CN109385899A - Aqueous carbon fiber sizing agent and preparation method thereof - Google Patents
Aqueous carbon fiber sizing agent and preparation method thereof Download PDFInfo
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- CN109385899A CN109385899A CN201811044152.6A CN201811044152A CN109385899A CN 109385899 A CN109385899 A CN 109385899A CN 201811044152 A CN201811044152 A CN 201811044152A CN 109385899 A CN109385899 A CN 109385899A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- 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
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Abstract
The invention discloses a kind of aqueous carbon fiber sizing agents and preparation method thereof.The aqueous carbon fiber sizing agent is made of following components by weight: 16~32 parts by weight of epoxy resin, 4~8 parts by weight of epoxy acrylate；2~15 parts by weight of hydrophilic emulsifier；0~20 parts by weight of aqueous polyurethane emulsion；0~10 parts by weight of aqueous polyurethane acrylate；0~5 parts by weight of higher fatty acid amides；0.01~3 parts by weight of photoinitiator；Aqueous 0.05~5 parts by weight of wetting dispersing agent；0.1~5 parts by weight of thickener；0.2~5 parts by weight of solvent；30~70 parts by weight of deionized water.Aqueous carbon fiber sizing agent of the invention is a kind of heat cure and the compound aqueous carbon fiber sizing agent of photocuring, carbon fiber after the starching, the method that high warm is dried can be first passed through to be dried, then solidified by way of photocuring, so that the performance of carbon fiber sizing agent further increases.
Description
Technical field
The present invention relates to carbon fiber sizing agent technical field, in particular to a kind of aqueous carbon fiber sizing agent and its
Preparation method.
Background technique
Currently, sizing agent occupies extremely important work in high-performance carbon fibre and fiber-resin composite application
With.After carbon fiber surface carries out starching processing, convergence, slipping, wearability, machinability of carbon fiber etc. can be promoted
Performance meets requirement of the carbon fiber in the manufacturing process such as subsequent weaving and processing.
The sizing agent used on existing market is broadly divided into two major classes: oiliness sizing agent and aqueous sizing agent.With country
Requirement to environmental protection is higher and higher, and the accounting of aqueous sizing agent is higher and higher in the market.Aqueous carbon fiber sizing agent is main
Flash baking is carried out in such a way that high warm is dried, is wound after drying, is used after placing a period of time.In general, existing
There are aqueous carbon fiber sizing agent used in technology, predominantly watersoluble modified epoxy-resin systems.Watersoluble modified epoxy resin body
System includes waterborne polyurethane modified epoxy resin, waterborne polyester modified epoxy resin, aqueous polyether modified epoxy resin, aqueous poly-
Acrylated epoxy, aqueous polyamide modified epoxy etc..Watersoluble modified epoxy-resin systems can be divided into list
Component epoxide resin system and bicomponent epoxy resin system.In general, single component epoxy system without curing agent or
Crosslinking agent, or it is not involved in containing room temperature the curing agent or crosslinking agent of reaction.Bicomponent epoxy resin system by matrix resin and
Curing agent or crosslinking agent composition, in use, being used after two components are mixed.Carbon fiber sizing agent without curing agent or crosslinking agent
Solidify after can not being carried out after system drying, carbon fiber surface hand easy to stick when touching, and performance is slightly worse.And contain curing agent or crosslinking
After the carbon fiber sizing agent system drying of agent, during rear cured, sizing agent resin is easy to happen over-curing, after starching
Carbon fiber it is really up to the mark, be easy to fracture, easily go wrong in spinning process, and the rear cured time is longer, efficiency is lower.
Existing carbon fiber sizing agent on the market is usually to be obtained by two kinds of preparation methods: chemical synthesis and physical dispersion obtain
It arrives.By the way that hydrophilic segment to be connected on epoxy resin, so that epoxy resin is with hydrophily or has the dispersible energy of water
Power is chemical synthesis.The carbon fiber sizing agent that chemical synthesis is prepared, advantage are storage stability height, and performance is outstanding；
The disadvantage is that: synthesis cycle is longer, to the more demanding of production equipment, needs to use the higher catalyst of toxicity in reaction process,
Environment friendly problem can not solve.Epoxy resin is emulsified by emulsifier, thickener etc., so that epoxy resin
The stable method being scattered in deionized water is physical dispersion method.The carbon fiber sizing agent that physical dispersion method is prepared, it is excellent
Point is that preparation process is simple, and the requirement to production equipment is lower；The disadvantage is that storage stability is slightly worse, performance is slightly weak, needs to be added
Other types of resin makes up its performance.In addition, the epoxy resin latex prepared by physics mode, during the drying process, cream
Agent is easy to dissociate to film surface layer, to influence the interface performance of carbon fiber surface, and in composite material preparation process, holds
The associativity with carbon fiber surface compound resin is easily influenced, to influence the mechanical property of composite material.
106637984 A of CN discloses a kind of preparation method of polyamide modified carbon fiber in epoxy, is related to carbon fiber/ring
The preparation field of O compoiste material, which comprises polyamide and epoxy resin are put into reaction kettle, obtain polyamides
Amine-modified epoxy resin；The polyamide modified epoxy resin is dissolved using solvent, Hydrophilicrto polyether and catalysis is then added
Agent obtains the polyamide modified epoxy resin of hydrophilic modifying；Deionized water is added into the Polyamide Epoxy of hydrophilic modifying,
By shear agitation, polyamide modified epoxy emulsion is obtained, finally using polyamide modified epoxy emulsion as sizing agent to described
Carbon fiber carries out starching processing, obtains the modified carbon fiber of the polyamide modified epoxy-surface.It is raw to solve existing carbon fiber
Modified method complicated condition in production, the processing time is not easy to control, be easy to cause the modulus and breaking strength decline of carbon fiber, from
And the problem of performance that it meets material is greatly reduced.But the polyamide modified epoxy resin of the patent disclosure, it is made in synthesis
During standby, need to use the higher boron trifluoride ether of toxicity as catalyst, environmentally friendly problem can not solve.
104448245 A of CN discloses a kind of hyperbranched type ring oxygen emulsion preparation method, the preparation method, including
Following steps: polyamine is reacted with epoxy resin, synthesis of super branched type epoxy resin；The hyperbranched type epoxy resin is being urged
It under the action of agent, is reacted with Hydrophilicrto polyether, obtains the hyperbranched type epoxy resin of hydrophilic modifying；In the hydrophilic modifying
Deionized water is added in hyperbranched epoxy resin, by shear agitation, is prepared into hyperbranched type epoxy emulsion.Invention preparation
Hyperbranched epoxy emulsion, the size that can be used as carbon fiber sizing agent, glass fibre and basalt fibre are used, are capable of providing
The excellent convergence of fibre bundle, fibrillation and the wellability with epoxy resin, the fiber using the epoxy emulsion starching can be used for
The high-rise shearing of preparation and high-temperature resistant composite material.But the hyperbranched epoxy resin lotion of the patent disclosure, it is being synthetically prepared
In the process, it needs to use the stronger boron trifluoride ether of toxicity as catalyst, environmentally friendly problem can not solve.By more
Interior cross-linking reaction easily occurs during high-temperature baking for first modified epoxy resin latex of amine, so that the brittleness of dry film increases,
It can not adapt to the post-processing step of carbon fiber.
103797183 A of CN discloses one kind and can assign to the reinforcing fiber beam to make fiber reinforced composite material
Give the fiber sizing agent of sufficient convergence Yu fibrillation.Wherein, a kind of fiber is with sizing agent constituent (E), and there are also 35
DEG C viscosity be 50Pa.s~3000Pa.s sizing agent (A), and thixotropic index be 3~15, wherein (A) is preferably asphalt mixtures modified by epoxy resin
Rouge, polyester resin, polyurethane formate resin, polyether resin and vinylite.The carbon fiber sizing agent of the patent disclosure, it is main
If being emulsified by the lower epoxy resin of emulsifier dispersing molecule amount, the outer cream being prepared by physical dispersion mode
The internal emulsification type epoxy resin latex that change type epoxy resin latex stability is prepared slightly poorer to chemical synthesis.It is general next
It says, outer emulsifier is not available for the epoxy resin of high molecular weight and carries out outer emulsification, and chemical synthesis can carry out molecule
Design reaches internal emulsification.Therefore, the epoxy resin latex performance of outer emulsifying is restricted, and is merely able to other by being additionally added
The lotion of type is made up, such as synthetic polyaminoester emulsion.
Summary of the invention
The present invention is intended to provide a kind of aqueous carbon fiber sizing agent and preparation method thereof, to improve aqueous carbon fiber sizing agent
Mechanical property.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of aqueous carbon fiber sizing agent.The water
Property carbon fiber sizing agent is made of following components by weight: 16~32 parts by weight of epoxy resin, and epoxy acrylate 4~
8 parts by weight；2~15 parts by weight of hydrophilic emulsifier；0~20 parts by weight of aqueous polyurethane emulsion；Aqueous polyurethane acrylate 0
~10 parts by weight；0~5 parts by weight of higher fatty acid amides；0.01~3 parts by weight of photoinitiator；Aqueous wetting dispersing agent 0.05
~5 parts by weight；0.1~5 parts by weight of thickener；0.2~5 parts by weight of solvent；30~70 parts by weight of deionized water.
Further, the additive amount of epoxy resin is 22~30 parts by weight, preferably 25~28 parts by weight；
Preferably, the additive amount of epoxy acrylate is 5~7 parts by weight, more preferably 6~6.5 parts by weight；
Preferably, the additive amount of hydrophilic emulsifier is 5~10 parts by weight, more preferably 6~8 parts by weight；
Preferably, the additive amount of aqueous polyurethane emulsion is 2~15 parts by weight, more preferably 3~10 parts by weight；
Preferably, the additive amount of aqueous polyurethane acrylate is 2~8 parts by weight, more preferably 3~5 parts by weight；
Preferably, the additive amount of higher fatty acid amides is 1~3 parts by weight, more preferably 1.5~2 parts by weight；
Preferably, the additive amount of photoinitiator is 0.05~2 parts by weight, more preferably 0.1~1 parts by weight；
Preferably, the additive amount of aqueous wetting dispersing agent is 0.1~3 parts by weight, more preferably 0.2~1 parts by weight；
Preferably, the additive amount of thickener is 0.2~3 parts by weight, more preferably 0.5~1 parts by weight；
Preferably, the additive amount of solvent is 0.5~3 parts by weight, more preferably 1~2 parts by weight；
Preferably, the additive amount of deionized water is 40~60 parts by weight, more preferably 45~50 parts by weight；
Preferably, the additive amount weight ratio of epoxy resin and solvent is 100:2~30, preferably 100:3~20, more preferably
For 100:4~10；
Preferably, the additive amount weight ratio of epoxy resin and higher fatty acid amides is 100:1~20, preferably: for 100:2
~10, more preferably 100:3~5.
Further, epoxy resin is selected from by bisphenol A type epoxy resin, bisphenol f type epoxy resin, Cresol formaldehyde type ring oxygen
One of group of resin, phenol novolak type epoxy and diglycidyl ether type epoxy resin composition is a variety of；
Preferably, epoxy acrylate is selected from by bisphenol-a epoxy acrylate, bisphenol F type epoxy acrylate, fat
Sour modified bisphenol A epoxy acrylate, amine modified bisphenol A epoxy acrylate, Cresol formaldehyde type epoxy acrylate, phenol phenol
One of group of aldehyde type epoxy acrylate and epoxy soybean oil modified acrylic ester composition is a variety of；
Preferably, aqueous polyurethane acrylate is water-dispersion type or aqueous emulsion type polyurethane acrylate prepolymer；
Preferably, hydrophilic emulsifier includes response type hydrophilic emulsifier and non-reactive hydrophilic emulsifier, wherein
The weight percent that response type hydrophilic emulsifier accounts for hydrophilic emulsifier is 50~100%；
Preferably, response type hydrophilic emulsifier is tristyryl phenol polyethylene glycol methacrylate-styrene polymer, alkoxy gathers
One of glycolmethacrylate, methoxy polyethylene glycol methacrylate-styrene polymer are a variety of；
Preferably, non-reactive hydrophilic emulsifier is nonylphenol polyoxyethylene ether, polyaryl polyethers, tristyryl phenol
One of polyoxyethylene ether is a variety of；
Preferably, non-reactive hydrophilic emulsifier is polyethylene glycol, poly glycol monomethyl ether, in polyethyleneglycol esters
One or more mixtures, molecular weight be 400~20000；
Preferably, it is anionic emulsifying to be further selected from union base phenolic nonionic emulsifier, nonyl phenolic for hydrophilic emulsifier
What agent, phosphate type anion emulsifier, non-nonyl phenolic nonionic emulsifier and non-nonyl phenolic anion emulsifier formed
One of group is a variety of；
Preferably, aqueous polyurethane emulsion is water dispersant type polyaminoester resin or aqueous emulsion type polyurethane resin；
Preferably, higher fatty acid amides be aliphatic monocarboxylic acid amide and/or aliphatic dicarboxylic acid amide, more preferably
, aliphatic monocarboxylic acid amide is selected from by oleamide, stearic amide, erucamide, moon silicic acid amide, palmitinic acid acyl
One of group of amine, castor oil acid acid amides and hydroxy stearic acid amide composition is a variety of；Aliphatic dicarboxylic acid amide be selected from by
Ethylene bis-stearamide, ethylidene dilaurate amide, ethylene oleamide, ethylene isostearic acid amide,
One of group of ethylene hydroxy stearic acid amide and hexa-methylene distearyl acid amide composition is a variety of；
Preferably, photoinitiator is cracking type initiator and/or hydrogen-abstraction initiator；It is furthermore preferred that cracking type initiator
Selected from by 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 1,1'- (two -4,1- phenylene of methylene) bis- [2- hydroxyls
Base-2- methyl-1-acetone], 2- methyl-1-[- 4- methyl mercapto) phenyl]-2- morpholinyl-1- acetone, 2,4,6- trimethylbenzene first
Acyl group-diphenyl phosphine oxide, benzoin dimethylether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyl
One of group of ketone and benzoyl derivatives composition is a variety of, and hydrogen-abstraction initiator is selected from by benzophenone, 4- benzene first
Acyl group -4'- methyl-diphenyl sulfide, 2- benzoyl methyl benzoate, isopropyl thioxanthone uh ketone (2,4 isomer mixture) and
One of group of 4- (N, N- dimethylamino) ethyl benzoate composition is a variety of；
Preferably, aqueous wetting dispersing agent is selected from total by alkylol amine salt, the acrylic compounds of high molecular weight acidic polymer
Alkane hydroxyl amine salt, the band of the polynary hydroxy acid polymer of polymers, the structured copolymers containing the affine organ of pigment, low molecular weight are acid
Alkanolamine, the multiple functional radical polymeric alkanolamine of the polymer copolymerization ester of group, contain the polymeric alkylammonium salt of multiple functional radical
One of the group or more of pigment affinity groups polymer copolymerization body and the acrylic copolymer composition with pigment affinity groups
Kind；
Preferably, thickener is selected from by polyhydroxycarboxylicacid amides solution, modified urea solution, urea-modified polyurethane solutions, height
Spend one of group of polyurethane solutions composition of branched structure or a variety of；
Preferably, solvent is selected from by propylene glycol monomethyl ether, butyl glycol ether, glycol dimethyl ether, butyl cellosolve, third
One of group of ketone, butanone and butyl acetate composition is a variety of.
Further, it needs to carry out heat cure and ultraviolet light solidification after aqueous carbon fiber sizing agent starching.
Further, the temperature of heat cure is 120~160 DEG C, preferably 130~150 DEG C；Ultraviolet light solidifies middle-ultraviolet lamp
Irradiate light quantity is 200~1000mj/m2, it is preferable that ultraviolet irradiation light quantity is 600~800mj/m2。
According to another aspect of the present invention, a kind of preparation method of above-mentioned aqueous carbon fiber sizing agent is provided.The preparation
Method includes: to weigh the component of following parts by weight:
It mixes the above components evenly and aqueous carbon fiber sizing agent is prepared.
Further, the preparation method of aqueous carbon fiber sizing agent is specifically includes the following steps: S1, by epoxy resin and ring
Oxypropylene acid esters is added appropriate stirring solvent and is uniformly mixed, and obtains the first epoxy-resin systems；S2, to the first epoxy-resin systems
Middle addition hydrophilic emulsifier, is stirring evenly and then adding into aqueous wetting dispersing agent, obtains the second epoxy-resin systems；S3, to
Deionized water is added in diepoxy resin system to be dispersed, aqueous polyurethane acrylate is then added, after mixing, with residue
The photoinitiator of partial solvent dissolution, obtains third epoxy-resin systems；S4 is added after diluting thickener with deionized water
Three epoxy-resin systems, stir evenly, and obtain aqueous carbon fiber sizing agent.
Further, S1 includes that appropriate solvent is added in the stirring for having condenser in epoxy resin and epoxy acrylate
It is uniformly mixed in device, temperature rises to 60~80 DEG C, is dispersed with stirring 0.5~2 hour, 500~1500r/min of mixing speed is obtained
First epoxy-resin systems；
Preferably, S2 includes, in the case where at the uniform velocity stirring, hydrophilic emulsifier being added into the first epoxy-resin systems
Agent, mixing time 0.5~2 hour, then 500~1500r/min of mixing speed is cooled to 60~80 DEG C, and aqueous wetting is added
Dispersing agent obtains the second epoxy-resin systems；
Preferably, S3 includes that the second epoxy-resin systems are reduced temperature to 45~70 DEG C, are slowly added to 50 parts of deionizations
Water, time for adding are 0.5~2 hour, after being added dropwise, continue to be dispersed with stirring 0.5~2 hour, mixing speed 1000~
Then second epoxy-resin systems are cooled to 45~70 DEG C, aqueous polyurethane acrylate are added, continues to stir by 3000r/min
Mix dispersion 0.5~2 hour, 500~1500r/min of mixing speed；Second epoxy-resin systems are cooled to 25~40 DEG C, then
The photoinitiator dissolved with remainder solvent is added, is dispersed with stirring 0.5 hour, 500~1500r/min of mixing speed is obtained
Third epoxy-resin systems；
Preferably, in S4, the time being dispersed with stirring is 0.5~2 hour, and mixing speed is 500~1500r/min.
Further, when higher fatty acid amides additive amount is not 0, S1 includes, by part epoxy and advanced rouge
Fat acid amide is uniformly mixed in the agitating device with condenser, and temperature rises to 130~150 DEG C, and it is small to be dispersed with stirring 0.5~2
When, system temperature is reduced to 60~80 DEG C, remainder epoxy resin and part is added by 500~1000r/min of mixing speed
Solvent is dispersed with stirring 0.5~2 hour, and 500~1500r/min of mixing speed obtains the first epoxy-resin systems；
Preferably, when aqueous polyurethane emulsion additive amount is not 0, in S3, further include before photoinitiator is added, by body
System is cooled to 45~70 DEG C, and aqueous polyurethane emulsion is added and continues to be dispersed with stirring 0.5~2 hour, mixing speed 500~1500.
Further, the additive amount of epoxy resin is 22~30 parts by weight, preferably 25~28 parts by weight；
Preferably, the additive amount of hydrophilic emulsifier is 5~10 parts by weight, more preferably 6~8 parts by weight；
Preferably, the additive amount of aqueous polyurethane emulsion is 2~15 parts by weight, more preferably 3~10 parts by weight；
Preferably, the additive amount of aqueous polyurethane acrylate is 2~8 parts by weight, more preferably 3~5 parts by weight；
Preferably, the additive amount of higher fatty acid amides is 1~3 parts by weight, more preferably 1.5~2 parts by weight；
Preferably, the additive amount of photoinitiator is 0.05~2 parts by weight, more preferably 0.1~1 parts by weight；
Preferably, the additive amount of aqueous wetting dispersing agent is 0.1~3 parts by weight, more preferably 0.2~1 parts by weight；
Preferably, the additive amount of thickener is 0.2~3 parts by weight, more preferably 0.5~1 parts by weight；
Preferably, the additive amount of solvent is 0.5~3 parts by weight, more preferably 1~2 parts by weight；
Preferably, the additive amount of deionized water is 40~60 parts by weight, more preferably 45~50 parts by weight；
Preferably, the additive amount weight ratio of epoxy resin and solvent is 100:2~30, preferably 100:3~20, more preferably
For 100:4~10；
Preferably, the additive amount weight ratio of epoxy resin and higher fatty acid amides is 100:1~20, preferably: for 100:2
~10, more preferably 100:3~5.
Further, epoxy resin is selected from by bisphenol A type epoxy resin, bisphenol f type epoxy resin, Cresol formaldehyde type ring oxygen
One of group of resin, phenol novolak type epoxy and diglycidyl ether type epoxy resin composition is a variety of；
Preferably, epoxy acrylate is selected from by bisphenol-a epoxy acrylate, bisphenol F type epoxy acrylate, fat
Sour modified bisphenol A epoxy acrylate, amine modified bisphenol A epoxy acrylate, Cresol formaldehyde type epoxy acrylate, phenol phenol
One of group of aldehyde type epoxy acrylate and epoxy soybean oil modified acrylic ester composition is a variety of；
Preferably, aqueous polyurethane acrylate is water-dispersion type or aqueous emulsion type polyurethane acrylate prepolymer；
Preferably, hydrophilic emulsifier includes response type hydrophilic emulsifier and non-reactive hydrophilic emulsifier, wherein
The weight percent that response type hydrophilic emulsifier accounts for hydrophilic emulsifier is 50~100%；
Preferably, response type hydrophilic emulsifier is tristyryl phenol polyethylene glycol methacrylate-styrene polymer, alkoxy gathers
One of glycolmethacrylate, methoxy polyethylene glycol methacrylate-styrene polymer are a variety of；
Preferably, non-reactive hydrophilic emulsifier is nonylphenol polyoxyethylene ether, polyaryl polyethers, tristyryl phenol
One of polyoxyethylene ether is a variety of；
Preferably, non-reactive hydrophilic emulsifier is polyethylene glycol, poly glycol monomethyl ether, in polyethyleneglycol esters
One or more mixtures, molecular weight be 400~20000；
Preferably, it is anionic emulsifying to be further selected from union base phenolic nonionic emulsifier, nonyl phenolic for hydrophilic emulsifier
What agent, phosphate type anion emulsifier, non-nonyl phenolic nonionic emulsifier and non-nonyl phenolic anion emulsifier formed
One of group is a variety of；
Preferably, aqueous polyurethane emulsion is water dispersant type polyaminoester resin or aqueous emulsion type polyurethane resin；
Preferably, higher fatty acid amides be aliphatic monocarboxylic acid amide and/or aliphatic dicarboxylic acid amide, more preferably
, aliphatic monocarboxylic acid amide is selected from by oleamide, stearic amide, erucamide, moon silicic acid amide, palmitinic acid acyl
One of group of amine, castor oil acid acid amides and hydroxy stearic acid amide composition is a variety of；Aliphatic dicarboxylic acid amide be selected from by
Ethylene bis-stearamide, ethylidene dilaurate amide, ethylene oleamide, ethylene isostearic acid amide,
One of group of ethylene hydroxy stearic acid amide and hexa-methylene distearyl acid amide composition is a variety of；
Preferably, photoinitiator is cracking type initiator and/or hydrogen-abstraction initiator；It is furthermore preferred that cracking type initiator
Selected from by 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 1,1'- (two -4,1- phenylene of methylene) bis- [2- hydroxyls
Base-2- methyl-1-acetone], 2- methyl-1-[- 4- methyl mercapto) phenyl]-2- morpholinyl-1- acetone, 2,4,6- trimethylbenzene first
Acyl group-diphenyl phosphine oxide, benzoin dimethylether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyl
One of group of ketone and benzoyl derivatives composition is a variety of, and hydrogen-abstraction initiator is selected from by benzophenone, 4- benzene first
Acyl group -4'- methyl-diphenyl sulfide, 2- benzoyl methyl benzoate, isopropyl thioxanthone uh ketone (2,4 isomer mixture) and
One of group of 4- (N, N- dimethylamino) ethyl benzoate composition is a variety of；
Preferably, aqueous wetting dispersing agent is selected from total by alkylol amine salt, the acrylic compounds of high molecular weight acidic polymer
Alkane hydroxyl amine salt, the band of the polynary hydroxy acid polymer of polymers, the structured copolymers containing the affine organ of pigment, low molecular weight are acid
Alkanolamine, the multiple functional radical polymeric alkanolamine of the polymer copolymerization ester of group, contain the polymeric alkylammonium salt of multiple functional radical
One of the group or more of pigment affinity groups polymer copolymerization body and the acrylic copolymer composition with pigment affinity groups
Kind；
Preferably, thickener is selected from by polyhydroxycarboxylicacid amides solution, modified urea solution, urea-modified polyurethane solutions, height
Spend one of group of polyurethane solutions composition of branched structure or a variety of；
Preferably, solvent is selected from by propylene glycol monomethyl ether, butyl glycol ether, glycol dimethyl ether, butyl cellosolve, third
One of group of ketone, butanone and butyl acetate composition is a variety of.
Aqueous carbon fiber sizing agent of the invention is a kind of heat cure and the compound aqueous carbon fiber sizing agent of photocuring, should
Carbon fiber after starching can first pass through the method that high warm is dried and be dried, then be solidified by way of photocuring,
So that the performance of carbon fiber sizing agent further increases；The curing mode that heat cure provided by the invention, photocuring combine, is improved
The production efficiency of carbon fiber sizing agent, enhances the convergence of fibre bundle, and bits, Neng Gouyu are not easy in fabrication processes
Epoxy prepreg perfect combination.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
A kind of typical embodiment according to the present invention provides a kind of aqueous carbon fiber sizing agent.On the aqueous carbon fiber
Slurry agent is made of following components by weight:
Aqueous carbon fiber sizing agent of the invention is a kind of heat cure and the compound aqueous carbon fiber sizing agent of photocuring, should
Carbon fiber after starching can first pass through the method that high warm is dried and be dried, then be solidified by way of photocuring,
So that the performance of carbon fiber sizing agent further increases；The curing mode that heat cure provided by the invention, photocuring combine, is improved
The production efficiency of carbon fiber sizing agent, enhances the convergence of fibre bundle, and bits, Neng Gouyu are not easy in fabrication processes
Epoxy prepreg perfect combination.
Preferably, the additive amount of epoxy resin is 22~30 parts by weight, more preferably 25~28 parts by weight；Preferably, institute
The additive amount for stating epoxy acrylate is 5~7 parts by weight, more preferably 6~6.5 parts by weight；Preferably, hydrophilic emulsifier
Additive amount is 5~10 parts by weight, more preferably 6~8 parts by weight；Preferably, the additive amount of aqueous polyurethane emulsion is 2~15 weights
Measure part, more preferably 3~10 parts by weight；Preferably, the additive amount of aqueous polyurethane acrylate is 2~8 parts by weight, more preferably
For 3~5 parts by weight；Preferably, the additive amount of higher fatty acid amides is 1~3 parts by weight, more preferably 1.5~2 parts by weight；
Preferably, the additive amount of photoinitiator is 0.05~2 parts by weight, more preferably 0.1~1 parts by weight；Preferably, aqueous wetting point
The additive amount of powder is 0.1~3 parts by weight, more preferably 0.2~1 parts by weight；Preferably, the additive amount of thickener is 0.2~3
Parts by weight, more preferably 0.5~1 parts by weight；Preferably, the additive amount of solvent is 0.5~3 parts by weight, more preferably 1~2 weight
Measure part；Preferably, the additive amount of deionized water is 40~60 parts by weight, more preferably 45~50 parts by weight；Preferably, asphalt mixtures modified by epoxy resin
The additive amount weight ratio of rouge and solvent is 100:2~30, preferably 100:3~20, more preferably 100:4~10；Preferably, ring
The additive amount weight ratio of oxygen resin and higher fatty acid amides is 100:1~20, preferably: for 100:2~10, more preferably 100:
3~5.
A kind of typical embodiment according to the present invention, epoxy resin are selected from by bisphenol A type epoxy resin, Bisphenol F type ring
In the group that oxygen resin, Cresol formaldehyde type epoxy resin, phenol novolak type epoxy and diglycidyl ether type epoxy resin form
It is one or more；Preferably, epoxy acrylate is selected from by bisphenol-a epoxy acrylate, bisphenol F type epoxy acrylic acid
Ester, fatty acid modified bisphenol A epoxy acrylate, amine modified bisphenol A epoxy acrylate, Cresol formaldehyde type epoxy acrylic
One of group of ester, phenol novolak type epoxy acrylate and epoxy soybean oil modified acrylic ester composition is a variety of；It is preferred that
, aqueous polyurethane acrylate is water-dispersion type or aqueous emulsion type polyurethane acrylate prepolymer；Preferably, hydrophily cream
Agent includes that response type hydrophilic emulsifier (as having double bond, can proceed with cross-linking reaction) and non-reactive are hydrophilic
Property emulsifier, wherein response type hydrophilic emulsifier account for hydrophilic emulsifier weight percent be 50~100%；Preferably,
Response type hydrophilic emulsifier is tristyryl phenol polyethylene glycol methacrylate-styrene polymer, alkoxy polyethylene glycol methacrylic acid
One of ester, methoxy polyethylene glycol methacrylate-styrene polymer are a variety of.Preferably, the non-reactive hydrophilic emulsifier is
One of nonylphenol polyoxyethylene ether, polyaryl polyethers, tristyryl phenol polyoxyethylene ether are a variety of, these hydrophilies cream
Agent polarity is medium, is common emulsifier, and obtained finished product performance is stablized；It is when product is higher to toughness reguirements, preferably
, non-reactive hydrophilic emulsifier is polyethylene glycol, poly glycol monomethyl ether, one of polyethyleneglycol esters or a variety of
Mixture, wherein the molecular weight of Hydrophilicrto polyether be 400~20000.Certainly, this kind of emulsifier can be according to actual needs
It is deployed.Preferably, it is anionic emulsifying to be further selected from union base phenolic nonionic emulsifier, nonyl phenolic for hydrophilic emulsifier
What agent, phosphate type anion emulsifier, non-nonyl phenolic nonionic emulsifier and non-nonyl phenolic anion emulsifier formed
One of group is a variety of；Preferably, aqueous polyurethane emulsion is water dispersant type polyaminoester resin or aqueous emulsion type polyurethane tree
Rouge；Preferably, higher fatty acid amides are aliphatic monocarboxylic acid amide and/or aliphatic dicarboxylic acid amide, it is furthermore preferred that fatty
Race mono is selected from by oleamide, stearic amide, erucamide, moon silicic acid amide, palmitamide, castor oil
One of group of sour amide and hydroxy stearic acid amide composition is a variety of；Aliphatic dicarboxylic acid amide is selected from hard by ethylene
Resin acid amide, ethylidene dilaurate amide, ethylene oleamide, ethylene isostearic acid amide, ethylidene dihydroxy
One of group of base stearic amide and hexa-methylene distearyl acid amide composition is a variety of；Preferably, photoinitiator is to split
Solution type initiator and/or hydrogen-abstraction initiator；It is furthermore preferred that cracking type initiator is selected from by 2- hydroxyl -4'- (2- hydroxyl ethoxy
Base)-2- methyl phenyl ketone, 1,1'- (two-4,1- phenylene of methylene) bis- [2- hydroxy-2-methyl-1- acetone], 2- methyl-1-
[- 4- methyl mercapto) phenyl] -2- morpholinyl -1- acetone, 2,4,6- trimethylbenzoy-dipheny phosphine oxide, the double first of styrax
The group of ether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyl ketone and benzoyl derivatives composition
One of or it is a variety of, hydrogen-abstraction initiator be selected from by benzophenone, 4- benzoyl -4'- methyl-diphenyl sulfide, 2- benzene first
Acyl group methyl benzoate, isopropyl thioxanthone uh ketone (2,4 isomer mixture) and 4- (N, N- dimethylamino) ethyl benzoate group
At one of group or a variety of；Preferably, aqueous wetting dispersing agent is selected from the alkyl alcoholamine by high molecular weight acidic polymer
Salt (high molecular weight is often referred to molecular weight greater than 20,000), acrylic copolymer, the structuring copolymerization containing pigment affinity groups
Alkane hydroxyl amine salt (low molecular weight is often referred to molecular weight less than 20,000), the band acidic-group of the polynary hydroxy acid polymer of object, low molecular weight
The alkanolamine (high molecular weight be often referred to molecular weight greater than 20,000) of polymer copolymerization ester, the polymeric alkanolamine of multiple functional radical, more
The polymeric alkylammonium salt of functional group, the polymer copolymerization body of affinity groups containing pigment and the acrylic acid with pigment affinity groups are total to
One of group of polymers composition is a variety of；Preferably, thickener is selected from by polyhydroxycarboxylicacid amides solution (usual concentration range
Can be 10%~100%), modified urea solution, urea-modified polyurethane solutions, hyperbranched structure polyurethane solutions compositions
One of group is a variety of；Preferably, solvent is selected from by propylene glycol monomethyl ether, butyl glycol ether, glycol dimethyl ether, ethylene glycol two
One of group of butyl ether, acetone, butanone and butyl acetate composition is a variety of.
Said components of the present invention can be selected from commercial product, for example, wetting dispersing agent, thickener be selected from BYK, TEGO, YCK,
De Qian company etc..
Aqueous carbon fiber sizing agent in the present invention, main ingredient is by different classes of epoxy resin and containing unsaturated double
The polyethenoxy ether class emulsifier of key forms.Epoxy resin is generally by bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic aldehyde
Epoxy resin, Cresol formaldehyde epoxy resin composition.The backbone structure of epoxy resin is the compound of phenyl ring class, has centainly rigid
Property, and the backbone structure of polyethenoxy ether class emulsifier is generally the carbon carbon oxygen class compound of repeatability, has centainly flexible
Property.In general, the rigidity and degree of functionality of novolac epoxy resin and Cresol formaldehyde epoxy resin be higher than bisphenol A type epoxy resin,
Bisphenol f type epoxy resin, therefore, the hardness and brittleness of novolac epoxy resin and Cresol formaldehyde epoxy resin are higher than bisphenol-A type ring
Oxygen resin, bisphenol f type epoxy resin.It, can by the collocation between variety classes epoxy resin and polyethenoxy ether class emulsifier
To achieve the purpose that the performances such as the hardness, toughness, smoothness, the convergence that adjust sizing agent.
Aqueous carbon fiber sizing agent in the present invention, main ingredient by different classes of epoxy resin, containing unsaturated double
The epoxy resin of key and containing unsaturated double-bond polyethenoxy ether class emulsifier composition.Epoxy resin is generally by bisphenol-A type ring
The composition such as oxygen resin, bisphenol f type epoxy resin, novolac epoxy resin, Cresol formaldehyde epoxy resin.The backbone structure of epoxy resin
For the compound of phenyl ring class, there is certain rigidity, and the backbone structure of polyethenoxy ether class emulsifier is generally repeatability
Carbon carbon oxygen class compound has certain flexibility.Epoxy acrylate contains unsaturated double-bond after ultraviolet light solidifies
It is crosslinked between epoxy acrylate, molecular weight increases sharply, the hardness of the resin after solidification resin hardness more before curing
It is promoted.It, can be with by the collocation between variety classes epoxy resin, epoxy acrylate and polyethenoxy ether class emulsifier
Achieve the purpose that adjust the performances such as hardness, toughness, smoothness, the convergence of sizing agent.
It is better can to provide carbon fiber due to its distinctive flexibility for the higher polyethenoxy ether class emulsifier of molecular weight
The better smoothness of flexibility and surface.The polyoxy of bisphenol A-type and bisphenol F epoxy resin the collocation high molecular weight of small molecular amount
Ethylene ethers emulsifier can make carbon fiber have preferable convergence and surface smoothness.It is grouped as by above two group
Sizing agent to carbon fiber carry out starching after, since the hardness of two kinds of components is lower, high temperature drying after, finger touch carbon fiber surface
There is slight sticky situation in face.Therefore, it is necessary to hardness of arranging in pairs or groups is higher and the preferable ultraviolet cured epoxy acrylic of surface drying
Resin, so that the hardness of system is promoted slightly, to reach the tack-free state of drying defensive position touching surface drying.If the higher purple of hardness
Outer light-cured epoxy acrylate additive amount is too big, and it will cause the carbon fibre tow brittleness increases after drying, is unfavorable for
The weaving process of next step.Therefore, the collocation of above-mentioned three kinds of compositions is particularly important.
The additive amount and curing degree of ultraviolet cured epoxy acrylic resin influence the hard of entire sizing agent system
Degree, flexibility and crosslinking degree.Initiator content is excessive, will lead to point after ultraviolet cured epoxy acrylic resin solidifies
Son amount is excessive, to have a certain impact to sizing agent in sprawling for carbon fiber surface.Also, crosslink density is excessive, then can lead
Fiber detaching is caused to reduce, when preparing composite material, carbon fiber cannot be soaked preferably, thereby reduce its composite material
Performance.Molecular weight is excessive, so that the flexibility of carbon fiber, flexibility, convergence reduce, and then affects its weaving process,
Cannot preferably protect the surface of carbon fiber, thus excessive Epocryl be fully cured after sizing agent using effect
It is undesirable；Initiator content is too low, and it is too low to will lead to the molecular weight after ultraviolet cured epoxy acrylic resin solidifies, and divides
Son amount is smaller, then the degree of cross linking is inadequate between will lead to single fiber.If the crosslinking degree between single fiber is low, reduce between fiber
Active force so that the composite property of preparation reduces, while having a certain impact to the convergence of carbon fiber entirety；Ultraviolet
Light-cured epoxy acrylate content is moderate, the epoxy acrylate point in the case that initiator content is moderate, after solidification
Son amount is moderate, and the sizing agent of intermediate molecular weight can guarantee the preferable convergence of fiber and fibrillation simultaneously.
Epocryl and water emulsifier in the present invention contain unsaturated double-bond, solidify by ultraviolet light and walk
After rapid, unsaturated double-bond reacts, and crosslinks, and epoxy resin is closely wrapped, is not easy from upper between emulsifier
Starch separate out in agent system.In contrast, the emulsifier in traditional aqueous carbon fiber sizing agent, due to not having reaction
Property, it is easy the separate out from sizing agent, to influence the interface performance of carbon fiber surface, and in composite material preparation process
In, it is easy to influence the associativity with carbon fiber surface compound resin, to influence the mechanical property of composite material.
The present invention is scattered in deionized water by the excellent emulsifier of hydrophily by epoxy resin is stable, to obtain
The carbon fiber sizing agent of performance stabilization, stable storing.Also, the emulsifier of the type has unsaturated double-bond, can participate in certainly
By base curing reaction, combine closely with epoxy resin.Traditional aqueous carbon fiber sizing agent is generally thermohardening type sizing agent, this
Aqueous carbon fiber sizing agent in invention is the sizing agent of heat cure and photocuring mating type.The aqueous carbon fiber sizing agent can be with
Heat cure is only carried out, without photocuring, to obtain performance similar to traditional sizing agent；It can also complete heat curing operation
Afterwards, further progress photocuring step, to obtain more excellent performance.
The present invention by the excellent response type hydrophilic emulsifier of hydrophily by epoxy resin it is stable be scattered in deionization
In water, to obtain the carbon fiber sizing agent of performance stabilization, stable storing.Epocryl in the present invention, can
Solidified under ultraviolet light, from the epoxy resin cross-linking reaction of small-molecular-weight at the epoxy resin of macromolecule, to obtain
Outstanding performance.Also, the emulsifier in the aqueous carbon fiber sizing agent has unsaturated double-bond, can participate in free radical
Curing reaction is combined closely with epoxy resin.The aqueous carbon fiber sizing agent can only carry out heat cure, without photocuring,
To obtain performance similar with traditional sizing agent；It can also be after completing heat curing operation, further progress photocuring step,
To obtain more excellent performance, it is preferred, therefore, that, it needs to carry out heat cure and ultraviolet light after aqueous carbon fiber sizing agent starching
Solidification.Preferably, the temperature of heat cure is 120~160 DEG C, preferably 130~150 DEG C；Ultraviolet light solidifies the irradiation of middle-ultraviolet lamp
Light quantity is 200~1000mj/m2, it is preferable that ultraviolet irradiation light quantity is 600~800mj/m2。
A kind of typical embodiment according to the present invention provides a kind of preparation method of above-mentioned aqueous carbon fiber sizing agent.
The preparation method includes: to weigh the component of following parts by weight:
It mixes the above components evenly and aqueous carbon fiber sizing agent is prepared.
The present invention by the excellent response type hydrophilic emulsifier of hydrophily by epoxy resin it is stable be scattered in deionization
In water, to obtain the carbon fiber sizing agent of performance stabilization, stable storing.Also, the emulsifier of the type has unsaturated double
Key can participate in radically curing reaction, combine closely with epoxy resin.Traditional aqueous carbon fiber sizing agent is generally thermosetting
Change type sizing agent, the present invention in aqueous carbon fiber sizing agent be heat cure and photocuring mating type sizing agent.The aqueous carbon
Fiber sizing agent can only carry out heat cure, without photocuring, to obtain performance similar with traditional sizing agent；It can also be with
After completing heat curing operation, further progress photocuring step, to obtain more excellent performance.Therefore, of the invention
Aqueous carbon fiber sizing agent has biggish industrialized production benefit and good application prospect.
Preferably, the preparation method of aqueous carbon fiber sizing agent is specifically includes the following steps: S1, by epoxy resin and epoxy
Acrylate is added appropriate stirring solvent and is uniformly mixed, and obtains the first epoxy-resin systems；S2, into the first epoxy-resin systems
Hydrophilic emulsifier is added, is stirring evenly and then adding into aqueous wetting dispersing agent, obtains the second epoxy-resin systems；S3, to second
Deionized water is added in epoxy-resin systems to be dispersed, aqueous polyurethane acrylate is then added, after mixing, uses remainder
The photoinitiator for dividing solvent dissolution, obtains third epoxy-resin systems；Third is added after diluting thickener with deionized water in S4
Epoxy-resin systems stir evenly, and obtain aqueous carbon fiber sizing agent.
Further, S1 includes that appropriate solvent is added in the stirring for having condenser in epoxy resin and epoxy acrylate
It is uniformly mixed in device, temperature rises to 60~80 DEG C, is dispersed with stirring 0.5~2 hour, and 500~1500r/min of mixing speed is obtained
To the first epoxy-resin systems.
Preferably, S2 includes, in the case where at the uniform velocity stirring, hydrophilic emulsifier being added into the first epoxy-resin systems
Agent, mixing time 0.5~2 hour, then 500~1500r/min of mixing speed is cooled to 60~80 DEG C, and aqueous wetting is added
Dispersing agent obtains the second epoxy-resin systems.
Preferably, S3 includes that the second epoxy-resin systems are reduced temperature to 45~70 DEG C, are slowly added to 50 parts of deionizations
Water, time for adding are 0.5~2 hour, after being added dropwise, continue to be dispersed with stirring 0.5~2 hour, mixing speed 1000~
Then second epoxy-resin systems are cooled to 45~70 DEG C, aqueous polyurethane acrylate are added, continues to stir by 3000r/min
Mix dispersion 0.5~2 hour, 500~1500r/min of mixing speed；Second epoxy-resin systems are cooled to 25~40 DEG C, then
The photoinitiator dissolved with remainder solvent is added, is dispersed with stirring 0.5 hour, 500~1500r/min of mixing speed is obtained
Third epoxy-resin systems.
Preferably, in S4, the time being dispersed with stirring is 0.5~2 hour, and mixing speed is 500~1500r/min.
Further, when higher fatty acid amides additive amount is not 0, S1 includes, by part epoxy and advanced rouge
Fat acid amide is uniformly mixed in the agitating device with condenser, and temperature rises to 130~150 DEG C, and it is small to be dispersed with stirring 0.5~2
When, system temperature is reduced to 60~80 DEG C, remainder epoxy resin and part is added by 500~1000r/min of mixing speed
Solvent, is dispersed with stirring 0.5~2 hour, and 500~1500r/min of mixing speed obtains the first epoxy-resin systems.
Preferably, when aqueous polyurethane emulsion additive amount is not 0, in S3, further include before photoinitiator is added, by body
System is cooled to 45~70 DEG C, and aqueous polyurethane emulsion is added and continues to be dispersed with stirring 0.5~2 hour, mixing speed 500~1500.
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment.
Chemical raw material used in comparative example and embodiment of the invention is as shown in table 1 below:
Table 1
Comparative example 1
This comparative example carbon fiber sizing agent is made after heat cure of following components (table 2) by weight:
Table 2
| Component | Specific ingredient | Parts by weight |
| Epoxy resin | E-51 | 29 parts |
| Higher fatty acid amides | Oleamide | 1.5 part |
| Surfactant | Tristyryl phenol polyoxyethylene ether 25EO | 9.5 part |
| Solvent | Propylene glycol monomethyl ether | 1 part |
| Solvent | Butyl acetate | 1 part |
| Thickener | BYK-420 | 0.5 part |
| Water | Deionized water | 57.5 parts |
The preparation method is as follows:
29 parts by weight E-51 and 1.5 parts by weight oleamides are put into reaction kettle together, temperature is increased to 135 DEG C, stirs
Mix dispersion 1 hour, mixing speed 800rpm.System temperature is reduced to 90 DEG C, by 1 parts by weight of propylene glycol methyl ether, 1 parts by weight second
Acid butyl ester and 9.5 parts by weight tristyryl phenol polyoxyethylene ether 25EO put into reaction kettle together, are dispersed with stirring 1 hour, stir
Mixing speed is 1000rpm, obtains fiber sizing agent constituent.Then, system temperature is reduced to 70 DEG C, then to the fiber
With the water that 50 parts by weight are added dropwise in sizing agent constituent, time for adding is 0.5 hour, and mixing speed 1500rpm continues to stir
Dispersion 1 hour.Finally, diluting 0.5 part of thickener BYK-420 with 7.5 parts of deionized waters, then it is added in above-mentioned system, continues
Stirring 1 hour, to obtain the fiber sizing agent aqueous solution that non-volatile components and concentration is about 40% solid content.
Comparative example 2
This comparative example carbon fiber sizing agent is made after heat cure of following components (table 3) by weight:
Table 3
| Component | Specific ingredient | Parts by weight |
| Epoxy resin | E-44 | 12 parts |
| Epoxy resin | N740S | 12 parts |
| Polyester resin | XCPA-195 | 4 parts |
| Higher fatty acid amides | Stearate acid amide | 2 parts |
| Surfactant | Tristyryl phenol polyoxyethylene ether 40EO | 10 parts |
| Solvent | Butyl glycol ether | 2 parts |
| Solvent | Butyl acetate | 1 part |
| Thickener | BYK-7420 | 0.5 part |
| Water | Deionized water | 56.5 parts |
The preparation method is as follows:
It by 12 parts by weight E-44,4 parts by weight XCPA-195,2 parts by weight stearic amides, puts into reaction kettle, rises together
High-temperature is dispersed with stirring 1 hour, mixing speed 800rpm to 140 DEG C.System temperature is reduced to 90 DEG C, by 2 parts by weight second two
Alcohol butyl ether, 1 parts by weight butyl acetate, 12 parts by weight N740S and 10 parts by weight tristyryl phenol polyoxyethylene ether 40EO, together
It puts into reaction kettle, is dispersed with stirring 1 hour, mixing speed 1000rpm, obtain fiber sizing agent constituent.Then, by body
It is that temperature is reduced to 70 DEG C, then to the fiber water that 50 parts by weight are added dropwise in sizing agent constituent, time for adding is 0.5 small
When, mixing speed 1500rpm continues to be dispersed with stirring 1 hour.Finally, diluting 0.5 part of thickener with 6.5 parts of deionized waters
Then BYK-7420 is added in above-mentioned system, continue stirring 1 hour, so that obtaining non-volatile components and concentration is about 40% to contain admittedly
The fiber of amount sizing agent aqueous solution.
Embodiment 1
The present embodiment carbon fiber sizing agent is made after heat cure and photocuring by following components (table 4) by weight
At:
Table 4
The preparation method is as follows:
By 24 part 0161 (E-54) (blue star Nantong stars synthetic material), 6 part 1703 (Double Bond Chemical Ind.,Co.,Ltd.),
1 part of propylene glycol monomethyl ether solvent is added in the agitator with condenser.Temperature is increased to 80 DEG C, is dispersed with stirring 1 hour, stirring speed
800r/min is spent, so that epoxy resin is uniformly mixed.Then, in the case where at the uniform velocity stirring, 8 parts of BOM-25 are slowly added to
It states in epoxy-resin systems, is dispersed in it in epoxy resin, mixing time 1 hour, mixing speed 1000r/min.So
Afterwards, 70 DEG C are cooled to, 0.35 part of wetting dispersing agent ANTI-TERRA-250 is added, is dispersed in it in system.Then, it drops
Low temperature is slowly added to 50 parts of deionized waters to 65 DEG C, and time for adding is 0.5 hour, after being added dropwise, continues to be dispersed with stirring 1
Hour, mixing speed 1500r/min.Above-mentioned aqueous epoxy resin systems are cooled to 40 DEG C, by 0.3 part of IRGACURE 184
(Ciba company) and 0.1 part of DAROCUR TPO are dissolved with 1 part of propylene glycol monomethyl ether and 1 part of butyl acetate, then, will be dissolved
Good initiator is added in above-mentioned epoxy-resin systems, is dispersed with stirring 0.5 hour, mixing speed 1000r/min.Finally, by 1.0
Part OPTIFLO-3300 is diluted with 7 parts of deionized waters, is then added in above-mentioned water-base resin system, it is small to be dispersed with stirring 0.5
When, mixing speed 1000r/min obtains water-base epoxy resin sizing agent for carbon fiber.
Embodiment 2
The present embodiment carbon fiber sizing agent is made after heat cure and photocuring by following components (table 5) by weight
At:
Table 5
The preparation method is as follows:
24 parts of WSR618 (E-51) (blue star Nantong stars synthetic material) and 0.7 part of oleamide are added and have condenser
Agitator in, increase temperature to 150 DEG C, be stirred to react 1 hour, mixing speed 600r/min.System temperature is reduced to 80
DEG C, 4 part 1636 (Double Bond Chemical Ind.,Co.,Ltd.) and 1 part of propylene glycol monomethyl ether solvent is added, is dispersed with stirring 1 hour, stirring speed
800r/min is spent, so that epoxy resin is uniformly mixed.Then, temperature is reduced to 70 DEG C, in the case where at the uniform velocity stirring, by 8.65
Part BOM-25 is slowly added in above-mentioned epoxy-resin systems, is dispersed in it in epoxy resin, mixing time 1 hour, is stirred
Mix speed 1000r/min.Then, 65 DEG C are cooled to, 0.4 part of wetting dispersing agent DISPERBYK-180 is added, keeps its evenly dispersed
In system.Then, 50 parts of deionized waters are slowly added to, time for adding is 0.5 hour, after being added dropwise, continues to be dispersed with stirring 2
Hour, mixing speed 1500r/min.Above-mentioned aqueous epoxy resin systems are cooled to 25 DEG C, by 0.25 part of IRGACURE 1173
(Ciba company) is dissolved with 1 part of propylene glycol monomethyl ether and 1 part of butyl acetate, then, the initiator dissolved is added above-mentioned
In epoxy-resin systems, it is dispersed with stirring 0.5 hour, mixing speed 1000r/min.Finally, by 1 part of OPTIFLO-7500 with 7 parts
Deionized water is diluted, and is then added in above-mentioned water-base resin system, is dispersed with stirring 0.5 hour, mixing speed 1000r/
Min obtains water-base epoxy resin sizing agent for carbon fiber.
Embodiment 3
The present embodiment carbon fiber sizing agent is made after heat cure and photocuring by following components (table 6) by weight
At:
Table 6
The preparation method is as follows:
By 25 part 830 (blue star Nantong stars synthetic material), 5 part 1702 (Double Bond Chemical Ind.,Co.,Ltd.) and 1 part third
Glycol methyl ether solvent is added in the agitator with condenser.Temperature is increased to 80 DEG C, is dispersed with stirring 0.5 hour, mixing speed
800r/min, so that epoxy resin is uniformly mixed.Then, temperature is reduced to 75 DEG C, in the case where at the uniform velocity stirring, by 6 parts
BOM-25 and 3 part of MPEG-MA-1000 is slowly added in above-mentioned epoxy-resin systems, is dispersed in it in epoxy resin, is stirred
Mix the time 1 hour, mixing speed 800r/min.Then, 70 DEG C are cooled to, 0.3 part of wetting dispersing agent DISPERBYK- is added
2010, it is dispersed in it in system.Then, 50 parts of deionized waters are slowly added to, time for adding is 0.5 hour, is dripped
Bi Hou continues to be dispersed with stirring 2 hours, mixing speed 1500r/min.Above-mentioned aqueous epoxy resin systems are cooled to 25 DEG C, it will
0.15 part of IRGACURE 127 (Ciba company) and 0.05 part of IRGACURE 819 (Ciba company) are with 1 part of propylene glycol monomethyl ether and 1
Part butyl acetate is dissolved, and then, the initiator dissolved is added in above-mentioned epoxy-resin systems, it is small to be dispersed with stirring 0.5
When, mixing speed 1000r/min.Finally, 0.5 part of BYK-7420 is diluted with 7 parts of deionized waters, above-mentioned water is then added
In property resin system, it is dispersed with stirring 0.5 hour, mixing speed 1000r/min, obtains the aqueous epoxy resins starching of carbon fiber Wesy
Agent.
Embodiment 4
The present embodiment carbon fiber sizing agent is made after heat cure and photocuring by following components (table 7) by weight
At:
Table 7
| Component | Specific ingredient | Parts by weight |
| Bisphenol A type epoxy resin | WSR618(E-51) | 20.5 parts |
| Bisphenol A epoxy acrylate | 1271 | 5 parts |
| Aqueous polyurethane acrylate | 7177 | 10 parts |
| Alkoxy polyethylene glycol methacrylate-styrene polymer | BOM-60 | 4 parts |
| Tristyryl phenol polyethenoxy ether metacrylic acid ester | BOM-25 | 5 parts |
| 2- hydroxy-2-methyl -1- phenyl -1- acetone | IRGACURE 1173 | 0.4 part |
| Dispersing agent | LACTIMON-WS | 0.4 part |
| Thickener | BYK-425 | 0.7 part |
| Solvent | Propylene glycol monomethyl ether | 1 part |
| Water | Deionized water | 53 parts |
The preparation method is as follows:
By 20.5 parts of WSR618 (E-51) (blue star Nantong stars synthetic material), 5 part of 1703 (limited public affairs of double bond chemical industry share
Department), 1 part of propylene glycol monomethyl ether solvent is added in the agitator with condenser.Temperature is increased to 80 DEG C, is dispersed with stirring 0.5 hour,
Mixing speed 800r/min, so that epoxy resin is uniformly mixed.Then, 75 DEG C are cooled to, in the case where at the uniform velocity stirring, by 5
Part BOM-25 and 4 part of BOM-60 is slowly added in above-mentioned epoxy-resin systems, is dispersed in it in epoxy resin, when stirring
Between 1 hour, mixing speed 800r/min.Then, 70 DEG C are cooled to, 0.4 part of wetting dispersing agent LACTIMON-WS is added, makes it
It is dispersed in system.Then, 50 parts of deionized waters are slowly added to, time for adding is 0.5 hour, after being added dropwise, and is continued
It is dispersed with stirring 2 hours, mixing speed 1500r/min.Then, above-mentioned system is cooled to 50 DEG C, 10 part of 7177 (profound new public affairs is added
Department), continue to be dispersed with stirring 1 hour, mixing speed 1500r/min.Above-mentioned water-base resin system is cooled to 30 DEG C, is added 0.4
Part IRGACURE 1173 (Ciba company), is dispersed with stirring 0.5 hour, mixing speed 1000r/min.Finally, by 0.7 part of BYK-
425 are diluted with 3 parts of deionized waters, are then added in above-mentioned water-base resin system, are dispersed with stirring 0.5 hour, mixing speed
1000r/min obtains water-base epoxy resin sizing agent for carbon fiber.
Carbon fiber end properties assessment result is shown in Table 8
Table 8
The performance of prepared carbon fiber sizing agent is used the following method to test and is evaluated in above-described embodiment.
1. carbon fiber starching: the lotion that solid content mass fraction is about 40% being diluted to 1% solid content with distilled water, so
Starching is carried out to carbon fiber afterwards, dip time is 15 seconds, after starching, and 150 DEG C are dried 3 minutes, are then placed in spare in drier.
2. sizing agent storage stability: aqueous carbon fiber sizing agent obtained is placed in 25 DEG C, the decentralization of 60%RH atmosphere
After setting 6 months, whether observation sizing agent is stable, no sedimentation phenomenon.
3. sizing agent stability in use: in observation carbon fiber sizing agent use process, if will appear creaming of emulsion or broken
The phenomenon of cream；And measure starching liquid bath upper, middle and lower layer solid content variation (zero: solid content stablizes constant, △: solid content is slight
Bianization, ╳: solid content changes greatly).
4. starching treated carbon fiber surface brightness: visually observing carbon fiber surface bright degree (zero: surface brightness
High, △: the high general, ╳ of surface brightness: surface brightness is lower).
5. starching treated carbon fiber surface slickness: touching the smooth degree in carbon fibre tow surface (zero: refreshing with finger
It is sliding it is submissive very well, △: smooth submissive general, ╳: it is slight puckery).
6. starching treated carbon fiber flexibility: touching the soft or hard degree of carbon fibre tow (zero: soft, △: slightly with finger
Ying, ╳: very hard).
7. starching treated carbon fiber convergence: taking the carbon fiber of certain standard length, both ends are after fastening, along hanging down
Directly therefrom trail fiber in the direction of length, observe later the net structure that degree and formation are completely embedded between monofilament and
The reply shape of carbon fiber after external force disappears (zero: convergence is excellent, △: the medium, ╳ of convergence: convergence is slightly worse).
Carbon fiber is easy fluffing in production and process, through mechanical friction, or phenomena such as single wire fracture occurs, makes
Fibre strength reduces.Also, due to the presence of lousiness, resin matrix cannot sufficiently infiltrate carbon fiber, prepare in composite material
Cheng Zhong is easy to produce gap, to influence the mechanical property of composite material.Starching be exactly in carbon fiber surface coating protective layer,
This layer of protective layer is usually organic matter.Main function is exactly the phenomenon that reducing fluffing fracture of wire, to make carbon fiber boundling, improve processability
Can, and play a protective role.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Aqueous carbon fiber sizing agent in the present invention, main ingredient is by different classes of epoxy resin and containing unsaturated double
The polyethenoxy ether class emulsifier of key forms.Epoxy resin is generally by bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic aldehyde
Epoxy resin, Cresol formaldehyde epoxy resin composition.The backbone structure of epoxy resin is the compound of phenyl ring class, has centainly rigid
Property, and the backbone structure of polyethenoxy ether class emulsifier is generally the carbon carbon oxygen class compound of repeatability, has centainly flexible
Property.In general, the rigidity and degree of functionality of novolac epoxy resin and Cresol formaldehyde epoxy resin be higher than bisphenol A type epoxy resin,
Bisphenol f type epoxy resin, therefore, the hardness and brittleness of novolac epoxy resin and Cresol formaldehyde epoxy resin are higher than bisphenol-A type ring
Oxygen resin, bisphenol f type epoxy resin.It, can by the collocation between variety classes epoxy resin and polyethenoxy ether class emulsifier
To achieve the purpose that the performances such as the hardness, toughness, smoothness, the convergence that adjust sizing agent.
Aqueous carbon fiber sizing agent in the present invention, main ingredient by different classes of epoxy resin, containing unsaturated double
The epoxy resin of key and containing unsaturated double-bond polyethenoxy ether class emulsifier composition.Epoxy resin is generally by bisphenol-A type ring
The composition such as oxygen resin, bisphenol f type epoxy resin, novolac epoxy resin, Cresol formaldehyde epoxy resin.The backbone structure of epoxy resin
For the compound of phenyl ring class, there is certain rigidity, and the backbone structure of polyethenoxy ether class emulsifier is generally repeatability
Carbon carbon oxygen class compound has certain flexibility.Epoxy acrylate contains unsaturated double-bond after ultraviolet light solidifies
It is crosslinked between epoxy acrylate, molecular weight increases sharply, the hardness of the resin after solidification resin hardness more before curing
It is promoted.It, can be with by the collocation between variety classes epoxy resin, epoxy acrylate and polyethenoxy ether class emulsifier
Achieve the purpose that adjust the performances such as hardness, toughness, smoothness, the convergence of sizing agent.
It is better can to provide carbon fiber due to its distinctive flexibility for the higher polyethenoxy ether class emulsifier of molecular weight
The better smoothness of flexibility and surface.The polyoxy of bisphenol A-type and bisphenol F epoxy resin the collocation high molecular weight of small molecular amount
Ethylene ethers emulsifier can make carbon fiber have preferable convergence and surface smoothness.It is grouped as by above two group
Sizing agent to carbon fiber carry out starching after, since the hardness of two kinds of components is lower, high temperature drying after, finger touch carbon fiber surface
There is slight sticky situation in face.Therefore, it is necessary to hardness of arranging in pairs or groups is higher and the preferable ultraviolet cured epoxy acrylic of surface drying
Resin, so that the hardness of system is promoted slightly, to reach the tack-free state of drying defensive position touching surface drying.If the higher purple of hardness
Outer light-cured epoxy acrylate additive amount is too big, and it will cause the carbon fibre tow brittleness increases after drying, is unfavorable for
The weaving process of next step.Therefore, the collocation of above-mentioned three kinds of compositions is particularly important.
The additive amount and curing degree of ultraviolet cured epoxy acrylic resin influence the hard of entire sizing agent system
Degree, flexibility and crosslinking degree.Initiator content is excessive, will lead to point after ultraviolet cured epoxy acrylic resin solidifies
Son amount is excessive, to have a certain impact to sizing agent in sprawling for carbon fiber surface.Also, crosslink density is excessive, then can lead
Fiber detaching is caused to reduce, when preparing composite material, carbon fiber cannot be soaked preferably, thereby reduce its composite material
Performance.Molecular weight is excessive, so that the flexibility of carbon fiber, flexibility, convergence reduce, and then affects its weaving process,
Cannot preferably protect the surface of carbon fiber, thus excessive Epocryl be fully cured after sizing agent using effect
It is undesirable；Initiator content is too low, and it is too low to will lead to the molecular weight after ultraviolet cured epoxy acrylic resin solidifies, and divides
Son amount is smaller, then the degree of cross linking is inadequate between will lead to single fiber.If the crosslinking degree between single fiber is low, reduce between fiber
Active force so that the composite property of preparation reduces, while having a certain impact to the convergence of carbon fiber entirety；Ultraviolet
Light-cured epoxy acrylate content is moderate, the epoxy acrylate point in the case that initiator content is moderate, after solidification
Son amount is moderate, and the sizing agent of intermediate molecular weight can guarantee the preferable convergence of fiber and fibrillation simultaneously.
Epocryl and water emulsifier in the present invention contain unsaturated double-bond, solidify by ultraviolet light and walk
After rapid, unsaturated double-bond reacts, and crosslinks, and epoxy resin is closely wrapped, is not easy from upper between emulsifier
Starch separate out in agent system.In contrast, the emulsifier in traditional aqueous carbon fiber sizing agent, due to not having reaction
Property, it is easy the separate out from sizing agent, to influence the interface performance of carbon fiber surface, and in composite material preparation process
In, it is easy to influence the associativity with carbon fiber surface compound resin, to influence the mechanical property of composite material.
The present invention is scattered in deionized water by the excellent emulsifier of hydrophily by epoxy resin is stable, to obtain
The carbon fiber sizing agent of performance stabilization, stable storing.Also, the emulsifier of the type has unsaturated double-bond, can participate in certainly
By base curing reaction, combine closely with epoxy resin.Traditional aqueous carbon fiber sizing agent is generally thermohardening type sizing agent, this
Aqueous carbon fiber sizing agent in invention is the sizing agent of heat cure and photocuring mating type.The aqueous carbon fiber sizing agent can be with
Heat cure is only carried out, without photocuring, to obtain performance similar to traditional sizing agent；It can also complete heat curing operation
Afterwards, further progress photocuring step, to obtain more excellent performance.Therefore, the aqueous carbon fiber that the present invention is introduced
Sizing agent has biggish industrialized production benefit and good application prospect.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of aqueous carbon fiber sizing agent, which is characterized in that the aqueous carbon fiber sizing agent is following by by weight
Component is made:
2. aqueous carbon fiber sizing agent according to claim 1, which is characterized in that the additive amount of the epoxy resin is 22
~30 parts by weight, preferably 25~28 parts by weight；
Preferably, the additive amount of the epoxy acrylate is 5~7 parts by weight, more preferably 6~6.5 parts by weight；
Preferably, the additive amount of the hydrophilic emulsifier is 5~10 parts by weight, more preferably 6~8 parts by weight；
Preferably, the additive amount of the aqueous polyurethane emulsion is 2~15 parts by weight, more preferably 3~10 parts by weight；
Preferably, the additive amount of the aqueous polyurethane acrylate is 2~8 parts by weight, more preferably 3~5 parts by weight；
Preferably, the additive amount of the higher fatty acid amides is 1~3 parts by weight, more preferably 1.5~2 parts by weight；
Preferably, the additive amount of the photoinitiator is 0.05~2 parts by weight, more preferably 0.1~1 parts by weight；
Preferably, the additive amount of the aqueous wetting dispersing agent is 0.1~3 parts by weight, more preferably 0.2~1 parts by weight；
Preferably, the additive amount of the thickener is 0.2~3 parts by weight, more preferably 0.5~1 parts by weight；
Preferably, the additive amount of the solvent is 0.5~3 parts by weight, more preferably 1~2 parts by weight；
Preferably, the additive amount of the deionized water is 40~60 parts by weight, more preferably 45~50 parts by weight；
Preferably, the additive amount weight ratio of the epoxy resin and the solvent is 100:2~30, preferably 100:3~20, more
Preferably 100:4~10；
Preferably, the additive amount weight ratio of the epoxy resin and the higher fatty acid amides is 100:1~20, preferably: for
100:2~10, more preferably 100:3~5.
3. aqueous carbon fiber sizing agent according to claim 1, which is characterized in that the epoxy resin is selected from by bisphenol-A
Type epoxy resin, bisphenol f type epoxy resin, Cresol formaldehyde type epoxy resin, phenol novolak type epoxy and glycidol ether
One of group of type epoxy resin composition is a variety of；
Preferably, the epoxy acrylate is selected from by bisphenol-a epoxy acrylate, bisphenol F type epoxy acrylate, fat
Sour modified bisphenol A epoxy acrylate, amine modified bisphenol A epoxy acrylate, Cresol formaldehyde type epoxy acrylate, phenol phenol
One of group of aldehyde type epoxy acrylate and epoxy soybean oil modified acrylic ester composition is a variety of；
Preferably, the aqueous polyurethane acrylate is water-dispersion type or aqueous emulsion type polyurethane acrylate prepolymer；
Preferably, the hydrophilic emulsifier includes response type hydrophilic emulsifier and non-reactive hydrophilic emulsifier, wherein
The weight percent that the response type hydrophilic emulsifier accounts for the hydrophilic emulsifier is 50~100%；
Preferably, the response type hydrophilic emulsifier is tristyryl phenol polyethylene glycol methacrylate-styrene polymer, alkoxy gathers
One of glycolmethacrylate, methoxy polyethylene glycol methacrylate-styrene polymer are a variety of；
Preferably, the non-reactive hydrophilic emulsifier is nonylphenol polyoxyethylene ether, polyaryl polyethers, tristyryl phenol
One of polyoxyethylene ether is a variety of；
Preferably, the non-reactive hydrophilic emulsifier is polyethylene glycol, poly glycol monomethyl ether, in polyethyleneglycol esters
One or more mixtures, molecular weight be 400~20000；
Preferably, it is anionic emulsifying to be further selected from union base phenolic nonionic emulsifier, nonyl phenolic for the hydrophilic emulsifier
What agent, phosphate type anion emulsifier, non-nonyl phenolic nonionic emulsifier and non-nonyl phenolic anion emulsifier formed
One of group is a variety of；
Preferably, the aqueous polyurethane emulsion is water dispersant type polyaminoester resin or aqueous emulsion type polyurethane resin；
Preferably, the higher fatty acid amides be aliphatic monocarboxylic acid amide and/or aliphatic dicarboxylic acid amide, more preferably
, the aliphatic monocarboxylic acid amide is selected from by oleamide, stearic amide, erucamide, moon silicic acid amide, palmitinic acid
One of group of amide, castor oil acid acid amides and hydroxy stearic acid amide composition is a variety of；The aliphatic dicarboxylic acid amide
Selected from by ethylene bis-stearamide, ethylidene dilaurate amide, ethylene oleamide, ethylene isostearic acid
One of group of amide, ethylene hydroxy stearic acid amide and hexa-methylene distearyl acid amide composition is a variety of；
Preferably, the photoinitiator is cracking type initiator and/or hydrogen-abstraction initiator；It is furthermore preferred that the cracking type draws
Agent is sent out to be selected from by 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 1,1'- (two -4,1- phenylene of methylene) bis- [2-
Hydroxy-2-methyl-1- acetone], 2- methyl-1-[- 4- methyl mercapto) phenyl]-2- morpholinyl-1- acetone, 2,4,6- trimethylbenzene
Formoxyl-diphenyl phosphine oxide, benzoin dimethylether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyciohexyl-benzene
One of group or a variety of of base ketone and benzoyl derivatives composition, the hydrogen-abstraction initiator be selected from by benzophenone,
4- benzoyl -4'- methyl-diphenyl sulfide, 2- benzoyl methyl benzoate, (the 2,4 isomers mixing of isopropyl thioxanthone uh ketone
Object) and 4- (N, N- dimethylamino) ethyl benzoate composition one of group or a variety of；
Preferably, the aqueous wetting dispersing agent is selected from total by alkylol amine salt, the acrylic compounds of high molecular weight acidic polymer
Alkane hydroxyl amine salt, the band of the polynary hydroxy acid polymer of polymers, the structured copolymers containing the affine organ of pigment, low molecular weight are acid
Alkanolamine, the multiple functional radical polymeric alkanolamine of the polymer copolymerization ester of group, contain the polymeric alkylammonium salt of multiple functional radical
One of the group or more of pigment affinity groups polymer copolymerization body and the acrylic copolymer composition with pigment affinity groups
Kind；
Preferably, the thickener is selected from by polyhydroxycarboxylicacid amides solution, modified urea solution, urea-modified polyurethane solutions, height
Spend one of group of polyurethane solutions composition of branched structure or a variety of；
Preferably, the solvent is selected from by propylene glycol monomethyl ether, butyl glycol ether, glycol dimethyl ether, butyl cellosolve, third
One of group of ketone, butanone and butyl acetate composition is a variety of.
4. aqueous carbon fiber sizing agent according to claim 1, which is characterized in that the aqueous carbon fiber sizing agent starching
After need carry out heat cure and ultraviolet light solidification.
5. aqueous carbon fiber sizing agent according to claim 4, which is characterized in that the temperature of the heat cure be 120~
160 DEG C, preferably 130~150 DEG C；The irradiate light quantity that the ultraviolet light solidifies middle-ultraviolet lamp is 200~1000mj/m2, it is preferable that
The ultraviolet irradiation light quantity is 600~800mj/m2。
6. a kind of preparation method of the aqueous carbon fiber sizing agent as described in any one of claims 1 to 5, which is characterized in that
Include: the component for weighing following parts by weight:
It mixes the above components evenly and the aqueous carbon fiber sizing agent is prepared.
7. preparation method according to claim 6, which is characterized in that the preparation method of the aqueous carbon fiber sizing agent has
Body the following steps are included:
The epoxy resin and the epoxy acrylate are added the appropriate stirring solvent and are uniformly mixed, obtains first by S1
Epoxy-resin systems；
The hydrophilic emulsifier is added in the first epoxy-resin systems of S2, Xiang Suoshu, is stirring evenly and then adding into the aqueous profit
Hygroscopic water powder obtains the second epoxy-resin systems；
Deionized water is added in the second epoxy-resin systems of S3, Xiang Suoshu to be dispersed, the aqueous polyurethane third is then added
Olefin(e) acid ester, after mixing, the photoinitiator of the dissolution of the solvent described in remainder obtains third epoxy-resin systems；
S4 is added the third epoxy-resin systems, stirs evenly after diluting the thickener with deionized water, obtain described
Aqueous carbon fiber sizing agent.
8. preparation method according to claim 7, which is characterized in that the S1 includes the epoxy resin and the ring
Oxypropylene acid esters is added the appropriate solvent and is uniformly mixed in the agitating device with condenser, and temperature rises to 60~80 DEG C,
It is dispersed with stirring 0.5~2 hour, 500~1500r/min of mixing speed, obtains first epoxy-resin systems；
Preferably, the S2 includes, in the case where at the uniform velocity stirring, being added in the first epoxy-resin systems of Xiang Suoshu described hydrophilic
Property emulsifier, mixing time 0.5~2 hour, 500~1500r/min of mixing speed, then, be cooled to 60~80 DEG C, institute be added
Aqueous wetting dispersing agent is stated, the second epoxy-resin systems are obtained；
Preferably, the S3 includes that second epoxy-resin systems are reduced temperature to 45~70 DEG C, 50 parts is slowly added to and goes
Ionized water, time for adding are 0.5~2 hour, after being added dropwise, continue to be dispersed with stirring 0.5~2 hour, mixing speed 1000~
Then second epoxy-resin systems are cooled to 45~70 DEG C, the watersoluble polyurethane acrylic acid are added by 3000r/min
Ester continues to be dispersed with stirring 0.5~2 hour, 500~1500r/min of mixing speed；Second epoxy-resin systems are cooled to
25~40 DEG C, the photoinitiator of the dissolution of the solvent described in remainder is then added, is dispersed with stirring 0.5 hour, stirring speed
500~1500r/min is spent, third epoxy-resin systems are obtained；
Preferably, in the S4, the time being dispersed with stirring is 0.5~2 hour, and mixing speed is 500~1500r/min.
9. preparation method according to claim 8, which is characterized in that when the higher fatty acid amides additive amount is not 0
When, the S1 includes, by the part epoxy and the higher fatty acid amides in the agitating device with condenser
It is uniformly mixed, temperature rises to 130~150 DEG C, is dispersed with stirring 0.5~2 hour, 500~1000r/min of mixing speed, by system
Temperature is reduced to 60~80 DEG C, and epoxy resin and the part solvent described in remainder is added, is dispersed with stirring 0.5~2 hour,
500~1500r/min of mixing speed obtains first epoxy-resin systems；
Preferably, it when the aqueous polyurethane emulsion additive amount is not 0, in the S3, is added before the photoinitiator also
Including, system is cooled to 45~70 DEG C, the aqueous polyurethane emulsion is added and continues to be dispersed with stirring 0.5~2 hour, stirring speed
Spend 500~1500r/min.
10. preparation method according to claim 6, which is characterized in that the additive amount of the epoxy resin is 22~30 weights
Measure part, preferably 25~28 parts by weight；
Preferably, the additive amount of the hydrophilic emulsifier is 5~10 parts by weight, more preferably 6~8 parts by weight；
Preferably, the additive amount of the aqueous polyurethane emulsion is 2~15 parts by weight, more preferably 3~10 parts by weight；
Preferably, the additive amount of the aqueous polyurethane acrylate is 2~8 parts by weight, more preferably 3~5 parts by weight；
Preferably, the additive amount of the higher fatty acid amides is 1~3 parts by weight, more preferably 1.5~2 parts by weight；
Preferably, the additive amount of the photoinitiator is 0.05~2 parts by weight, more preferably 0.1~1 parts by weight；
Preferably, the additive amount of the aqueous wetting dispersing agent is 0.1~3 parts by weight, more preferably 0.2~1 parts by weight；
Preferably, the additive amount of the thickener is 0.2~3 parts by weight, more preferably 0.5~1 parts by weight；
Preferably, the additive amount of the solvent is 0.5~3 parts by weight, more preferably 1~2 parts by weight；
Preferably, the additive amount of the deionized water is 40~60 parts by weight, more preferably 45~50 parts by weight；
Preferably, the additive amount weight ratio of the epoxy resin and the solvent is 100:2~30, preferably 100:3~20, more
Preferably 100:4~10；
Preferably, the additive amount weight ratio of the epoxy resin and the higher fatty acid amides is 100:1~20, preferably: for
100:2~10, more preferably 100:3~5.
11. preparation method according to claim 6, which is characterized in that the epoxy resin is selected from by bisphenol type epoxy tree
Rouge, bisphenol f type epoxy resin, Cresol formaldehyde type epoxy resin, phenol novolak type epoxy and diglycidyl ether type epoxy tree
One of group of rouge composition is a variety of；
Preferably, the epoxy acrylate is selected from by bisphenol-a epoxy acrylate, bisphenol F type epoxy acrylate, fat
Sour modified bisphenol A epoxy acrylate, amine modified bisphenol A epoxy acrylate, Cresol formaldehyde type epoxy acrylate, phenol phenol
One of group of aldehyde type epoxy acrylate and epoxy soybean oil modified acrylic ester composition is a variety of；
Preferably, the aqueous polyurethane acrylate is water-dispersion type or aqueous emulsion type polyurethane acrylate prepolymer；
Preferably, the hydrophilic emulsifier includes response type hydrophilic emulsifier and non-reactive hydrophilic emulsifier, wherein
The weight percent that the response type hydrophilic emulsifier accounts for the hydrophilic emulsifier is 50~100%；
Preferably, the response type hydrophilic emulsifier is tristyryl phenol polyethylene glycol methacrylate-styrene polymer, alkoxy gathers
One of glycolmethacrylate, methoxy polyethylene glycol methacrylate-styrene polymer are a variety of；
Preferably, the non-reactive hydrophilic emulsifier is nonylphenol polyoxyethylene ether, polyaryl polyethers, tristyryl phenol
One of polyoxyethylene ether is a variety of；
Preferably, the non-reactive hydrophilic emulsifier is polyethylene glycol, poly glycol monomethyl ether, in polyethyleneglycol esters
One or more mixtures, molecular weight be 400~20000；
Preferably, it is anionic emulsifying to be further selected from union base phenolic nonionic emulsifier, nonyl phenolic for the hydrophilic emulsifier
What agent, phosphate type anion emulsifier, non-nonyl phenolic nonionic emulsifier and non-nonyl phenolic anion emulsifier formed
One of group is a variety of；
Preferably, the aqueous polyurethane emulsion is water dispersant type polyaminoester resin or aqueous emulsion type polyurethane resin；
Preferably, the higher fatty acid amides be aliphatic monocarboxylic acid amide and/or aliphatic dicarboxylic acid amide, more preferably
, the aliphatic monocarboxylic acid amide is selected from by oleamide, stearic amide, erucamide, moon silicic acid amide, palmitinic acid
One of group of amide, castor oil acid acid amides and hydroxy stearic acid amide composition is a variety of；The aliphatic dicarboxylic acid amide
Selected from by ethylene bis-stearamide, ethylidene dilaurate amide, ethylene oleamide, ethylene isostearic acid
One of group of amide, ethylene hydroxy stearic acid amide and hexa-methylene distearyl acid amide composition is a variety of；
Preferably, the photoinitiator is cracking type initiator and/or hydrogen-abstraction initiator；It is furthermore preferred that the cracking type draws
Agent is sent out to be selected from by 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, 1,1'- (two -4,1- phenylene of methylene) bis- [2-
Hydroxy-2-methyl-1- acetone], 2- methyl-1-[- 4- methyl mercapto) phenyl]-2- morpholinyl-1- acetone, 2,4,6- trimethylbenzene
Formoxyl-diphenyl phosphine oxide, benzoin dimethylether, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyciohexyl-benzene
One of group or a variety of of base ketone and benzoyl derivatives composition, the hydrogen-abstraction initiator be selected from by benzophenone,
4- benzoyl -4'- methyl-diphenyl sulfide, 2- benzoyl methyl benzoate, (the 2,4 isomers mixing of isopropyl thioxanthone uh ketone
Object) and 4- (N, N- dimethylamino) ethyl benzoate composition one of group or a variety of；
Preferably, the aqueous wetting dispersing agent is selected from total by alkylol amine salt, the acrylic compounds of high molecular weight acidic polymer
Alkane hydroxyl amine salt, the band of the polynary hydroxy acid polymer of polymers, the structured copolymers containing the affine organ of pigment, low molecular weight are acid
Alkanolamine, the multiple functional radical polymeric alkanolamine of the polymer copolymerization ester of group, contain the polymeric alkylammonium salt of multiple functional radical
One of the group or more of pigment affinity groups polymer copolymerization body and the acrylic copolymer composition with pigment affinity groups
Kind；
Preferably, the thickener is selected from by polyhydroxycarboxylicacid amides solution, modified urea solution, urea-modified polyurethane solutions, height
Spend one of group of polyurethane solutions composition of branched structure or a variety of；
Preferably, the solvent is selected from by propylene glycol monomethyl ether, butyl glycol ether, glycol dimethyl ether, butyl cellosolve, third
One of group of ketone, butanone and butyl acetate composition is a variety of.
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| CN113355916B (en) * | 2021-06-22 | 2022-09-06 | 江苏恒神股份有限公司 | Carbon fiber bundling agent, carbon fiber bundle for winding forming, and preparation method and application thereof |
| CN113278173A (en) * | 2021-07-07 | 2021-08-20 | 中科英华长春高技术有限公司 | Application of lignin-based sizing agent in epoxy acrylate composite material |
| CN114213751A (en) * | 2021-12-09 | 2022-03-22 | 福建师范大学泉港石化研究院 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN114213751B (en) * | 2021-12-09 | 2022-07-15 | 福建师范大学泉港石化研究院 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN115787147A (en) * | 2022-11-30 | 2023-03-14 | 上海丰泽源科技有限公司 | Oiling agent for polyacrylonitrile-based carbon fiber precursor and preparation method thereof |
| CN115787147B (en) * | 2022-11-30 | 2024-05-17 | 上海丰泽源科技有限公司 | Oiling agent for polyacrylonitrile-based carbon fiber precursor and preparation method thereof |
| CN115807341A (en) * | 2022-12-20 | 2023-03-17 | 武汉纺织大学 | Preparation method and application of UV (ultraviolet) photocuring environment-friendly nitride fiber sizing agent |
| CN115807341B (en) * | 2022-12-20 | 2024-06-07 | 武汉纺织大学 | Preparation method and application of UV (ultraviolet) light-cured environment-friendly nitride fiber sizing agent |
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