CN105401422B - A kind of size and its application in alkali-free glass fibre varicosity yarn is produced - Google Patents
A kind of size and its application in alkali-free glass fibre varicosity yarn is produced Download PDFInfo
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- CN105401422B CN105401422B CN201510745854.7A CN201510745854A CN105401422B CN 105401422 B CN105401422 B CN 105401422B CN 201510745854 A CN201510745854 A CN 201510745854A CN 105401422 B CN105401422 B CN 105401422B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—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
- D06M13/46—Compounds containing quaternary nitrogen atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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Abstract
A kind of application the invention discloses size and its in alkali-free glass fibre varicosity yarn is produced, the raw material for preparing of the size includes coupling agent, lubricant, film forming agent, surfactant, pH adjusting agent and deionized water, the solid masses of the size accounts for the 3~10% of size gross mass, and surplus is water;The coupling agent uses silane coupling agent;The lubricant uses water-soluble organic compounds;The film forming agent is epoxy emulsion and the blend of polypropylene lotion;The surfactant is cationic surfactant;The pH adjusting agent is acid.The direct yarn of alkali-free glass produced using size of the present invention is suitable as alkali-free glass fibre varicosity yarn, and not only expansion rate is high, with target resin compatible it is good, be impregnated with, and the mechanical performance of product can be made high, meet the requirement of standard.
Description
(1) technical field
The present invention relates to a kind of glass-fiber reinforced thermo-setting resin technology, particularly a kind of size and its production nothing
Application in alkali containing glass fibre varicosity yarn.
(2) background technology
Bulked glass yarn be using glass fiber bulk strand yarn through being passed through pressure-air special device it is puffing and
Into although process and uncomplicated, imparting the effect of glass fibre is special, it has the high intensity of continuous fiber and short concurrently
The bulkiness of fiber, be a kind of high temperature resistant, low thermal conductivity, it is corrosion-resistant, high hold empty amount, filtration efficiency it is harmless
New material.
Because of peculiar advantage of the bulked glass yarn in performance, it is widely used in automobile, building, heat preservation, sound insulation etc.
Application field.Such as clutch disc, muffler, thermostable heat insulation material, the wall wall cloth of building field.Wide in range application neck
Domain imparts the huge market prospects of bulked glass yarn product.It is continuous with global economy and composite industry
Development, under the stimulation of the macro policies such as country's " adjusting structure ", the development of the high-end fields such as automobile, architectural shape, high temperature resistant
It is placed on the position more protruded.With the continuous development of composite material application technology, buiky yarn application field has new again
It expands, for example in drawing and extruding section bar, the particularly position of structure and surface complexity, the introducing of buiky yarn can increase the suction of fiber
Glue amount ensures to obtain good filling at some labyrinths of product, so as to promote the quality of product surface and mechanics
Intensity.
Meet the performance requirement of more than buiky yarn, it is generally following (using not with yarn performance requirement to glass fiber bulk strand
Saturated polyester resin, content of glass fiber is 75%, by taking 600tex as an example):
● performance indicator:
Test event | Shear strength | Expansion rate |
≥40MPa | 3%-5% |
The test of woven glass roving fabric impregnation sample shear strength:Method is shown in that instrument is set described in ASTM D2344
It is standby to include gumming device, drawing force machine, fixture etc., reference standard ASTM D2344.
Bulked glass yarn expansion rate is tested:Test puffing preceding line density T1, the line density T2 after test is puffing, meter
Calculate (T2-T1)/T1*100%, as expansion rate.
It, need to be by developing a kind of novel size thus under the premise of constant using E glass ingredients:Reach good
Expansion effect, i.e., it is puffing after fiber can fully and uniformly scatter, expansion rate is high.The compatibility requirements of product and resin simultaneously
It is good, to meet the requirement of end article mechanical property.
(3) invention content
The technical problems to be solved by the invention are to provide a kind of size and its application, the nothing produced using the size
The direct yarn of alkali glass is suitable as alkali-free glass fibre varicosity yarn, and not only expansion rate is high, with target resin compatible it is good, be impregnated with
It is good, and the mechanical performance of product can be made high, meet the requirement of standard.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
The present invention provides a kind of size, the size prepare raw material include coupling agent, lubricant, film forming agent,
Surfactant, pH adjusting agent and deionized water, (solid masses is remainder after drying to the solid masses of the size
Quality) account for the 3~10% of size gross mass, (water including raw material components itself band is plus preparing size for water for surplus
The deionized water of addition);The coupling agent uses silane coupling agent;The lubricant uses water-soluble organic compounds;It is described
Film forming agent is epoxy emulsion and the blend of polypropylene lotion;The surfactant is cationic surfactant;It is described
PH adjusting agent for acid;The percentage that the quality dosage of following ingredients accounts for size solid masses represents as follows, if component
It is added in the form of dispersion, then its quality dosage is in terms of its solid masses:
Further, the present invention preferably size is adjusted by coupling agent, lubricant, film forming agent, surfactant, pH value
Agent and deionized water are made.
Further, the present invention preferably each component quality dosage account for size solid masses percentage represent it is as follows:
Further, the quality dosage of the present invention preferably each component accounts for the following institute of percentage of size solid masses
Show:
Again further, the quality dosage of the present invention preferably each component accounts for the following institute of percentage of size solid masses
Show:
The pH value of size of the present invention is 2~10, and preferable ph is 3~7.
Coupling agent of the present invention is generally even using the silylation with epoxy group, acryloxy, vinyl or amino
Joining the combination of one or more of agent, the applicable available product grade of silane coupling agent of the present invention has A-172, A-174,
A-1100, A-187 etc., preferably methacryloxypropyl trimethoxy silane coupling agent, i.e. A-174.The use of coupling agent,
Fiber can be protected impaired in drawing process, and play the role of " bridge joint " between glass fibre and matrix resin, therefore be shadow
The key of glass fiber strength and glass fiber reinforced plastics product intensity is rung, suitable coupling agent selection can make the product produced
With better mechanical performance.The percentage that the quality dosage of silane coupling agent accounts for size solid masses in the present invention is 3
~15%, preferably 4~14%, more preferable 6~12%, still more preferably 8~10%.
Water-soluble organic compound can be used in the lubricant that the present invention uses, using one in silicone oil, PEG series lubricant agents
Kind, preferably silicone oil.The use of lubricant predominantly meets glass fibre in wire drawing, post processing, the lubricant effect using process, but
Excessive lubricant can influence the convergence of glass fiber yarn, and can influence the mechanical performance of final glass fiber reinforced plastics product, therefore this
The percentage that the quality dosage of lubricant described in invention accounts for size solid masses is 4~18%, preferably 5~16%, more
It is preferred that 7~14%, still more preferably 9~11%.
The surfactant that the present invention uses is cationic surfactant, using in Fixanol, quaternary ammonium salt, amine salt
One kind, preferably quaternary cationic surfactant, most preferably organic quaternary ammonium salt 1831.Preferred cationic surface of the present invention
The percentage that the quality dosage of activating agent accounts for size solid masses is 0.1~10%, preferably 1.5~9.5%, more preferable 3
~8%, still more preferably 4.5~6%.
The quantity-produced that film forming agent plays the role of protecting fiber, meeting fiber as the main component of size, and
Conclusive influence is played on the mechanical strength of glass fibre end article, therefore, the selection of film forming agent is the emphasis of the present invention.
The film forming agent that the present invention uses is epoxy emulsion and the combination of polypropylene lotion.The present invention is made using the collocation of different types of lotion
With being on the one hand to glass fibre is enable to reach good expansion effect, be on the other hand to make glass fiber product
It is good with the compatibility of resin, to meet the requirement of end article mechanical property.The gross mass dosage of film forming agent of the present invention accounts for
The percentage of size solid masses is 60~85%, preferably 64~80%, more preferably 67~77%, still more preferably
It is 69~75%.
The epoxy emulsion that the present invention uses is water-soluble epoxy resin lotion or bisphenol A type epoxy resin lotion, molecular weight
It is 200~1200, preferably 300~800 range, 0.2~2.0 μm of particle diameter of dispersing phase.Epoxy emulsion can in the present invention
It is voluntarily prepared or using commercial goods according to existing literature.The quality dosage of the epoxy emulsion accounts for the hundred of size solid masses
It is 40~68%, preferably 40~65% to divide ratio, more preferable 44~60%, still more preferably 48~56%
The polypropylene lotion that the present invention uses is aqueous polyacrylamide lotion, and molecular weight is 10000~20000, preferably
13000~18000 range, 0.2~2.0 μm of particle diameter of dispersing phase.Polypropylene lotion can be according to existing literature in the present invention
It voluntarily prepares or using commercial goods.The percentage that the quality dosage of the polypropylene lotion accounts for size solid masses is 12
~25%, preferably 15~24%, more preferable 17~23%, still more preferably 18~21%.
Citric acid, acetic acid, formic acid, second such as can be used using acid, organic acid or inorganic acid in the pH adjusting agent of the present invention
Acid etc..The effect of pH adjusting agent is primarily used to ancillary coupling agent dispersion and adjusts the pH value of prepared size, the present invention
The pH value of the size is 2~10, and preferable ph is 3~7.
The preparation method of size of the present invention uses conventional method, includes the following steps:In a clean container
Middle 40%~50% deionized water for adding in total amount, then adds the pH adjusting agent in size ingredient, it is sufficiently stirred 3~
After five minutes, the silane coupling agent being slow added into size ingredient persistently stirs 40~50 minutes;In size ingredient
Lubricant, surfactant add in container after dilution is sufficiently stirred in the warm deionized water (40~50 DEG C) of 5 times of its amounts;Leaching
Film forming agent adds in container after being diluted using 2 times of water of film forming dosage in profit agent ingredient, if size pH value cannot reach
Optimum range adds in suitable pH adjusting agent and is adjusted and stirs evenly, until pH value reaches optimum range.
The present invention provides application of the size in alkali-free glass fibre varicosity yarn is produced.
(i.e. the coated amount on the glass fibers of size accounts for glass fiber quality to the combustible content of glass fibre of the present invention
Ratio) 0.2~0.8%, specific value needs to be determined according to the performance of raw material in itself general control.Reach from product needs
Performance indicator and experimental results from the point of view of, product that combustible content is produced at 0.3~0.6%, mechanical strength and swollen
Rate is best able to meet the requirements.
Compared with prior art, size of the present invention can make the expansion rate of glass fiber product high, and with tree
Lipid phase capacitive is good, good penetrability, and the mechanical performance of product is high, so as to meet market and application demand.
(4) specific embodiment
The present invention is specifically described by the following examples, but present disclosure is not by following embodiment
Any restriction.
The size each component that the embodiment of the present invention uses is as follows:
The coupling agent uses methacryloxypropyl trimethoxy silane coupling agent, product grade A-174;
The lubricant uses silicone oil;
The film forming agent epoxy resin latex, product grade are DSM JS129 (manufacturers:Dutch DSM N. V.);
The film forming agent polypropylene lotion, product grade are Michem Emulsion 42035A (manufacturers:
MICHELMAN, solid content 34.5~35.5%, pH:3.5~6.5);
The cationic surfactant uses organic quaternary ammonium salt 1831;
The pH adjusting agent uses acetic acid.
The following table 1 is direct by specific formulation examples and according to the 600Tex that certain glass fibre production technology is produced
The specific test result of yarn.In the embodiment of the present invention, the content of water accounts for the 94% of size gross mass, and numerical value therein is each
Component accounts for the percentage of size solid masses in terms of its solid content.
Table 1
From above formula test case, we can therefrom find out, by the design to component and constituent content, we
The size that can be meeted the requirements, wherein especially better with example 3,4.It the above is only the preferred implementation side of the present invention
Formula, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of size, the raw material for preparing of the size includes coupling agent, lubricant, film forming agent, surfactant, pH value
Conditioning agent and deionized water, the solid masses of the size account for the 3~10% of size gross mass, and surplus is water, described
Water includes the water of raw material components itself band plus the deionized water for preparing size addition;The coupling agent is using silane coupled
Agent;The lubricant uses water-soluble organic compounds;Blend of the film forming agent for epoxy emulsion and polypropylene lotion, institute
The epoxy emulsion stated is water-soluble epoxy resin lotion or bisphenol A type epoxy resin lotion, and molecular weight is 200~1200, dispersion
0.2~2.0 μm of phase average grain size;The polypropylene lotion is aqueous polyacrylamide lotion, and molecular weight is 10000~20000, point
0.2~2.0 μm of dephasing average grain diameter;The surfactant is cationic surfactant;The pH adjusting agent is acid;
The percentage that the quality dosage of following ingredients accounts for size solid masses represents as follows, if component is in the form of dispersion
It adds in, then its quality dosage is in terms of its solid masses:
Wherein, the percentage that the gross mass dosage of film forming agent accounts for size solid masses is 60~85%.
2. size as described in claim 1, it is characterised in that:The quality dosage of each component accounts for the hundred of size solid masses
Divide ratio as follows:
Wherein, the percentage that the gross mass dosage of film forming agent accounts for size solid masses is 64~80%.
3. size as claimed in claim 2, it is characterised in that:The quality dosage of each component accounts for the hundred of size solid masses
Divide ratio as follows:
Wherein, the percentage that the gross mass dosage of film forming agent accounts for size solid masses is 67~77%.
4. size as claimed in claim 3, it is characterised in that:The quality dosage of each component accounts for the hundred of size solid masses
Divide ratio as follows:
Wherein, the percentage that the gross mass dosage of film forming agent accounts for size solid masses is 69~75%.
5. the size as described in one of Claims 1 to 4, it is characterised in that:The silane coupling agent is band epoxy group, third
One or more of combinations of the silane based coupling agents of alkene acyloxy, vinyl or amino.
6. size as claimed in claim 5, it is characterised in that:The silane coupling agent is methacryloxypropyl
Trimethoxysilane coupling agent.
7. the size as described in one of Claims 1 to 4, it is characterised in that:The lubricant is moistened using silicone oil, PEG classes
One kind in lubrication prescription;The cationic surfactant is using one kind in Fixanol, quaternary ammonium salt, amine salt.
8. size as claimed in claim 7, it is characterised in that:The silane coupling agent is band epoxy group, acryloyl-oxy
One or more of combinations of the silane based coupling agents of base, vinyl or amino.
9. the size as described in one of Claims 1 to 4 or 8, it is characterised in that:The size by coupling agent, lubricant,
Film forming agent, surfactant, pH adjusting agent and deionized water are made.
10. application of the size as described in claim 1 in alkali-free glass fibre varicosity yarn is produced.
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CN106283316A (en) * | 2016-08-31 | 2017-01-04 | 巨石集团有限公司 | A kind of preparation method of high-strength pultrusion bulked glass yarn |
CN106630683A (en) * | 2016-12-07 | 2017-05-10 | 巨石集团有限公司 | Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT |
CN108996923B (en) * | 2017-06-07 | 2021-07-27 | 巨石集团有限公司 | High-impregnation alkali-free glass fiber impregnating compound for LFT (Long fiber reinforced thermoplastic) reinforced polypropylene and application thereof |
US11577995B2 (en) * | 2017-08-29 | 2023-02-14 | Mitsui Chemicals, Inc. | Fiber-sizing agent, inorganic reinforcement material, resin composition, and molded article |
CN112458586B (en) * | 2020-12-14 | 2022-04-26 | 东台市华阳玻纤有限责任公司 | Method for manufacturing core yarn pre-bulked core-spun yarn for asbestos-free brake band |
CN115124262A (en) * | 2022-08-25 | 2022-09-30 | 淄博卓意玻纤材料有限公司 | Glass fiber impregnating compound for milk bottle |
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JPS63230543A (en) * | 1987-03-19 | 1988-09-27 | Nippon Glass Fiber Co Ltd | Glass fiber sizing agent composition for reinforcing glass fiber |
CN101343396B (en) * | 2008-08-18 | 2011-03-02 | 巨石集团有限公司 | Glass fiber reinforced acetal resin composite material |
CN103570255B (en) * | 2012-08-07 | 2016-08-10 | 重庆国际复合材料有限公司 | A kind of glass fiber infiltration agent composition, preparation method and application |
CN102978938B (en) * | 2012-11-29 | 2015-08-19 | 山东玻纤集团股份有限公司 | Expanded yarn sizing agent special of a kind of glass fibre and preparation method thereof |
CN104030577B (en) * | 2014-05-29 | 2016-04-27 | 巨石集团有限公司 | A kind of refinforced cement short glass fiber treating compound |
CN104045244B (en) * | 2014-05-29 | 2017-02-01 | 巨石集团有限公司 | Alkali-free direct roving impregnating compound for continuous fiber reinforced polyolefin |
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