CN110512427A - A kind of collection of filaments agent - Google Patents
A kind of collection of filaments agent Download PDFInfo
- Publication number
- CN110512427A CN110512427A CN201910873425.6A CN201910873425A CN110512427A CN 110512427 A CN110512427 A CN 110512427A CN 201910873425 A CN201910873425 A CN 201910873425A CN 110512427 A CN110512427 A CN 110512427A
- Authority
- CN
- China
- Prior art keywords
- resin
- filaments
- collection
- agent
- bisphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
The invention discloses a kind of collection of filaments agent, by as effective component vinylester resin and polyurethane resin dispersion formed in an aqueous medium.Vinylester resin is reacted to obtain by bisphenol-type epoxy resin with unsaturated carboxylic acid；Polyurethane resin is reacted to obtain by aromatic polyol with polyisocyanates.There is good convergence using the processed fiber of collection of filaments agent, there is good compatibility with resin matrixes such as vinylester resin and unsaturated polyester resins, the molded product with excellent mechanical property can be produced.
Description
Technical field
The present invention relates to fiber correlative technology fields, specifically, being related to a kind of carbon fiber, glass fibre etc. of can be used for
Collection of filaments agent.
Background technique
Carbon fiber and glass fibre are common reinforcing fibers in fiber-reinforced resin sill.Use unsaturated polyester (UP)
The thermosetting resins such as resin, vinylester resin, epoxy resin, phenolic resin, the composite material being compounded to form with glass fibre, tool
There is very extensive application.Wherein, vinylester resin and unsaturated polyester resin, it is viscous due to having compared with epoxy resin
The advantages such as adjustable, solidification temperature range is wide, curing time is short, shaping efficiency is high are spent, demand and actual use amount are in recent years
Quickly improve.
Carbon fiber when using vinylester resin or unsaturated polyester resin as matrix resin, as reinforcing fiber
Or the interface affinity between glass fibre and resin matrix, it is a key factor for influencing composite materials property.
It will use fiber collection in fiber-reinforced resin matrix compound material field in order to improve the interface affinity between matrix and fiber
Beam agent (being also referred to as sizing agent, collecting agent, size etc. according to different occasions) is surface-treated fiber.These are for fibre
In the inorganic agent of dimension, certain resin component is usually contained, after handling fiber, pitch deposition is in fiber surface.Fiber with
Resin base material carries out compound tense, and the resin and substrate of fiber surface have similar Surface Physical Chemistry performance, to make fiber
There is good compatibility with resin, composite molding can be carried out by various forming methods.
It is towards epoxy resin substrate mostly currently, being suitable for the collecting agent of the reinforcing fibers such as carbon fiber and glass fibre
's.Effective component in these collecting agents, and based on epoxy resin.But when resin base material vinylester resin or
It is traditional using epoxy resin as the collection of filaments agent of principle active component when unsaturated polyester resin, although can also be mentioned to fiber
For good convergence, but due to the difference on molecular structure, the compatibility that treated between fiber and resin base material is not
Can be of great satisfaction, molded product and component after molding cannot fully play the mechanical property of fiber.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide one kind for glass fibre and carbon fiber with excellent
Convergence, while treated substrates such as fiber and vinylester resin and unsaturated polyester resin have good surface affine
Property, the collection of filaments agent of component and molded product with excellent mechanical performance can be obtained after composite molding.
To achieve the goals above, the following technical solutions are proposed by the present invention:
A kind of collection of filaments agent, by as effective component vinylester resin and polyurethane resin dispersion in an aqueous medium
It is formed.
Preferably, in above-mentioned collection of filaments agent: some or all of described vinylester resin is wrapped in poly-
The inside of urethane resin forms the resin particle of core-shell structure.
Preferably, in above-mentioned collection of filaments agent: the mass ratio of the vinylester resin and polyurethane resin
70:30-20:80.It is preferred that between 55:45-30:70.If the content of vinylester resin is too low, the compatibility with resin base material
Deficiency influences the realization of the object of the invention；If the content of polyurethane resin is too low, fiber after emulsion intercalation method and processing
Boundling fibrillation balance etc. can all be affected, and equally influence effect of the invention.
In collection of filaments agent of the invention, other components can also be added as needed, such as crosslinking agent, curing agent, lubrication
Agent, heat stabilizer, defoaming agent, antioxidant, antibacterial agent etc..
Preferably, in above-mentioned collection of filaments agent: the vinylester resin is by bisphenol-type epoxy resin and insatiable hunger
It is obtained with carboxylic acid reaction；The reaction temperature that the bisphenol-type epoxy resin is reacted with unsaturated carboxylic acid is 60-150 DEG C, is being reacted
In the process, thermal polymerization occurs for the unsaturated group in unsaturated carboxylic acid in order to prevent, adds polymerization inhibitor during the reaction.
The bisphenol-type epoxy resin be bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring oxygen resin,
One of bisphenol-s epoxy resin, resorcinol formaldehyde epoxy resin or two or more mixing；The epoxy of epoxy resin is worked as
Amount is 150-2000g/mol.In the reaction process of epoxy resin and unsaturated carboxylic acid, the epoxy of 80~100mol% should ensure that
Group reacts with the carboxylic acid group in unsaturated carboxylic acid, and preferably whole epoxy groups all reacts, end of reaction
No longer contain active epoxy group in product afterwards.
The usage amount of the polymerization inhibitor, relative to total quality of bisphenol-type epoxy resin and unsaturated carboxylic acid, 500~
Between 5000ppm；The polymerization inhibitor be 2,6- diisobutyl -4- methylphenol, hydroquinone (quinhydrones), methyl hydroquinone,
Hydroquinone monomethyl ether's (first quinone), dibutyl hydroxy toluene, butylated hydroxyanisole (BHA), nitrobenzene, nitrobenzoic acid, adjacent dinitro
Base benzene, paradinitrobenzene, m-dinitrobenzene, 2,4- dinitrophenol, trinitrobenzen etc..Wherein especially with hydroquinone, to benzene two
The mixture of one or more of phenol monomethyl ether, dibutyl hydroxy toluene, butylated hydroxyanisole (BHA).
In view of dispersion stabilization of the resin particle in water-medium, the weight of the vinylester resin reacted (A) is equal
Molecular weight should be between 500~10000, between preferably 1000~6000.
Preferably, in above-mentioned collection of filaments agent: what the bisphenol-type epoxy resin was reacted with unsaturated carboxylic acid
Catalyst is added in the process, and the use weight of catalyst is bisphenol-type epoxy resin 0.1~5%, and the catalyst is urged for amine
Agent, imidazoles catalyst, phosphorus series catalysts or boron series catalysts.In order to improve reaction speed, catalyst can be used.
Preferably, in above-mentioned collection of filaments agent: the polyurethane resin is by aromatic polyol and polyisocyanate cyanogen
Acid esters reacts to obtain, and reaction is mixed in the presence of solvent-free or organic solvent, in 40~120 DEG C of temperature range
It is interior, it reacts 3~20 hours.The equivalent proportion of the isocyanate group in hydroxyl and polyisocyanates in aromatic polyol is 0.5
~3.5.The organic solvent is the ketones solvents such as acetone, methyl ethyl ketone, the ether solvents such as tetrahydrofuran, ethyl acetate, acetic acid fourth
The amide solvents such as the esters solvents such as ester, dimethylformamide.Consider from the compatibility of resin matrix, the polyurethane resin
Weight average molecular weight should be between 3000~200000.Consider from safety, environmentally friendly etc., preferably by vacuum distillation etc.
Method all removes organic solvent.In this manner it is possible to achieve resin particle (D) is dispersed in water the collection of filaments agent to be formed.
The aromatic polyol is that aromatic polyester polyol, aromatic polyether polyalcohol, aromatic copolycarbonate are more
First alcohol, bisphenol-A one or more of alkoxy addition product mixture.Consider from the compatibility of resin matrix, with virtue
The alkoxy addition product of fragrant adoption ester polyol and bisphenol-A be it is best, therefore, in the aforementioned polyalcohol (b1) containing aromatic rings,
One of the two should at least be contained.
The aromatic polyester polyol is obtained by polyacid and polyol reaction, therefore, in polyacid or
In polyalcohol, at least one kind contains aromatic rings.Wherein, the polynary acid-specific containing aromatic rings is such as: phthalic acid, to benzene two
The aromatic diacids such as formic acid, M-phthalic acid or its ester.Polynary acid-specific without aromatic rings is such as: succinic acid, glutaric acid, oneself
Aliphatic diacids or its ester such as diacid, maleic acid, clothing be antiacid, malic acid, fumaric acid.Polyacid can be used alone, can also
To mix two or more uses.Polyalcohol containing aromatic rings is specifically such as: Benzenediol, toluene glycol, Xylene glycol fragrance
Race's glycol, the polyalcohol without containing aromatic rings specifically such as: ethylene glycol, propylene glycol, Isosorbide-5-Nitrae butanediol, 1, the aliphatic such as 6 hexylene glycols two
Alcohol.Polyalcohol may be used singly or in combination of two or more.Aromatic rings concentration in the aromatic polyol is
1.5-8mol/kg。
Preferably, in above-mentioned collection of filaments agent: aromatic polyester polyol in the synthesis process, in order to promote
Catalyst can be used in esterification.The gold such as common catalyst such as titanium compound, tin compound, zinc compound, aluminium compound
Belong to class catalyst.
Preferably, in above-mentioned collection of filaments agent: it is more that the aromatic polyol includes at least aromatic polyether
One of the alkoxy addition product of the pure and mild bisphenol-A of member.The alkoxy addition product of the bisphenol-A refers to the hydroxyl of bisphenol-A and more
Substance after first alcohol addition.Polyalcohol used such as ethylene glycol, propylene glycol etc..The addition molal quantity of alkoxy in each bisphenol-A
It should be between 1~8, between preferably 1~4.
Preferably, in above-mentioned collection of filaments agent: the polyisocyanates is aromatic diisocyanate or rouge
Fat (cyclo) aliphatic diisocyanates.In order to improve the intensity of final molding product, it is preferred to use aromatic diisocyanate, in polyisocyanic acid
Mass ratio in ester (b2), between Ying 15~35%.
Preferably, in above-mentioned collection of filaments agent: the unsaturated carboxylic acid be acrylic acid, methacrylic acid or
The mixture of one or more of itaconic acid.Carbon-carbon double bond etc. should be contained no simultaneously in its molecular structure of the unsaturated carboxylic acid
Saturated group and carboxylic acid group.Condensation reaction occurs by the epoxy group in carboxylic acid group and epoxy resin, by unsaturated group
It is introduced into aforementioned vinylester resin A.Angularly consider from the complexity of reaction, is best with acrylic acid.Acrylic acid is at it
In accounting be not lower than 50wt%.
Above-mentioned vinylester resin (A) is the production reacted by bisphenol-type epoxy resin (a1) with unsaturated carboxylic acid (a2)
Object.In the reaction, aforementioned unsaturated carboxylic acid (a2) is reacted by carboxyl with epoxy resin, and unsaturated functional group then obtains
To retain, that is to say, that in vinylester resin (A), contain the unsaturated functional group that polymerization reaction can occur, these insatiable hungers
Polymerization reaction occurs with the unsaturated functional group in functional group and matrix resin, forms macromolecular network structure, thus the present invention
Collection of filaments agent and matrix resin between have strong compatibility.
So-called water-medium (C), can be the mixture etc. of pure water, water and organic solvent in the present invention.From safety,
Environment friendly and cost etc. consider, it is best to use pure water.
In collection of filaments agent of the invention, the mass ratio of water-medium (C) should between 10~90%, preferably 30~
Between 70%.
Collection of filaments agent in the present invention is that aforementioned vinylester resin (A) and aforementioned polyurethane resin (B) are dispersed in water
It is to be formed in medium (C).At this point, vinylester resin (A) and polyurethane resin (B) are dispersed in water or one respectively
Or whole vinylester resins (A) is located at the inside of polyurethane resin (B), forms compound resin ion (D) and is ok.More
For concretely, it is core that compound particle (D), which is vinylester resin (A), polyurethane resin (B) be hull shape at core-shell structure tree
Fat granule.
Aforementioned resin particle (D), can be by first producing vinylester resin (A) and polyurethane resin (B), so respectively
Afterwards, vinylester resin (A), alkali compounds and water-medium and urethane resin (B) are mixed to get.
Collection of filaments agent of the invention can be used for the boundling to carbon fiber and glass fibre, treated fiber, can be with
With vinylester resin, unsaturated polyester resin, phenolic resin, polycarbonate resin, polyimide resin, polyester resin, epoxy
The progress of the resin matrixes such as resin is compound, especially with vinylester resin and unsaturated polyester resin, has good compatibility, energy
It is enough to obtain the molded product with excellent mechanical property, it can be used for component, the pressure vessel, household electrical appliances system of automobile and aircraft
The extensive field such as component, the component for wind power generation of product.
Compared with prior art, the invention has the following beneficial effects:
Collection of filaments agent in the present invention has excellent convergence to carbon fiber and glass fibre, can be effectively improved
The compatibility of itself and vinylester resin and unsaturated polyester resin, therefore may be used as the collection of filaments of carbon fiber and glass fibre
Agent.
Using treated carbon fiber or the glass fibre of the collection of filaments agent in the present invention, with resin base material it is compound after energy
It is enough to obtain the molded product with excellent mechanical property, it can be used for component, the pressure vessel, household electrical appliances system of automobile and aircraft
The extensive field such as component, the component for wind power generation of product.
Specific embodiment
Below by way of specific embodiment, the present invention is further detailed.
The synthesis of aromatic polyester polyol:
In the reaction vessel for being equipped with thermometer, nitrogen tube, blender, 26.3 mass parts of terephthalic acid (TPA) are added,
26.3 parts of phthalic acid, 23.5 parts of butanediol, 27.2 parts of neopentyl glycol, 0.04 part of Dibutyltin oxide, it is passed through nitrogen, is heated to
230 DEG C are reacted 24 hours, and aromatic polyester polyol (acid value 0.2, hydroxyl valence 112.2, aromatic rings concentration 3.98mol/kg) is obtained
The synthesis of vinylester resin:
Addition 68.6 mass parts of bisphenol A type epoxy resin in the reaction vessel, 19.5 parts of acrylic acid, 0.11 part of first quinone, first
It 11.3 parts of ethyl ketone, stirs uniform.Then it is added 0.55 part of triphenyl phasphine.Kept for 80 DEG C of reaction temperature, reaction to acid value is less than 1.5.
Obtain 75% vinylester resin solution.
The synthesis of polyurethane resin:
It is added 100 mass parts of aromatic polyester polyol of above-mentioned synthesis in the reaction vessel, decompression dehydration at 100 DEG C,
80 DEG C are cooled to, 111 parts of methyl ethyl ketone is added, stirs evenly.Then 8.1 parts of 2,2- dimethoxy propionic acid is added, triphenyl two is different
28.0 parts of cyanate, 0.08 mass parts of Dibutyltin oxide are reacted 12 hours at 80 DEG C, complete polyurethane-reinforcement.Work as isocyanic acid
When ester is below 0.1%, it is added 0.3 part of n- butanol, the reaction was continued 2 hours, is cooled to 50 DEG C, obtains the poly- ammonia containing hydrophilic group
55% solution of ester resin.
Embodiment 1 (preparation of collection of filaments agent A)
In 55% solution, 100 mass parts of aforementioned obtained polyurethane resin, 75% vinylester resin solution is added
It 73.3 parts, 3.6 parts of triethylamine, is dissolved being slowly added to 263.1 parts of deionized water.Then vacuum distillation is carried out at 50 DEG C to remove
Methyl ethyl ketone is gone, the collection of filaments agent A that solid content is 30% or so is obtained.Because having remaining acid during previous reaction, this
Place is neutralized using triethylamine.In addition, the reaction product of triethylamine can also destroy the azeotropic of methyl ethyl ketone and water, after being conducive to
Continuous vacuum distillation separation process.
Embodiment 2-5 (preparation of collecting agent B-E)
According to different proportion shown in table 1, step obtains different collection of filaments agent according to embodiment 1, and solid content is equal
It is 40%.
The evaluation of the convergence of collection of filaments agent
Unsized PAN base carbon fibre beam (7 μm of filament diameter, 6K) are taken, infusion process collecting agent obtained above is used
It is handled, adjusting its adhesion amount on fiber by pressure roller is 1%.It is dry.Friction test device is made by oneself, in 50g
Tension under, rub 1000 times in friction-bar, observe its lousiness situation.
A: with about the same, absolutely not lousiness before test；
B: a small amount of lousiness, but do not influence to use completely；
C: there are many lousiness, a small amount of fracture of wire；
D: there are many lousiness and fracture of wire.
Interlaminar shear strength: it is carried out according to method specified in national standard GB/T 1450.1-2005.
Table 1
Claims (10)
1. a kind of collection of filaments agent, it is characterised in that: by as effective component vinylester resin and polyurethane resin be dispersed in
It is formed in aqueous medium.
2. collection of filaments agent according to claim 1, it is characterised in that: some or all of described vinylester resin, quilt
The inside for being wrapped in polyurethane resin forms the resin particle of core-shell structure.
3. collection of filaments agent according to claim 1 or 2, it is characterised in that: the vinylester resin and polyurethane resin
Mass ratio 70:30-20:80.
4. collection of filaments agent as described in claim 1, it is characterised in that: the vinylester resin by bisphenol-type epoxy resin with
Unsaturated carboxylic acid reacts to obtain；
The bisphenol-type epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring oxygen resin, bis-phenol
One of S type epoxy resin, resorcinol formaldehyde epoxy resin or two or more mixing；The epoxide equivalent of epoxy resin is
150-2000g/mol；
The unsaturated carboxylic acid is the mixture of one or more of acrylic acid, methacrylic acid or itaconic acid.
5. collection of filaments agent as claimed in claim 4, it is characterised in that: the bisphenol-type epoxy resin and unsaturated carboxylic acid are anti-
The reaction temperature answered is 60-150 DEG C, and adds polymerization inhibitor during the reaction；The usage amount of the polymerization inhibitor, relative to bis-phenol
Total quality of type epoxy resin and unsaturated carboxylic acid, between 500 ~ 5000ppm；The polymerization inhibitor is 2,6- diisobutyl-
4- methylphenol, hydroquinone (quinhydrones), methyl hydroquinone, hydroquinone monomethyl ether's (first quinone), dibutyl hydroxy toluene, fourth
Base hydroxyanisol, nitrobenzene, nitrobenzoic acid, o-dinitrobenzene, paradinitrobenzene, m-dinitrobenzene, 2,4- dinitro
Phenol, trinitrobenzen etc..
6. collection of filaments agent as claimed in claim 4, it is characterised in that: the bisphenol-type epoxy resin and unsaturated carboxylic acid are anti-
Catalyst is added during answering, the use weight of catalyst is bisphenol-type epoxy resin 0.1 ~ 5%, and the catalyst is amine
Catalyst, imidazoles catalyst, phosphorus series catalysts or boron series catalysts.
7. collection of filaments agent as described in claim 1, it is characterised in that: the polyurethane resin is by aromatic polyol and more
Isocyanates reacts to obtain, and reaction is mixed in the presence of solvent-free or organic solvent, in 40 ~ 120 DEG C of temperature
In range, react 3 ~ 20 hours；The equivalent proportion of the isocyanate group in hydroxyl and polyisocyanates in aromatic polyol is
0.5~3.5；
The aromatic polyol be aromatic polyester polyol, aromatic polyether polyalcohol, aromatic copolycarbonate polyalcohol,
The mixture of one or more of the alkoxy addition product of bisphenol-A.
8. collection of filaments agent as claimed in claim 7, it is characterised in that: the alkoxy addition product of the bisphenol-A refers to bis-phenol
Substance after the hydroxyl of A and polyalcohol addition, the addition molal quantity of alkoxy should be between 1 ~ 8 in each bisphenol-A；
The aromatic polyester polyol is obtained by polyacid and polyol reaction, in polyacid or polyalcohol,
At least one kind contains aromatic rings, and the aromatic rings concentration in aromatic polyol is 1.5-8mol/kg.
9. collection of filaments agent according to claim 8, it is characterised in that: the polyisocyanates is aromatic diisocyanates
Ester or aliphatic diisocyanate.
10. collection of filaments agent according to claim 7, it is characterised in that: the organic solvent is ketones solvent, ethers is molten
Agent, esters solvent or amide solvent；The weight average molecular weight of polyurethane resin is between 3000 ~ 200000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910873425.6A CN110512427A (en) | 2019-09-17 | 2019-09-17 | A kind of collection of filaments agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910873425.6A CN110512427A (en) | 2019-09-17 | 2019-09-17 | A kind of collection of filaments agent |
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| CN110512427A true CN110512427A (en) | 2019-11-29 |
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ID=68631115
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355916A (en) * | 2021-06-22 | 2021-09-07 | 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 |
| CN115679702A (en) * | 2022-10-18 | 2023-02-03 | 广东裕田霸力科技股份有限公司 | Yellowing-resistant flying-weaving treating agent and preparation method thereof |
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|---|---|---|---|---|
| CN101755089A (en) * | 2007-05-22 | 2010-06-23 | 三洋化成工业株式会社 | Fiber sizing agent |
| CN103797183A (en) * | 2011-09-22 | 2014-05-14 | 三洋化成工业株式会社 | Fiber sizing agent composition |
| JP2015175065A (en) * | 2014-03-13 | 2015-10-05 | Dic株式会社 | fiber sizing agent |
| CN107207346A (en) * | 2015-01-19 | 2017-09-26 | 帝人株式会社 | Cement reinforcement fibrous material |
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2019
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101755089A (en) * | 2007-05-22 | 2010-06-23 | 三洋化成工业株式会社 | Fiber sizing agent |
| CN103797183A (en) * | 2011-09-22 | 2014-05-14 | 三洋化成工业株式会社 | Fiber sizing agent composition |
| JP2015175065A (en) * | 2014-03-13 | 2015-10-05 | Dic株式会社 | fiber sizing agent |
| CN107207346A (en) * | 2015-01-19 | 2017-09-26 | 帝人株式会社 | Cement reinforcement fibrous material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355916A (en) * | 2021-06-22 | 2021-09-07 | 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 |
| 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 |
| CN115679702A (en) * | 2022-10-18 | 2023-02-03 | 广东裕田霸力科技股份有限公司 | Yellowing-resistant flying-weaving treating agent and preparation method thereof |
| CN115679702B (en) * | 2022-10-18 | 2023-09-12 | 广东裕田霸力科技股份有限公司 | Yellowing-resistant fly-weaving treating agent and preparation method thereof |
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