EP4141168A1 - Agent de collage pour des fibres de carbone - Google Patents

Agent de collage pour des fibres de carbone Download PDF

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Publication number
EP4141168A1
EP4141168A1 EP22192514.2A EP22192514A EP4141168A1 EP 4141168 A1 EP4141168 A1 EP 4141168A1 EP 22192514 A EP22192514 A EP 22192514A EP 4141168 A1 EP4141168 A1 EP 4141168A1
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EP
European Patent Office
Prior art keywords
agent
carbon fibers
sizing agent
weight
parts
Prior art date
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EP22192514.2A
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German (de)
English (en)
Inventor
Ching-Cheng Chung
Yu-Sheng Li
Cheng-Chun Chou
Sheng-Shiun Lin
Yi-Chuan Chang
Chen-Hsu Chou
Long-Tyan Hwang
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Formosa Plastics Corp
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Formosa Plastics Corp
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Publication of EP4141168A1 publication Critical patent/EP4141168A1/fr
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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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/152—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 oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • D06M2101/40—Fibres of carbon
    • 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
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present disclosure relates to a sizing agent for carbon fibers, and more particularly to a sizing agent that can prolong the hardening time of carbon fiber bundles.
  • Carbon fiber is a kind of important reinforcing material and could be widely used in various fields. Carbon fibers could be used to enhance material properties because carbon fibers have the advantages of high specific strength, high specific modulus, high temperature resistance, chemical resistance, low friction coefficient, good electrical conductivity, and so on. Carbon fiber composite material could be used in various fields. For example, it could be used in aviation, aerospace, sporting goods, civil construction, electronic products, medical equipment, and other fields.
  • the processability of carbon fibers may be affected by the low expansion rate and brittleness of carbon fibers.
  • the strength of carbon fibers may be reduced because of hairiness or broken filaments of carbon fibers caused by mechanical friction.
  • Carbon fiber hardness is one factor that affects hairiness or broken filaments caused by mechanical friction during processing. The higher the hardness of the carbon fiber, the easier it is for the carbon fibers to generate hairiness or broken filaments during processing.
  • the present disclosure provides a sizing agent for carbon fibers. Based on an amount of the sizing agent as 100 parts by weight, the sizing agent includes 2 to 30 parts by weight of a resin main agent (A) having at least one epoxy compound, 2 to 30 parts by weight of a resin main agent (B) having at least one acrylate compound, 0.5 to 15 parts by weight of a surfactant (C), 0.01 to 0.5 parts by weight of a hindered phenol agent (D), and a balance of a solvent, in which a particle diameter of the sizing agent is in a range from 0.01 to 0.5 ⁇ m.
  • a resin main agent A having at least one epoxy compound
  • a resin main agent (B) having at least one acrylate compound 0.5 to 15 parts by weight of a surfactant (C), 0.01 to 0.5 parts by weight of a hindered phenol agent (D), and a balance of a solvent, in which a particle diameter of the sizing agent is in a range from 0.01 to
  • the resin main agent (A) having at least one epoxy compound includes a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, novolac epoxy, or combinations thereof.
  • the resin main agent (A) having at least one epoxy compound accounts for 10 to 25 parts by weight.
  • an epoxy equivalent of the resin main agent (A) having at least one epoxy compound is in a range from about 100 g/eq to about 1500 g/eq.
  • the resin main agent (B) having at least one acrylate compound includes acrylate having an oxyalkylene group in a molecule, methacrylate having an oxyalkylene group in a molecule, acrylate having an oxyalkyl group in a molecule, methacrylate having an oxyalkyl group in a molecule, acrylate excluding an oxyalkylene group in a molecule, methacrylate excluding an oxyalkylene group in a molecule, acrylate excluding an oxyalkyl group in a molecule, methacrylate excluding an oxyalkyl group in a molecule, or combinations thereof.
  • the resin main agent (B) having at least one acrylate compound accounts for 10 to 25 parts by weight.
  • the surfactant (C) includes a non-ionic surfactant, an anionic surfactant, a cationic surfactant, or combinations thereof.
  • the non-ionic surfactant includes an alcohol ethylene oxide additive, polyol polyoxyethylene ether, C16-18 alcohol polyethylene glycol ether, alkyl polyoxyethylene ether, or polyethylene glycol fatty acid ester.
  • the non-ionic surfactant includes polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, or polyethylene glycol bisphenol A derivatives.
  • the anionic surfactant includes alcohol sulfate, alkyl polyethylene glycol ether sulfate, polycyclic phenyl ether polyethylene glycol ether sulfate, alkybenzoyl sulfonate, polycyclic phenyl ether sulfonate, alkyl sulfonate, dialkyl sulfonic succinate, polyoxyethylene nonylphenyl phosphate, triethanolamine polyoxyethylene alkylphenyl ether phosphate, or polyoxyethylene styrenated aryl ether phosphate.
  • the cationic surfactant includes alkyl dimethylphenyl quaternary ammonium salt, alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, ester quaternary ammonium salt, imidazoline quaternary ammonium salt.
  • the surfactant (C) accounts for 5 to 12.5 parts by weight.
  • an amount of the resin main agent (B) having at least one acrylate compound is the same as an amount of the surfactant (C).
  • the hindered phenol agent (D) has a structural formula represented by following formula (II): where R represents long-chain ester.
  • the hindered phenol agent (D) has a structural formula represented by following formula (II-1): where n is in a range from 7 to 9.
  • the hindered phenol agent (D) has a structural formula represented by following formula (II-2).
  • the hindered phenol agent (D) accounts for 0.05 to 0.1 parts by weight.
  • the solvent is deionized water.
  • the present disclosure provides carbon fibers applied with the aforementioned sizing agent, and a sizing ratio of the carbon fibers is in a range from 0.1 to 5 weight percent.
  • the present disclosure provides carbon fibers applied with the aforementioned sizing agent, and an increasing of a hardness of the carbon fibers is less than 100 % after 14 days of an age-hardening test.
  • a range represented by "one value to another value” is a general representation that avoids listing all the values in the range in the specification. Therefore, the recitation of a particular numerical range includes any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range. This arbitrary numerical value and this smaller numerical range are as if it is recited in the specification.
  • a sizing agent may be applied to carbon fibers to keep the original favorable properties and avoid reducing the processability of carbon fibers.
  • the sizing agent may be applied to carbon fibers, so that carbon fibers may reduce hairiness or broken filaments caused by mechanical friction during processing, thereby increasing the processability of carbon fibers.
  • the processability, workability, and binding ability of carbon fibers to the base resin could be improved through the treatment of the sizing agent, so the carbon fiber composite material could have better mechanical properties.
  • a sizing agent may improve are as follows. (1) Bunching, which enables carbon fibers to collect into rolls, makes it easy to store and transport, and could be neatly arranged for operations when manufacturing a composite material. (2) Protecting carbon fibers, which reduces the hairiness or broken filaments of carbon fibers caused by mechanical friction during processing. (3) Acting as an interface coupling agent between carbon fibers and resin, which may improve the problem of poor impregnation of carbon fibers and resin.
  • a main component of a sizing agent includes epoxy resin. This is because epoxy resin has good film-forming properties forming a strong and firm film on the surfaces of fibers to protect carbon fibers. In addition, most composite matrix resins are epoxy resin systems.
  • Epoxy resin has epoxy functional groups with reactivity. Therefore, under proper catalysis, epoxy resin could react with different types of hardening agents (for example, functional groups such as amines or acid anhydrides) to form three-dimensional net structures. Epoxy resin is one of the excellent thermoset materials. In some embodiments, bisphenol A epoxy resin may be used as the main component of the sizing agent.
  • a conventional sizing agent composition includes epoxy resin, acrylate (and/or methacrylate), and polyester resin with bisphenol A backbone and polyoxyethylene chain.
  • ester structures of the conventional sizing agent are easy to absorb moisture in the air and have stacking arrangements of dipole-dipole bonds, making the carbon fiber bundles adhere to each other.
  • double bonds of the propylene group may also be cross-linked due to the free radical reaction, thereby accelerating the hardening of carbon fibers.
  • Carbon fibers may be challenging to spread yarns during processing a composite material, or tend to have problems such as hairiness caused by mechanical friction, thus reducing the processability of carbon fibers.
  • the hardening of carbon fibers is due to an epoxide ring-opening and a cleavage of a double bond of vinyl ester resin, resulting in a free radical reaction (free radical polymerization).
  • the double bond react with the sunlight and oxygen to generate the free radical reaction.
  • the free radical reaction three-dimensional net structures are formed among molecules and then hardened, thereby decreasing the machinability of carbon fibers.
  • the free radical reaction is a chain reaction, the chain reaction will continue to react after a free radical is first produced. Therefore, delaying (or termination) the occurrence of the free radical reaction can prolong carbon fibers to be hardened.
  • An activation energy (E) of a double bond of acrylic acid is 124 KJ/mol, where stored at 25 °C, and a reaction rate becomes 5 times for every 10 °C rise in temperature. Therefore, the accelerated day is 5 ⁇ [(Tt-25)/10], where Tt is a test temperature.
  • the above-mentioned sizing agent for carbon fibers has problems of being easy to absorb moisture and producing adhesiveness and hardening over time, which further leads to a decrease in carbon fibers' bonding force and machinability. Therefore, the present disclosure provides a sizing agent for carbon fibers to overcome the above-mentioned problems.
  • the sizing agent of the present disclosure could strengthen a bonding force between carbon fibers and a matrix resin, prevent the carbon fibers from generating hairiness or broken filaments during processing, inhibit hardening over time, and increase long-term storage stability.
  • the sizing agent composition of the present disclosure includes a hindered phenol agent (D).
  • a hindered phenol agent (D) By adding the hindered phenol agent (D), hydrogen radicals are provided to block a chain reaction generated by oxygen radicals in the process of polymer hardening.
  • the hindered phenol agent (D) generates relatively stable aromatic oxygen radicals, and the aromatic oxygen radicals have the ability to further capture active free radicals. Therefore, a free radical reaction can be terminated to delay the hardening of carbon fibers.
  • the addition of an inhibitor (such as the hindered phenol agent (D)) that captures free radicals can delay the occurrence of the free radical reaction.
  • the hindered phenol is a kind of inhibitor for the free radical reaction. Please refer to the following reaction formula (I).
  • a hydroxyl (-OH) on a benzene ring of a hindered phenol has alkyl substituents with larger steric barriers on both sides of the benzene ring, a hydrogen (H) atom of the hydroxyl tends to fall off from the hindered phenol.
  • the hydrogen (H) atom further combines with a free radical to terminate a chain reaction of free radicals, thereby achieving the effect of delaying hardening.
  • the disclosed sizing agent for carbon fibers includes a resin main agent (A) having at least one epoxy compound, a resin main agent (B) having at least one acrylate compound, a surfactant (C), the hindered phenol agent (D), and a balance of a solvent, in which a particle diameter of the sizing agent is in a range from 0.01 to 0.5 ⁇ m.
  • an amount of the resin main agent (B) having at least one acrylate compound is the same as an amount of the surfactant (C).
  • the disclosed resin main agent (A) having at least one epoxy compound includes a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, novolac epoxy, or combinations thereof.
  • an epoxy equivalent of the resin main agent (A) having at least one epoxy compound is in a range from about 100 g/eq to about 1500 g/eq. For example, in a range from about 130 g/eq to about 1000 g/eq, or to about 160 g/eq to about 900 g/eq.
  • the epoxy equivalent is less than about 100 g/eq, the hardening degree of a fiber bundle (such as, a carbon fiber bundle) would be enhanced over time.
  • the epoxy equivalent is more than about 1500 g/eq, the bondability with the matrix resin would be reduced.
  • an amount of the resin main agent (A) having at least one epoxy compound is about 2 to about 30 parts by weight. In other embodiments, the amount of the resin main agent (A) having at least one epoxy compound is about 10 to about 25 parts by weight, such as 12.5, 15, 17.5, 20, or 22.5 parts by weight. When the amount of the resin main agent (A) having at least one epoxy compound is less than 2 parts by weight, the fiber bundle would be loose and soft. When the amount of the resin main agent (A) having at least one epoxy compound more than 30 parts by weight, the bondability with the matrix resin may be affected.
  • the bisphenol A type epoxy compound could be a commercial product.
  • BE TM 114, BE TM 186, or BE TM 188 manufactured by Chang Chun Plastics Co., Ltd.
  • epoxy compounds such as ADEKA Resin EP-4100, ADEKA Resin EP-4300, or ADEKA Resin EP-4700, manufactured by ADEKA Co.
  • the bisphenol F type epoxy compound could be a commercial product.
  • NPEL TM 170 manufactured by Nan Ya Plastics Co.
  • EPON TM Resin 869 manufactured by Hexion Inc.
  • jER TM 806 or jER TM 807 manufactured by Mitsubishi Chemical Co.
  • epoxy compounds such as BE TM 170, BE TM 235, or BE TM 283, manufactured by Chang Chun Plastics Co.
  • the bisphenol S type epoxy compound could be a commercial product.
  • epoxy compounds such as 185S or 300S, manufactured by Compton.
  • Novolac epoxy could be a commercial product.
  • NPEL TM 630, NPEL TM 638, or NPEL TM 640 manufactured by Nan Ya Plastics Co.
  • NPCN TM 701, NPCN TM 702, NPCN TM 703, NPCN TM 704, NPCN TM 704L manufactured by Nan Ya Plastics Co.
  • H series or HF series manufactured by Meiwa Plastic Industries, Ltd.
  • epoxy compounds such as PNE TM 171, PNE TM 172, PNE TM 174, PNE TM 175, PNE TM 176, or PNE TM 177, manufactured by Chang Chun Plastics Co., Ltd.
  • an amount of the resin main agent (B) having at least one acrylate compound is about 2 to about 30 parts by weight. In other embodiments, the amount of the resin main agent (B) having at least one acrylate compound is about 10 to about 25 parts by weight, such as 12.5, 15, 17.5, 20, or 22.5 parts by weight. When the amount of the resin main agent (B) having at least one acrylate compound is less than 2 parts by weight, the bondability with the matrix resin may be affected. When the amount of the resin main agent (B) having at least one acrylate compound is more than 30 parts by weight, the fiber bundle would be less prone to bunching or being too soft.
  • the resin main agent (B) having at least one acrylate compound could be a commercial product.
  • acrylate compounds such as QualiCure TM GM62S70, QualiCure TM GM62V20, QualiCure TM GM62V40, QualiCure TM GM62V60, etc., manufactured by Qualipoly Chemical Corp.
  • the disclosed surfactant (C) includes a non-ionic surfactant, an anionic surfactant, a cationic surfactant, or combinations thereof.
  • the non-ionic surfactant could be used with any one of the anionic surfactant or the cationic surfactant.
  • an amount of the surfactant (C) is about 0.5 to about 15 parts by weight. In other embodiments, the amount of the surfactant (C) is about 5 to about 12.5 parts by weight, such as 6.5, 8, 9.5, or 11 parts by weight. When the amount of the surfactant (C) is less than 0.5 parts by weight, it would not have an emulsification. When the amount of the surfactant (C) is more than 15 parts by weight, it would reduce the machinability of carbon fibers.
  • the non-ionic surfactant could be, for example, an aliphatic type non-ionic surfactant or an aromatic type non-ionic surfactant.
  • the aliphatic type non-ionic surfactant could be an alcohol ethylene oxide additive, polyol polyoxyethylene ether, C16-18 alcohol polyethylene glycol ether, alkyl polyoxyethylene ether, polyethylene glycol fatty acid ester, etc.
  • the aromatic type non-ionic surfactant could be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol bisphenol A derivatives, etc.
  • the anionic surfactant could be, for example, sulfates, sulfonates, phosphates, etc.
  • Sulfates could be alcohol sulfate, alkyl polyethylene glycol ether sulfate, polycyclic phenyl ether polyethylene glycol ether sulfate, etc.
  • Sulfonates could be alkybenzoyl sulfonate, polycyclic phenyl ether sulfonate, alkyl sulfonate, dialkyl sulfonic succinate, etc.
  • Phosphates could be polyoxyethylene nonylphenyl phosphate, triethanolamine polyoxyethylene alkylphenyl ether phosphate, polyoxyethylene styrenated aryl ether phosphate, etc.
  • the cationic surfactant could be quaternary ammonium salt.
  • quaternary ammonium salt alkyl dimethylphenyl quaternary ammonium salt, alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, ester quaternary ammonium salt, imidazoline quaternary ammonium salt, etc.
  • the disclosed hindered phenol agent (D) of the sizing agent could have a structural formula represented by formula (II), where R represents long-chain ester.
  • the hindered phenol agent (D) could be a commercial product.
  • Everaox ® 101 has a structural formula represented by formula (11-1), where n is in a range from 7 to 9.
  • AO-1135 has a structural formula represented by formula (II-2).
  • the hydrogen (H) atom of the hydroxyl tends to fall off from the hindered phenol.
  • the hydrogen (H) atom further combines with free radicals to terminate the chain reaction of free radicals, thereby achieving the effect of delaying hardening.
  • an amount of the hindered phenol agent (D) is about 0.01 to about 0.5 parts by weight, such as 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, or 0.45 parts by weight. In other embodiments, the amount of the hindered phenol agent (D) is about 0.05 to about 0.1 parts by weight, such as 0.06, 0.07, 0.08, or 0.09 parts by weight. When the amount of the hindered phenol agent (D) is less than 0.01 parts by weight, it would not tend to terminate the chain reaction of free radicals and so may not have the effect of delaying the hardening of carbon fibers. When the amount of the hindered phenol agent (D) is more than 0.5 parts by weight, it would not have a positive effect on delaying the hardening of carbon fibers.
  • the disclosed solvent of the sizing agent could be deionized water.
  • an amount of the solvent is about is about 25 to about 95.5 parts by weight, such as 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 parts by weight.
  • the disclosed sizing agent could be applied to carbon fibers in the form of a dispersion in water and the disclosed sizing agent does not contain any organic solvent.
  • the disclosed sizing agent for carbon fibers uniformly dispersed in an emulsion type is prepared by mechanical shearing force.
  • the device for making the sizing agent could be a paddle stirring blade, in which a type of the blade could be a dissolving type, a three-blade type, or a four-blade type.
  • the device is equipped with an anchor stirring blade.
  • the sizing agent for carbon fibers could be prepared by using an ultrasonic crushing homogenizer, a high-speed homogenizer, a high-speed emulsifier, or other devices.
  • the disclosed sizing agent is an aqueous solution that is self-emulsified and/or emulsified and dispersed in water, and a mean diameter of the sizing agent is less than 1 ⁇ m.
  • the mean diameter of the sizing agent is in a range from about 0.01 to about 0.5 ⁇ m, such as, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, or 0.45 ⁇ m.
  • the mean diameter is greater than 1 ⁇ m, the sizing agent may not be uniformly attached to carbon fibers, and free energy of particles is insufficient for Brownian motion to cause sedimentation. Therefore, the storage stability of the sizing agent is poor.
  • the mean diameter of the sizing agent was measured according to the principle of laser light scattering. When the laser light is irradiated on particles in the solution, the particles will scatter the laser light. Since the Brownian motions of different particle sizes are different, the degrees of laser light scattering are also different, and then a collective size and a size distribution are calculated. In some embodiments of the present disclosure, the mean diameter of the sizing agent was measured by using the Brookhaven Nanobrook Omni instrument.
  • the carbon fiber TC35R-24K (TARIFIL, manufactured by Formosa Plastics Co., a total of 24,000 fibers in a single bundle, a strength of the single fiber bundle is about 4000 MPa, a modulus of the single fiber bundle is 240 GPa) was immersed in a dipping tank having the sizing agent. Then, a thermal drying was performed at about 100 ⁇ 250 °C, where a drying time was about 2 to 10 minutes. When the drying temperature was less than 100 °C, the water in the sizing agent could not evaporate completely. When the drying temperature was greater than 250°C, the sizing agent would undergo a thermal reaction and cause deterioration.
  • the thermal drying method such as a hot air method, a heating roller contact method, an infrared ray method, or combinations of two or three of the aforementioned methods could be appropriately used and then collected the carbon fiber into a roll.
  • the aforementioned emulsion type sizing agent for the carbon fiber can be used in carbon fiber composite materials as an interface layer connecting the carbon fiber and a matrix resin.
  • a weight of the sizing agent is about 0.1 to about 5% by weight relative to a weight of the carbon fiber. For example, from about 0.5 to about 3 wt. %, such as 1, 1.5, 2, or 2.5 wt. %.
  • the sizing amount is less than 0.1 wt. %, the sizing agent could not provide the carbon fiber with good bunching, interfacial bonding force with the matrix resin, and abrasion resistance.
  • the sizing amount is more than 5 wt. %, the carbon fiber would not be easily spread out, so it would be difficult to spread the yarn after the subsequent processing of composite materials.
  • Fig. 1 is a schematic view of a tester 100 for testing a carbon fiber hairiness.
  • 100 meters length of a carbon fiber bundle 110 treated with the sizing agent is taken.
  • the carbon fiber bundle 110 undergoes the friction of 7 metal rollers 120 (without transmission and special surface treatment).
  • sponge pads 130 are disposed after the metal rollers 120 and configured to collect the hairiness caused by mechanical friction of the carbon fiber bundle 110.
  • the hairiness is dried at about 105 °C for about 40 minutes, and the hairiness is weighed (unit: mg).
  • Fig. 2A and Fig. 2B are schematic views of a tester 200 for testing a carbon fiber hardness.
  • Fig. 2A is a view of the carbon fiber bundle before applying a force source 210
  • Fig. 2B is a view of the carbon fiber bundle after applying the force source 210.
  • the carbon fiber bundle 110 treated with the sizing agent is laid on a platform 220 with a gap 230.
  • the force required by the force source 210 to bend the carbon fiber bundle 110 and press down to a fixed depth is the carbon fiber hardness (unit: g).
  • the gap 230 of the tester for testing the carbon fiber hardness is about 5 millimeters (mm).
  • the carbon fiber bundle is placed in the thermohygrostat chamber to accelerate hardening, where a temperature is about 70 °C and a relative humidity (RH) is about 85 %. Every 1 day, 3 days, 7 days, and 14 days, the carbon fiber bundle is taken out for the carbon fiber hairiness test and the carbon fiber hardness test.
  • RH relative humidity
  • the resin main agent (A) having at least one epoxy compound, resin main agent (B) having at least one acrylate compound, and the surfactant (C) were uniformly mixed by an IKA stirring machine at a temperature higher than melting points of the resin main agent (A) and the resin main agent (B).
  • the mixed state was cooled to a cloud point of the surfactant (C), and the solution was dripped at a rotation speed of about 5000 to about 10000 rpm for 6 hours.
  • an emulsified and uniformly dispersed solution was obtained, which was the sizing agent of Comparative Example.
  • a particle diameter (Dv50: nm) of the sizing agent of Comparative Example was in a range from about 0.01 to about 0.5 ⁇ m.
  • the melting points of the resin main agent (A) and the resin main agent (B) were in a range from about 60 °C to about 95 °C.
  • the could point of the surfactant (C) was in a range from about 60°C to about 70°C.
  • the resin main agent (A) having at least one epoxy compound, the resin main agent (B) having at least one acrylate compound, and the surfactant (C) were uniformly mixed by the IKA stirring machine at a temperature higher than melting points of the resin main agent (A) and the resin main agent (B).
  • the mixed state was cooled to a cloud point of the surfactant (C), and the solution was dripped at a rotation speed of about 5000 to about 10000 rpm for 6 hours.
  • An emulsified and uniformly dispersed solution was obtained.
  • the hindered phenol agent (D) was added to the solution to obtain the sizing agents of Examples (Example 1 to Example 5).
  • a particle diameter (Dv50 ; nm) of each sizing agent of Examples was in a range from about 0.01 to about 0.5 ⁇ m.
  • the melting points of the resin main agent (A) and the resin main agent (B) were in a range from about 60 °C to about 95 °C.
  • the could point of the surfactant (C) was in a range from about 60°C to about 70°C.
  • the hindered phenol agent (D) may also be mixed with the resin main agent (A), the resin main agent (B), and the surfactant (C) at the same time.
  • the same operations mentioned above are performed to form the sizing agents of Examples.
  • the sizing agents of Comparative Example and Example 1 to Example 5 were prepared according to the composition formulas in the following Table 1, with reference to the sizing agent preparations of Comparative Example and Examples mentioned above.
  • the sizing agents in Table 1 have been tested by the carbon fiber hardness test and the carbon fiber age-hardening test. The testing results are shown in Table 2 below. As can be learned from Table 2, compared with Comparative Example, it can reduce the amount of carbon fiber hairiness and improve the carbon fiber hardness when the sizing agent contains the hindered phenol agent (D).
  • Example 1 to Example 5 For example, on the 7 th and 14 th day of age-hardening, the amounts of carbon fiber hairiness in Example 1 to Example 5 were smaller than that in Comparative Example. Specifically, the increased amounts of carbon fiber hairiness in Example 1 to Example 5 were smaller than that in Comparative Example. In addition, under the age-hardening test, the variances of carbon fiber hardness of Example 1 to Example 5 were also smaller than that of Comparative Example.
  • the carbon fiber hardness was about 13 g on the 0 th day of age-hardening, and the carbon fiber hardness was about 39 g on the 14 th day of age-hardening, in which an increasing of the hardness was about 200 %.
  • the carbon fiber hardness was about 13 g on the 0 th day of age-hardening, and the carbon fiber hardness were about 26 g on the 14 th day of age-hardening, in which an increasing of the hardness was about 100 %.
  • Example 2 Comparative Example Example 1 Amount of hindered phenol agent (%) - 0.01 Day of age-hardening (day) 0 1 3 7 14 0 1 3 7 14 Amount of carbon fiber hairiness (mg) 17.7 17.8 17.9 19.3 43.2 17.6 17.5 17.8 18.9 40.3 Carbon fiber hardness (g) 13.1 13.5 15.8 18.3 39.2 13.0 13.2 14.7 17.5 38.8 Example 2 Example 3 Amount of hindered phenol agent (%) 0.05 0.1 Day of age-hardening (day) 0 1 3 7 14 0 1 3 7 14 Amount of carbon fiber hairiness (mg) 17.7 17.8 17.8 18.2 30.8 17.6 17.8 17.8 18.1 31.0 Carbon fiber hardness (g) 13.1 13.3 13.9 15.6 26.5 13.2 13.3 14.0 15.8 26.3
  • Example 4 Example 5 Amount of hindered phenol agent (%) 0.2 0.5 Day of age-hardening (day) 0 1 3 7 14 0 1 3 7 14 Amount of carbon fiber hairiness (
  • the disclosed sizing agent contains hindered phenol agent (D), it can solve moisture absorption and adhesiveness problems of the conventional carbon fiber. Therefore, the problem of hardening over time can be suppressed, and the effect of prolonging the hardening time of carbon fiber bundles can be achieved.
  • the disclosed sizing agent can strengthen the bonding force between the carbon fibers and the matrix resin, prevent the carbon fibers from generating hairiness or broken filaments during processing, and inhibit hardening over time, thereby reducing carbon fibers' machinability be prevented from being lowered.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
EP22192514.2A 2021-08-27 2022-08-27 Agent de collage pour des fibres de carbone Pending EP4141168A1 (fr)

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