CN115010383A - Glass fiber with at least two coating layers, preparation method and application thereof - Google Patents

Glass fiber with at least two coating layers, preparation method and application thereof Download PDF

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CN115010383A
CN115010383A CN202210770920.6A CN202210770920A CN115010383A CN 115010383 A CN115010383 A CN 115010383A CN 202210770920 A CN202210770920 A CN 202210770920A CN 115010383 A CN115010383 A CN 115010383A
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coating layer
glass fiber
coating
slurry
sintering
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CN115010383B (en
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苗伟峰
周良
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Tianjin Stanley New Material Co ltd
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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
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/52—Coatings containing inorganic materials only
    • 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
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/54—Combinations of one or more coatings containing organic materials only with one or more coatings containing inorganic materials only
    • 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
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/483—Containers

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Abstract

The invention discloses a glass fiber with at least two coating layers, which comprises a glass fiber body, wherein the glass fiber body is surrounded by the at least two coating layers, and the coating layers comprise a metal oxide coating layer or a high-temperature-resistant polymer coating layer. The modified glass fiber with at least two coating layers is used for improving the strength, reflectivity and surface gloss of the LED support and reducing the cost. The invention also relates to application of the modified glass fiber in the field of LED supports.

Description

Glass fiber with at least two coating layers, preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to glass fiber with at least two coating layers, a preparation method and application thereof.
Background
LED technology has been rapidly developed for low energy consumption, high brightness and high safety. The semi-aromatic nylon is mainly applied to an LED support in the LED industry, and the LED support is required to have high reflectivity. The white filler is enhanced by whitening minerals such as titanium dioxide and the like, and the resin is required to have good stability, high heat resistance, high reflectivity and no obvious yellowing at high temperature. In the prior art, titanium dioxide, silicon fiber (calcium silicate), barium sulfate and the like are mostly adopted as white fillers, but the reflection performance of the silicon fiber to light is general mainly because the whiteness of the silicon fiber is not enough. Although the whiteness of the titanium dioxide is higher and the reflection performance to light is better than that of silicon fiber, the reinforcing capability of the titanium dioxide in a nanometer sphere shape is insufficient, and simultaneously, the polymer can be catalyzed and degraded, so that the mechanical property of the composition can be greatly reduced.
CN105143332A discloses a resin composition for molding a reflector of a light emitting semiconductor diode, comprising about 25 to about 80 wt.% of a heat resistant aromatic polyester, about 5 to 50 wt.% of a titanium dioxide filler; and about 5 to 50 wt.% of a glass fiber having a flat surface. The data show that the maximum reflectivity of the added glass fiber is about 91 percent, the glass fiber can also ensure the strength of the composition, but the obtained composition has fiber floating on an injection-molded reflector (the glass fiber is exposed out of the surface in a needle shape), the roughness of the reflector is increased, and the reflectivity is reduced, so that the chip is not beneficial to attaching.
The glass fiber is an inorganic non-metallic material with excellent performance, has various varieties, has the advantages of good insulativity, strong heat resistance, good corrosion resistance, low price and high mechanical strength, but has the defects of brittle performance and poor wear resistance. It is made up by using glass ball or waste glass as raw material through the processes of high-temp. melting, wire-drawing, winding and weaving. Glass fibers are commonly used as reinforcing materials in composite materials, electrical and thermal insulation materials, circuit substrates, and other various fields of the national economy.
At present, a great deal of glass fiber reinforced materials are researched, but some defects such as low product strength, poor high temperature resistance, low reflectivity and the like exist, and the composite advantage of glass fiber cannot be fully exerted.
Disclosure of Invention
It is an object of the present invention to provide glass fibers having at least two coating layers, a method for their preparation and their use, solving one or more of the above mentioned prior art problems.
In a first aspect, the present invention provides a glass fiber having at least two coating layers, comprising a glass fiber body surrounded by at least two coating layers, the coating layers comprising a metal oxide coating layer or a high temperature resistant polymer coating layer.
In certain embodiments, the glass fiber body is surrounded by two coating layers, including a first coating layer that is a metal oxide coating layer and a second coating layer that is a metal oxide coating layer.
In certain embodiments, the glass fiber body is surrounded by three coating layers including a first coating layer that is a metal oxide coating layer, a second coating layer that is a metal oxide coating layer, and a third coating layer that is a high temperature resistant polymer coating layer.
In certain embodiments, the glass fiber is E, A, C, D, AR, basalt and the like, has the performance characteristics of high strength, high quality and low price, and is widely used for reinforcing and modifying plastics.
In certain embodiments, the E-glass fibers consist of the following components in mass percent: 52% to 62% silica, 12% to 16% alumina, 16% to 25% calcium oxide, 0% to 10% borax, 0% to 5% magnesium oxide, 0% to 2% alkali metal oxide, 0% to 1.5% titanium dioxide and 0% to 0.3% iron oxide.
In certain embodiments, the a glass fibers consist of the following components in mass percent: 63% to 72% silica, 6% to 10% calcium oxide, 14% to 16% sodium and potassium oxides, 0% to 6% alumina, 0% to 6% boron oxide and 0% to 4% magnesium oxide.
In certain embodiments, the C glass fibers consist of the following components in mass percent: 64% to 68% silica, 11% to 15% calcium oxide, 7% to 10% sodium and potassium oxides, 3% to 5% alumina, 4% to 6% boron oxide and 2% to 4% magnesium oxide.
In certain embodiments, the D glass fibers consist of the following components in mass percent: 72% to 75% silica, 0% to 1% calcium oxide, 0% to 4% sodium and potassium oxides, 0% to 1% alumina and 21% to 24% boron oxide.
In certain embodiments, the basalt fibers consist of the following components in mass percent: 52% SiO 2 17% of Al 2 O 3 9% of CaO, 5% of MgO and 5% of Na 2 O and 5% iron oxide.
In certain embodiments, the AR glass fibers consist of the following components in mass percent: 55% to 75% silica, 1% to 10% calcium oxide, 11% to 21% sodium oxide and potassium oxide, 0 to 5% alumina, 0% to 8% boron oxide, 0% to 12% titania, 1% to 18% zirconia, and 0% to 5% iron oxide.
In certain embodiments, the glass fibers are in the form of staple fibers or continuous filament fibers (rovings).
In certain embodiments, the short fibers are chopped glass having a length of from 0.2mm to 20 mm.
In certain embodiments, the glass fibers may have respective cross-sections.
In certain embodiments, the glass fibers are glass fibers having a circular cross-section (round fibers) or a non-circular cross-section (flat fibers).
In certain embodiments, the diameter of the glass fibers having a circular cross-section (i.e., circular glass fibers) is between 3 μm and 20 μm.
In certain embodiments, the diameter of the glass fibers having a circular cross-section (i.e., circular glass fibers) is between 5 μm and 13 μm.
In certain embodiments, the diameter of the glass fibers having a circular cross-section (i.e., circular glass fibers) is between 5 μm and 10 μm.
In certain embodiments, the short glass fibers have a length of 0.2mm to 20 mm.
In certain embodiments, the short glass fibers have a length of 2mm to 12 mm.
In certain embodiments, the material from which the first coating layer is made comprises a sintering aid comprising a first chemical bondA compound selected from the group consisting of aluminum phosphate, boron oxide, lithium fluoride, lithium carbonate, calcium fluoride, calcium oxide, bismuth oxide, tin oxide, lead oxide, indium oxide, or mixtures thereof; the second compound is selected from a low temperature glass frit comprising aluminate glass or borosilicate glass; preferably, the low temperature glass enamel frit comprises or does not comprise an alkali metal oxide and/or an alkaline earth metal oxide; more preferably, the low temperature glass enamel frit further comprises an oxide selected from B 2 O 3 、SiO 2 、Al 2 O 3 、CdO、CaO、BaO、ZnO、Na 2 O、Li 2 O、PbO、ZrO 2 Or mixtures thereof;
the second coating layer is selected from a high melting point compound selected from a compound of aluminum, a compound of titanium, a compound of magnesium, a compound of zinc, an oxide of tin, or a compound of molybdenum; the aluminum compound is selected from aluminum hydroxide, aluminum isopropoxide, aluminum ethoxide, tert-butyl aluminum, aluminum nitrate, aluminum acetylacetonate or aluminum acetate; the titanium compound is selected from titanium n-butoxide, tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, lithium titanate, magnesium titanate, bismuth titanate, lead titanate, lithium titanate or potassium titanate; the magnesium compound is selected from magnesium hydroxide, magnesium oxalate, magnesium ethoxide, magnesium acetate, magnesium phosphate, magnesium pyrophosphate, magnesium phosphate, magnesium sulfate, magnesium chloride or magnesium citrate; the zinc compound is selected from zinc borate, zinc fluoride, zinc acetate, zinc isopropoxide, zinc phosphate, zinc acetate, zinc carbonate, zinc borate, zinc propionate, zinc molybdate or zinc sulfate; the tin oxide is selected from tin oxide, tin acetate, sodium stannate, tin pyrophosphate, tetrabutyltin, tin tetrachloride, tin chloride, tin phosphide or tin acetylacetonate; the molybdenum compound is selected from sodium molybdate, molybdenum pentachloride, molybdenum acetylacetonate, molybdenum acetate or molybdenum chloride.
In certain embodiments, the third coating layer is selected from high temperature resistant polymers.
In certain embodiments, the high temperature resistant polymer is selected from the group consisting of polyester compounds, polyamide compounds, or imine compounds.
In certain embodiments, the high temperature resistant polymer is selected from the group consisting of poly (1, 4-cyclohexanedimethanol terephthalate), poly (hexamethylene terephthalamide), or a polyesterimide.
In a second aspect, the present invention provides a method for preparing a glass fiber having at least two coating layers, comprising the steps of:
coating the first coating layer and the second coating layer on the surface of the glass fiber in a slurry form, and then sintering to form the glass fiber coated with the two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
and then coating the second coating layer slurry, and sintering the second coating layer slurry to obtain the glass fiber coated with two coating layers.
In certain embodiments, the method specifically comprises the steps of:
mixing a sintering aid, a binder, a dispersant and a solvent according to a ratio, grinding for 5-24 hours by using a sand mill to form uniform slurry, then attaching a layer of sintering aid slurry on the surface of glass fiber by a dip coating process, and drying solvent components in the slurry by using an oven to form a first coating layer slurry layer; then coating according to the same method to form a second coating layer slurry layer, then placing the glass fiber in a common sintering furnace for heat treatment, removing the adhesive, sintering the glass fiber into the first coating layer and the second coating layer, and controlling the sintering temperature to be 300-800 ℃, preferably 350-650 ℃; or
Adhering a layer of sintering aid slurry to the surface of the glass fiber by a dip-coating process, drying solvent components in the slurry by using an oven to form a first coating slurry layer, then sintering to form a first coating, and controlling the sintering temperature to be 300-600 ℃, preferably 400-550 ℃; and adhering a second coating layer slurry on the surface of the first coating layer by a dip coating process, and then sintering to form the second coating layer, wherein the sintering temperature is controlled to be 300-800 ℃, and preferably 350-650 ℃.
In certain embodiments, the components of the first coating layer slurry comprise, in weight percent:
Figure BDA0003724189520000041
Figure BDA0003724189520000051
in certain embodiments, the binder is selected from PVA, PVB, or acrylates.
In certain embodiments, the dispersant is selected from a sodium salt of a polycarboxylic acid, tributyl phosphate, glycerol trioleate, or triethanolamine.
In certain embodiments, the solvent is selected from one or more of water, toluene, ethanol, isopropanol, butanol, acetone, butanone, ethyl acetate.
In certain embodiments, the thickness of the first coating layer is 0.1 to 1 μm.
In certain embodiments, the thickness of the first coating layer is 0.2 to 0.8 μm.
In certain embodiments, the thickness of the second coating layer is from 1 to 20 μm.
In certain embodiments, the thickness of the second coating layer is from 3 to 5 μm.
In certain embodiments, the thickness of the third coating layer is from 0.1 to 10 μm.
Wherein: the thickness of the coating layer was observed with an optical microscope and statistically calculated.
The first coating layer is a transition layer and is also a sintering aid layer for improving the adhesive force between the second coating layer and the glass fiber. The first coating layer is a low-melting-point substance, the second coating layer is a higher-melting-point substance, and the second coating layer increases the bonding force between the glass fiber and the resin. The third coating layer is made of high-temperature-resistant polymer materials, and the melting point of the third coating layer is higher than that of the modified plastic, so that the glass fiber is prevented from melting when being added into plastic particles for modification.
In a third aspect, the present invention provides a method for preparing a glass fiber having at least two coating layers, comprising the steps of:
coating the first coating layer and the second coating layer on the surface of the glass fiber in a slurry form, and sintering to form the glass fiber coated with the two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
coating the second coating layer slurry, and sintering to obtain glass fiber coated with two coating layers;
and reacting the glass fiber coated with the first coating layer and the second coating layer, the 1, 4-cyclohexanedimethanol and the terephthalic acid to prepare the glass fiber coated with the third coating layer and the poly (1, 4-cyclohexanedimethanol terephthalate).
In certain embodiments, the glass fiber coated with the first and second coating layers, 1, 4-cyclohexanedimethanol, and terephthalic acid are placed in a reactor and reacted at 280 ℃ for 3 hours at normal pressure, followed by 300 ℃ for 1.5 hours at 120Pa vacuum to produce a glass fiber coated with a third coating layer of poly (1, 4-cyclohexanedimethanol terephthalate).
In certain embodiments, a method of making a glass fiber having at least two coating layers, comprises the steps of:
coating the first coating layer and the second coating layer on the surface of the glass fiber in a slurry form, and then sintering to form the glass fiber coated with the two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
coating the second coating layer slurry, and sintering to obtain glass fiber coated with two coating layers;
and reacting the glass fiber coated with the first coating layer and the second coating layer, the hexamethylene diamine and the terephthalic acid to prepare the glass fiber coated with the polyhexamethylene terephthalamide of the third coating layer.
In certain embodiments, the glass fiber coated with the first and second coating layers, hexamethylenediamine and terephthalic acid are placed in a reactor and reacted for 6 hours at 230 ℃ under a vacuum of 500Pa to produce a glass fiber coated with polyhexamethylene terephthalamide with a third coating layer.
In certain embodiments, a method of making a glass fiber having at least two coating layers, comprises the steps of:
coating the first coating layer and the second coating layer on the surface of the glass fiber in a slurry form, and sintering to form the glass fiber coated with the two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
coating the second coating layer slurry, and sintering to obtain the glass fiber coated with two coating layers;
and reacting the glass fiber coated with the first coating layer and the second coating layer, diaminodiphenyl sulfide, hexamethylene diamine, isophthalic acid, trimellitic anhydride and propylene glycol to obtain the glass fiber coated with the polyester imine of the third coating layer.
In some embodiments, the glass fiber coated with the first coating layer and the second coating layer, diaminodiphenyl sulfide, hexamethylene diamine, isophthalic acid, trimellitic anhydride, and propylene glycol are subjected to reflux reaction at 150 ℃ for 3 hours, then to heat preservation reaction at 190 ℃ for 10 hours, and finally to reaction at 210 ℃ for 8 hours to prepare the glass fiber coated with the polyesterimide of the third coating layer.
In a fourth aspect, the present invention provides a polymer composition comprising the above glass fiber having at least two coating layers, the polymer composition being prepared by a method comprising the steps of:
uniformly mixing glass fiber with at least two coating layers and PPA, and adding the mixture into an extruder, wherein the extrusion temperature is controlled to be 280-330 ℃;
carrying out water-cooling granulation after extrusion, wherein the conditions for controlling the water-cooling granulation are as follows: below 60 deg.C and normal pressure;
drying, controlling the temperature to be 150 ℃ until the water content is lower than 0.1%;
wherein: the PPA includes PA6T, PA9T, PA10T, and PA 12T.
In a fifth aspect, the invention provides a use of the polymer composition, and a use of the polymer composition in an LED support.
Wherein: the modified glass fiber with at least two coating layers is used for improving the strength, reflectivity and surface gloss of the LED support and reducing the cost.
The preparation method of the polymer composition comprises the following steps:
uniformly mixing the glass fiber with at least two coating layers and PPA, adding the mixture into an extruder, and controlling the extrusion temperature to be 280-330 ℃;
carrying out water-cooling granulation after extrusion, wherein the conditions for controlling the water-cooling granulation are as follows: below 60 deg.C and normal pressure;
drying, controlling the temperature to be 150 ℃ until the water content is lower than 0.1%;
wherein: the PPA includes PA6T, PA9T, PA10T, and PA 12T.
Has the advantages that: according to the glass fiber with at least two coating layers, the first coating layer increases the binding force between the second coating layer and the glass fiber, the second coating layer increases the binding force between the glass fiber and resin, the two coating layers jointly increase or maintain the mechanical property of the resin composition, increase the light reflectivity (under the condition of white materials), reduce the occurrence of floating fibers and increase the brightness of an injection molding piece. And secondly, by coating the third coating layer and selecting the high-temperature-resistant polymer, the glass fiber is prevented from melting when being added into plastic particles for modification. Meanwhile, with the arrangement of the third coating layer, the organic matter and the plastic particles can be better combined, and the mechanical property and the aging resistance of the resin composition can be further improved.
Detailed Description
The present invention will be described in further detail below with reference to embodiments.
Example 1
First coating layer
100g (10 wt.%) of aluminum phosphate as sintering aid, 30g (3 wt.%), 10g (1 wt.%) of sodium polycarboxylate salt as dispersant and 860g (86 wt.%) of distilled water are mixed and ground in a sand mill for 5h to form uniform slurry. And coating the glass fiber with the slurry to form first coating layer slurry, and then putting the first coating layer slurry into an oven to be dried at 60 ℃ for coating the first coating layer slurry.
Second coating layer
170g (16.3 wt.%) of aluminum isopropoxide, 30g (2.9 wt.%) of zinc borate, 30g (2.8 wt.%), 15g (1.4 wt.%) of sodium polycarboxylate dispersant, and 800g (76.6 wt.%) of distilled water were mixed and ground in a sand mill for 10 hours to form a uniform slurry. And coating the glass fiber with the first coating layer slurry on a second coating layer, drying after coating, and sintering in a high-temperature furnace to form the glass fiber with the first and second coating layers, wherein the sintering temperature is 500 ℃, and the sintering time is 4 hours.
Modification of plastics
3kg of glass fiber with the first coating layer and 3kg of PA10T with the second coating layer are uniformly mixed and extruded by an extruder, the extrusion temperature is 300 ℃, water cooling granulation is carried out under the conditions of normal pressure and the temperature lower than 60 ℃, then drying is carried out (the drying is carried out under the control of 150 ℃ until the water content is lower than 0.1 percent), the mixture is injection molded into a plate with the size of 60 x 40 x 2mm, and the reflectivity and the mechanical property of 460nm are tested.
Example 2
First coating layer
20g (2 wt.%) of sintering aid calcium fluoride, 90g (9 wt.%) of boron oxide, 30g (3 wt.%) of PVB30g, 10g (1 wt.%) of dispersant triolein and 850g (85 wt.%) of ethanol are mixed and then put into a sand mill to be ground for 5 hours to form uniform slurry. And coating the glass fiber with the slurry to form first coating layer slurry, and then putting the first coating layer slurry into an oven to be dried and coated with second coating layer slurry at 60 ℃.
Second coating layer
210g of tetrabutyl titanate (18.3 wt.%), 90g of magnesium phosphate (7.9 wt.%), 30g g of PVB (2.6 wt.%), 15g of triolein as a dispersant (1.3 wt.%), and 800g of butanone (69.9 wt.%) were mixed and ground in a sand mill for 12 hours to form a homogeneous slurry. And coating the glass fiber with the first coating layer slurry on a second coating layer, drying after coating, and sintering in a high-temperature furnace to form the glass fiber with the first and second coating layers, wherein the sintering temperature is 350 ℃, and the sintering time is 2 hours.
Modification of plastics
3kg of glass fiber with the first coating layer and 3kg of PA6T/66 with the second coating layer are uniformly mixed and extruded by an extruder, the extrusion temperature is 330 ℃, water cooling granulation is carried out under the conditions of normal pressure and lower than 60 ℃, then drying is carried out (the drying is carried out under the control of 150 ℃ till the water content is lower than 0.1 percent), and the glass fiber is molded into a plate with the size of 60 x 40 x 2mm, and the reflectivity and the mechanical property of 460nm are tested.
Example 3
First coating layer
The components of the coating layer are the same as those of the embodiment 2, and the coating layer is directly sintered after being dried, wherein the sintering temperature is 450 ℃, and the sintering time is 2 hours.
Second coating layer
And coating the glass fiber with the first coating layer with a second coating layer, drying after coating, and sintering in a high-temperature furnace to form the glass fiber with the first and second coating layers, wherein the sintering temperature is 550 ℃, and the sintering time is 2 hours.
Modification of plastics
3kg of glass fiber with the first coating layer and 3kg of PA10T with the second coating layer are uniformly mixed and extruded by an extruder, the extrusion temperature is 300 ℃, water cooling granulation is carried out under the conditions of normal pressure and the temperature lower than 60 ℃, then drying is carried out (the drying is carried out under the control of 150 ℃ until the water content is lower than 0.1 percent), the mixture is injection molded into a plate with the size of 60 x 40 x 2mm, and the reflectivity and the mechanical property of 460nm are tested.
Example 4
First coating layer
100g (10 wt.%) of aluminum phosphate as sintering aid, 30g (3 wt.%), 10g (1 wt.%) of sodium polycarboxylate salt as dispersant and 860g (86 wt.%) of distilled water are mixed and ground in a sand mill for 5h to form uniform slurry. And coating the glass fiber with the slurry to form first coating layer slurry, and then putting the first coating layer slurry into an oven to be dried at 60 ℃ for coating the first coating layer slurry.
Second coating layer
170g (16.3 wt.%) of aluminum isopropoxide, 15g (1.45 wt.%) of ethyl orthosilicate, 15g (1.45 wt.%) of zinc borate, 30g (2.8 wt.%) of PVA, 15g (1.4 wt.%) of sodium polycarboxylate, dispersant, and 800g (76.6 wt.%) of distilled water were mixed and ground in a sand mill for 10 hours to form a homogeneous slurry. And coating the glass fiber with the first coating layer slurry on a second coating layer, drying after coating, and sintering in a high-temperature furnace to form the glass fiber with the first and second coating layers, wherein the sintering temperature is 650 ℃, and the sintering time is 4 hours.
Third coating layer
10kg of glass fiber with the first and second coating layers, 500g of 1, 4-cyclohexanedimethanol and 400g of terephthalic acid were charged into a reactor, reacted at 280 ℃ for 3 hours under normal pressure, and then reacted at 300 ℃ for 1.5 hours under vacuum of 120 Pa. Thereby forming the modified glass fiber with the third coating layer of the poly (1, 4-cyclohexanedimethanol terephthalate).
Modification of plastics
3kg of glass fiber with the first coating layer and 3kg of PA10T with the second coating layer are uniformly mixed and extruded by an extruder, the extrusion temperature is 300 ℃, water cooling granulation is carried out under the conditions of normal pressure and the temperature lower than 60 ℃, then drying is carried out (the drying is carried out under the control of 150 ℃ until the water content is lower than 0.1 percent), the mixture is injection molded into a plate with the size of 60 x 40 x 2mm, and the reflectivity and the mechanical property of 460nm are tested.
Example 5
First coating layer
20g (2 wt.%) of sintering aid calcium fluoride, 90g (9 wt.%) of boron oxide, 30g (3 wt.%) of PVB30g, 10g (1 wt.%) of dispersant triolein and 850g (85 wt.%) of ethanol are mixed and then put into a sand mill to be ground for 5 hours to form uniform slurry. And coating the glass fiber with the slurry to form first coating layer slurry, and then putting the first coating layer slurry into an oven to be dried and coated with second coating layer slurry at 60 ℃.
Second coating layer
210g of tetrabutyl titanate (18.3 wt.%), 90g of magnesium phosphate (7.9 wt.%), 30g g of PVB (2.6 wt.%), 15g of triolein as a dispersant (1.3 wt.%), and 800g of butanone (69.9 wt.%) were mixed and ground in a sand mill for 12 hours to form a homogeneous slurry. And coating the glass fiber with the first coating layer slurry on a second coating layer, drying after coating, and sintering in a high-temperature furnace to form the glass fiber with the first and second coating layers, wherein the sintering temperature is 300 ℃, and the sintering time is 2 hours.
Third coating layer
10kg of glass fibers with a first and a second coating layer, 116g of hexamethylenediamine and 160g of terephthalic acid were introduced into a reactor and reacted for 6h at 230 ℃ under a vacuum of 500 Pa. Thereby forming the modified glass fiber with the third coating layer of the poly-hexamethylene terephthalamide.
Modification of plastics
3kg of glass fiber with the first coating layer and 3kg of PA6T/66 with the second coating layer are uniformly mixed and extruded by an extruder, the extrusion temperature is 330 ℃, water cooling granulation is carried out under the conditions of normal pressure and lower than 60 ℃, then drying is carried out (the drying is carried out under the control of 150 ℃ till the water content is lower than 0.1 percent), and the glass fiber is molded into a plate with the size of 60 x 40 x 2mm, and the reflectivity and the mechanical property of 460nm are tested.
Example 6
First coating layer
100g (10 wt.%) of aluminum phosphate as sintering aid, 30g (3 wt.%), 10g (1 wt.%) of sodium polycarboxylate salt as dispersant and 860g (86 wt.%) of distilled water are mixed and ground in a sand mill for 5h to form uniform slurry. And coating the glass fiber with the slurry to form first coating layer slurry, and then putting the first coating layer slurry into an oven to be dried at 60 ℃ for coating the first coating layer slurry.
Second coating layer
170g (16.3 wt.%) of aluminum isopropoxide, 15g (1.45 wt.%) of ethyl orthosilicate, 15g (1.45 wt.%) of zinc borate, 30g (2.8 wt.%) of PVA, 15g (1.4 wt.%) of sodium polycarboxylate, dispersant, and 800g (76.6 wt.%) of distilled water were mixed and ground in a sand mill for 10 hours to form a homogeneous slurry. And coating the glass fiber with the first coating layer slurry on a second coating layer, drying after coating, and sintering in a high-temperature furnace to form the glass fiber with the first and second coating layers, wherein the sintering temperature is 800 ℃, and the sintering time is 4 hours.
Third coating layer
10kg of glass fiber with a first coating layer and a second coating layer, 20g of diaminodiphenyl sulfide, 10g of hexamethylene diamine, 30g of isophthalic acid, 50g of trimellitic anhydride and 5g of propylene glycol are subjected to reflux reaction at 150 ℃ for 3h, then the temperature is kept at 190 ℃ for 10h, and finally the reaction is carried out at 210 ℃ for 8h to generate polyesterimide with a third coating layer. Thereby forming the modified glass fiber with the third coating layer of the polyester-imide.
Modification of plastics
3kg of glass fiber with the first coating layer and the second coating layer and 3kg of PA9T are uniformly mixed and extruded by an extruder, the extrusion temperature is 300 ℃, water cooling granulation is carried out under the conditions of normal pressure and the temperature of lower than 60 ℃, then drying is carried out (the temperature is controlled to be 150 ℃ until the water content is lower than 0.1%), a plate with the size of 60 x 40 x 2mm is formed by injection molding, and the reflectivity and the mechanical property of 460nm are tested.
Comparative example 1
The glass fiber is not modified, 3kg of glass fiber and 3kg of PA10T are uniformly mixed and extruded by an extruder, the extrusion temperature is 300 ℃, water cooling granulation is carried out under the conditions of normal pressure and the temperature lower than 60 ℃, then drying is carried out (the temperature is controlled to be 150 ℃ until the water content is lower than 0.1 percent), the mixture is injection-molded into a plate with the size of 60 x 40 x 2mm, and the reflectance and the mechanical property of 460nm are tested.
Example 7
The plastics of examples 1 to 6 and comparative example 1 were tested for properties. The method comprises the following specific steps:
white combination test 460nm reflectivity, light reflectivity test method: the reflectance of the molded plaques at 460nm, with dimensions of 60 x 40 x 2mm, was measured by spectrocolorimeter Datacolor 600 using the ASTM E1331 standard, CIE D65 daylight standard illuminant at 10 ℃.
Mechanical property test standard:
tensile property: measured according to ISO 527-2, the test conditions are 23 ℃ and 10 mm/min;
bending property: measured according to ISO 178, the test conditions are 23 ℃ and 2 mm/min;
notched impact strength: the test conditions were 23 ℃ and the notch type was type A, determined according to ISO 180/1A.
The test results are shown in table 1.
TABLE 1
Figure BDA0003724189520000121
In summary, the following steps: according to the glass fiber with at least two coating layers, the first coating layer increases the bonding force between the second coating layer and the glass fiber, the second coating layer increases the bonding force between the glass fiber and resin, the two coating layers jointly increase or maintain the mechanical property of the resin composition, increase the light reflectivity (under the condition of white materials), reduce the occurrence of floating fibers and increase the brightness of injection molding parts. And secondly, by coating the third coating layer and selecting the high-temperature-resistant polymer, the glass fiber is prevented from melting when being added into plastic particles for modification. Meanwhile, with the arrangement of the third coating layer, the organic matter and the plastic particles can be better combined, and the mechanical property and the aging resistance of the resin composition can be further improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the inventive concept, and these should also be considered as within the scope of the invention.

Claims (10)

1. Glass fiber with at least two coating layers, comprising a glass fiber body, characterized in that the glass fiber body is surrounded by at least two coating layers, which comprise a metal oxide coating layer or a high temperature resistant polymer coating layer.
2. The glass fiber having at least two coating layers according to claim 1, comprising a glass fiber body, wherein the glass fiber body is surrounded by two coating layers, the coating layers comprising a first coating layer that is a metal oxide coating layer and a second coating layer that is a metal oxide coating layer.
3. The glass fiber having at least two coating layers according to claim 1, comprising a glass fiber body, wherein the glass fiber body is surrounded by three coating layers, the coating layers comprising a first coating layer, a second coating layer, and a third coating layer, the first coating layer being a metal oxide coating layer, the second coating layer being a metal oxide coating layer, the third coating layer being a high temperature resistant polymer coating layer.
4. The glass fiber having at least two coating layers according to claim 2 or 3, wherein the material for preparing the first coating layer comprises a sintering aid comprising a first compound selected from low-melting compounds selected from aluminum phosphate, boron oxide, lithium fluoride, lithium carbonate, calcium fluoride, calcium oxide, bismuth oxide, tin oxide, lead oxide, indium oxide or a mixture thereof; the second compound is selected from a low temperature glass frit comprising aluminate glass or borosilicate glass; preferably, the low temperature glass enamel frit comprises or does not comprise an alkali metal oxide and/or an alkaline earth metal oxide; more preferably, the low temperature glass enamel frit further comprises an oxide selected from B 2 O 3 、SiO 2 、Al 2 O 3 、CdO、CaO、BaO、ZnO、Na 2 O、Li 2 O、PbO、ZrO 2 Or mixtures thereof;
the second coating layer is selected from a high melting point compound selected from a compound of aluminum, a compound of titanium, a compound of magnesium, a compound of zinc, an oxide of tin, or a compound of molybdenum; the aluminum compound is selected from aluminum hydroxide, aluminum isopropoxide, aluminum ethoxide, tert-butyl aluminum, aluminum nitrate, aluminum acetylacetonate or aluminum acetate; the titanium compound is selected from titanium n-butoxide, tetrabutyl titanate, isopropyl titanate, tetraethyl titanate, lithium titanate, magnesium titanate, bismuth titanate, lead titanate, lithium titanate or potassium titanate; the magnesium compound is selected from magnesium hydroxide, magnesium oxalate, magnesium ethoxide, magnesium acetate, magnesium phosphate, magnesium pyrophosphate, magnesium phosphate, magnesium sulfate, magnesium chloride or magnesium citrate; the zinc compound is selected from zinc borate, zinc fluoride, zinc acetate, zinc isopropoxide, zinc phosphate, zinc acetate, zinc carbonate, zinc borate, zinc propionate, zinc molybdate or zinc sulfate; the tin oxide is selected from tin oxide, tin acetate, sodium stannate, tin pyrophosphate, tetrabutyltin, tin tetrachloride, tin chloride, tin phosphide or tin acetylacetonate; the molybdenum compound is selected from sodium molybdate, molybdenum pentachloride, molybdenum acetylacetonate, molybdenum acetate or molybdenum chloride.
5. Glass fiber with at least two coating layers according to claim 3, characterized in that the third coating layer is selected from high temperature resistant polymers selected from polyester, polyamide or imine based compounds, preferably poly 1, 4-cyclohexanedimethanol terephthalate, poly hexamethylene terephthalamide or polyesterimide.
6. A method of making a glass fiber having at least two coating layers according to claim 2, comprising the steps of:
coating the first coating layer and the second coating layer on the surface of the glass fiber in a slurry form, and then sintering to form the glass fiber coated with the two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
and then coating the second coating layer slurry, and sintering the second coating layer slurry to obtain the glass fiber coated with two coating layers.
7. The method for preparing a glass fiber with at least two coating layers according to claim 6, comprising the following steps:
mixing a sintering aid, a binder, a dispersant and a solvent according to a ratio, grinding for 5-24 hours by using a sand mill to form uniform slurry, then attaching a layer of sintering aid slurry on the surface of glass fiber by a dip coating process, and drying solvent components in the slurry by using an oven to form a first coating layer slurry layer; then coating according to the same method to form a second coating layer slurry layer, then placing the glass fiber in a common sintering furnace for heat treatment, removing the adhesive, sintering the glass fiber into the first coating layer and the second coating layer, and controlling the sintering temperature to be 300-800 ℃, preferably 350-650 ℃; or
Adhering a layer of sintering aid slurry to the surface of the glass fiber by a dip-coating process, drying solvent components in the slurry by using an oven to form a first coating slurry layer, then sintering to form a first coating, and controlling the sintering temperature to be 300-600 ℃, preferably 400-550 ℃; and adhering a second coating layer slurry on the surface of the first coating layer by a dip coating process, and then sintering to form the second coating layer, wherein the sintering temperature is controlled to be 300-800 ℃, and preferably 350-650 ℃.
8. A method of making a glass fiber having at least two coating layers according to claim 3, comprising the steps of:
coating the first coating layer and the second coating layer on the surface of the glass fiber in a slurry form, and then sintering to form the glass fiber coated with the two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
coating the second coating layer slurry, and sintering to obtain glass fiber coated with two coating layers;
reacting the glass fiber coated with the first coating layer and the second coating layer, 1, 4-cyclohexanedimethanol and terephthalic acid to prepare a glass fiber coated with a third coating layer and made of poly (1, 4-cyclohexanedimethanol terephthalate);
or coating the first coating layer and the second coating layer on the surface of the glass fiber in the form of slurry, and then sintering to obtain the glass fiber coated with two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
coating the second coating layer slurry, and sintering to obtain glass fiber coated with two coating layers;
reacting the glass fiber coated with the first coating layer and the second coating layer, hexamethylenediamine and terephthalic acid to prepare a glass fiber coated with polyhexamethylene terephthalamide of a third coating layer;
or coating the first coating layer and the second coating layer on the surface of the glass fiber in the form of slurry, and then sintering to obtain the glass fiber coated with two coating layers; or
Coating the first coating layer on the surface of the glass fiber in the form of slurry, and sintering the glass fiber;
coating the second coating layer slurry, and sintering to obtain glass fiber coated with two coating layers;
and reacting the glass fiber coated with the first coating layer and the second coating layer, diaminodiphenyl sulfide, hexamethylene diamine, isophthalic acid, trimellitic anhydride and propylene glycol to obtain the glass fiber coated with the polyester imine of the third coating layer.
9. Polymer composition comprising glass fibers having at least two coating layers according to any of claims 1 to 5, characterized in that the preparation process of the polymer composition comprises the following steps:
uniformly mixing glass fiber with at least two coating layers and PPA, and adding the mixture into an extruder, wherein the extrusion temperature is controlled to be 280-330 ℃;
carrying out water-cooling granulation after extrusion, wherein the conditions for controlling the water-cooling granulation are as follows: below 60 deg.C and normal pressure;
drying, controlling the temperature at 150 ℃ to dry until the water content is lower than 0.1%;
wherein: the PPA includes PA6T, PA9T, PA10T, and PA 12T.
10. Use of a polymer composition, characterized in that the polymer composition is used in an LED support.
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