CN108409163A - A kind of glass fiber infiltration agent and its preparation method and application - Google Patents
A kind of glass fiber infiltration agent and its preparation method and application Download PDFInfo
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- CN108409163A CN108409163A CN201710071725.3A CN201710071725A CN108409163A CN 108409163 A CN108409163 A CN 108409163A CN 201710071725 A CN201710071725 A CN 201710071725A CN 108409163 A CN108409163 A CN 108409163A
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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
- C03C25/42—Coatings containing inorganic materials
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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
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/30—Polyolefins
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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Abstract
The present invention provides a kind of glass fiber infiltration agents, the size includes coupling agent, lubricant, film forming agent A, film forming agent B, antifoaming agent, antioxidant, pH adjusting agent and deionized water, wherein, the solid masses of size accounts for the 2~6% of size gross mass, the present invention is compounded using different types of film forming agent, and matched with suitable coupling agent, lubricant, antifoaming agent, antioxidant and pH adjusting agent keeps glass dispersion good to be prepared, the size that filoplume amount is few and com-patibilising effect is good.The present invention also provides the purposes of the preparation method of the size and the size in the CFRT techniques of glass fiber reinforced polypropylene resin.
Description
Technical field
The present invention relates to size fields more particularly to a kind of glass fiber infiltration agent and its preparation method and application.
Background technology
CFRT is the abbreviation of Continue Fiber Reinforced Thermoplastic, and Chinese is translated into continuous fiber
Reinforced thermoplastics.In past half a century, the advanced configuration material of aerospace and the application of other high-tech sectors
Always occupied by high-performance thermosetting composite material, until in the early 1970s, continuous fiber reinforced thermoplastic composite wood
Material starts to be used in above-mentioned field as a kind of new advanced material.In recent years, continuous fiber reinforced thermoplastic plastic
(CFRT) increasingly paid attention to by countries in the world, study and apply and is very active.Its application field is concentrated mainly on space flight, boat
The fields such as sky, automobile, building materials, chemical industry, electronic/electrical device.
China takes up to study CFRT techniques from middle and later periods the 1980s, compares thermosets, even
Continuous fiber-reinforced thermoplastic has the outstanding advantages of following several respects：(1) prepreg can long-term preservation；(2) comprehensive performance
It is excellent, good mechanical property is especially still can guarantee under high temperature, high humility；(3) wide adaptability, production efficiency are molded
It is high；(4) the repeatable processing of product, regeneration and it is certain can toolability.Therefore, in the past 10 years, the development of CFRT materials
Speed several times higher than same with thermosetting compound material, yield are increased with 25% speed every year, wherein continuous fiber reinforced polypropylene
The demand still sustainable growth of thermoplastic (account for about total amount 80%).
Continuous fiber reinforced thermoplastic plastic technique (CFRT techniques) is usually first to use the thermoplastic resin-impregnated fibers of controlled quentity controlled variable
Or unidirectional pre-immersion material is formed after fabric, which has the fiber/resin composite effect of stable and consistent, fiber can be made to soak completely
Thoroughly, to ensure superior mechanical strength, then again by other forming methods, such as molding, pultrusion or winding process are made multiple
Condensation material structural member.Include glass fibre, carbon fiber, aramid fiber etc., wherein glass fibers in the continuous fiber that the technique uses
Dimension is most widely used.
Glass fibre as CFRT techniques can carry out size coating processing, and size using and selecting to glass fibers
The performance of dimension is most important, not only influences dispersibility of the glass fibre in forming unidirectional pre-immersion material technique, but also after having an effect on
Continuous glass fibre and the compatibility of matrix resin and the mechanical performance of product.With the rapid development of CFRT materials, high-end visitor
Requirement of the family to glass fibre performance is stringenter, by taking continuous fiber reinforced polypropylene resin material as an example：First, yarn with
Acrylic resin combines preceding with good dispersed (index：Under the tension of 1kg, yarn all scatters, and yarn sheet width >=
8mm)；Secondly, it is desirable that filoplume is few, it is low to go out yarn tension；Again, there is good compatibility with acrylic resin in cohesive process,
And with excellent mechanical performance, (key index is the sheet material of 60% glass fiber content to end article, and tensile strength >=900MPa is surveyed
The quasi- ISO527-5 of test-object)；Finally, also there is specific requirement to the color of glass fibre and product.
Therefore, in order to solve the above-mentioned technical problem, a kind of dedicated glass fiber infiltration agent is developed, especially for enhancing
The glass fiber infiltration agent of acrylic resin is extremely urgent, and to the production technology meaning weight of continuous reinforced thermoplastics
Greatly.
Invention content
Present invention seek to address that problem as described above.The object of the present invention is to provide a kind of glass fiber infiltration agents, should
Size makes glass fibre have good dispersibility, and hair by the physics and chemical property of change fiberglass surfacing
It is low that plumage goes out yarn tension less, while having good resin compatible, greatly improves the mechanical performance of composite article.
The present invention provides a kind of glass fiber infiltration agent, and the size includes coupling agent, lubricant, film forming agent A, film forming
Agent B, antifoaming agent, antioxidant, pH adjusting agent and deionized water, wherein the solid masses of the size accounts for the total matter of size
The 2~6% of amount；Also, the percentage that the solid masses of each component accounts for the size solid gross mass is as follows：
The percentage that the solid masses of each component accounts for the size solid gross mass is as follows：
Also, the ratio between the solid masses of the film forming agent A and the solid masses of the film forming agent B are 1:0.5~3.
Wherein, the film forming agent A is polypropylene wax emulsion, and the film forming agent B is polypropylene wax emulsion, the film forming agent A
Number-average molecular weight be higher than the number-average molecular weight of the film forming agent B, also, the solid masses of the film forming agent A and the film forming
The ratio between solid masses of agent B is 1:0.5~3.
Wherein, the film forming agent A is lotion, and number-average molecular weight is 30000~80000；The film forming agent B is polypropylene
Wax emulsion, number-average molecular weight are 5000~30000.
Wherein, the lubricant is fatty acid lubricant or microwax；The antifoaming agent be BYK011, BYK012,
It is one or more in BYK014, BYK018, BYK023, BYK024 and BYK025；The antioxidant is SD1688, inorganic phosphate
It is one or more in salt and sodium hypophosphite.
Wherein, the solid masses of each component account for the size solid gross mass percentage it is as follows：
Also, the coupling agent is double amino silicane coupling agents；The lubricant is microwax；The film forming agent A's consolidates
The ratio between weight and the solid masses of the film forming agent B are 1:1.4~2.
Wherein, the coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy
Silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane and γ-(2,3- glycidoxies) propyl trimethoxy silicane
In it is one or more.
Wherein, the pH adjusting agent is organic acid or inorganic acid, and the pH value control of the size is 6~10.
Wherein, the size is the size of the direct yarn of alkali-free of reinforced polypropylene resin.
On the other hand, the present invention also provides the preparation method of above-mentioned size, the preparation method includes the following steps：
The pre-dispersed coupling agents of 1S：The deionized water that quality is total amount half is added in preparing container, the coupling is added
Agent is persistently stirred 25~30 minutes；
2S dilutes lubricant, film forming agent, antifoaming agent and antioxidant：Deionization is used to dilute size each component respectively,
In, in lubricant dilution, the quality using deionized water is 2-3 times of lubricant quality；Film forming agent include film forming agent A and at
Film B uses deionized water dilution film forming agent A and film forming agent B respectively, is made the dilution of corresponding film forming agent respectively, then by two
Kind film forming agent dilution is uniformly mixed, and the quality using deionized water is respectively 2-3 times of corresponding film forming agent quality；Antifoaming agent is dilute
It releases in liquid, the quality using deionized water is 2-3 times of antifoaming agent quality；In antioxidant dilution, the matter of deionized water is used
Amount is 4-5 times of antioxidant quality；
3S prepares size：Container is prepared be completed step 1S, sequentially adds lubricant, film forming agent, antifoaming agent
With the dilution of antioxidant, after being uniformly mixed, pH adjusting agent is added, control size pH value is 6~10.
The third aspect, the present invention is especially suitable for the CFRT techniques of reinforced polypropylene resin, particularly, the present invention also provides
Purposes of the above-mentioned size in the CFRT techniques of glass fiber reinforced polypropylene resin.
According to glass fiber infiltration agent provided by the invention, main innovative point be by compounding suitable film forming agent, and
It is combined with suitable coupling agent, lubricant, antifoaming agent, antioxidant and pH adjusting agent, glass fibre dispersion is prepared
Property good, the good size of com-patibilising effect, specifically, size include coupling agent, lubricant, film forming agent A, film forming agent B, defoaming
Agent, antioxidant, pH adjusting agent and deionized water, wherein the solid masses of the size account for size gross mass 2~
6%；Also, the percentage that the solid masses of each component accounts for the size solid gross mass is as follows：
The effect of each component and content are described as follows in the size：
The present invention is generally silane coupling agent using coupling agent, and the general formula of silane coupling agent is RSIX3, R represents ammonia in formula
The groups such as base, sulfydryl, vinyl, methacryloxy, epoxy group.Silane coupling agent is substantially a kind of with organic functional
The silane of group, having simultaneously can react in the molecule thereof with the chemical group of the i.e. glass fibre of inorganic material, while also can be with base
The chemical group reaction of group's resin, forms the bridge of an interface cohesion between glass fibre and matrix resin.
The use of coupling agent can play the coupled action between glass fibre and matrix resin, on the one hand can reduce glass fibers
The extent of damage in drawing process is tieed up, the key of glass fiber strength and composite article intensity is on the other hand still influenced.
Inventors discovered through research that coupling agent containing metacryloxy, amino or epoxy group with it is provided by the present application
Film forming agent, lubricant cooperate, and can effectively improve the compatibility of glass fibre and resin.The present invention limits consolidating for coupling agent
Weight accounts for 10~30%, preferably 15~25%, more preferably the 18~22% of size solid gross mass.Further,
Inventor has found γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, N- β-(ammonia second
Base)-γ-aminopropyltrimethoxysilane and γ-(2,3- glycidoxies) propyl trimethoxy silicane be highly suitable for this hair
It is bright, especially there is N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane of double amino structures.Use above-mentioned coupling agent system
Standby size can make glass fibre composite article have better mechanical performance.
Film forming agent is the main component of size, plays conclusive influence to the processing performance of glass fibre, plays guarantor
The effect for protecting glass fibre, the compatibility for improving glass fibre and matrix resin, should ensure glass fibre in CFRT techniques
In good dispersibility and convergence, ensure glass fibre and the compatibility of matrix resin and the machine of final composite article again
Tool intensity, therefore, the selection of film forming agent are the emphasis of the present invention.
The larger film forming agent of number-average molecular weight is generally used alone in currently used size because higher molecular weight at
Film is more conducive to the coating of size in glass fibre production, but higher want is not achieved in the comprehensive performance of glass fibre obtained
It asks.In order to realize that the balance of glass dispersion and convergence, film forming agent of the invention using two kinds of components compound
It arriving, wherein the solid content of film forming agent A accounts for the 20~60% of size solid gross mass, and preferably 20~50%, more preferable 25
~30%；The solid content of film forming agent B accounts for the 20~60% of size solid gross mass, and preferably 30~60%, more preferable 40
~50%.The solid content of film forming agent accounts for the 55~80% of size solid amount, preferably 63~79%, more preferable 70~
75%.
Common film forming agent has polyaminoester emulsion, polyester resin emulsion, polyvinyl acetate emulsion, polypropylene lotion and ring
Oxygen class lotion, inventor by it is a large amount of the study found that polypropylene wax emulsion be very suitable for the present invention film forming agent, and should
Lotion can improve the compatibility of size and acrylic resin, reach the requirement of mechanical strength.
The present invention also further has studied the relationship of the number-average molecular weight and size performance of film forming agent emulsion, works as use
When the agent emulsion molecular weight that forms a film is smaller, corresponding glass fiber yarn is soft, good dispersion, and yarn is more smooth；And use molecular weight
When big lotion, corresponding glass fiber yarn is slightly hard, and convergence is good.The film forming agent of the present invention has selected two kinds of different molecular weights
Polypropylene wax emulsion compound to obtain, preferably maleic anhydride grafting alkali neutralization polypropylene wax emulsion.Wherein, film forming agent A
Number-average molecular weight is more than the number-average molecular weight of film forming agent B, and the solid matter of the solid masses of film forming agent A and the film forming agent B
The ratio between amount is 1:0.5~3, preferably 1:1.4~2, it is used in compounding with the ratio, higher dispersibility, boundling can be reached
The requirements such as property and compatibility.
Further, the number-average molecular weight of film forming agent A of the present invention is preferably 30000~80000, more preferably 30000~
75000.The number-average molecular weight of film forming agent B of the present invention is preferably 5000~30000.The present invention is not only met using such combination
The technological requirement of size coating, it is also ensured that the performance of glass fibre more preferably, is particularly suitable for CFRT techniques.
The effect of lubricant is primarily to ensure glass fibre in wire drawing, post-processing and the lubrication effect for the processes such as using
Fruit.Lubricant content is excessively few to be then not achieved lubricant effect, can excessively influence the caking property between precursor, reduce the stiffness of yarn
So that being impregnated in matrix resin and compatibility can be influenced, the mechanical performance to final composite material is caused to have negative shadow
It rings, the solid content of lubricant of the present invention accounts for the 5~10% of size solid amount, preferably 5~8%, and more preferable 6~7%.
Glass fiber infiltration agent frequently with lubricant be water-soluble organic compound, such as PEG series lubricant agents etc., hair
A person of good sense is easy to cause in glass fibre drying course by the study found that this kind of soluble oil is not appropriate for the present invention
There is the migration problem of size.In order to solve this problem, the lubricant that the present invention selects is fatty acid lubricant or micro-
Brilliant wax.Wherein, microwax and polypropylene wax emulsion compatibility are more preferable, and size obtained is better.
Film forming agent emulsion and lubricant contain certain surface reactive material in size, during stirring and use
It is also easy to produce foam and production and performance is impacted.The polypropylene wax breast and lubricant for being particularly suitable for the present invention exist
It also will appear a large amount of foams during stirring and use, it is therefore necessary to add antifoaming agent appropriate.The antifoaming agent of the present invention is selected
Water-soluble antifoaming agent, such as organosiloxane or polyethers antifoaming agent.It is preferred that the trade mark be BYK019, BYK023, BYK028 and
In the organosilicon series of BYK034 it is one or more wherein, the solid masses of antifoaming agent account for size solid amount 0.01~
0.2%, preferably 0.01~0.05%.
Since CFRT materials are more demanding to color, and the component that the present invention uses, especially film forming agent are easy baking
Occurs oxidation xanthochromia in the process, therefore, to solve this technical problem, the present invention selects aromatic amine antioxidant and auxiliary antioxygen
One or more of agent is combined, the xanthochromia problem during preventing yarn from baking.Preferably, antioxidant SD1688,
One or more in inorganic phosphate and sodium hypophosphite, wherein SD1688 is that paracresol and dicyclopentadiene butylation react
Object, No. CAS is 68610-51-5.Wherein, the solid masses of antioxidant accounts for the 0.01~0.2% of size solid amount, preferably
It is 0.1~0.15%.
Using organic acid or inorganic acid, as pH adjusting agent, formic acid, acetic acid, oxalic acid, boric acid and lemon can be selected in the present invention
It is one or more in lemon acid, it is main to play a part of to adjust size pH value.It is solid that the solid masses of pH adjusting agent accounts for size
The 0.1~5% of body gross mass, preferably 0.5~3%, more preferable 0.5~1%.
The size of the present invention need to control as slight alkali environment, and pH value range control is 6~10, preferably 7~9.
According to another aspect of the present invention, a kind of preparation method of above-mentioned size is provided, including pre-dispersed coupling agent,
It dilutes lubricant, film forming agent, antifoaming agent and antioxidant, and prepares size.
First, in preparing container be added quality be total amount half deionized water, be added coupling agent, persistently stir 25~
30 minutes；Then deionization is used to dilute size each component respectively, wherein in lubricant dilution, to use deionized water
Quality is 2-3 times of lubricant quality；Film forming agent includes film forming agent A and film forming agent B, uses deionized water to dilute film forming agent respectively
A and film forming agent B, is made the dilution of corresponding film forming agent respectively, then two kinds of film forming agent dilutions are uniformly mixed, and uses deionization
The quality of water is respectively 2-3 times of corresponding film forming agent quality；In antifoaming agent dilution, the quality using deionized water is antifoaming agent
2-3 times of quality；In antioxidant dilution, the quality using deionized water is 4-5 times of antioxidant quality；Finally, by each group
Point dilute solution be added to coupling agent disperseed complete prepare in container.
The used in amounts of each component meets proportionate relationship of the present invention during made above, and those skilled in the art can
To be adaptively adjusted based on above-mentioned preparation method according to actual conditions.
According to the third aspect of the invention we, the present invention is especially suitable for the CFRT techniques of reinforced polypropylene resin, particularly,
The present invention also provides purposes of the above-mentioned size in the CFRT techniques of glass fiber reinforced polypropylene resin.
If it should be noted that the component compound form of the present invention, the solid masses of the component is compound quality,
If component lotion or solution form, the solid masses of the component is the quality of remainder after drying, is liquid for solute
The component of body or gas, such as when pH adjusting agent is formic acid solution, solid masses then in nail acid solution solute formic acid matter
Amount.
Compared with prior art, the present invention advantage is embodied in：
First, size provided by the invention compounds suitable film forming agent and suitable coupling agent, lubrication by introducing
The components such as agent, antifoaming agent, antioxidant and pH adjusting agent are effectively improved the dispersibility of glass fibre, and filoplume is few, goes out
Yarn tension is low, more conducively the CFRT techniques of galss fiber reinforced resin.
Second, size provided by the invention is compounded using the polypropylene wax emulsion of different molecular weight by certain ratio
It for film forming agent, and is matched with other components such as suitable coupling agent, lubricants, not only effectively improves the dispersibility of glass fibre
And convergence, and it is good with acrylic resin compatibility, finally obtained composite article mechanical performance is excellent.
Third, size provided by the invention have selected suitable component and proportioning, and coating effect is good, not only glass fibre
It is had excellent performance in CFRT techniques, composite article mechanical performance is excellent, and glass fibre appearance color meets related request.
The size each component of the present invention and its advantageous effect of the selection of content will provide specific experiment by embodiment
Data illustrate.
Description of the drawings
It is incorporated into specification and the attached drawing of a part for constitution instruction shows the embodiment of the present invention, and with
Principle for explaining the present invention together is described, in the drawings, similar reference numeral is used to indicate similar element, under
Attached drawing in the description of face is some embodiments of the present invention, rather than whole embodiments, and those of ordinary skill in the art are come
It says, it without creative efforts, can be obtain other attached drawings according to these attached drawings.
Fig. 1 shows a kind of preparation flow figure of size according to the present invention；
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.It should be noted that
In the case of not conflicting, the features in the embodiments and the embodiments of the present application mutually can be combined arbitrarily.
Embodiment 1
Each component is weighed according to infiltration agent prescription, wherein the content of water accounts for the 96.5% of size gross mass, each component
Solid masses accounts for size solid gross mass：Coupling agent 10%, lubricant 10%, film forming agent A 20%, film forming agent B
59.34%, the solid content ratio of antifoaming agent 0.01%, antioxidant 0.15%, pH adjusting agent 0.5%, each component is total
100%.
Wherein, coupling agent is double amino silicane coupling agents, product grade A-1120；Lubricant is microwax, product board
Number for Mike door Hydrolube 496；Film forming agent A is the polypropylene lotion of higher molecular weight, and product grade is the F of Mai Kemen
Glass X35；Film forming agent B is the polypropylene wax emulsion of lower molecular weight, and product grade is the PP2-01 of Mai Kemen；Antifoaming agent is
Organosiloxane BYK019；Antioxidant is sodium hypophosphite；PH adjusting agent is acetic acid.
Said components are carried out to the preparation of size as follows：
The pre-dispersed coupling agents of 1S：The deionized water that quality is total amount half is added in preparing container, is added to weigh and complete
Coupling agent, persistently stir 25 minutes；
2S dilutes lubricant, film forming agent, antifoaming agent and antioxidant：Deionization is used to dilute size each component respectively,
In, in lubricant dilution, the quality using deionized water is 3 times of lubricant quality；Film forming agent includes film forming agent A and film forming
Agent B uses deionized water dilution film forming agent A and film forming agent B, the dilution of corresponding film forming agent is made respectively, then by two kinds respectively
Film forming agent dilution is uniformly mixed, and the quality using deionized water is respectively 3 times of corresponding film forming agent quality；Antifoaming agent dilution
In, the quality using deionized water is 3 times of antifoaming agent quality；In antioxidant dilution, the quality using deionized water is anti-
5 times of oxygen agent quality；
3S prepares size：Container is prepared be completed step 1S, sequentially adds lubricant, film forming agent, antifoaming agent
With the dilution of antioxidant, after being uniformly mixed, pH adjusting agent is added, control size pH value is 7.
The size combustible content index finally prepared is 0.35%.
The preparation process of 2~6 reference implementation example 1 of embodiment, the used in amounts of each component meet ratio of the present invention and close
System, those skilled in the art can be adaptively adjusted according to actual conditions based on above-mentioned preparation method.Implement in the present invention
In example, the content of water accounts for the 96.5% of size gross mass, also, the selection of each component substance is consistent with embodiment 1.Table
1 shows the percent value of size solid gross mass shared by each component solid masses in size, the corresponding numerical value of each component
For mass percent/%.
1 size specific embodiment list of table
Comparative example
Advantageous effect in order to further illustrate the present invention selects more common glass fiber reinforced polypropylene tree at present
The size of fat CFRT techniques embodiment as a comparison, the content of water accounts for the 96% of size gross mass in the size, respectively
Component and its content indicate as follows：
Wherein, coupling agent is gamma-aminopropyl-triethoxy-silane, and lubricant is odium stearate, and film forming agent is high molecular weight
Polypropylene wax, product grade is ME 91735, and pH adjusting agent is acetic acid, and LOI values are 0.5%.
Test case
Above-described embodiment and comparative example are applied to the production of glass fibre, and by corresponding glass fiber applications in enhancing
The performance of performance and finally obtained fiber glass reinforcement in the CFRT techniques of acrylic resin, and to glass fibre
It is tested, the results are shown in Table 2.Wherein, the line density of glass fibre is 1200tex, glass in glass fiber compound material
Fiber content is 60%.
2 different glass fibre property test result of table
It is partially yellow using color after glass fiber yarn drying made from comparative example from the point of view of glass fiber yarn appearance, and use
Do not occur to aoxidize xanthochromia after glass fiber yarn drying made from Examples 1 to 6, meets the color requirement to glass fiber yarn.
From above-mentioned test case it will be seen that using glass fibre performance made from size provided by the invention compared with
It is good, it is embodied in two aspect of mechanical performance (tensile strength) and glass fibre CFRT processing performances (dispersibility, filoplume amount)：
In terms of reinforcing material measuring mechanical property, the tensile strength of 1~embodiment of embodiment 6 is above 900MPa, symbol
Close the requirement that continuous fiber reinforced polypropylene resin material is directed to mechanical performance, and the average tensile of 1~embodiment of embodiment 6
Intensity is 1002.7MPa, and compared with comparative example, tensile strength improves 34.59%.It is tested in glass fibre CFRT processing performances
The convergence of aspect, different glass fiber is preferable, i.e., filoplume amount is relatively low, and in addition to embodiment 5,6, the filoplume amount of other embodiment is equal
Less than comparative example；Moreover, the dispersion performance of glass fibre made from different embodiments is good, it is satisfied by the phase of yarn sheet width >=8mm
It closes and requires, and the mean yarn width of 1~embodiment of embodiment 6 is 8.97mm, compared with comparative example, yarn sheet width improves
19.6%.And embodiment 3 and the comprehensive performance of embodiment 4 are more excellent, disclosure satisfy that more strict requirements in actual production.
In conclusion the present invention has following advantageous effects：
First, size provided by the invention compounds suitable film forming agent and suitable coupling agent, lubrication by introducing
The components such as agent, antifoaming agent, antioxidant and pH adjusting agent are effectively improved the dispersibility of glass fibre, and filoplume is few, goes out
Yarn tension is low, more conducively the CFRT techniques of galss fiber reinforced resin.
Second, size provided by the invention is compounded using the polypropylene wax emulsion of different molecular weight by certain ratio
It for film forming agent, and is matched with other components such as suitable coupling agent, lubricants, not only effectively improves the dispersibility of glass fibre
And convergence, and it is good with acrylic resin compatibility, finally obtained composite article mechanical performance is excellent.
Third, size provided by the invention have selected suitable component and proportioning, and coating effect is good, not only glass fibre
It is had excellent performance in CFRT techniques, composite article mechanical performance is excellent, and glass fibre appearance color meets related request.
Finally it should be noted that：Herein, the terms "include", "comprise" or its any other variant are intended to non-
It is exclusive to include, so that the process, method, article or equipment comprising a series of elements includes not only those elements,
But also include other elements that are not explicitly listed, or further include solid by this process, method, article or equipment
Some elements.In the absence of more restrictions, the element limited by sentence " including one ... ", it is not excluded that including institute
State in the process, method, article or equipment of element that there is also other identical elements.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations.Although with reference to the foregoing embodiments
Invention is explained in detail, it will be understood by those of ordinary skill in the art that：It still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of glass fiber infiltration agent, which is characterized in that the glass fiber infiltration agent includes coupling agent, lubricant, film forming
Agent A, film forming agent B, antifoaming agent, antioxidant, pH adjusting agent and deionized water, wherein the solid masses of the size accounts for leaching
Moisten the 2~6% of agent gross mass；Also, the percentage that the solid masses of each component accounts for the size solid gross mass is as follows：
2. glass fiber infiltration agent as described in claim 1, which is characterized in that the solid masses of each component accounts for the size
The percentage of solid gross mass is as follows：
Also, the ratio between the solid masses of the film forming agent A and the solid masses of the film forming agent B are 1:0.5~3.
3. glass fiber infiltration agent as described in claim 1, which is characterized in that the film forming agent A is polypropylene wax emulsion, institute
It is polypropylene wax emulsion to state film forming agent B, and the number-average molecular weight of the film forming agent A is higher than the number-average molecular weight of the film forming agent B, and
And the ratio between the solid masses of the film forming agent A and the solid masses of the film forming agent B are 1:0.5~3.
4. glass fiber infiltration agent as described in claim 1, which is characterized in that the film forming agent A is polypropylene wax emulsion,
Number-average molecular weight is 30000~80000；The film forming agent B is polypropylene wax emulsion, and number-average molecular weight is 5000~30000.
5. glass fiber infiltration agent as described in claim 1, which is characterized in that the lubricant be fatty acid lubricant or
Microwax；The antifoaming agent is one kind in BYK011, BYK012, BYK014, BYK018, BYK023, BYK024 and BYK025
Or it is a variety of；The antioxidant is one or more in SD1688, inorganic phosphate and sodium hypophosphite.
6. glass fiber infiltration agent as claimed in claim 3, which is characterized in that the solid masses of each component accounts for the size
The percentage of solid gross mass is as follows：
Also, the coupling agent is double amino silicane coupling agents；The lubricant is microwax；The solid matter of the film forming agent A
The ratio between amount and the solid masses of the film forming agent B are 1:1.4~2.
7. glass fiber infiltration agent as described in claim 1, which is characterized in that the coupling agent is γ-(methacryls
Oxygen) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane
With it is one or more in γ-(2,3- glycidoxies) propyl trimethoxy silicane；The pH adjusting agent be organic acid or
Inorganic acid, and the pH value control of the size is 6~10.
8. such as glass fiber infiltration agent according to any one of claims 1 to 7, which is characterized in that the size is enhancing
The size of the direct yarn of alkali-free of acrylic resin.
9. a kind of preparation method of such as glass fiber infiltration agent according to any one of claims 1 to 8, which is characterized in that institute
Preparation method is stated to include the following steps：
The pre-dispersed coupling agents of 1S：The deionized water that quality is total amount half is added in preparing container, the coupling agent is added, holds
Continuous stirring 25~30 minutes；
2S dilutes lubricant, film forming agent, antifoaming agent and antioxidant：Deionization is used to dilute size each component respectively, wherein profit
In lubrication prescription dilution, the quality using deionized water is 2-3 times of lubricant quality；Film forming agent includes film forming agent A and film forming agent
B uses deionized water dilution film forming agent A and film forming agent B respectively, is made the dilution of corresponding film forming agent respectively, then by two kinds at
Film dilution is uniformly mixed, and the quality using deionized water is respectively 2-3 times of corresponding film forming agent quality；Antifoaming agent dilution
In, the quality using deionized water is 2-3 times of antifoaming agent quality；In antioxidant dilution, it is using the quality of deionized water
4-5 times of antioxidant quality；
3S prepares size：Container is prepared be completed step 1S, sequentially adds lubricant, film forming agent, antifoaming agent and anti-
After being uniformly mixed, pH adjusting agent is added in the dilution of oxygen agent, and control size pH value is 6~10.
10. a kind of if glass fiber infiltration agent according to any one of claims 1 to 8 is in glass fiber reinforced polypropylene resin
CFRT techniques in purposes.
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| CN201710071725.3A CN108409163A (en) | 2017-02-09 | 2017-02-09 | A kind of glass fiber infiltration agent and its preparation method and application |
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| CN109265020A (en) * | 2018-11-07 | 2019-01-25 | 安徽省绩溪县华宇防火滤料有限公司 | A kind of novel glass fiber size |
| CN109455953A (en) * | 2018-12-03 | 2019-03-12 | 巨石集团有限公司 | A kind of reinforced polypropylene glass fiber infiltration agent and its preparation method and application |
| CN111018366A (en) * | 2019-12-20 | 2020-04-17 | 内江华原电子材料有限公司 | Impregnating compound for glass fiber direct roving for LFT (Long fiber reinforced thermoplastic) process and preparation method thereof |
| CN112266186A (en) * | 2020-11-06 | 2021-01-26 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
| CN112341711A (en) * | 2020-11-26 | 2021-02-09 | 江苏金发科技新材料有限公司 | Special glass fiber reinforced polypropylene composition for automobile intake manifold and preparation method thereof |
| CN112647300A (en) * | 2020-12-18 | 2021-04-13 | 泰山玻璃纤维有限公司 | GF/PP composite fiber impregnating compound and application thereof |
| CN113896436A (en) * | 2021-10-29 | 2022-01-07 | 巨石集团有限公司 | Glass fiber impregnating compound and application thereof |
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| CN104045244A (en) * | 2014-05-29 | 2014-09-17 | 巨石集团有限公司 | Alkali-free direct roving impregnating compound for continuous fiber reinforced polyolefin |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265020A (en) * | 2018-11-07 | 2019-01-25 | 安徽省绩溪县华宇防火滤料有限公司 | A kind of novel glass fiber size |
| CN109455953A (en) * | 2018-12-03 | 2019-03-12 | 巨石集团有限公司 | A kind of reinforced polypropylene glass fiber infiltration agent and its preparation method and application |
| CN109455953B (en) * | 2018-12-03 | 2022-02-01 | 巨石集团有限公司 | Glass fiber impregnating compound for reinforced polypropylene and preparation method and application thereof |
| CN111018366A (en) * | 2019-12-20 | 2020-04-17 | 内江华原电子材料有限公司 | Impregnating compound for glass fiber direct roving for LFT (Long fiber reinforced thermoplastic) process and preparation method thereof |
| CN112266186A (en) * | 2020-11-06 | 2021-01-26 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
| CN112266186B (en) * | 2020-11-06 | 2022-08-30 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
| CN112341711A (en) * | 2020-11-26 | 2021-02-09 | 江苏金发科技新材料有限公司 | Special glass fiber reinforced polypropylene composition for automobile intake manifold and preparation method thereof |
| CN112647300A (en) * | 2020-12-18 | 2021-04-13 | 泰山玻璃纤维有限公司 | GF/PP composite fiber impregnating compound and application thereof |
| CN112647300B (en) * | 2020-12-18 | 2022-05-20 | 泰山玻璃纤维有限公司 | GF/PP composite fiber impregnating compound and application thereof |
| CN113896436A (en) * | 2021-10-29 | 2022-01-07 | 巨石集团有限公司 | Glass fiber impregnating compound and application thereof |
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