CN106630683A - Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT - Google Patents
Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT Download PDFInfo
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- CN106630683A CN106630683A CN201611115556.0A CN201611115556A CN106630683A CN 106630683 A CN106630683 A CN 106630683A CN 201611115556 A CN201611115556 A CN 201611115556A CN 106630683 A CN106630683 A CN 106630683A
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- pbt
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- alkali
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- glass fibre
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses an impregnating compound for an alkali-free glass fiber rough yarn for strengthened PP or PBT. The impregnating compound is prepared from a coupling agent, a lubricating agent, a film-forming agent, a surface active agent, a pH value conditioning agent and water, the solid mass of the impregnating compound accounts for 3% to 10% of the total mass of the impregnating compound, and the balance is water; the coupling agent is a silane coupling agent; the lubricating agent is a water-soluble PEG-type lubricating agent; the film-forming agent is the blend of an epoxy emulsion and a crylic acid modified epoxide resin emulsion; the surface active agent is the blend of a non-ionic surface active agent and a cationic surface active agent; the pH value conditioning agent is acid; the mass percentage of each compound accounting for the solid mass of the impregnating compound is expressed as follows: 5% to 20% of the coupling agent, 5% to 15% of the lubricating agent, 60% to 80% of the film-forming agent, 1% to 15% of the surface active agent and 1% to 5% of the pH value conditioning agent. The impregnating compound disclosed by the invention is high in compatibility with PP and PBT resin, and also can enable glass fiber to be easy to shear, so that the mechanical property of the final compound material can be guaranteed, and the processing process of strengthened PP and PBT of twistless rough yarn can be smooth.
Description
First, technical field：
The present invention relates to glass fibre manufacturing technology field, be specifically to provide it is a kind of strengthen PP (polypropylene) or
PBT (polybutylene terephthalate (PBT)) alkali-free glass fibre rove sizes.
2nd, background technology：
PP composite reinforced by glass and enhancing PBT composite are widely used in engineering field, wherein strengthening
PP composites due to being substantially better than other conventional engineering plastics on sexual valence, meanwhile, the introducing of glass fibre is to PP composite woods
Every mechanical property of material has a huge impact, such as：High tensile strength, bending modulus is higher, and heat-resisting quantity is more preferable etc..Closely
Glass fiber reinforcement PP materials apply increasing in household electrical appliance, auto industry, building industry over a little years, to glass fibre
Demand also grow with each passing day.Glass fiber reinforcement PBT composite has outstanding heat resistance, long-term ageing and fire-retardant because of it
Performance, can be applicable to include automobile, electronic/electrical device, machinery industry：Home appliances (food processing blade, vacuum cleaner element,
Electric fan, Hair drier housing, coffee vessel etc.)；Electric elements (press by switch, motor casing, fuse box, computer keyboard
Key etc.)；Auto industry (radiator lattice window, body panel, wheel cover, door and window part etc.).Both the above composite is all fortune
With one of most commonly used composite, it popularizes the application that scope is even more than nylon products.But because PP and PBT resin exist
Generally in the range of extrusion design temperature, resin viscosity is low, due to close non-newtonian fluid, there is the characteristic of shear shinning, shearing speed
Rate is higher, and viscosity is lower, particularly PP resins, more sensitive to shear rate.When industrialized production rove strengthens PP and PBT
All easily there is glass fibre and shear problem bad, that dispersion is irregular, i.e., so-called " glass fibre does not melt ".Therefore, develop a kind of
Not only well but also glass fibre can be made to be easy to the size sheared to improve the production performance of glass fibre with PP and PBT resin compatibility
It is very necessary with mechanical property.Need to meet shearing requirement, while also needing to meet following general performance requirement (glass fibre
30%) content is：
Tensile property (according to ISO527 method of testings)
| Resin | PP | PBT |
| Tensile strength | ≥80 | ≥120 |
Cutting performance (shears the method for testing of dispersive property, the patent No. according to a kind of-glass fibre in thermoplastic
ZL201410286033.7)
| Resin | PP | PBT |
| Cutting performance | It is good | It is good |
For this reason, it may be necessary to pass through to develop a kind of new size：Can possess excellent compatibility with target resin, with full
The index request of sufficient mechanical performance, and with good cutting performance so that it is good using smoothness.
3rd, the content of the invention：
It is an object of the invention to provide a kind of strengthen PP or PBT alkali-free glass fibre rove sizes, the size
Not only with PP and PBT resin compatibility well but also can make glass fibre be easy to shearing, both can guarantee that the mechanical property of final composite,
The process of roving enhancing PP and PBT can be made smooth again.
To solve the above problems, the present invention is adopted the following technical scheme that：
One kind strengthen PP or PBT alkali-free glass fibre rove sizes, the size by coupling agent, lubricant,
Film forming agent, surfactant, pH value conditioning agent and water are made, the solid masses of the size account for size gross mass 3～
10%, balance of water；The coupling agent adopts silane coupler；The lubricant adopts water miscible PEG series lubricant agents；It is described
Film forming agent is the blend of epoxy emulsion and acrylic modified epoxy resin emulsion, wherein epoxy emulsion and acrylated epoxy
The mass ratio of resin emulsion is calculated as 1-10 with respective solid masses ratio:1；Described surfactant is non-ionic surface active
Agent and the blend of cationic surfactant；Described pH value conditioning agent is acid；Each component quality accounts for size solid masses
Percentage it is as follows, if wherein component with dispersion addition, its quality is in terms of its solid masses：
, 4～12, preferred pH value is 6～10 for the pH value of size of the present invention.
Coupling agent of the present invention typically adopts the silane coupler with epoxy radicals, vinyl or amino, and the present invention is suitable
The available product grade of silane coupler has A-172, A-174, A-1100, A-187 etc..The use of coupling agent, can protect
Shield fiber is impaired in drawing process, and plays " bridge joint " between glass fibre and matrix resin, while affecting glass fibre
Soft durometer, therefore be the key for affecting glass fiber strength and strengthening PP and PBT resin intensity, be also the weight of the present invention
Point.Suitable coupling agent is selected, and the GF for producing can be made to strengthen PP composites and GF to be strengthened PBT composite and have more
Good mechanical performance.Silane coupler quality accounts for the 5～20% of size solid masses in the present invention, and preferably 6～18%, it is more excellent
Select 7～15%, still more preferably 8～12%.
Film forming agent plays a part of to protect fiber as the main component of size, and to glass fibre end article
Mechanical strength plays conclusive impact, therefore, the selection of film forming agent is also one of emphasis of the present invention.The present invention use into
Film is the combination of epoxy emulsion and acrylic modified epoxy resin.The present invention is used using the collocation of different types of emulsion, is removed
The convergence and soft or hard for taking into account glass fibre is outside one's consideration, while also cause size that there is good compatibility with PBT and PP resins,
Strengthen the mechanical strength of PP composites and GF enhancing PBT composites so as to improve GF.
The epoxy emulsion that the present invention is used be using epoxy resin emulsification make, its relative molecular mass MW be 350～
1500, preferably 400～1200, emulsion mean particle diameter is 0.2～2.0 micron.Epoxy emulsion can be according to existing in the present invention
There is document voluntarily to prepare or use commercial goods.
The acrylic modified epoxy resin emulsion that the present invention is used is changed by acrylate obtained in emulsion polymerisation process
Property epoxy resin emulsion, can voluntarily prepare or use commercial goods according to existing document.
The gross mass of film forming agent of the present invention is calculated as size solid masses 60～80% with its solid masses, and preferably 65
～75%, more preferably 68～74.5%, it is still more preferably 69～72%.Epoxy emulsion of the present invention and acrylic acid
The mass ratio of modified epoxy resin emulsion is calculated as 1-10 with the ratio of respective solid masses:1, preferably 1.5-6.0:1, more preferably
For 1.7-4.5:1, still more preferably 2-4:1.
The lubricant that the present invention is used can adopt water miscible organic compound, particularly PEG series lubricant agents, such as
PEG400, PEG600, PEG1000, PEG3000 etc..The use of lubricant is mainly located to meet glass fibre in wire drawing, afterwards
Lubricant effect during reason, use, but excessive lubricant can affect the convergence of glass fiber yarn, and affect final GF
Strengthening PP composites and GF strengthens the mechanical performance of PBT composite, therefore the quality of lubricant of the present invention accounts for size
The 5～15% of solid masses, preferably 5～13%, more preferably 7～11%, still more preferably 9～11%.
The surfactant that the present invention is used is the blend of nonionic surfactant and cationic surfactant, its
Described in nonionic surfactant using the one kind in polyethenoxy ether class, esters, amide-type, chemical modification mineral oils；
Cationic surfactant is using the one kind in polyoxyethylene amine salt, quaternary ammonium salt, imidazoline.Described nonionic surfactant
It is 3-5 with the mass ratio of described cationic surfactant:1.Preferred surfactant of the present invention is that polyethenoxy ether class is non-
The blend of ionic surface active agent and quaternary ammonium salt surface active agent.Further, polyethenoxy ether class non-ionic surface is lived
Property agent and quaternary ammonium salt surface active agent mass ratio be 3-5:1.
The pH value conditioning agent of the present invention is inorganic acid, organic acid, can such as use citric acid, acetic acid, formic acid, acetic acid
Deng.The effect of pH value conditioning agent is primarily used to ancillary coupling agent dispersion and adjusts the pH value of the size for preparing, the present invention
, 4～12, preferred pH value is 6～10 for the pH value of the size.
With in alkali-free glass fibre rove size, each component quality accounts for size to the preferred PP or PBT that strengthens of the invention
The percentage of solid masses is as follows：
With in alkali-free glass fibre rove size, each component quality is accounted for the PP or PBT that further preferably strengthens of the invention
The percentage of size solid masses is as follows：
The present invention still more preferably strengthens PP or PBT with alkali-free glass fibre rove size, each component quality
The percentage for accounting for size solid masses is as follows：
The most preferably described size of the present invention is by coupling agent, lubricant, film forming agent, surfactant, pH value conditioning agent
Make with water；Described silane coupler is the silane coupler with epoxy radicals, vinyl or amino；Described lubricant is water
The PEG series lubricant agents of dissolubility；Described film forming agent is the blend of epoxy emulsion and modified epoxy, both mass ratioes with
The ratio of respective solid masses is calculated as 2-4：1；The surfactant is polyethenoxy ether class and quaternary surfactant
Blend, both mass ratioes are 3-5:1, described pH value conditioning agent is acid；Each component quality accounts for size solid masses
Percentage is as follows：
Compound method for strengthening PP or PBT alkali-free glass fibre rove sizes of the present invention can be using normal
Rule method, specifically includes following steps：The 40～50% of total amount deionized water, Ran Houzai are added in a clean container
Add the pH value conditioning agent in size composition, after being sufficiently stirred for 3～5 minutes, the silane being slow added into size composition
Coupling agent, persistently stirs 40～50 minutes；Lubricant, surfactant in size composition the temperature of 5 times of its amounts go from
Fully dilution adds container after stirring in sub- water (40～50 DEG C)；Film forming agent adopts 2 times of film forming dosage in size composition
Water adds container after being diluted, if size pH value can not reach optimum range, adds appropriate pH value conditioning agent to be adjusted
It is whole and stir, until pH value reaches optimum range.
(i.e. size coating amount on the glass fibers accounts for the ratio of glass fiber quality to the combustible of glass fibre of the present invention
Example) general control 0.2～9.0%, specific value needs the performance according to raw material itself, from the performance indications that product needed reaches
From the point of view of experimental results, in the product of 0.3～0.8% production, mechanical performance can with extrusion smoothness for combustible content
Meet and require.
Compared with prior art, the size that the present invention is provided not only well but also can make glass fibers with PP and PBT resin compatibility
Dimension is easy to shearing, and the woven glass roving fabric Jing after size of the present invention process was extruded when PP and PBT is strengthened
Cheng Shunchang, without broken strip, leakage is fine the problems such as, final composite product function admirable, especially with good mechanical property,
With good production technology and application performance, so as to meet market and application demand.
4th, specific embodiment：
The present invention is specifically described by the following examples, but present disclosure is not by following examples
Any restriction.
The size each component that the enforcement of the present invention is used is as follows：
The coupling agent uses amino silicane coupling agent, product grade A-1100 (manufacturers：Step figure)；
The lubricant uses PEG400 (manufacturers：DOW)；
The film forming agent epoxy resin latex, product grade TX777 (manufacturers:Megalith)
The film forming agent modified epoxy resin emulsion, using acrylic modified epoxy resin emulsion.(self-control, bibliography:
Mu Rui, Yan Huizhi, Deng Aimin.A kind of preparation of acrylic acid modified emulsion epoxy resin and research, chemistry and bonding, 200830
(1)：62-64)；
The cationic surfactant adopts 1231MS (manufacturers：Suzhou Heng Nuo nations chemical science and technology)；
The nonionic surfactant adopts AEO (manufacturer：Xingtai blue star auxiliary reagent factory)
The pH adjusting agent uses acetic acid.
The 2000tex that following table is produced by specific formulation examples and according to certain glass fibre production technology is straight
Connect the concrete test result of yarn.In the embodiment of the present invention, the content of water accounts for the 96% of size gross mass, and numerical value therein is
Each component quality accounts for the percentage of size solid masses, wherein with the constituent mass of dispersion addition with its solid masses
Meter.
Formula test case more than, we can therefrom find out, by the design to component and constituent content, we
The size for meeting the requirements can be obtained, wherein especially optimal with example 3,4 resultant effects.The above is only being preferable to carry out for the present invention
Mode, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, also
Some improvements and modifications can be made, these improvements and modifications should also be considered as protection scope of the present invention.
The embodiment of the present invention according to the PP and PBT technical characterstics of alkali-free glass fibre rove, by size raw material
Select, the optimization of formula, using suitable glass fibre production technology, produces the alkali-free glass fibre for meeting the domain requirement
Rove product.
Claims (10)
1. it is a kind of to strengthen PP or PBT alkali-free glass fibre rove sizes, the size by coupling agent, lubricant, into
Film, surfactant, pH value regulator and water are made, the solid masses of the size account for size gross mass 3～
10%, balance of water；The coupling agent adopts silane coupler；The lubricant adopts water miscible PEG series lubricant agents；It is described
Film forming agent is the blend of epoxy emulsion and acrylic modified epoxy resin emulsion, wherein epoxy emulsion and acrylated epoxy
The mass ratio of resin emulsion is calculated as 1-10 with respective solid masses ratio:1；Described surfactant is non-ionic surface active
Agent and the blend of cationic surfactant；Described pH value regulator is acid；Each component quality accounts for size solid masses
Percentage it is as follows, if wherein component with dispersion addition, its quality is in terms of its solid masses：
It is 2. as claimed in claim 1 to strengthen PP or PBT alkali-free glass fibre rove sizes, it is characterised in that：It is described
In size, the percentage that each component quality accounts for size solid masses is as follows：
It is 3. as claimed in claim 2 to strengthen PP or PBT alkali-free glass fibre rove sizes, it is characterised in that：It is described
In size, the percentage that each component quality accounts for size solid masses is as follows：
It is 4. as claimed in claim 3 to strengthen PP or PBT alkali-free glass fibre rove sizes, it is characterised in that：It is described
In size, the percentage that each component quality accounts for size solid masses is as follows：
5. alkali-free glass fibre rove sizes of the enhancing PP or PBT as described in one of Claims 1 to 4, its feature exists
In：Described epoxy emulsion is made using epoxy resin emulsification, and its relative molecular mass MW is 350～1500, and emulsion is average
Particle diameter is 0.2～2.0 micron.
6. alkali-free glass fibre rove sizes of the enhancing PP or PBT as described in one of Claims 1 to 4, its feature exists
In：Described epoxy emulsion is calculated as 1.5- with the mass ratio of acrylic modified epoxy resin emulsion with the ratio of respective solid masses
6.0:1。
It is 7. as claimed in claim 6 to strengthen PP or PBT alkali-free glass fibre rove sizes, it is characterised in that：It is described
The mass ratio of epoxy emulsion and acrylic modified epoxy resin emulsion 1.7-4.5 is calculated as with the ratio of respective solid masses:1.
It is 8. as claimed in claim 7 to strengthen PP or PBT alkali-free glass fibre rove sizes, it is characterised in that：It is described
The mass ratio of epoxy emulsion and acrylic modified epoxy resin emulsion 2-4 is calculated as with the ratio of respective solid masses:1.
9. alkali-free glass fibre rove sizes of the enhancing PP or PBT as described in one of Claims 1 to 4, its feature exists
In：The nonionic surfactant is using the one kind in polyethenoxy ether class, esters, amide-type, chemical modification mineral oils；
Cationic surfactant is using the one kind in polyoxyethylene amine salt, quaternary ammonium salt, imidazoline；Described nonionic surfactant
It is 3-5 with the mass ratio of described cationic surfactant:1.
10. alkali-free glass fibre rove sizes of the enhancing PP or PBT as described in one of Claims 1 to 4, its feature exists
In：Described silane coupler is the silane coupler with epoxy radicals, vinyl or amino；Described film forming agent is epoxy emulsion
With the blend of acrylic modified epoxy resin emulsion, both mass ratioes are calculated as 2-4 with the ratio of respective solid masses：1；Institute
The blend that surfactant is polyethenoxy ether class and quaternary surfactant is stated, both mass ratioes are 3-5:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611115556.0A CN106630683A (en) | 2016-12-07 | 2016-12-07 | Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT |
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| CN201611115556.0A CN106630683A (en) | 2016-12-07 | 2016-12-07 | Impregnating compound for alkali-free glass fiber rough yarn for strengthened PP or PBT |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107574663A (en) * | 2017-10-19 | 2018-01-12 | 广州鼎昊纺织品有限公司 | A kind of composite assistant handled for down jackets sewing thread, down jackets sewing thread and preparation method thereof |
| CN110066121A (en) * | 2019-06-11 | 2019-07-30 | 巨石集团有限公司 | A kind of size and its preparation method and application |
| CN110922069A (en) * | 2019-11-25 | 2020-03-27 | 巨石集团有限公司 | Glass fiber impregnating compound for wet weaving and puffing, and preparation method, product and application thereof |
| CN114735950A (en) * | 2022-02-25 | 2022-07-12 | 陕西汇友友基新材料有限公司 | Glass fiber impregnating compound special for mica cloth |
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| CN105401422A (en) * | 2015-11-04 | 2016-03-16 | 巨石集团有限公司 | Impregnating compound and application thereof in production of non-alkali bulked glass fiber yarn |
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| CN104556739A (en) * | 2014-06-30 | 2015-04-29 | 江苏九鼎新材料股份有限公司 | Special alkali-free direct yarn wetting agent for grinding wheel reinforcing sheets and preparation method thereof |
| CN105174750A (en) * | 2015-09-02 | 2015-12-23 | 巨石集团有限公司 | Impregnating agent for winding reinforcement medium-alkali glass fiber direct yarns |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107574663A (en) * | 2017-10-19 | 2018-01-12 | 广州鼎昊纺织品有限公司 | A kind of composite assistant handled for down jackets sewing thread, down jackets sewing thread and preparation method thereof |
| CN107574663B (en) * | 2017-10-19 | 2020-04-28 | 广州鼎昊纺织品有限公司 | Composite auxiliary agent for processing down jacket sewing thread, down jacket sewing thread and preparation method thereof |
| CN110066121A (en) * | 2019-06-11 | 2019-07-30 | 巨石集团有限公司 | A kind of size and its preparation method and application |
| CN110066121B (en) * | 2019-06-11 | 2022-02-01 | 巨石集团有限公司 | Impregnating compound and preparation method and application thereof |
| CN110922069A (en) * | 2019-11-25 | 2020-03-27 | 巨石集团有限公司 | Glass fiber impregnating compound for wet weaving and puffing, and preparation method, product and application thereof |
| CN114735950A (en) * | 2022-02-25 | 2022-07-12 | 陕西汇友友基新材料有限公司 | Glass fiber impregnating compound special for mica cloth |
| CN114735950B (en) * | 2022-02-25 | 2024-05-28 | 陕西汇友友基新材料有限公司 | Glass fiber impregnating compound special for mica cloth |
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