤维表面环保浸渍处理体系，双浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000018
第一浴浸胶液的制备方法：将山梨醇缩水甘油醚、ε-己内酰胺封端的二苯基甲烷二异氰酸酯和去离子水按实验配方加入烧杯中，在25℃下用电动搅拌器在500rpm强力搅拌1h。第二浴浸胶液的制备方法：将马来酸酐接枝的聚丁二烯、丙三醇缩水甘油醚、1-氰基乙基-2-乙基-4甲基咪唑按预定的投料比加入去离子水中，在25℃下用电动搅拌器在500rpm强力搅拌1h。然后将苯乙烯-丁二烯-乙烯基吡啶胶乳缓慢加入溶液中继续搅拌2h。在搅拌的过程中，通过添加氨水溶液以将溶液的pH调节至9.0。
浸渍处理方法：首先将纤维置于第一浴浸胶液中，在室温下浸渍3s后，在150℃干燥1.5min，在230℃下固化1.5min；然后将纤维置于第二浴浸胶液中，在室温下浸渍3s后，在 150℃干燥1.5min，在250℃下固化1.5min。
实施例12
一种纤维表面环保浸渍处理体系，双浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000019
第一浴浸胶液的制备方法：将山梨醇缩水甘油醚、ε-己内酰胺封端的二苯基甲烷二异氰酸酯、苯酚封端的异佛尔酮二异氰酸酯按实验配方加入去离子水中，在25℃下用电动搅拌器在500rpm强力搅拌1.5h。第二浴浸胶液的制备方法：将纳米二氧化钛和去离子水加入烧杯中，将改性剂KH550/乙醇(KH550/乙醇体积比2:1，乙醇(纯度≥95wt％))的混合溶液(KH550用量为填料用量的10wt％)缓慢加入纳米二氧化钛和去离子水的混合溶液中，进行超声搅拌，超声设备的功率为400W，超声搅拌的时间为1h，得到分散的改性纳米填料。然后，将所有组分(胶乳除外)以预定的重量比加入去离子水中，并将溶液在25℃下用电动搅拌器在500rpm强力搅拌1h。最后，将苯乙烯-丁二烯-乙烯基吡啶胶乳添加到混合溶液中，并将该装置保持在25℃下强力搅拌2.5h。在搅拌期间，添加氢氧化钾以将溶液的pH调节至8.7。
浸渍处理方法：首先将纤维置于第一浴浸胶液中，在室温下浸渍3秒后，在150℃干燥1.5min，在230℃下固化1.5min；然后将纤维置于第二浴浸胶液中，在室温下浸渍3s后，在150℃干燥1.5min，在240℃下固化2min。
实施例13
一种纤维表面环保浸渍处理体系，双浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000020
浸胶液的制备方法同实施例12。
浸渍处理方法：首先将纤维置于第一浴浸胶液中，在室温下浸渍3s后，在150℃干燥1.5min，在220℃下反应1.5min；然后将纤维置于第二浴浸胶液中，在室温下浸渍3秒后，在150℃干燥1.5min，在230℃下固化2min。
实施例14
一种纤维表面环保浸渍处理体系，双浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000021
浸胶液的制备方法同实施例12。
浸渍处理方法：首先将纤维置于第一浴浸胶液中，在室温下浸渍3s后，在150℃干燥1.5min，在230℃下固化1.5min；然后将纤维置于第二浴浸胶液中，在室温下浸渍3秒后，在 150℃干燥1.5min，在250℃下固化2min。
实施例15
一种纤维表面环保浸渍处理体系，双浴法配方比例按重量份计如下：
Figure PCTCN2020099939-appb-000022
浸胶液的制备方法同实施例12。
浸渍处理方法：首先将纤维置于第一浴浸胶液中，在室温下浸渍3s后，在150℃干燥1.5min，在230℃下固化1.5min；然后将纤维置于第二浴浸胶液中，在室温下浸渍3秒后，在150℃干燥1.5min，在240℃下固化2min。
对比例4
对比例4为传统RFL二浴法处理芳纶纤维。
Figure PCTCN2020099939-appb-000023
预处理液的配制：将山梨醇缩水甘油醚、ε-己内酰胺封端的二苯基甲烷二异氰酸酯按实验配方加入去离子水中，在25℃下用电动搅拌器在500rpm强力搅拌1.5h。RFL浸胶液的配制：第一步将0.1份氢氧化钠和100份去离子水加入烧杯中，用电动搅拌器在500rpm强力搅拌10min，再加入间苯二酚3.7份搅拌10min，最后加入甲醛水溶液(37wt％)5.4份在常温下搅拌6h，得到均匀的反应液；第二步加入VP胶乳(固含量40wt％)80份，在常温下搅拌20h，搅拌快结束前，加入氨水1份，最终得到RFL浸胶液。
浸渍处理方法：首先将纤维置于预浸渍液中，在室温下浸渍3s后，在150℃干燥1.5min，在230℃下固化1.5min；然后将纤维置于RFL浸胶液中，在室温下浸渍3s后，在150℃干燥1.5min，在250℃下固化1.5min。
对比例5、6的浸胶液配方及处理工艺与对比例4相同，只是处理的纤维不同，对比例4所用帘线所用帘线为芳纶帘线(1670dtex/2)，对比例5所用帘线为聚酯帘线(1440dtex/2)，对比例6所用帘线为芳纶/尼龙66复捻帘线(A1670dtex/1+N1400dtex/1)。
将实施例11-15以及对比例4-6浸渍处理后的纤维帘线，按照以上方法制备测试样品，进行H抽出测试、剥离测试以及帘线强度测试，测试得到的结果如表2所示。
表2双浴法处理纤维帘线数据
Figure PCTCN2020099939-appb-000024
Figure PCTCN2020099939-appb-000025
备注：EP指代环氧树脂，PBMA指代马来酸酐接枝的聚合物。
从上表的数据可以看出，实施例11(未添加填料)的H抽出力和剥离力与对比例RFL相当。实施例12-15(添加改性填料)的H抽出力比对比例RFL高了15-20％，剥离力较RFL也有明显提高。这说明了该新型纤维表面环保浸渍体系具有优异的粘合效果，达到乃至超过了RFL处理的粘合水平。从实施例11-15来看，改性填料的加入进一步提升了纤维与橡胶之间的粘合效果，这与实施例1-10处理聚酰胺帘线的结果是相吻合的。所有组别的帘线在剥离测试后表面粘覆的橡胶均达到了100％，说明了浸渍体系效果的稳定性，符合工业应用的条件。此外，芳纶帘线、聚酯帘线在浸渍后，其拉断强度没有明显的变化，说明该方法不会对纤维的强度造成损伤，不会对纤维的性能产生影响。

Claims (20)

  1. 一种用于纤维表面处理的组合物，包括以下组分：
    马来酸酐化的聚合物；
    环氧树脂；
    封闭型异氰酸酯；
    固化剂；
    橡胶胶乳；
    溶剂；以及
    任选组分填料。
  2. 根据权利要求1所述的组合物，其特征在于，各组分的重量份数如下：
    Figure PCTCN2020099939-appb-100001
  3. 根据权利要求1或2所述的组合物，其特征在于，所述马来酸酐化的聚合物选自马来酸酐接枝聚丁二烯、马来酸酐接枝聚异戊二烯、马来酸酐接枝苯乙烯-丁二烯二元共聚物中的至少一种；优选地，马来酸酐的接枝率为10-50％，马来酸酐化的聚合物的数均分子量为3000-10000；
  4. 根据权利要求1-3中任一项所述的组合物，其特征在于，
    所述环氧树脂为水溶性环氧树脂，优选选自双酚A型环氧树脂、环氧化线性酚醛树脂、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、1，2-丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、1，4-丁二醇二缩水甘油醚、二缩水甘油醚、丙三醇缩水甘油醚、山梨醇缩水甘油醚、三羟甲基丙烷缩水甘油醚、四酚基乙烷四缩水甘油醚环氧树脂、间苯二酚双缩水甘油醚型环氧树脂和双间苯二酚缩甲醛四缩水甘油醚中的一种或多种。
  5. 根据权利要求1-4中任一项所述的组合物，其特征在于，
    所述固化剂为咪唑类固化剂、胺类固化剂和/或酸酐类固化剂；
    优选地，所述咪唑类固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4- 甲基咪唑和1-氰乙基-2-十一烷基咪唑中的一种或多种；
    优选地，所述胺类固化剂选自超支化聚酰胺、超支化聚乙烯亚胺、超分子聚氧乙烯胺、聚氧乙烯双胺和聚酰胺中的一种或多种；
    优选地，所述酸酐类固化剂选自邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、偏苯三甲酸酐甘油酯、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐、均苯四甲酸酐、乙二醇双偏苯三甲酸酐、甲基环己烯四酸二酐、偏苯三甲酸酐和聚壬二酸酐中的一种或多种。
  6. 根据权利要求1-5中任一项所述的组合物，其特征在于，
    所述封闭型异氰酸酯为由异氰酸酯和封端剂形成的封闭型异氰酸酯，优选所述异氰酸酯选自三甲基-1,6-六亚甲基二异氰酸酯、四亚甲基二异氰酸酯、四甲基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-苯二异氰酸酯、1,4-苯二异氰酸酯、异佛尔酮二异氰酸酯和二苯基甲烷二异氰酸酯中的一种或多种，所述封端剂选自ε-己内酰胺、丁酮肟和苯酚中一种或多种。
  7. 根据权利要求1-6中任一项所述的组合物，其特征在于，
    所述溶剂为水性溶剂，优选为水，更优选为去离子水；
    所述填料选自纳米二氧化硅、炭黑、纳米二氧化钛，纳米氧化锌、纳米氧化铁、纳米氧化钙、纳米碳酸钙、碳纳米管、凹凸棒石、纳米纤维素、埃洛石、纳米芳纶纤维、玄武岩纤维、纳米晶须、氧化石墨烯、蒙脱石、云母、高岭土和水滑石的一种或多种。
  8. 根据权利要求1-7中任一项所述的组合物，其特征在于，所述填料为经填料表面改性剂处理后的填料；
    优选地，所述填料表面改性剂选自氨基硅烷偶联剂、环氧基硅烷偶联剂、烷基硅烷偶联剂、异氰酸酯基硅烷偶联剂、聚醚硅烷偶联剂的一种或多种；优选自γ―氨丙基三乙氧基硅烷(KH550)、γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、γ-巯丙基三乙氧基硅烷(KH580)、双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)和乙烯基三乙氧基硅烷(A151)中的至少一种。
  9. 根据权利要求1-8中任一项所述的组合物，其特征在于，所述橡胶胶乳选自丁吡胶乳、丁苯胶乳、丁苯吡胶乳、氯丁胶乳、丁腈胶乳、氯磺化聚乙烯胶乳和天然胶乳中的至少一种；优选地，所述橡胶胶乳的固含量为20～60wt％。
  10. 一种纤维的处理方法，包括：
    步骤1)将纤维置于浸胶液中进行浸渍，其中所述浸胶液由根据权利要求1-9中任一项所述的组合物制备而成；
    步骤2)将步骤1)得到的浸渍后的纤维进行干燥和固化。
  11. 根据权利要求10所述的处理方法，其特征在于，实施所述浸渍的温度为15-40℃，时间为2-60s；实施所述干燥的温度为100～150℃，时间为1～10min；实施所述固化的温度为180～260℃，时间为1～10min，使用前将所述浸胶液的pH调节为8.0-11.0。
  12. 一种纤维的处理方法，包括以下步骤：
    步骤A)将纤维置于第一浸胶液中进行浸渍，其中第一浸胶液包含环氧树脂、封闭型异氰酸酯和溶剂；
    步骤B)将步骤A)处理后的纤维进行干燥，然后进行固化；
    步骤C)将步骤B)处理后的纤维置于第二浸胶液中进行浸渍，其中第二浸胶液含马来酸酐化的聚合物、环氧树脂、固化剂、橡胶胶乳、溶剂以及任选组分填料；
    步骤D)将步骤C)处理后的纤维进行干燥和固化。
  13. 根据权利要求12所述的处理方法，其特征在于，步骤A)中，实施所述浸渍的温度为15-40℃，时间为2-30s；步骤B)中，实施所述干燥的温度为100-150℃，时间为1-10min；步骤B)中，实施所述固化的温度为180-250℃，时间为1-10min。
  14. 根据权利要求12或13所述的处理方法，其特征在于，步骤C)中，实施所述浸渍的温度为15-40℃，时间为2-60s；步骤D)中，实施所述干燥的温度为100-150℃，时间为1-10min；步骤B)中，实施所述固化的温度为180-260℃，时间为1-10min。
  15. 根据权利要求12-14中任一项所述的处理方法，其特征在于，使用前将所述第二浸胶液的pH调节为大于7.5，优选为8.0-11.0。
  16. 根据权利要求12-15中任一项所述的处理方法，其特征在于，所述马来酸酐化的聚合物选自马来酸酐接枝聚丁二烯、马来酸酐接枝聚异戊二烯、马来酸酐接枝苯乙烯-丁二烯二元共聚物中的至少一种；优选地，马来酸酐的接枝率为10-50％，马来酸酐化的聚合物的数均分子量为3000-10000；
    所述环氧树脂为水溶性环氧树脂，优选选自双酚A型环氧树脂、环氧化线性酚醛树脂、乙二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、1，2-丙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、1，4-丁二醇二缩水甘油醚、二缩水甘油醚、丙三醇缩水甘油醚、三羟甲基丙烷缩水甘油醚、四酚基乙烷四缩水甘油醚环氧树脂、间苯二酚双缩水甘油醚型环氧树脂、山梨醇缩水甘油醚和双间苯二酚缩甲醛四缩水甘油醚中的一种或多种。
    所述固化剂为咪唑类固化剂、胺类固化剂和/或酸酐类固化剂；
    优选地，所述咪唑类固化剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑和1-氰乙基-2-十一烷基咪唑中的一种或多种；
    优选地，所述胺类固化剂选自超支化聚酰胺、超支化聚乙烯亚胺、超分子聚氧乙烯胺、聚氧乙烯双胺和聚酰胺中的一种或多种；
    优选地，所述酸酐类固化剂选自邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、偏苯三甲酸酐甘油酯、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐、均苯四甲酸酐、乙二醇双偏苯三甲酸酐、甲基环己烯四酸二酐、偏苯三甲酸酐和聚壬二酸酐中的一种或多种；
    所述封闭型异氰酸酯为由异氰酸酯和封端剂形成的封闭型异氰酸酯，优选所述异氰酸酯选自三甲基-1,6-六亚甲基二异氰酸酯、四亚甲基二异氰酸酯、四甲基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-苯二异氰酸酯、1,4-苯二异氰酸酯、异佛尔酮二异氰酸酯和二苯基甲烷二异氰酸酯中的一种或多种，所述封端剂选自ε-己内酰胺、丁酮肟和苯酚中一种或多种；
    所述溶剂为水性溶剂，优选为水，更优选为去离子水；
    所述填料选自纳米二氧化硅、炭黑、纳米二氧化钛，纳米氧化锌、纳米氧化铁、纳米氧化钙、纳米碳酸钙、碳纳米管、凹凸棒石、纳米纤维素、埃洛石、纳米芳纶纤维、玄武岩纤维、纳米晶须、氧化石墨烯、蒙脱石、云母、高岭土和水滑石的一种或多种；
    所述橡胶胶乳选自丁吡胶乳、丁苯胶乳、丁苯吡胶乳、氯丁胶乳、丁腈胶乳、氯磺化聚乙烯胶乳和天然胶乳中的至少一种；优选地，所述橡胶胶乳的固含量为20～60wt％
  17. 根据权利要求12-16中任一项所述的处理方法，其特征在于，所述填料为经填料表面改性剂处理后的填料；
    优选地，所述填料表面改性剂选自氨基硅烷偶联剂、环氧基硅烷偶联剂、烷基硅烷偶联剂、异氰酸酯基硅烷偶联剂、聚醚硅烷偶联剂的一种或多种；优选自γ―氨丙基三乙氧基硅烷(KH550)、γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、γ-巯丙基三乙氧基硅烷(KH580)、双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)和乙烯基三乙氧基硅烷(A151)中的至少一种。
  18. 根据权利要求12-17中任一项所述的处理方法，其特征在于，第一浸胶液的制备原料包括：
    溶剂                                100份；
    第一环氧树脂                        0.5～4份；优选0.5～2.5份；
    封闭型异氰酸酯                      2～10份；优选4～8份；
  19. 根据权利要求12-18中任一项所述的处理方法，其特征在于，
    第二浸胶液的制备原料包括：
    Figure PCTCN2020099939-appb-100002
    Figure PCTCN2020099939-appb-100003
  20. 根据权利要求12-19中任一项所述的处理方法，其特征在于，
    所述纤维为人造丝、尼龙6、尼龙66、间位或对位芳纶纤维、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺、碳纤维或上述纤维的混编加捻帘线；和/或
    所述纤维的形式选自单丝、束丝、加捻帘线、帆布、帘子布或其组合。
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