CN114263043A - Sizing agent for carbon fibers - Google Patents
Sizing agent for carbon fibers Download PDFInfo
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- CN114263043A CN114263043A CN202210064600.9A CN202210064600A CN114263043A CN 114263043 A CN114263043 A CN 114263043A CN 202210064600 A CN202210064600 A CN 202210064600A CN 114263043 A CN114263043 A CN 114263043A
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- carbon fiber
- sizing agent
- weight
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- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- D06M15/21—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
- 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
- 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
Landscapes
- 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)
Abstract
A sizing agent for carbon fibers comprises 2 to 30 parts by weight of a resin main agent (A) of at least one epoxy compound, 2 to 30 parts by weight of a resin main agent (B) of at least one acrylate compound, 0.5 to 15 parts by weight of a surfactant (C) and 0.01 to 0.5 part by weight of a hindered phenol-based agent (D), wherein the particle size of the sizing agent is between 0.01 and 0.5 [ mu ] m. The sizing agent of the present invention contains hindered phenol-based agent (D), and thus suppresses the problem of hardening with time, and achieves the effect of prolonging the hardening time of the carbon fiber bundle. The sizing agent of the invention can strengthen the binding force between the carbon fiber and the matrix resin, prevent the carbon fiber from generating hairiness or broken filaments in the processing process, inhibit hardening with time, and prevent the reduction of the machinability.
Description
Technical Field
The present invention 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.
Background
Carbon fiber is an important reinforcing material, which is widely used in various fields. Carbon fibers can be used to enhance material properties due to their advantages of high specific strength, specific modulus, high temperature resistance, chemical resistance, low coefficient of friction, and good electrical conductivity. The carbon fiber composite material can be applied to various fields, for example, fields of aviation, aerospace, sporting goods, civil construction, electronic products, medical instruments, and the like.
However, the processability of carbon fibers is affected by the low degree of stretchability and brittleness of the carbon fibers. During the processing of carbon fibers, hairiness or filament breakage may occur due to mechanical friction, resulting in a decrease in the strength of the carbon fibers. The hardness of carbon fiber is one of the factors influencing the generation of hairiness or yarn breakage due to mechanical friction in the processing process. If the hardness of the carbon fiber is higher, the carbon fiber is more likely to generate hairiness or yarn breakage during processing.
In view of the foregoing, there is a need to develop a method for increasing the processability of carbon fibers to overcome the aforementioned problems.
Disclosure of Invention
The invention provides a sizing agent for carbon fibers, which comprises 2 to 30 parts by weight of a resin main agent (A) of at least one epoxy compound, 2 to 30 parts by weight of a resin main agent (B) of at least one acrylate compound, 0.5 to 15 parts by weight of a surfactant (C) and 0.01 to 0.5 part by weight of a hindered phenol agent (D), wherein the particle size of the sizing agent is between 0.01 and 0.5 mu m.
In some embodiments, the resin primary agent (a) of at least one epoxy-based compound comprises a bisphenol a-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac epoxy resin, or a combination thereof.
In some embodiments, the resin main agent (a) of the at least one epoxy-based compound accounts for 10 to 25 parts by weight.
In some embodiments, the resin main agent (B) of at least one acrylate compound comprises an acrylate having an oxyalkylene group in a molecule, a methacrylate having an oxyalkylene group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkylene group in a molecule, or a combination thereof.
In some embodiments, the resin main agent (B) of at least one acrylate compound is 10 to 25 parts by weight.
In some embodiments, the surfactant (C) comprises a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a combination thereof.
In some embodiments, the surfactant (C) comprises 5 to 12.5 parts by weight.
In some embodiments, hindered phenolic agent (D) comprises 0.05 to 0.1 parts by weight.
The present disclosure provides a carbon fiber having a sizing agent applied thereto as described above, the carbon fiber having a sizing agent ratio of between 0.1 and 5 weight percent.
The present disclosure provides a carbon fiber having applied thereto a sizing agent as described above, the carbon fiber having an increase in hardness of less than 100% as measured by a change over time of 14 days.
The above description will be described in detail by embodiments, and further explanation will be provided for the technical solution of the present disclosure.
Drawings
The detailed description of the present disclosure will be best understood when read in conjunction with the appended drawings. It should be noted that, in accordance with standard practice in the industry, the various features are not drawn to scale and are used for illustrative purposes only. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion.
Fig. 1 is a schematic diagram of an apparatus for detecting carbon fiber hairiness according to some embodiments of the present disclosure.
Fig. 2A and 2B are schematic diagrams illustrating an apparatus for detecting hardness of carbon fiber according to some embodiments of the present disclosure.
Detailed Description
In this context, a range denoted by "a numerical value to another numerical value" is a general expression avoiding a recitation of all numerical values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
As used herein, "about", "approximately", "essentially", or "substantially" includes the stated value and the average value within an acceptable range of deviation of the specified value as determined by one of ordinary skill in the art, taking into account the measurement in question and the specified amount of error associated with the measurement (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or within, for example, ± 30%, ± 20%, ± 15%, ± 10%, ± 5%. Further, as used herein, "about", "approximately", "essentially", or "substantially" may be selected with respect to measured properties, coating properties, or other properties, to more acceptable ranges of deviation or standard deviations, and not all properties may be applied with one standard deviation.
In order to make the carbon fiber exert its original good performance and avoid reducing the processability of the carbon fiber, sizing agent (sizing agent) can be applied to the carbon fiber (carbon fiber), so that the carbon fiber has good processability by reducing the generation of hairiness or yarn breakage caused by mechanical friction during processing. By means of the treatment of the sizing agent, the processability and the operability of the carbon fiber and the binding force of matrix resin can be improved, so that the carbon fiber composite material has excellent mechanical properties.
The sizing agent can improve the main functions as follows. (1) The carbon fibers can be collected into coils, so that the carbon fibers are easy to store and transport, and the carbon fibers can be orderly arranged for operation during the manufacturing and processing of the composite material. (2) Protect the carbon fiber and reduce the mechanical friction hairiness or broken filament generated in the processing of the carbon fiber. (3) The carbon fiber-resin composite material is used as an interface coupling agent between carbon fibers and resin, and the problem of poor impregnation of the carbon fibers and the resin is solved.
Generally, the main component of the sizing agent includes epoxy resin, because epoxy resin has good film-forming property, a strong and firm thin film can be formed on the surface of the fiber to protect the carbon fiber, and most of the composite matrix resin is epoxy resin system.
The epoxy resin has reactive epoxy functional groups, so that under the action of a proper catalyst, the epoxy resin can be mutually reacted and bonded with different hardeners (such as amine or acid anhydride functional groups) to form a three-dimensional network structure. Epoxy resins are excellent thermosets. In some embodiments, a bisphenol a epoxy resin may be utilized as the main component of the sizing agent.
The conventional sizing composition contains an epoxy resin, an acrylate (and/or a methacrylate), and a polyester resin having a bisphenol a skeleton and a polyoxyethylene chain. However, the ester structure thereof easily adsorbs moisture in the air and has a stacked arrangement of polar-polar (dipole-dipole) bonds, so that adhesion is generated between the carbon fiber bundles. In addition, the double bond structure of the acryl group may also generate cross-linking due to a radical reaction, thereby accelerating the hardening of the carbon fiber, so that the carbon fiber is not easily spread during the processing of the composite material, or is easily subjected to problems such as hairiness due to mechanical friction, and the like, thereby reducing the processability of the carbon fiber.
It is known that the hardening of carbon fibers is due to the ring opening of the epoxy resin and the breaking of the double bond structure of the vinyl ester resin, resulting in radical polymerization. For example, the double bond is subjected to sunlight and oxygen to generate radical reaction. After the reaction, a network three-dimensional cross-linking is generated between molecules and is hardened (hardened), thereby causing a reduction in subsequent machinability. Since the radical reaction that has been initiated is a chain reaction, the reaction is always circulated, and therefore, the occurrence of the radical reaction is delayed (or terminated), and the hardening of the carbon fiber can be delayed.
With respect to the hardening of carbon fibers, it is known that the rate is much slower than the double bond radical reaction, since the epoxy system is only affected by the rate of ring opening of the epoxy concentration ([ epoxy ]). Therefore, double bonds are used to determine the hardening factor, wherein K is represented by the Arrhenius reaction rate formula K is A exp (-E/RT), VE is the resin concentration, the resin concentration and the open system oxygen free radical concentration are both set as constants, the acrylic double bond activation energy is 124KJ/mol, the acrylic double bond activation energy is stored at 25 ℃, the reaction speed is increased by 5 times at 10 ℃ per liter, and the test temperature Tt and the accelerated days are 5 [ (Tt-25)/10 ].
In view of the above-mentioned problems of easy moisture absorption, adhesion and hardening with time, the carbon fibers are further degraded in binding force and machinability. Accordingly, the present disclosure provides a sizing for carbon fibers to overcome the above-mentioned problems. The sizing agent of the invention can strengthen the binding force between the carbon fiber and the matrix resin, prevent the carbon fiber from generating filoplume or broken filaments in the processing process, inhibit hardening with time and increase the stability of long-term storage.
The sizing composition of the present disclosure includes a hindered phenol-based agent (D). By adding hindered phenol reagent (D), hydrogen free radical (hydrogen chemical) is provided, and chain reaction generated by oxygen free radical in the process of polymer hardening is blocked. In the process of forming the sizing agent of the present invention, the hindered phenol-based agent (D) generates a relatively stable aromatic oxygen radical, which has a relatively high ability to further trap a reactive radical, and thus, the radical reaction is terminated, and the hardening of the carbon fiber is delayed.
The addition of an inhibitor for trapping radicals (e.g., hindered phenol-based reagent (D)) can delay the radical reaction from occurring. The hindered phenol is a free radical reaction inhibitor, and the action principle of the hindered phenol is shown in the following reaction formula (I): hydroxyl (-OH) on the benzene ring of the hindered phenol is replaced by alkyl with larger space barrier at two sides, and hydrogen (H) atoms of the hindered phenol are easy to fall off from molecules and are further combined with free radicals to stop the chain reaction of the free radicals, thereby achieving the effect of delaying hardening.
The invention provides a sizing agent for carbon fibers, which comprises at least one resin main agent (A) of an epoxy compound, at least one resin main agent (B) of an acrylate compound, a surfactant (C), a hindered phenol agent (D) and the balance of a solvent, wherein the particle size of the sizing agent is between 0.01 and 0.5 mu m. In some embodiments, the content of the resin main agent (B) of the at least one acrylate compound is the same as the content of the surfactant (C).
The resin main agent (a) of the at least one epoxy-based compound of the sizing agent of the present disclosure comprises a bisphenol a-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac epoxy resin, or a combination thereof. In some embodiments, the epoxy equivalent of the resin main agent (A) of the at least one epoxy-based compound is between about 100g/eq and about 1500g/eq, for example, between about 130g/eq and about 1000g/eq, or between about 160g/eq and about 900 g/eq. If the epoxy equivalent is less than about 100g/eq, the degree of hardening of the fiber bundle (e.g., carbon fiber bundle) with time is enhanced. If the epoxy equivalent is more than about 1500g/eq, the bondability to the matrix resin is lowered.
In some embodiments, the resin main agent (a) of the at least one epoxy-based compound is contained in an amount of about 2 to about 30 parts by weight, based on 100 parts by weight of the total weight of the sizing agent. In other embodiments, the resin main agent (a) of the at least one epoxy-based compound is present in an amount of about 10 to about 25 parts by weight, for example, 12.5, 15, 17.5, 20, 22.5 parts by weight. If the content of the resin main agent (a) of the at least one epoxy-based compound is less than 2 parts by weight, the fiber bundle is looser and softer. If the content of the resin main agent (a) of at least one epoxy compound is more than 30 parts by weight, the bondability to the matrix resin may be affected.
The bisphenol A epoxy compound may be a commercially available product, for example, NPEL manufactured by Nanya plastics industriesTM 127、NPELTM 128、NPELTM 134、NPELTM 901、NPELTM 902、NPELTM904; EPON manufactured by HEXION IncTMResin 828、EPONTM Resin 830、EPONTM Resin 834、EPONTMResin 1001F; BE produced by Catharanthus roseus Artificial resin factory CoTM 114、BETM 186、BETM188; and epoxy compounds such as ADEKA Resin EP-4100, ADEKA Resin EP-4300 and ADEKA Resin EP-4700, manufactured by ADEKA corporation.
The bisphenol F-based epoxy compound may be a commercially available product, for example, NPEL manufactured by Nanya plastics industriesTM170; EPON manufactured by HEXION IncTMResin 869; JeR manufactured by Mitsubishi chemical corporationTM 806、jERTM807; BE produced by Catharanthus roseus Artificial resin factory CoTM 170、BETM 235、BETM283, and the like.
The bisphenol S epoxy compound may be a commercially available product, for example, 185S and 300S epoxy compounds produced by Compton.
The novolac epoxy resin may be a commercially available product, for example, NPEL manufactured by south Asia plastics industries, IncTM 630、NPELTM 638、NPELTM640; NPCN from south Asia plastics industriesTM 701、NPCNTM 702、NPCNTM 703、NPCNTM 704、NPCNTM704L; h, HF-series manufactured by Minghua chemical Co., Ltd; PNE manufactured by Vinca Artificial resin works IncTM 171、PNETM 172、PNETM 174、PNETM 175、PNETM 176、PNETM177, etc.
The resin main agent (B) of at least one acrylate compound of the sizing agent of the present invention contains an acrylate having an oxyalkylene group in a molecule, a methacrylate having an oxyalkylene group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkylene group in a molecule, or a combination thereof.
In some embodiments, the resin main agent (B) of the at least one acrylate compound is contained in an amount of about 2 to about 30 parts by weight, based on 100 parts by weight of the total weight of the sizing agent. In yet other embodiments, the resin main agent (B) of the at least one acrylate compound is present in an amount of about 10 to about 25 parts by weight, for example, 12.5, 15, 17.5, 20, 22.5 parts by weight. If the content of the resin main agent (B) of at least one acrylate compound is less than 2 parts by weight, the bondability to the matrix resin is affected. If the content of the resin main agent (B) of the at least one acrylate compound is more than 30 parts by weight, the fiber bundle may be less easily bundled or too soft.
The resin main agent (B) of at least one acrylate compound may be a commercially available product, for example, QualiCure manufactured by national chemical CoTM GM62S70、QualiCureTM GM62V20、QualiCureTM GM62V40、QualiCureTMAcrylate compounds such as GM62V 60.
The surfactant (C) of the sizing agent of the present disclosure comprises a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a combination thereof. In some embodiments, the nonionic surfactant may be used in combination with one of an anionic surfactant or a cationic surfactant.
In some embodiments, the surfactant (C) is present in an amount of about 0.5 to about 15 parts by weight, based on 100 parts by weight of the total weight of the sizing agent. In yet other embodiments, the surfactant (C) is present in an amount of about 5 to about 12.5 parts by weight, for example, 6.5, 8, 9.5, 11 parts by weight. If the content of the surfactant (C) is less than 0.5 parts by weight, no emulsification effect is obtained. If the content of the surfactant (C) is more than 15 parts by weight, the processability of the fiber bundle may be reduced.
The nonionic surfactant may be, for example, an aliphatic nonionic surfactant or an aromatic nonionic surfactant. The aliphatic nonionic surfactant can be, for example, a higher alcohol ethylene oxide additive, a polyhydric alcohol polyoxyethylene ether, a C16-C18 alcohol polyoxyethylene ether, an alkyl polyoxyethylene ether, a polyethylene glycol fatty acid ester, or the like. The aromatic nonionic surfactant may be, for example, polyethylene glycol octyl phenyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol bisphenol a derivative, or the like.
The anionic surfactant may be, for example, a sulfate, a sulfonate, a phosphate, or the like. Examples of the sulfate ester include higher alcohol sulfate ester salts, higher alkyl polyethylene glycol ether sulfate ester salts, and polycyclic phenyl ether polyethylene glycol ether sulfate ester salts. Examples of the sulfonate include alkylbenzenesulfonate, polycyclic phenyl ether sulfonate, alkylsulfonate, and dialkylsulfosuccinate. Examples of the phosphate salts include polyethylene glycol nonylphenyl phosphate, polyoxyethylene alkylphenyl ether phosphate triethanolamine salt, and polyethylene glycol styrenated aryl ether phosphate.
The cationic surfactant may, for example, be quaternary ammonium salts, such as alkyldimethylbenzyl quaternary ammonium salts, alkyltrimethyl quaternary ammonium salts, dialkyldimethyl quaternary ammonium salts, ester quaternary ammonium salts, imidazoline quaternary ammonium salts, and the like.
The hindered phenolic agent (D) of the sizing agent of the present disclosure may have a structural formula represented by formula (II), wherein R is a long carbon chain ester.
The hindered phenol agent (D) may be a commercially available one, for example, produced by Everlight Chemical
101, a first electrode and a second electrode; AO-1135 or XP-690. In particular, the method of manufacturing a semiconductor device,
101 has a structural formula represented by formula (II-1), wherein n is between 7 and 9. AO-1135 has a structural formula represented by the formula (II-2).
In detail, hydroxyl (-OH) groups on the benzene ring of hindered phenols are substituted by alkyl groups having large steric hindrance on both sides, so that hydrogen (H) atoms are easily dropped from the molecule, and further bond with radicals to terminate the chain reaction of the radicals, thereby achieving the effect of delaying hardening.
In some embodiments, hindered phenolic agent (D) is present in an amount of about 0.01 to about 0.5 parts by weight, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 parts by weight, based on 100 parts by weight of the total sizing agent. In yet other embodiments, the hindered phenolic agent (D) is present in an amount of about 0.05 to about 0.1 parts by weight, for example, 0.06, 0.07, 0.08, 0.09 parts by weight. If the content of the hindered phenol agent (D) is less than 0.01 part by weight, the radical chain reaction is not easily terminated, and thus the effect of delaying the hardening of the carbon fiber is not exhibited. If the content of the hindered phenol agent (D) is more than 0.5 parts by weight, there is no beneficial effect in delaying the hardening of the carbon fiber.
The solvent of the sizing agent of the present disclosure may be deionized water. In some embodiments, the solvent of the sizing agent is present in an amount of about 25 to about 95.5 parts by weight, for example, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 parts by weight. In some embodiments, the sizing of the present invention is applied to the carbon fibers in the form of a dispersion dispersed in water, without any organic solvent.
The device for preparing the sizing agent of the invention utilizes mechanical shearing force to prepare the emulsion type uniformly dispersed carbon fiber sizing agent. In some embodiments, the device may be a paddle-type stirring blade, wherein the blade shape may be a dissolving type, a trilobe type, or a quadralobe type. In yet other embodiments, the device is fitted with anchor type stirring blades. In some embodiments, the carbon fiber sizing agent can be prepared using a sonicator homogenizer, a high speed emulsifier, or the like.
The sizing agent of the present disclosure is an aqueous solution that is self-emulsified and/or emulsion-dispersed in water, and has an average particle size of less than 1 μm, for example, between about 0.01 and about 0.5 μm, such as 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 μm. When the average particle diameter is larger than 1 μm, the sizing agent may not be uniformly attached to the carbon fiber, and the free energy of the particles may be insufficient to undergo brownian motion to cause sedimentation, and thus, the storage stability is poor.
< analysis of particle size of sizing agent >
The average particle size of the sizing agent is measured according to the laser light scattering principle. When laser light is irradiated to a particle solution, the particles in the solution scatter the laser light, and the degree of scattering of the laser light varies depending on the degree of brownian motion of the particles having different sizes, and the size and size distribution of the mass are calculated. In some embodiments of the present disclosure, the average particle size of the sizing agent is measured using a Brookhaven Nanobrook Omni instrument.
< sizing agent for carbon fiber >
The sizing agent of the invention is used for sizing the surface of the carbon fiber in an impregnation mode. Carbon fibers TC35R-24K (24000 single fibers with the strength of about 4000MPa and the modulus of 240GPa) without sizing agent are soaked in a soaking tank filled with sizing agent, and then are subjected to heat drying treatment at the temperature of about 100-250 ℃ for about 2-10 minutes. If the temperature is lower than 100 ℃, the water cannot be completely evaporated. If the temperature is higher than 250 ℃, the sizing agent may cause thermal reaction to cause deterioration. The heat drying method may be hot air, hot roller contact, infrared ray, or 2 or 3 of the above materials, and collecting into roll.
The emulsion type carbon fiber sizing agent can be used in a carbon fiber composite material as an interface layer for connecting carbon fibers and matrix resin. In some embodiments, the weight of the sizing agent relative to the weight of the carbon fiber is about 0.1 to about 5 weight percent, for example, about 0.5 to about 3 weight percent, such as 1, 1.5, 2, 2.5 weight percent. If the sizing amount is less than 0.1 wt%, the sizing agent cannot provide good bundling property of the carbon fibers, interfacial bonding force with the matrix resin, and abrasion resistance. If the sizing amount exceeds 5 weight percent, the carbon fiber is not easy to unfold, so that the subsequent composite material is not easy to unfold.
< evaluation of carbon fiber sizing >
Weighing the carbon fiber bundle which is 1 meter (m) long and is treated by the sizing agent, weighing the carbon fiber bundle, weighing the weight W1, putting the carbon fiber bundle in an oven at the temperature of about 400 ℃, burning out the sizing agent, taking out the carbon fiber bundle after about 40 minutes, weighing the weight W2 after the carbon fiber bundle is cooled for about 10 minutes, and weighing the carbon fiber bundle with the sizing rate of (W2-W1)/W1 x 100%. In some embodiments, the carbon fiber sizing rate is about 0.1 to about 5 weight percent, for example, about 0.5 to about 3 weight percent. It should be noted that the sizing ratio of the comparative examples and examples 1 to 5 herein was fixed at 1.0. + -. 0.2% by weight.
< evaluation of moisture absorption Rate of sizing agent >
A carbon fiber bundle (fiber bundle 1) having a length of 5 centimeters (cm) and not treated with a sizing agent was weighed to obtain a weight W3. Then, 5 cm of the carbon fiber bundle (fiber bundle 2) treated with the sizing agent was weighed to obtain a front weight W4. Fiber bundle 1 and fiber bundle 2 were placed in a constant temperature and humidity environment cabinet at about 70 ℃ and a humidity of about 85% RH, and after at least 35 days, the rear weight W5 of fiber bundle 1 and the rear weight W6 of fiber bundle 2 were weighed. The moisture absorption rate of the sizing agent is [ (W6-W4) - (W5-W3) ]/W4 is 100%. In some embodiments, the sizing agent has a moisture absorption of less than about 0.05%, e.g., 0.01, 0.02, 0.03, 0.04%.
< detection of carbon fiber hairiness >
Referring to fig. 1, fig. 1 is a schematic view of an apparatus 100 for detecting carbon fiber hairiness. The carbon fiber bundle 110 treated by sizing agent with the length of 100 meters is taken and rubbed by 7 metal rollers 120 (without transmission and special surface treatment) under the tension of 600cN, and a spongy cushion 130 is arranged behind the metal rollers 120 to collect the hair feather generated by the abrasion of the carbon fiber bundle 110. Finally, the hairs were dried at a temperature of about 105 ℃ for about 40 minutes and weighed (unit: mg).
< measurement of carbon fiber hardness >
Please refer to fig. 2A and 2B, which are schematic diagrams of an apparatus 200 for detecting hardness of carbon fiber. In detail, fig. 2A is a schematic diagram before the carbon fiber bundle applies a force by the force application source 210, and fig. 2B is a schematic diagram before the carbon fiber bundle applies a force by the force application source 210. The carbon fiber bundle 110 treated with the sizing agent is laid on the platform 220 with the gap 230, the force source 210 applies a force to bend the carbon fiber bundle 110, and the force required when the carbon fiber bundle is pressed down to a fixed depth is the carbon fiber hardness (unit: g). The gap 230 of the apparatus for measuring the hardness of carbon fiber according to the present invention is about 5 millimeters (mm).
< detection of change of carbon fiber with time >
The carbon fiber bundle is placed in a constant-temperature constant-humidity environment box with the temperature of about 70 ℃ and the humidity of about 85% RH for accelerated hardening, and the carbon fiber bundle is taken out for carbon fiber hairiness detection and carbon fiber hardness detection every 1 day, 3 days, 7 days and 14 days.
< preparation of sizing agent for comparative example >
After uniformly mixing the resin main agent (a) of at least one epoxy compound, the resin main agent (B) of at least one acrylate compound, and the surfactant (C) at a temperature higher than the melting points of the resin main agent (a) and the resin main agent (B) with an IKA stirrer, the mixed state was cooled to the cloud point temperature of the surfactant (C), and then, 6 hours of water was dropped at a rotation speed of about 5000 to about 10000rpm, whereby a uniformly emulsified and dispersed solution, that is, a sizing agent of a comparative example was obtained. The sizing agents of the comparative examples had particle sizes (Dv 50; nm) of between about 0.01 and about 0.5 μm. The melting point temperature of the resin main agent (A) and the resin main agent (B) is between about 60 ℃ and about 95 ℃. The surfactant (C) has a cloud point temperature of from about 60 ℃ to about 70 ℃.
< preparation of example sizing agent >
The sizing agent of example (example 1 to example 5) can be obtained by uniformly mixing the resin main agent (a) of at least one epoxy compound, the resin main agent (B) of at least one acrylate compound, and the surfactant (C) at a temperature higher than the melting points of the resin main agent (a) and the resin main agent (B) with an IKA stirrer, then cooling the mixture to the cloud point temperature of the surfactant (C), then dripping at a rotation speed of about 5000 to about 10000rpm for 6 hours to obtain a uniformly dispersed solution, and finally adding the hindered phenol-based agent (D). The particle size (Dv 50; nm) of the sizing agents of the examples was between about 0.01 to about 0.5 μm. The melting point temperature of the resin main agent (A) and the resin main agent (B) is between about 60 ℃ and about 95 ℃. The surfactant (C) has a cloud point temperature of from about 60 ℃ to about 70 ℃.
In some alternative embodiments, the hindered phenol-based agent (D) may be mixed with the resin main agent (a), the resin main agent (B), and the surfactant (C) at the same time, and then the same operation as described above may be performed to form the sizing agent of the example.
Experimental example: evaluation of carbon fiber hardness and carbon fiber change with time
The sizing agents of the comparative examples and the sizing agents of examples 1 to 5 were prepared according to the formulation of the composition of table one below, referring to the formulations of the sizing agents of the comparative examples and examples described above.
Watch 1
| Comparative example | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| A (％) | 30 | 29.995 | 29.975 | 29.95 | 29.9 | 29.75 |
| B(％) | 15 | 14.9975 | 14.9875 | 14.975 | 14.95 | 14.875 |
| C(％) | 15 | 14.9975 | 14.9875 | 14.975 | 14.95 | 14.875 |
| D(％) | 0 | 0.01 | 0.05 | 0.1 | 0.2 | 0.5 |
| Water (%) | 40 | 40 | 40 | 40 | 40 | 40 |
According to the sizing agent in the first table, the carbon fiber hardness test and the carbon fiber time-dependent change test are carried out, and the test results are shown in the second table. As is clear from table two, the application of the sizing agent containing the hindered phenol-based agent (D) to the carbon fibers reduced the amount of hairiness of the carbon fibers and also improved the hardness of the carbon fibers, as compared with the comparative examples.
For example, the amount of hairiness of examples 1 to 5 was smaller than that of comparative example on days 7 and 14 over time. In detail, the increase in the hairiness of examples 1 to 5 was smaller than that of the comparative example. In addition, the carbon fiber hardness change amount of examples 1 to 5 was also smaller than that of the comparative example in the elapsed days test.
In detail, please refer to table two below. In the comparative example, the hardness of the carbon fiber on the 0 th day of elapsed time was about 13g, while the hardness of the carbon fiber on the 14 th day of elapsed time was about 39g, which was an increase in the hardness of about 200%. In examples 2 to 5, the hardness of the carbon fiber on the 0 th day of elapsed time was about 13g, while the hardness of the carbon fiber on the 14 th day of elapsed time was about 26g, which was increased by about 100%.
Watch two
The sizing agent of the present invention contains hindered phenol-based agent (D), and thus solves the problems of hygroscopicity and tackiness of the originally sized carbon fiber, thereby suppressing the problem of hardening with time and achieving the effect of prolonging the hardening time of the carbon fiber bundle. The sizing agent of the invention can strengthen the binding force between the carbon fiber and the matrix resin, prevent the carbon fiber from generating hairiness or broken filaments in the processing process, inhibit hardening with time, and prevent the reduction of the machinability.
Although the present disclosure has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present disclosure.
[ notation ] to show
100 device for detecting carbon fiber hairiness
110 carbon fiber bundle
120 metal roller
130 sponge cushion
200 device for detecting hardness of carbon fiber
210 force source
220 platform
And 230, clearance.
Claims (10)
1. A sizing agent for carbon fibers, comprising:
a resin main agent (A) of at least one epoxy compound in an amount of 2 to 30 parts by weight;
at least one resin main agent (B) of an acrylate compound in an amount of 2 to 30 parts by weight;
0.5 to 15 parts by weight of a surfactant (C);
0.01 to 0.5 parts by weight of a hindered phenol-based agent (D); and
the balance of solvent, wherein the particle size of the sizing agent is between 0.01 and 0.5 μm.
2. The sizing agent according to claim 1, wherein the resin main agent (a) of the at least one epoxy-based compound comprises a bisphenol a-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac epoxy resin, or a combination thereof.
3. The sizing agent according to claim 1, wherein the resin main agent (a) of the at least one epoxy-based compound accounts for 10 to 25 parts by weight.
4. The sizing agent according to claim 1, wherein the resin main agent (B) of the at least one acrylate compound comprises an acrylate having an oxyalkylene group in a molecule, a methacrylate having an oxyalkylene group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkylene group in a molecule, or a combination thereof.
5. The sizing agent according to claim 1, wherein the resin main agent (B) of the at least one acrylate compound accounts for 10 to 25 parts by weight.
6. The sizing agent according to claim 1, wherein the surfactant (C) comprises a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a combination thereof.
7. The sizing agent according to claim 1, wherein the surfactant (C) is 5 to 12.5 parts by weight.
8. The sizing agent according to claim 1, wherein the hindered phenol-based agent (D) is contained in an amount of 0.05 to 0.1 parts by weight.
9. A carbon fiber to which the sizing agent according to claim 1 is applied, characterized in that the sizing ratio of the carbon fiber is between 0.1 and 5 weight percent.
10. A carbon fiber to which the sizing agent according to claim 1 is applied, characterized in that the hardness of the carbon fiber increases by less than 100% as measured by a change over time of 14 days.
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| TW110131956A TWI784693B (en) | 2021-08-27 | 2021-08-27 | Sizing agent for carbon fiber |
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| US20230093719A1 (en) | 2023-03-23 |
| TW202309370A (en) | 2023-03-01 |
| EP4141168A1 (en) | 2023-03-01 |
| JP2023033242A (en) | 2023-03-09 |
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