CN114263043B - Sizing agent for carbon fibers - Google Patents
Sizing agent for carbon fibers Download PDFInfo
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- CN114263043B CN114263043B CN202210064600.9A CN202210064600A CN114263043B CN 114263043 B CN114263043 B CN 114263043B CN 202210064600 A CN202210064600 A CN 202210064600A CN 114263043 B CN114263043 B CN 114263043B
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- sizing agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 136
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 121
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 121
- 238000004513 sizing Methods 0.000 title claims abstract description 95
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000004593 Epoxy Substances 0.000 claims abstract description 37
- -1 acrylate compound Chemical class 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 11
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 206010020112 Hirsutism Diseases 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 10
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- 150000003254 radicals Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 238000007348 radical reaction Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
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- 241000863480 Vinca Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- UUIPAJHTKDSSOK-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)(O)=O UUIPAJHTKDSSOK-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NHFDKKSSQWCEES-UHFFFAOYSA-N dihydrogen phosphate;tris(2-hydroxyethyl)azanium Chemical compound OP(O)(O)=O.OCCN(CCO)CCO NHFDKKSSQWCEES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000011899 heat drying method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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
- 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
- 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
- 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 comprising 2 to 30 parts by weight of at least one epoxy compound resin main agent (a), 2 to 30 parts by weight of at least one acrylate compound resin main agent (B), 0.5 to 15 parts by weight of a surfactant (C) and 0.01 to 0.5 parts by weight of a hindered phenol agent (D), wherein the sizing agent has a particle diameter of 0.01 to 0.5 μm. The sizing agent of the invention, because of containing the hindered phenol reagent (D), suppresses the problem of hardening with time and achieves the effect of prolonging the hardening time of the carbon fiber bundles. 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 wires in the processing process and inhibit the hardening with time, thereby preventing the decrease of the mechanical processing property.
Description
Technical Field
The present invention relates to a sizing agent for carbon fibers, and more particularly, to a sizing agent capable of prolonging the hardening time of carbon fiber bundles.
Background
Carbon fiber is an important reinforcing material, and is widely used in various fields. Carbon fibers can be used to enhance material properties due to their high specific strength, specific modulus, high temperature resistance, chemical resistance, low coefficient of friction, good electrical conductivity, and the like. The carbon fiber composite material can be applied to various fields, such as aviation, aerospace, sports goods, civil construction, electronic products, medical appliances, and the like.
However, the processability of the carbon fiber is affected by the low elongation and brittleness of the carbon fiber. In the process of processing the carbon fiber, hairiness or broken filaments are generated due to mechanical friction, so that the strength of the carbon fiber is reduced. Carbon fiber hardness is one of factors affecting hairiness or broken filaments due to mechanical friction during processing. The higher the hardness of the carbon fiber, the more easily the carbon fiber is subjected to 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 foregoing problems.
Disclosure of Invention
The present invention provides a sizing agent for carbon fibers, comprising 2 to 30 parts by weight of at least one epoxy compound resin main agent (a), 2 to 30 parts by weight of at least one acrylate compound resin main agent (B), 0.5 to 15 parts by weight of a surfactant (C), and 0.01 to 0.5 parts by weight of a hindered phenol agent (D), wherein the sizing agent has a particle diameter of 0.01 to 0.5 μm.
In some embodiments, the resin host (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 phenolic epoxy resin, or a combination thereof.
In some embodiments, the resin main agent (a) of the at least one epoxy-based compound is 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 within a molecule, a methacrylate having an oxyalkylene group within a molecule, an acrylate having no oxyalkylene group within a molecule, a methacrylate having no oxyalkylene group within a molecule, or a combination thereof.
In some embodiments, the resin main agent (B) of the 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, the hindered phenolic agent (D) comprises 0.05 to 0.1 parts by weight.
The invention provides a carbon fiber with the sizing agent, wherein the sizing agent rate of the carbon fiber is between 0.1 and 5 weight percent.
The present disclosure provides a carbon fiber having less than 100% increase in stiffness after 14 days of time-varying testing by applying a sizing agent as described above.
The following description will make detailed description of the above embodiments, and provide further explanation of the technical solutions of the present disclosure.
Drawings
The detailed description of the present disclosure will be fully understood when read in conjunction with the accompanying drawings. It should be noted that, in accordance with industry standard practice, the features are not drawn to scale and are for illustration purposes only. In fact, the dimensions of the various features may be arbitrarily increased or decreased for clarity of discussion.
Fig. 1 is a schematic diagram of an apparatus for detecting hairiness of carbon fibers according to some embodiments of the present disclosure.
Fig. 2A and 2B are schematic diagrams of an apparatus for detecting hardness of carbon fibers according to some embodiments of the present disclosure.
Detailed Description
In this document, a range from "one value to another value" is a shorthand way of referring individually to all the values in the range, which are avoided in the specification. Thus, recitation of a particular numerical range includes any numerical value within that range, as well as the smaller numerical range bounded by any numerical value within that range, as if the any numerical value and the smaller numerical range were written in the specification in the clear.
As used herein, "about," "approximately," "essentially," or "substantially" includes both the values and average values within an acceptable deviation of the particular values determined by those of skill in the art, taking into account the particular number of measurements and errors associated with the measurements (i.e., limitations of the measurement system) in question. For example, "about" may mean within one or more standard deviations of the stated values, or within, for example, ±30%, ±20%, ±15%, ±10%, ±5%. Further, as used herein, "about," "approximately," "essentially," or "substantially" may be used to select a more acceptable deviation range or standard deviation based on measured, coated, or other properties, and not one standard deviation may be used for all properties.
In order to enable the carbon fiber to exert its original good performance and at the same time avoid reducing the processability of the carbon fiber, a sizing agent (sizing agent) may be applied to the carbon fiber (carbon fiber) so that the carbon fiber reduces the occurrence of hairiness or broken filaments due to mechanical friction during the processing, thereby having good processability. By means of the sizing agent, the processability and 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) Bundling, the carbon fiber can be collected into a roll, and the roll is easy to store and transport, and the carbon fiber can be orderly arranged and operated during the manufacturing and processing of the composite material. (2) The carbon fiber is protected, and the mechanical friction hairiness or broken wire of the carbon fiber generated during processing is reduced. (3) As an interface coupling agent between the carbon fiber and the resin, the problem of poor impregnation of the carbon fiber and the resin is solved.
In general, the main component of the sizing agent contains epoxy resin, because the epoxy resin has good film forming property, a strong and firm film can be formed on the surface of the fiber, the effect of protecting the carbon fiber is achieved, and most of composite matrix resins are epoxy resin systems.
The epoxy resin has reactive epoxy functional groups, so that the epoxy resin can be mutually reacted and bonded with different types of hardening agents (such as amine or anhydride functional groups) under the action of a proper catalyst to form a three-dimensional network structure. Epoxy resins are excellent thermosets. In some embodiments, bisphenol a epoxy resin may be utilized as the primary component of the sizing agent.
The conventional sizing agent composition contains an epoxy resin, an acrylate (and/or methacrylate), and a polyester resin having a bisphenol a skeleton and a polyoxyethylene chain. However, the ester structure thereof is liable to adsorb moisture in the air and has a polar-polar (dipole-dipole) bond stacking arrangement, so that tackiness is generated between carbon fiber bundles. In addition, the double bond structure of the acryl group may be crosslinked by radical reaction, thereby accelerating the hardening of the carbon fiber, making the carbon fiber difficult to spread yarn during the composite processing, or easily causing the problems of Cheng Maoyu due to mechanical friction, etc., thus 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 cleavage of the double bond structure of the vinyl ester resin, resulting in free radical polymerization. For example, double bonds undergo radical reactions by sunlight and oxygen. After the reaction, network three-dimensional crosslinking is generated between molecules to be hard (hardened), so that the subsequent machinability is reduced. Since the initiated radical reaction is a chain reaction, the reaction is circulated all the time, and thus, the occurrence of the radical reaction is delayed (or terminated), and the hardening of the carbon fiber can be delayed.
Regarding the hardening of carbon fibers, it has been known that the rate of ring opening is much slower than the double bond radical reaction due to the epoxy concentration ([ epoxy ]) only ring opening rate effect of the epoxy system. The hardening factor is determined by the double bond, the reaction rate=kve ] [ oxygen radical ], where K is exp (-E/RT) with the apriniz reaction rate formula k=a, VE is the resin concentration, both the resin concentration and the open system oxygen radical concentration are set to be constant, the activation energy of the acrylic double bond is 124KJ/mol, stored at 25 ℃, the reaction rate increases 5 times per 10 ℃ increase, the test temperature Tt and the number of days of acceleration are 5 [ (Tt-25)/10 ].
In view of the problems that the sized carbon fibers are liable to absorb moisture and cause tackiness and hardening with time, the bonding force and mechanical workability of the carbon fibers are further lowered. Accordingly, the present disclosure provides a sizing for carbon fibers to overcome the above-described 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 hairiness or broken filaments in the processing process, inhibit the hardening with time and increase the stability of long-term storage.
The sizing composition of the present disclosure comprises a hindered phenolic agent (D). By adding the hindered phenol reagent (D), a hydrogen radical (hydrogen radical) is supplied, and a chain reaction generated by oxygen radicals during the curing process of the polymer is blocked. In the process of forming the sizing agent, the hindered phenol reagent (D) generates more stable aromatic oxygen free radicals, and the aromatic oxygen free radicals have the capability of further capturing active free radicals, so that the free radical reaction can be stopped, and the hardening of the carbon fiber can be delayed.
The addition of an inhibitor that traps free radicals (e.g., hindered phenolic agent (D)) can delay the free radical reaction from occurring. The hindered phenols are free radical reaction inhibitors, please refer to the following reaction formula (I), and the action principle is as follows: the hydroxyl (-OH) on benzene ring of hindered phenols is replaced by alkyl with larger steric hindrance at two sides, so that hydrogen (H) atoms are easier to fall off from molecules, and are further combined with free radicals to terminate free radical chain reaction, thereby achieving the effect of deferring 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 reagent (D) and the balance of 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 component (a) of at least one epoxy-based compound of the sizing agent of the present disclosure contains bisphenol a-based epoxy compound, bisphenol F-based epoxy compound, bisphenol S-based epoxy compound, novolac epoxy resin, or a combination thereof. In some embodiments, the epoxy equivalent of the resin main agent (a) of 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 bundles (e.g., carbon fiber bundles) with time is reinforced. If the epoxy equivalent is more than about 1500g/eq, the bonding with the matrix resin is reduced.
In some embodiments, the at least one epoxy-based compound resin main agent (a) 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 content of the resin main agent (a) of the at least one epoxy-based compound is 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 at least one epoxy-based compound is less than 2 parts by weight, the fiber bundles may be loose and soft. If the content of the resin main agent (a) of at least one epoxy compound is more than 30 parts by weight, the bonding with the matrix resin may be affected.
Bisphenol A type epoxy compounds are commercially available, for example NPEL produced by Nanya plastics industry Co TM 127、NPEL TM 128、NPEL TM 134、NPEL TM 901、NPEL TM 902、NPEL TM 904; EPON manufactured by hexin corporation TM Resin 828、EPON TM Resin 830、EPON TM Resin834、EPON TM Resin 1001F; BE produced by vinca resin works TM 114、BE TM 186、BE TM 188; an epoxy compound such as ADEKAResin EP-4100, ADEKA Resin EP-4300, and ADEKA Resin EP-4700, both manufactured by ADEKA Co.
Bisphenol F type epoxy compounds are commercially available, for example NPEL produced by Nanya plastics industry Co TM 170, a step of; EPON manufactured by hexin corporation TM Resin 869; jER produced by mitsubishi chemical company TM 806、jER TM 807; BE produced by vinca resin works TM 170、BE TM 235、BE TM 283, and the like.
Bisphenol S type epoxy compounds are commercially available, for example, 185S and 300S epoxy compounds produced by Compton.
The phenolic epoxy resin may be commercially available, for example NPEL manufactured by Nanya plastics industry Co TM 630、NPEL TM 638、NPEL TM 640, a base; NPCN produced by Nanya plastics industry Co TM 701、NPCN TM 702、NPCN TM 703、NPCN TM 704、NPCN TM 704L; h, HF-series from Ming He Cheng Co., ltd; PNE produced by vinca resin works TM 171、PNE TM 172、PNE TM 174、PNE TM 175、PNE TM 176、PNE TM 177, and the like.
The resin main component (B) of at least one acrylate compound of the sizing agent of the present disclosure contains an acrylate having an oxyalkylene group in a molecule, a methacrylate having an oxyalkylene group in a molecule, an acrylate having an oxyalkylene group in a molecule, a methacrylate having an oxyalkyl group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkylene group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkyl 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 host (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 bonding with the matrix resin is affected. If the content of the resin main agent (B) of at least one acrylate compound is more than 30 parts by weight, the fiber bundles may be less likely to be bundled or too soft.
The resin main component (B) of at least one acrylic acid ester compound may be commercially available, for example, qualliCure produced by national chemical Co TM GM62S70、QualiCure TM GM62V20、QualiCure TM GM62V40、QualiCure TM GM62V60, etc.
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, e.g., 6.5, 8, 9.5, 11 parts by weight. If the content of the surfactant (C) is less than 0.5 parts by weight, the effect of emulsification is not exhibited. If the content of the surfactant (C) is more than 15 parts by weight, the processability of the fiber bundle is lowered.
The nonionic surfactant may be, for example, an aliphatic nonionic surfactant or an aromatic nonionic surfactant. The aliphatic nonionic surfactant may 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 octylphenyl ether, polyethylene glycol nonylphenyl ether, polyethylene glycol bisphenol a derivative, or the like.
The anionic surfactant may be, for example, a sulfate, sulfonate or phosphate. Examples of the sulfate include higher alcohol sulfate, higher alkyl polyglycol ether sulfate, and polycyclic phenyl ether polyglycol ether sulfate. Examples of the sulfonates include alkylbenzene sulfonate, polycyclic phenyl ether sulfonate, alkyl sulfonate, 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 be, for example, quaternary ammonium salts such as alkyl dimethyl benzene quaternary ammonium salt, alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, ester quaternary ammonium salt, imidazoline quaternary ammonium salt, and the like.
The hindered phenolic reagent (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 reagent (D) may be commercially available, for example, produced by Everlight Chemical101; AO-1135 or XP-690. Specifically, the->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 formula (II-2).
In detail, the hydroxyl (-OH) on benzene ring of hindered phenols is replaced by alkyl with larger space obstacle at two sides, so that hydrogen (H) atoms are easier to fall off from molecules, and are further combined with free radicals to terminate free radical chain reaction, thereby achieving the effect of deferring hardening.
In some embodiments, the hindered phenolic agent (D) is present in an amount of about 0.01 to about 0.5 parts by weight, e.g., 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 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 reagent (D) is less than 0.01 parts 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 type 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 sizing agent has a solvent content 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 agent of the present invention is applied to the carbon fibers in the form of a dispersion that is dispersed in water, without any organic solvent.
The sizing agent device for preparing the sizing agent of the invention utilizes mechanical shearing force to prepare 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, trilobal, or quadrulobal shape. In yet other embodiments, the device is equipped with anchor stirring vanes. In some embodiments, the carbon fiber sizing agent may be prepared using a device such as an ultrasonic break up homogenizer, a high speed emulsifier, or the like.
The sizing agent of the present disclosure is an aqueous solution self-emulsifying and/or emulsifying dispersed in water, the sizing agent having an average particle size of less than 1 μm, for example, between about 0.01 to 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. Mu.m, the sizing agent may not be uniformly adhered to the carbon fiber, and the free energy of the particles may be insufficient to perform Brownian movement to cause sedimentation, and thus the storage stability may be poor.
< analysis of particle size of sizing agent >
The average particle size of the sizing agent is measured according to the principle of laser light scattering. When laser light irradiates the particle solution, particles in the solution scatter the laser light, and the degree of scattering of the laser light is different due to the different Brownian motion degrees of the particles with different sizes, so that collective size and size distribution are calculated. In some embodiments of the present disclosure, the sizing agent average particle size is measured using a Brookhaven Nanobrook Omni instrument.
< sizing agent for carbon fiber application >
The sizing agent of the invention is used for sizing the surface of the carbon fiber in an impregnation mode. Carbon fibers TC35R-24K (TARIFIL, manufactured by Taiwan plastics industry, china) without sizing agent, which are 24000 single-bundle fibers, the strength of the single-bundle fibers is about 4000MPa, and the modulus of the single-bundle fibers is 240GPa, are immersed in an immersion 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 moisture cannot be completely evaporated. Above 250 ℃, the sizing agent reacts thermally and causes deterioration. The heat drying method can be suitably selected from hot air method, hot roller contact method, infrared ray, etc., or 2 or 3 of the above materials can be used together and collected 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 sizing agent is about 0.1 to about 5 weight percent relative to the weight of the carbon fibers, 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 properties of carbon fibers, interfacial bonding force with matrix resin, and abrasion resistance. If the sizing amount exceeds 5 wt%, the carbon fiber is not easy to spread, so that the yarn is not easy to spread in the subsequent composite material processing and forming.
< evaluation of carbon fiber sizing Rate >
Taking a carbon fiber bundle with the length of 1 meter (m) and treated by the sizing agent, weighing the weight W1, placing the carbon fiber bundle in an oven at about 400 ℃ to burn out the sizing agent, taking out the carbon fiber bundle after about 40 minutes, and weighing the weight W2 of the carbon fiber bundle after about 10 minutes of temperature return, wherein the sizing rate of the carbon fiber bundle is (W2-W1)/W1 is 100 percent. In some embodiments, the carbon fiber sizing is from about 0.1 to about 5 wt%, for example, from about 0.5 to about 3 wt%. The sizing ratios of the comparative examples and examples 1 to 5 herein were fixed at 1.0±0.2 wt%.
< evaluation of moisture absorption Rate of sizing agent >
The carbon fiber bundles (bundles 1) having a length of 5 centimeters (cm) and not treated with the sizing agent were weighed by weight W3. Then, 5 cm of the sizing agent-treated carbon fiber bundle (fiber bundle 2) was taken, and the front weight W4 was weighed. The fiber bundles 1 and 2 were placed in a constant temperature and humidity environment box at about 70 ℃ and a humidity of about 85% RH, and after at least 35 days, the rear weight W5 of the fiber bundle 1 and the rear weight W6 of the fiber bundle 2 were weighed. The sizing agent moisture absorption% = [ (W6-W4) - (W5-W3) ]/W4 ×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%.
< carbon fiber hairiness detection >
Referring to fig. 1, fig. 1 is a schematic diagram of an apparatus 100 for detecting hairiness of carbon fibers. The carbon fiber bundle 110 with the length of 100 meters and treated by the sizing agent is rubbed by 7 metal rollers 120 (without transmission and special surface treatment) under the tension of 600cN, and a foam cushion 130 is arranged behind the metal rollers 120 to collect hairiness generated by abrasion of the carbon fiber bundle 110. Finally, the hairiness was dried at a temperature of about 105℃for about 40 minutes, and the hairiness was weighed (unit: mg).
< carbon fiber hardness detection >
Referring to fig. 2A and 2B, an apparatus 200 for detecting hardness of carbon fibers is shown. In detail, fig. 2A is a schematic diagram of the carbon fiber bundle before the carbon fiber bundle is applied by the force application source 210, and fig. 2B is a schematic diagram of the carbon fiber bundle after the carbon fiber bundle is applied by the force application source 210. The carbon fiber bundles 110 treated by the sizing agent are laid on a platform 220 with a gap 230, and the force required by the force application source 210 for bending the carbon fiber bundles 110 and pressing down to a fixed depth is the carbon fiber hardness (unit: g). The gap 230 of the apparatus for measuring hardness of carbon fiber of the present invention is about 5 millimeters (mm).
< detection of carbon fiber aging >
The carbon fiber bundles were placed in a constant temperature and humidity environment box at about 70 ℃ and a humidity of about 85% RH, and hardened at a rapid rate, and the carbon fiber bundles were taken out every 1 day, 3 days, 7 days, and 14 days for carbon fiber hairiness detection and carbon fiber hardness detection.
< preparation of comparative sizing agent >
At least one epoxy compound resin main agent (A), at least one acrylic ester compound resin main agent (B) and a surfactant (C) are uniformly mixed by an IKA mixer at a temperature higher than the melting point of the resin main agent (A) and the resin main agent (B), the mixed state is cooled to the cloud point temperature of the surfactant (C), and then water is dropped at a rotating speed of about 5000 to about 10000rpm for 6 hours, so that a uniformly dispersed emulsion solution, namely the sizing agent of the comparative example, can be obtained. The particle size (Dv 50; nm) of the sizing agent of the comparative example was between about 0.01 and about 0.5. Mu.m. The melting point temperatures of the resin main agent (A) and the resin main agent (B) are between about 60 ℃ and about 95 ℃. The cloud point temperature of the surfactant (C) is between about 60 ℃ and about 70 ℃.
< preparation of sizing agent >
Uniformly mixing at least one epoxy compound resin main agent (A), at least one acrylate compound resin main agent (B) and a surfactant (C) at a temperature higher than the melting point of the resin main agent (A) and the resin main agent (B) by an IKA mixer, cooling the mixed state to the cloud point temperature of the surfactant (C), dripping at a rotation speed of about 5000 to about 10000rpm for 6 hours to obtain a uniformly dispersed emulsion, and finally adding a hindered phenol reagent (D) to obtain the sizing agent of the embodiment (embodiment 1 to embodiment 5). The particle size (Dv 50; nm) of the sizing agent of the examples is between about 0.01 to about 0.5 μm. The melting point temperatures of the resin main agent (A) and the resin main agent (B) are between about 60 ℃ and about 95 ℃. The cloud point temperature of the surfactant (C) is between about 60 ℃ and about 70 ℃.
In some alternative embodiments, the hindered phenol agent (D) may be mixed with the resin main agent (a), the resin main agent (B) and the surfactant (C) simultaneously, and then subjected to the same operations as described above 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 composition formulations of the following table one with reference to the formulation of the sizing agents of the comparative examples and examples.
List one
| 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 |
The sizing agent according to the above table one was subjected to a carbon fiber hardness test and a carbon fiber aging test, and the test results are shown in the following table two. As is clear from table two, the application of the sizing agent containing the hindered phenol type agent (D) to the carbon fiber reduced the hairiness of the carbon fiber and also improved the hardness of the carbon fiber, as compared with the comparative example.
For example, the hairiness amounts of examples 1 to 5 were smaller than those of the comparative examples on the 7 th and 14 th days of the elapsed time. Specifically, the hairiness increase amount of examples 1 to 5 is smaller than that of the comparative example. In addition, the carbon fiber hardness change amounts of examples 1 to 5 were smaller than those of the comparative examples also in the days of time test.
For details, please refer to the following table two. In the comparative example, the hardness of the carbon fiber on the 0 th day of the time course was about 13g, and the hardness of the carbon fiber on the 14 th day of the time course was about 39g, which was increased by about 200%. In examples 2 to 5, the hardness of the carbon fiber on the 0 th day of the time course was about 13g, and the hardness of the carbon fiber on the 14 th day of the time course was about 26g, which was increased by about 100%.
Watch II
The sizing agent of the invention solves the problems of hygroscopicity and adhesiveness of the original sized carbon fiber because of containing the hindered phenol reagent (D), thus inhibiting 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 wires in the processing process and inhibit the hardening with time, thereby preventing the decrease of the mechanical processing property.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but may be variously modified and modified by those skilled in the art without departing from the spirit and scope of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.
[ symbolic description ]
100 device for detecting hairiness of carbon fiber
110 carbon fiber bundle
120 metal roller
130 sponge cushion
200 device for detecting hardness of carbon fiber
210 force source
220 platform
230, gap.
Claims (8)
1. A sizing agent for carbon fibers, characterized by comprising, based on 100 parts by weight of the total weight of the sizing agent:
2 to 30 parts by weight of a resin main agent (a) of at least one epoxy compound, wherein the resin main agent (a) of at least one epoxy compound comprises bisphenol a type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, novolac epoxy resin, or a combination thereof;
2 to 30 parts by weight of a resin main agent (B) of at least one acrylate compound, 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 an oxyalkyl group in a molecule, a methacrylate having an oxyalkyl group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkylene group in a molecule, an acrylate having no oxyalkylene group in a molecule, a methacrylate having no oxyalkyl group in a molecule, or a combination thereof;
surfactant (C) accounting for 0.5 to 15 parts by weight;
0.01 to 0.5 part by weight of a hindered phenol reagent (D) having a structural formula represented by the formula (II-1)
Wherein n is between 7 and 9; and
The balance of solvent, wherein the size 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 is 10 to 25 parts by weight.
3. The sizing agent according to claim 1, wherein the resin main agent (B) of the at least one acrylate compound is 10 to 25 parts by weight.
4. 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.
5. The sizing agent according to claim 1, wherein the surfactant (C) is 5 to 12.5 parts by weight.
6. The sizing agent according to claim 1, wherein the hindered phenol-based agent (D) is present in an amount of 0.05 to 0.1 parts by weight.
7. A carbon fiber to which the sizing agent according to claim 1 is applied, characterized in that the sizing agent ratio of the carbon fiber is between 0.1 and 5 weight percent.
8. A carbon fiber to which a sizing agent according to claim 1 is applied, characterized in that the carbon fiber has an increase in stiffness of less than 100% after 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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| TWI784693B (en) | 2022-11-21 |
| US20230093719A1 (en) | 2023-03-23 |
| JP7429268B2 (en) | 2024-02-07 |
| CN114263043A (en) | 2022-04-01 |
| JP2023033242A (en) | 2023-03-09 |
| EP4141168A1 (en) | 2023-03-01 |
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