CN116119948A - Glass fiber impregnating compound and preparation method and application thereof - Google Patents
Glass fiber impregnating compound and preparation method and application thereof Download PDFInfo
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- CN116119948A CN116119948A CN202310049756.4A CN202310049756A CN116119948A CN 116119948 A CN116119948 A CN 116119948A CN 202310049756 A CN202310049756 A CN 202310049756A CN 116119948 A CN116119948 A CN 116119948A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 115
- 150000001875 compounds Chemical class 0.000 title claims description 39
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 41
- 239000004902 Softening Agent Substances 0.000 claims abstract description 37
- 238000004513 sizing Methods 0.000 claims abstract description 36
- 239000002216 antistatic agent Substances 0.000 claims abstract description 27
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 27
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 12
- 230000005494 condensation Effects 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- IQABYJAGCHINIG-UHFFFAOYSA-N octadecanoic acid phthalic acid Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)O.C(CCCCCCCCCCCCCCCCC)(=O)O.C(C=1C(C(=O)O)=CC=CC1)(=O)O IQABYJAGCHINIG-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 polyoxyethylene Polymers 0.000 claims abstract description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 150000002193 fatty amides Chemical class 0.000 claims abstract description 4
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 14
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 14
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 13
- 206010020112 Hirsutism Diseases 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003068 static effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C03C25/465—Coatings containing composite materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/01—Liners for load platforms or load compartments
- B60R13/011—Liners for load platforms or load compartments for internal load compartments, e.g. car trunks
-
- 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
-
- 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
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The application discloses a glass fiber sizing agent, which comprises an effective component and water, wherein the effective component comprises a silane coupling agent, a film forming agent, an antistatic agent, a softening agent and a pH value regulator; the film forming agent is the mixture of epoxy emulsion and polyvinyl acetate emulsion; the softening agent is one or a mixture of more than one of di-fatty acid amine condensation polymer, phthalic acid distearate, alkanolamide and polyoxyethylene fatty amide. The glass fiber produced by coating the sizing agent can change the physical and chemical properties of the surface of the glass fiber, effectively improve the softness and dispersion performance of the glass fiber, and ensure that the glass fiber product has low hairiness and excellent antistatic performance; meanwhile, the compatibility of glass fibers and matrix resin can be effectively improved, so that the prepared glass fiber chopped strand mat material for the PHC automobile interior trim has the characteristics of uniform glass fiber distribution, soft mat surface, good volt-pasting performance, high tensile strength of the chopped strand mat and the like.
Description
Technical Field
The application relates to the technical field of glass fiber sizing agents, in particular to a glass fiber sizing agent for a high-voltage modulus chopped strand mat, and a preparation method, a product and application thereof.
Background
In recent years, the automobile market speed is slowed down by epidemic situation influence and chip productivity restriction, but the automobile market speed is still in an increasing situation. In 2020-2021, the production and marketing of Chinese automobiles are respectively completed by 2608 ten thousand and 2628 ten thousand, and the same ratio is respectively increased by 3.4 percent and 3.8 percent. Along with the solution of the chip problem and the past of epidemic situation, the automobile yield in China will be further increased, and the market prospect is huge.
At present, a luggage cover plate in a middle-high-grade automobile interior trim part and a storage plate in an SUV automobile type are generally produced by adopting a PHC process (interlayer plate forming process). PHC is a processing technology that paper honeycomb is wrapped by two layers of glass fiber chopped strand mats, PU glue is sprayed, and finally the PHC is put into a die for hot press molding. The PHC technology has higher technical requirements on the adopted glass fiber chopped strand mat products (generally, the surface of the adopted glass fiber chopped strand mat has no drawing and hairiness, the glass fibers are uniformly dispersed, the mat surface is soft, and the tensile strength is higher); the glass fiber chopped strand mats for PHC process automotive upholsteries have higher requirements on the glass fiber yarns used, for example, products need low hairiness, have higher flexibility, and simultaneously have excellent chopped dispersion, good antistatic performance and good product bundling performance.
Disclosure of Invention
The application aims to provide a glass fiber impregnating compound, a preparation method, a product and application thereof, so as to solve the problems of the related technology.
According to the first aspect of the application, the glass fiber sizing agent is provided, and the glass fiber produced by coating the sizing agent can change the physical and chemical properties of the surface of the glass fiber, so that the softness and dispersion performance of the glass fiber are effectively improved, and the glass fiber product has low hairiness and excellent antistatic performance; meanwhile, the compatibility of glass fibers and matrix resin can be effectively improved, so that the prepared glass fiber chopped strand mat material for the PHC automobile interior trim has the characteristics of uniform glass fiber distribution, soft mat surface, good volt-pasting performance, high tensile strength of the chopped strand mat and the like.
Specifically, a glass fiber sizing agent is provided, which comprises an effective component and water, and is characterized in that the effective component comprises a silane coupling agent, a film forming agent, an antistatic agent, a softening agent and a pH value regulator; the solid mass of each component in the effective components accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the film forming agent is a mixture of epoxy emulsion and polyvinyl acetate emulsion;
the softening agent is one or a mixture of more than one of a double fatty acid amine condensation polymer, phthalic acid distearate, alkanolamide and polyoxyethylene fatty amide.
Wherein the percentage of the solid mass of each component in the effective components to the total mass of the impregnating compound is expressed as follows:
wherein the softening agent is a di-fatty acid amine condensation polymer and/or phthalic acid distearate.
Wherein the silane coupling agent is a mixture of methacryloxypropyl trimethoxysilane and gamma-glycidyl ether propyl trimethoxysilane.
Wherein the mass ratio of the methacryloxypropyl trimethoxy silane to the gamma-glycidyl ether propyl trimethoxy silane is 10-5:1.
Wherein the epoxy emulsion adopts a mixture of bisphenol A type epoxy resin emulsion and polyurethane modified epoxy emulsion; wherein the mass ratio of the bisphenol A type epoxy resin emulsion to the polyurethane modified epoxy emulsion is 3-10:1.
Wherein the polyvinyl acetate emulsion is a non-crosslinked polyvinyl acetate emulsion.
Wherein the antistatic agent is lithium nitrate; the pH value regulator is acetic acid, citric acid, formic acid, ammonia water or organic amine.
Wherein the percentage of the solid mass of each component in the effective components to the total mass of the impregnating compound is expressed as follows:
wherein the silane coupling agent is a mixture of methacryloxypropyl trimethoxysilane and gamma-glycidyl ether propyl trimethoxysilane; the epoxy emulsion is a mixture of bisphenol A type epoxy resin emulsion and polyurethane modified epoxy emulsion; the polyvinyl acetate emulsion is non-crosslinked polyvinyl acetate emulsion; the softening agent is a di-fatty acid amine condensation polymer and/or phthalic acid distearate; the antistatic agent is lithium nitrate; the pH value regulator is acetic acid.
In the glass fiber impregnating compound provided by the application, the functions and the contents of the components are as follows:
the glass fiber sizing agent provided by the application comprises an effective component and water; wherein the effective components comprise a silane coupling agent, a film forming agent, an antistatic agent, a softening agent and a pH value regulator.
The film forming agent is used as the main component of the impregnating compound, plays a decisive role in the processability of glass fibers, can play a role in protecting the glass fibers, and can improve the cutting performance, the dispersion performance, the bundling performance and the compatibility with matrix resin of the glass fibers. The method ensures the smoothness of glass fiber production and plays a role in subsequent processing performance and service performance. Thus, the choice of film former is one of the focus of this application. Experiments show that the dosage of the film forming agent needs to be controlled in a proper range, the dosage of the film forming agent is too low, the impregnating compound is poor in protection, and the yarn Yi Mao is dyed; excessive film forming agent, slow yarn resin penetration and low production efficiency of downstream customers. Therefore, the solid mass of the film forming agent is controlled to be 2.50-11.00%, preferably 3.50-10.00%, more preferably 3.50-9.00% of the total mass of the glass fiber sizing agent.
The film forming agent has a plurality of types, the polyvinyl acetate emulsion and the epoxy resin emulsion are compounded to serve as the film forming agent, and the compounded composition of the polyvinyl acetate emulsion and the epoxy resin emulsion can improve the soaking speed and the dispersing performance of the glass fiber and can improve the bundling performance and the wear resistance of the glass fiber product. The epoxy emulsion specifically selects the compound combination of bisphenol A type epoxy resin emulsion and polyurethane epoxy resin emulsion, and simultaneously, the mass ratio of the bisphenol A type epoxy resin emulsion to the polyurethane epoxy resin emulsion is controlled to be 3-10:1, and if the bisphenol A type epoxy resin emulsion is too much, the yarn is easy to produce poor dispersion phenomenon; however, polyurethane epoxy resin has excessive emulsion and good yarn elasticity, but can lead to slow yarn penetration. The two epoxy resin emulsions can well improve the soaking performance and the dispersing performance of glass fibers by adopting the mass ratio; preferably 4 to 9:1. The polyvinyl acetate emulsion in the film forming agent selects non-crosslinked polyvinyl acetate, the non-crosslinked polyvinyl acetate emulsion ensures the rapid penetration speed of the non-crosslinked polyvinyl acetate emulsion in the resin, and meanwhile, the mixing epoxy emulsion can obviously improve the bundling property and the dispersion property of the glass fiber product.
Specifically, in the application, the mass of the epoxy resin emulsion in the film forming agent is controlled to be 1.00-6.00%, preferably 2.00-5.50%, more preferably 2.00-4.80% of the total mass of the glass fiber impregnating compound; the weight of the polyvinyl acetate emulsion is controlled to be 1.50-5.00%, preferably 1.50-4.50%, more preferably 1.50-4.20% of the total weight of the glass fiber sizing agent. The inventor finds that the film forming agent with the content has a good protective effect on the processability of glass fibers by adopting the component proportion, and can remarkably improve the cutting performance, the dispersion performance, the bundling performance and the compatibility with matrix resin of the glass fibers.
The silane coupling agent is used as a bridge for combining inorganic glass fibers and film forming agent organic polymers, is another important component of the impregnating agent, and has the function of enabling the surfaces of the glass fibers to be rich in hydroxyl hydrophilic groups, the film forming agent belongs to a hydrophobic substance, the silane coupling agent is tightly connected with the glass fibers and the film forming agent through physical and chemical actions, so that good interface combination is realized, and the selection of the silane coupling agent is also a key for influencing the strength of the glass fibers and the strength of glass fiber reinforced products. In the application, the dosage of the silane coupling agent needs to be controlled in a proper range, and researches show that the composite material has low strength when the content of the silane coupling agent is too small; and excessive amounts result in wasted coupling agent and high costs. The solid mass of the silane coupling agent accounts for 0.20-2.00% of the total mass of the glass fiber impregnating compound, and the impregnating compound prepared by the silane coupling agent with the content accounting for the ratio can enable the glass fiber reinforced material to have better mechanical properties. Preferably 0.20 to 1.50%, more preferably 0.20 to 1.00%.
Through researches, the compatibility of glass fibers and resin can be effectively improved by adopting the combination of methacryloxypropyl trimethoxy silane and gamma-glycidyl ether propyl trimethoxy silane coupling agent and the mutual coordination of the coupling agent and the film forming agent. The mass ratio of the methacryloxypropyl trimethoxysilane to the gamma-glycidyl ether propyl trimethoxysilane is controlled to be 10-5:1, excessive methacryloxypropyl trimethoxysilane can cause yarn hardening, excessive gamma-glycidyl ether propyl trimethoxysilane can cause slower penetration, influence the mechanical properties of products and the like, and the preferable ratio is 8-6:1.
The antistatic agent plays an important role in the smoothness of glass fiber chopping in the impregnating compound system, and the addition of the raw materials can enable the glass fiber to have good antistatic performance, reduce the problems of static accumulation of products during high-speed chopping and static adsorption of the glass fiber during chopping, and further avoid serious quality problems such as fuzzing caused by repeated chopping of the glass fiber. In the present application, the antistatic agent is lithium nitrate. The application of the antistatic agent in the content range controls the solid mass of the antistatic agent to be 0.05-1.00% of the total mass of the glass fiber impregnating compound, so that the glass fiber has good antistatic performance, and finally, static accumulation of a product during high-speed chopping is avoided, repeated chopping and hairiness of the glass fiber are avoided, and the smooth performance of production is improved; preferably 0.10 to 1.00%, more preferably 0.10 to 0.80%.
In the application, the softening agent mainly reduces the stiffness of the glass fiber, so that the product has better flexibility, and simultaneously has the effects of improving the soaking speed, reducing friction and the like. Yet another important aspect of the present application is the inclusion of a softening agent in the size formulation. The softening agent can well endow glass fiber with soft performance, and meanwhile, the dispersion uniformity performance of the product is not affected, so that the produced glass fiber chopped strand mat has the advantages of softness and volt-paste performance, and the die-paste performance is more excellent when the composite material is used.
The softening agent is one or the mixture of any one of double fatty acid amine condensation polymer, phthalic acid distearate, alkanolamide and polyoxyethylene fatty amide, and can effectively improve the softness of glass fibers, reduce hairiness and improve antistatic performance, and simultaneously improve the compatibility of the glass fibers and matrix resin, so that the prepared glass fiber chopped strand mat material for the PHC automobile interior trim has the advantages of uniform glass fiber distribution, good mat surface softness and laminating performance, high tensile strength of the glass fiber chopped strand mat and the like. Preferably, the softening agent is a di-fatty acid amine condensation polymer and/or a phthalate distearate. Meanwhile, the dosage of the softening agent needs to be controlled in a proper range, the softening agent is used too little, the product has high stiffness and high friction coefficient, the produced glass fiber chopped strand mat needs to consume more powder and emulsion, and meanwhile, the produced glass fiber has the quality problems of hard chopped strand mat, poor die sticking performance, easiness in rebound and bubble generation, more hairiness, more yarn falling and the like; if the softener is too much, the yarn is too soft, is not easy to cut, and is unfavorable for uniformity of dispersion. Therefore, the solid mass of the softening agent is controlled to be 0.10-2.00%, preferably 0.15-1.50%, more preferably 0.20-1.50% of the total mass of the impregnating agent.
The pH regulator mainly plays a role in regulating the pH value of the impregnating compound, and common pH regulators comprise acetic acid, citric acid, formic acid, ammonia water or organic amines and the like. In order to meet the hydrolysis and dispersion requirements of the coupling agent in the application, the impregnating compound in the application needs to be controlled to be in a meta-acidic environment, and acetic acid is preferably used as a pH value regulator, and meanwhile, the solid mass of the pH value regulator is controlled to be in a range of 0.05-1.00%, preferably 0.05-0.80%, more preferably 0.06-0.65% of the total mass of the impregnating compound.
The water in the present application is the dispersed phase of each active component in the glass fiber sizing, wherein the water is preferably deionized water.
According to a second aspect of the present application, there is provided a method for preparing the above glass fiber sizing agent, comprising the steps of:
adding a silane coupling agent into water for pre-dispersing to prepare a silane coupling agent solution;
dispersing a film forming agent, a softening agent and an antistatic agent in water respectively;
adding the dispersed film forming agent, softening agent and antistatic agent solution into the silane coupling agent solution, supplementing the balance of water, and uniformly stirring to obtain the glass fiber sizing agent.
Preferably, the specific operation of the preparation method is as follows:
adding water with the mass of 20-30 times of that of the silane coupling agent into a first container, adding a pH value regulator, and adding the silane coupling agent under stirring until the silane coupling agent is uniformly stirred and dispersed until the silane coupling agent is clear, so as to obtain a silane coupling agent solution;
dispersing the epoxy resin and polyvinyl acetate in the film forming agent by normal temperature water respectively; dispersing the softening agent by adopting water at 60-80 ℃ and placing the softening agent at normal temperature; dispersing the antistatic agent by adopting normal-temperature water;
adding the dispersed film forming agent, softening agent and antistatic agent solution into the silane coupling agent solution, supplementing the balance of water, and uniformly stirring to obtain the glass fiber sizing agent.
According to a third aspect of the present application, there is provided a glass fiber product produced by the above-described glass fiber sizing coating.
According to a fourth aspect of the application, the application of the glass fiber product in the field of manufacturing of PHC process automotive upholsteries is provided.
Compared with the prior art, the glass fiber sizing agent has the following beneficial effects:
1. the film forming agent and the softening agent are compounded by using the polyvinyl acetate emulsion and the epoxy emulsion, and the proper content ratio is researched, so that the stiffness and the impregnation performance of the yarn are greatly reduced on the basis of ensuring the dispersion performance of the product, and the produced glass fiber chopped strand mat is softer, more uniform and more excellent in volt-patch performance.
2. The preparation method researches the proportioning composition of the epoxy resin emulsion in the impregnating compound formula, selects the compound combination of the bisphenol A type epoxy resin emulsion and the polyurethane epoxy resin emulsion, simultaneously controls the mass ratio of the bisphenol A type epoxy resin emulsion and the polyurethane epoxy resin emulsion, effectively improves the compatibility of glass fibers and resin, and obviously improves the mechanical property of the glass fiber chopped strand mat composite material; and effectively improves the bundling performance of glass fibers, reduces hairiness and improves dispersion performance.
3. The sizing agent provided by the application selects proper components such as the silane coupling agent, the antistatic agent, the softening agent, the film forming agent, the pH value regulator and the like and the proportion thereof, so that the prepared glass fiber is softer, and has good dispersion performance, small static electricity, less hairiness, high production efficiency, high yield and high mechanical property.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the present application will be clearly and completely described in conjunction with the specific embodiments of the present application, and it is apparent that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.
The glass fiber impregnating compound comprises effective components and water, wherein the effective components comprise a coupling agent, a film forming agent, an antistatic agent, a softening agent and a pH value regulator, the solid content of the impregnating compound is 1.9-8.2%, and the solid mass of each effective component in the impregnating compound accounts for the total mass of the impregnating compound and is expressed as follows: 0.20 to 2.00 percent of silane coupling agent; 2.50 to 11.00 percent of film forming agent; 0.05 to 1.00 percent of antistatic agent; 0.10 to 2.00 percent of softening agent; 0.05 to 1.00 percent of pH value regulator; wherein the film forming agent is a mixture of epoxy emulsion and polyvinyl acetate emulsion; the softening agent is one or a mixture of two of double fatty acid amine condensation polymers and phthalic acid distearate.
Preferably, the percentage of the solid mass of each component in each effective component in the impregnating compound to the total mass of the impregnating compound is expressed as follows: 0.20 to 1.50 percent of silane coupling agent; 3.50 to 10.00 percent of film forming agent; 0.10 to 1.00 percent of antistatic agent; 0.15 to 1.50 percent of softening agent; pH regulator 0.05-0.80%.
Preferably, the epoxy emulsion is a compound combination of bisphenol A type epoxy resin emulsion and polyurethane epoxy resin emulsion, and the mass ratio of the two is 3-10:1; the polyvinyl acetate emulsion is non-crosslinked polyvinyl acetate emulsion; the silane coupling agent is the compound of methacryloxypropyl trimethoxy silane and gamma-glycidyl ether propyl trimethoxy silane, and the mass ratio of the methacryloxypropyl trimethoxy silane to the gamma-glycidyl ether propyl trimethoxy silane is 10-5:1, preferably 8-6:1.
The preparation method of the glass fiber impregnating compound specifically comprises the following steps:
adding water with the mass of 20-30 times of that of the silane coupling agent into a first container, adding a pH value regulator, and adding the silane coupling agent under stirring until the silane coupling agent is uniformly stirred and dispersed until the silane coupling agent is clear, so as to obtain a silane coupling agent solution;
dispersing the epoxy resin and polyvinyl acetate in the film forming agent by normal temperature water respectively; dispersing the softening agent by adopting water at 60-80 ℃ and placing the softening agent at normal temperature; dispersing the antistatic agent by adopting normal-temperature water;
adding the dispersed film forming agent, softening agent and antistatic agent solution into the silane coupling agent solution, supplementing the balance of water, and uniformly stirring to obtain the glass fiber sizing agent.
Some specific examples of the glass fiber sizing agents of the present application are set forth below.
Examples
In order to further illustrate the beneficial effects of the selected types of components and ranges of component content in the glass fiber size of the present application, examples of partial values of the components included in the glass fiber size of the present application are listed below.
The specific formulations of some examples of the glass fiber sizing of the present application are shown in table 1, with the values in table 1 being the percentage of the active ingredient solids mass to the total sizing mass.
It should be noted that the specific types and amounts of the components selected in table 1 and combinations thereof do not limit the scope of the present application.
Table 1 list of specific examples of impregnating compounds of the present application
TABLE 1 list of specific examples of impregnating compounds of the present application
Comparative test example
In order to further illustrate the beneficial effects of the application, the impregnating compound combinations with different proportions and the impregnating compound for the chopped strand mats commonly used at present are selected as comparative examples, and comparative tests are carried out.
Comparative example 1 (sizing agent for chopped strand mat commonly used):
the impregnating compound comprises the following components in percentage by mass:
silane coupling agent: methacryloxypropyl trimethoxysilane, 0.55%;
film forming agent: 5.40% of polyvinyl acetate emulsion;
antistatic agent: fatty tertiary amine ethyl sulfate, 0.20%;
2.00% of nonionic polyurethane emulsion;
pH regulator: acetic acid, 0.16%;
deionized water: 91.69%.
Comparative example 2:
silane coupling agent: methacryloxypropyl trimethoxysilane 0.085%, gamma-glycidyl ether propyl trimethoxysilane 0.55%;
film forming agent: 3.65% of bisphenol A type epoxy resin emulsion, 0.45% of polyurethane modified epoxy emulsion and 2.9% of polyvinyl acetate emulsion;
antistatic agent: lithium nitrate, 0.20%;
softening agent: 0.15% of a di-fatty acid amine condensation polymer;
pH regulator: acetic acid, 0.16%;
deionized water: 91.855%.
Comparative example 3:
silane coupling agent: 1.55% of methacryloxypropyl trimethoxysilane and 0.25% of gamma-glycidyl ether propyl trimethoxysilane;
film forming agent: bisphenol A type epoxy resin emulsion 0.65%, polyurethane modified epoxy emulsion 3.45% polyvinyl acetate emulsion 2.70%;
antistatic agent: lithium nitrate 0.20%;
softening agent: 1.30% of a di-fatty acid amine condensation polymer; 0.8% of phthalic acid distearate;
pH regulator: acetic acid, 0.36%;
deionized water: 89.39%.
The above examples and comparative examples are applied to the production of glass fibers and the corresponding glass fibers are applied to the preparation of glass chopped strand mats and composites. The preparation method of the chopped strand mats comprises the following steps: chopping glass fiber into a length of 25-75mm by a chopping machine, and uniformly spreading the chopped fiber on a forming mesh belt under the adsorption of air flow; the fiber on the forming net belt is transmitted to a powdering net belt through the net belt, and a chopped layer containing a binder is formed through spraying, powdering and vibrating; the chopped layers on the powder spreading net belt are transmitted to an oven net belt, and are heated in a natural gas oven to remove the moisture in the chopped layers, and meanwhile, the adhesive is melted to generate adhesive force; and (5) drying the chopped strand, cooling, and rolling to obtain the finished chopped strand mat.
The processing performance and the chopped strand mat performance of the modified polyester fiber are tested and compared. The results were as follows:
TABLE 2 powder chopped strand mat performance test results for 450 grams per square meter produced from different glass fibers
TABLE 2 test results of powder chopped strand mat performance for 450 g/square meter production of different glass fibers
In the aspect of antistatic performance test, the average discharge half life of the example 12 is 1.2 seconds, the comparative example is 7.2 seconds, and compared with the static half life of the comparative example, the antistatic performance of the example 12 is obviously improved, which indicates that the impregnating compound can greatly improve the smoothness of glass fiber chopped use.
From the above test examples, it can be seen that the examples 1 to 12 using the impregnating compound of the present application have better overall properties than the comparative examples, and are particularly embodied in that the glass fibers have uniform dispersibility, the chopped strand mats are soft, quick to soak, good in mold-forming performance, less in yarn falling during use, more friendly to the environment, and the like. In particular, the glass fiber chopped strand mat prepared from the sizing agent provided in example 7 has the best comprehensive performance.
In summary, the impregnating compound is adopted to coat and produce the glass fiber, so that the physical and chemical properties of the surface of the glass fiber can be changed, the bundling performance of the glass fiber is improved, meanwhile, the electrostatic discharge during chopping is increased, the smoothness of using the glass fiber is improved, and accumulation of hairiness and the like is reduced; the prepared glass fiber chopped strand mats have the characteristics of low stiffness, good softness and molding property, high soaking speed, less yarn falling waste and the like.
The above description may be implemented alone or in various combinations and these variants are all within the scope of the present application.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (12)
1. A glass fiber sizing agent comprising an effective component and water, characterized in that the effective component comprises a silane coupling agent, a film forming agent, an antistatic agent, a softening agent and a pH regulator; the solid mass of each component in the effective components accounts for the total mass of the impregnating compound and is expressed as follows:
wherein the film forming agent is a mixture of epoxy emulsion and polyvinyl acetate emulsion;
the softening agent is one or a mixture of more than one of a double fatty acid amine condensation polymer, phthalic acid distearate, alkanolamide and polyoxyethylene fatty amide.
2. The glass fiber sizing of claim 1, wherein the effective components have a solids mass as a percentage of the total mass of the sizing expressed as follows:
3. the glass fiber sizing of claim 1, wherein the softening agent is a di-fatty acid amine condensation polymer and/or a phthalate distearate.
4. The glass fiber sizing of claim 1, wherein the silane coupling agent is a mixture of methacryloxypropyl trimethoxysilane and gamma-glycidylether propyl trimethoxysilane.
5. The glass fiber sizing of claim 4, wherein the mass ratio of the methacryloxypropyl trimethoxysilane to the gamma-glycidylether propyl trimethoxysilane is from 10 to 5:1.
6. The glass fiber sizing of claim 1, wherein the epoxy emulsion is a mixture of bisphenol a type epoxy resin emulsion and polyurethane modified epoxy emulsion; wherein the mass ratio of the bisphenol A type epoxy resin emulsion to the polyurethane modified epoxy emulsion is 3-10:1.
7. The glass fiber sizing of claim 1, wherein the polyvinyl acetate emulsion is a non-crosslinked polyvinyl acetate emulsion.
8. The glass fiber sizing of claim 1, wherein the antistatic agent is lithium nitrate; the pH value regulator is acetic acid, citric acid, formic acid, ammonia water or organic amine.
9. The glass fiber sizing of any of claims 1 to 7, wherein the percentage of the solid mass of each of the active components to the total mass of the sizing is expressed as follows:
wherein the silane coupling agent is a mixture of methacryloxypropyl trimethoxysilane and gamma-glycidyl ether propyl trimethoxysilane; the epoxy emulsion is a mixture of bisphenol A type epoxy resin emulsion and polyurethane modified epoxy emulsion; the polyvinyl acetate emulsion is non-crosslinked polyvinyl acetate emulsion; the softening agent is a di-fatty acid amine condensation polymer and/or phthalic acid distearate; the antistatic agent is lithium nitrate; the pH value regulator is acetic acid.
10. A method for preparing the glass fiber sizing agent according to any one of claims 1 to 7, comprising the steps of:
adding a silane coupling agent into water for pre-dispersing to prepare a silane coupling agent solution;
dispersing a film forming agent, a softening agent and an antistatic agent in water respectively;
adding the dispersed film forming agent, softening agent and antistatic agent solution into the silane coupling agent solution, supplementing the balance of water, and uniformly stirring to obtain the glass fiber sizing agent.
11. A glass fiber product produced by coating the glass fiber treating compound according to any one of claims 1 to 7.
12. Use of the glass fiber product according to claim 10 in the field of PHC technology automotive upholstery.
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