CN117326807A - Glass fiber impregnating compound for coloring-grade SMC, and preparation method, product and application thereof - Google Patents
Glass fiber impregnating compound for coloring-grade SMC, and preparation method, product and application thereof Download PDFInfo
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- CN117326807A CN117326807A CN202311278157.6A CN202311278157A CN117326807A CN 117326807 A CN117326807 A CN 117326807A CN 202311278157 A CN202311278157 A CN 202311278157A CN 117326807 A CN117326807 A CN 117326807A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 95
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 188
- 239000007787 solid Substances 0.000 claims abstract description 51
- 239000000839 emulsion Substances 0.000 claims abstract description 41
- 238000004513 sizing Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 24
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000002216 antistatic agent Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 238000004040 coloring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- DNXKVOCRSQBZHO-UHFFFAOYSA-M lithium;dodecane-1-sulfonate Chemical compound [Li+].CCCCCCCCCCCCS([O-])(=O)=O DNXKVOCRSQBZHO-UHFFFAOYSA-M 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- LQAZPMXASFNKCD-UHFFFAOYSA-M potassium;dodecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCS([O-])(=O)=O LQAZPMXASFNKCD-UHFFFAOYSA-M 0.000 claims description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 2
- 239000000835 fiber Substances 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 4
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 34
- 239000003677 Sheet moulding compound Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 18
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 230000008901 benefit Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 206010020112 Hirsutism Diseases 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 3
- -1 amino, mercapto Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- RRLUJJJKORUBSJ-UHFFFAOYSA-N diazonio(isocyanato)azanide Chemical group [N-]=[N+]=NN=C=O RRLUJJJKORUBSJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C03C25/24—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
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/323—Polyesters, e.g. alkyd resins
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The application discloses a glass fiber impregnating compound for coloring-grade SMC, which comprises effective components and water; the solid content of the impregnating compound is 3.8% -13.8%; the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows: 9.0 to 20 percent of coupling agent, 36 to 72 percent of film forming agent, 3.0 to 9.0 percent of antistatic agent, 4.0 to 11 percent of flatting agent and 12 to 27 percent of handfeel agent; wherein, the handfeel agent is a high molecular polymer polymerized by silicone oil which contains long-chain alkyl and is modified by end capping; the film forming agent is a mixture of a first film forming agent and a second film forming agent, the mass ratio is 1:1-1:5, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is a fast-penetrating unsaturated polyester emulsion. The glass fiber yarn coated and produced by the sizing agent has smooth surface and good mould pressing fluidity, so that the fiber is uniformly dispersed in the product and the surface glass fiber patterns are not easy to generate; and the product has good compatibility with polyester resin, strong interface bonding and capability of remarkably improving the mechanical property of the product.
Description
Technical Field
The application relates to the technical field of impregnating compounds for glass fiber coating, in particular to a glass fiber impregnating compound for coloring-grade SMC, and a preparation method, a product and application of the impregnating compound.
Background
SMC products have the advantages of light weight, high strength, corrosion resistance, good designability, easy forming, easy coloring and the like, and have been widely applied in the building industry. Applications such as in the electrical utility field include electrical cabinets, instrument boxes, etc.; the applications for the residential area are mainly waterproof boards, door panels, water tanks, etc. The requirement of the application is that the product has better appearance quality on the basis of ensuring certain strength. These products are usually light colors and do not undergo secondary spraying, so the glass fibers need to have good coloring properties to ensure the appearance quality of the products, i.e. the products have no obvious glass fiber texture; meanwhile, the resin can be well combined with unsaturated resin of a matrix, so that good mechanical properties of the product are ensured.
Along with the continuous improvement of SMC technology and living standard, downstream customers put forward more severe requirements on the mechanical properties, appearance quality and various special properties of products in the field; for example, the structural and integrated design of the electrical cabinet requires higher strength of components, the waterproof board is more attractive in design, and better product appearance quality is required to be matched to play an advantage. Developments in these areas have placed higher, multi-dimensional demands on the properties of color grade glass fibers. The colored glass fiber is characterized in that in the glass fiber reinforced resin composite material, the glass fiber is not easy to develop the original color, namely the surface is not easy to generate obvious glass fiber lines.
Disclosure of Invention
The technical problem to be solved by the application is to provide the glass fiber impregnating compound for the coloring-level SMC, and the glass fiber produced by coating the impregnating compound has smooth surface and good mould pressing fluidity, so that the fiber is uniformly dispersed in a product and is not easy to generate surface glass fiber lines; the product has good compatibility with polyester resin and strong interface bonding, thereby remarkably improving the mechanical property of the product; meanwhile, the glass fiber has the advantages of good cutting dispersibility, less hairiness in production and use, and the like.
In order to achieve the technical effects, the application is realized through the following technical scheme:
according to one aspect of the present application, there is provided a glass fiber sizing for a color grade SMC comprising an effective component and water; the solid content of the impregnating compound is 3.8-13.8%; the effective components comprise a coupling agent, a film forming agent, an antistatic agent, a leveling agent and a handfeel agent; the solid mass of each effective component of the impregnating compound is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified;
wherein the film forming agent is a mixture of a first film forming agent and a second film forming agent; the first film forming agent is organic silicon modified epoxy emulsion, and the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1-1:5.
Wherein, the percentage of the solid mass of each effective component of the impregnating compound to the total solid mass of the impregnating compound is expressed as follows:
wherein the coupling agent is a silane coupling agent containing unsaturated bonds.
Wherein the leveling agent is polyether modified organosilicon compound.
Wherein the antistatic agent is at least one of sodium dodecyl sulfonate, lithium dodecyl sulfonate and potassium dodecyl sulfonate.
The organosilicon modified epoxy emulsion is prepared by mixing epoxy polyether organosilicon serving as an emulsifier with epoxy resin and uniformly dispersing the mixture in water.
Wherein the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol S epoxy resin and bisphenol F epoxy resin; the epoxy equivalent of the epoxy resin is 600-3300 g/eq.
Wherein, the quick-soaking unsaturated polyester emulsion is obtained by carrying out polycondensation reaction on maleic anhydride doped with phthalic anhydride and propylene glycol, and uniformly dispersing the product in water; the molecular weight of the fast-saturated unsaturated polyester is 4000-15000 Da.
The functions and the contents of the components in the glass sizing agent for the coloring-level SMC are described as follows:
the coupling agent of the application adopts a silane coupling agent (the structural general formula is YSiX 3 ). Wherein Y in the general structural formula is an organic end, and is usually alkene or hydrocarbon group with terminal functional groups such as amino, mercapto, epoxy, azido, isocyanate group and the like; x is a hydrolyzable group such as chlorine, alkoxy, and the like. Because of the special chemical structure, the silane coupling agent can be used as a bridge for combining inorganic glass fibers and organic polymer film forming agents, so that the whole sizing agent film can be fixed on the surface of the glass fibers through chemical bonds, and the good bundling property, toughness and stiffness of the glass fibers in the processing or cutting process are maintained. Preferably, the coupling agent is a silane coupling agent containing unsaturated bonds, more preferably, the coupling agent is a silane coupling agent containing double bonds, and the coupling agent contains double bonds and can form stable combination with the film forming agent selected in the application through chemical bonds, so that the service performance of the glass fiber can be effectively improved. Illustratively, the coupling agents herein may be vinyl trimethoxy silane coupling agents. Meanwhile, the amount of the coupling agent to be used is controlled within a proper range. Researches show that the coupling agent with too small content can not effectively play an excessive bridge role between the inorganic glass fiber and the organic polymer film forming agent; excessive content may be inserted into the film-forming agent to prevent the film-forming agent from exerting its effect. Therefore, the solid mass of the coupling agent is controlled to be 9.0-20.0% of the total solid mass of the impregnating compound; preferably 10.0 to 19.0%; more preferably 11.0 to 18.0%.
The film forming agent is a main component of the glass fiber impregnating compound, has the functions of protecting glass fibers, improving the cuttability and bundling property of the glass fibers and the compatibility with matrix resin, and has decisive influence on the continuous production and subsequent application of the glass fibers. Thus, the choice of film former is one of the focus of this application. Meanwhile, the dosage of the film forming agent needs to be controlled in a proper range; the usage amount of the film forming agent is too small, and glass fibers are easy to damage to generate fuzzing after mechanical friction, and the compatibility with matrix resin can be reduced; excessive use of the resin can cause slow resin penetration of the yarn and difficult monofilaments, so that more glass fiber lines are formed in the product. Thus, the present application controls the solids mass of the film former to be 36.0 to 72.0%, preferably 40.0 to 69.0%, more preferably 44.0 to 66.0% of the total solids mass of the sizing agent.
The film forming agent adopts a combination of a first film forming agent and a second film forming agent, and the film forming agent is in the form of emulsion. The first film forming agent is organosilicon modified epoxy emulsion, which is obtained by mixing epoxy-terminated polyether organosilicon serving as an emulsifier with epoxy resin and uniformly dispersing the mixture in water (reference document: organosilicon modified epoxy resin emulsion preparation and performance research [ J ]. Peng Jun, chemical novel material [ 2021 (12)). Compared with the common epoxy resin emulsion, the organosilicon modified epoxy resin emulsion has better toughness and heat resistance after film formation, so that the glass fiber can keep the integrity as much as possible when in use. Preferably, the epoxy resin is at least one of bisphenol a type epoxy resin, bisphenol S type epoxy resin and bisphenol F type epoxy resin; further preferably, the epoxy resin has an epoxy equivalent of 600 to 3300g/eq. The solid content of the organosilicon modified epoxy emulsion is 32-52%.
The second film forming agent adopts unsaturated polyester emulsion which is quickly soaked, and is obtained by carrying out polycondensation reaction on maleic anhydride doped with phthalic anhydride and propylene glycol, and uniformly dispersing the product in water. The preparation method comprises the following steps: adding maleic anhydride and propylene glycol doped with phthalic anhydride into a four-mouth bottle, wherein the molar ratio of the maleic anhydride to the propylene glycol is 1:0.6-1:1.8, starting a stirring program, and heating. When the temperature reaches 200-220 ℃, maintaining the temperature for polycondensation reaction, and controlling the reaction end point when the acid value is tested to be 15-30; then cooling the reaction product to room temperature, adding an emulsifying agent, and then adding water to perform high-speed dispersion at a rotating speed of 2000-6000 rpm to prepare the unsaturated polyester emulsion which is quickly soaked. Wherein the temperature is preferably 210 ℃; the emulsifier can be a conventional emulsifier system, preferably a mixture of branched fatty alcohol polyoxyethylene ether, modified fatty alcohol polyoxy and vinyl ether EO-PO block copolymer. The doping of phthalic anhydride can improve the hardness of polyester after film formation, keep the higher stiffness of glass fiber, and improve the cutting property and the molding fluidity. After the unsaturated polyester emulsion is quickly soaked to form a film, the glass fiber can be quickly soaked by the unsaturated resin, the compatibility is good, and the mechanical property of the product can be effectively improved. In addition, the surface sizing agent of the soaked glass fiber can be well dissolved into a resin system, and the glass fiber can be in a monofilament state in the resin, so that glass fiber lines in the product are less. Preferably, the molecular weight of the fast-penetrating unsaturated polyester emulsion is 4000-15000 Da; the solid content of the quick-soaking unsaturated polyester emulsion is 25-35%.
In addition, the application needs to control the dosage relation of the first film forming agent and the second film forming agent, and researches show that when the mass ratio of the first film forming agent to the second film forming agent is controlled to be 1:1-1:5, the yarn bundling property is good, hairiness is less, stiffness is high, compatibility with unsaturated resin is good, mechanical strength of a product is high, and surface glass fiber lines are less. When the proportion of the first film forming agent is too high, the resin of the glass fiber product is easy to soak slowly, the mechanical property of the product is reduced, and the glass fiber on the surface is increased; when the proportion of the second film forming agent is too high, the bundling property of the glass fiber product is easy to be poor, hairiness is increased in the production and use of the product, and the stiffness is reduced. Preferably, the mass ratio of the first film forming agent to the second film forming agent is 1:1.4-1:4.7; further preferably 1:1.6 to 1:4.5.
Because the glass fiber is extremely easy to generate static electricity in the cutting process, and the problem of uneven dispersion is caused, the antistatic agent is adopted to improve the antistatic performance of the glass fiber. Preferably, the antistatic agent is at least one of sodium dodecyl sulfonate, lithium dodecyl sulfonate and potassium dodecyl sulfonate. Meanwhile, the dosage of the antistatic agent needs to be controlled in a proper range, and too much dosage can cause damage to a film forming agent system, and too little dosage can cause the problem of static electricity of glass fibers. Thus, the antistatic agent is controlled to have a solids mass of 3.0 to 9.0%, preferably 3.5 to 8.0%, more preferably 4.0 to 7.5% of the total solids mass of the sizing agent.
The use of the leveling agent can effectively reduce the surface tension of the sizing agent, can lead the sizing agent to spread uniformly on the surface of the glass fiber, reduces the occurrence of soft and hard segments of the glass fiber, leads the glass fiber to have better fluidity during mould pressing, leads the distribution in the product to be more uniform, and is beneficial to reducing the glass fiber lines on the surface. Preferably, the leveling agents described herein are polyether modified organosilicon compounds. Meanwhile, the consumption of the leveling agent needs to be controlled in a proper range, and too much consumption can cause the damage of a film forming agent system, and too little consumption can not play a role in reducing the tension of the impregnating compound. Therefore, the solid mass of the leveling agent is controlled to be 4.0-11.0% of the total solid mass of the impregnating compound; preferably 4.5 to 10.0%; more preferably 5.0 to 9.5%.
The use of the handfeel agent can effectively reduce the binding force among yarn bundles, thereby reducing the tension of the yarns which are separated from the original yarn cylinder during stranding, and avoiding yarn abrasion, tearing, generating a head and the like as much as possible. Meanwhile, the smoothness of the surface of the finished glass fiber can be improved, and Mao Sansi generated in the using process is reduced. Preferably, the handfeel agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; long chain alkyl is a saturated alkyl chain, the number of carbons may be 12, 14, 16, 18 or 20; the hand feeling agent in the application is selected from commercial products (Shanghai Hui research New Material Co., trade name HY-51Z series). Meanwhile, the dosage of the hand feeling agent needs to be controlled in a proper range, and too much dosage can damage the film forming structure of the film forming agent, and too little dosage can not play a role. Therefore, the solid mass of the hand feeling agent is controlled to be 12.0-27.0%, preferably 13.0-26.0%, and more preferably 14.0-25.0% of the total solid mass of the impregnating agent.
Water in this application is the dispersed phase of the components of the size. Wherein the water is preferably deionized water.
According to a second aspect of the present application, there is provided a method for preparing the glass fiber sizing agent for color-grade SMC, comprising the steps of:
s1: adding a coupling agent and a handfeel agent into water respectively for pre-dispersing to prepare a coupling agent solution and a handfeel agent solution respectively, and then uniformly mixing the two solutions;
s2: pre-dissolving an antistatic agent, and then adding the pre-dissolved antistatic agent into the solution obtained in the step S1;
s3: diluting the first film forming agent with 6-12 times of water; diluting the second film forming agent with water 3-9 times the volume of the second film forming agent, sequentially adding the second film forming agent into the solution obtained in the step S2, and uniformly mixing and stirring the second film forming agent;
s4: and (3) pre-dissolving the leveling agent, adding the pre-dissolved leveling agent into the solution obtained in the step (S3), and mixing and stirring uniformly.
According to a third aspect of the present application, there is provided a glass fiber product produced from the color grade SMC coated with a glass fiber sizing.
According to a fourth aspect of the present application there is provided the use of the glass fibre product in the construction field.
The glass fiber reinforced resin matrix produced by coating the coloring-grade SMC with the glass fiber impregnating compound is unsaturated polyester resin.
The glass fiber produced by the impregnating compound coating has smooth surface and good mould pressing fluidity, so that the fiber is uniformly dispersed in the product and the surface glass fiber lines are not easy to generate; the product has good compatibility with unsaturated polyester resin and strong interface bonding, so that the mechanical property of the product can be obviously improved; meanwhile, the glass fiber has the advantages of good cutting dispersibility, less hairiness in production and use, and the like.
The beneficial effects of selecting the above content ranges for each component for the glass fiber sizing agent for the coloring-grade SMC of the present application will be illustrated by the specific experimental data given in the examples.
The following are examples of preferred ranges of values for the components included in the glass fiber compositions according to the present application.
Preferred examples one
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 3.8-13.8%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified;
the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1-1:5.
Preferred example two
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 4.2-13.3%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified;
the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1.4-1:4.7.
Preferred examples three
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 4.6-12.5%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1.6-1:4.5.
Wherein the coupling agent is a silane coupling agent containing unsaturated bonds.
Preferred example four
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 4.2-13.3%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1.4-1:4.7.
Wherein the coupling agent is a silane coupling agent containing unsaturated bonds; the leveling agent is polyether modified organosilicon compound.
Preferred example five
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 4.6-12.5%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1.6-1:4.5.
Wherein the coupling agent is a silane coupling agent containing double bonds; the leveling agent is polyether modified organosilicon compound; the antistatic agent is at least one of sodium dodecyl sulfonate, lithium dodecyl sulfonate and potassium dodecyl sulfonate.
Preferred example six
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 5.0-12%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:2.0-1:3.8. Wherein the coupling agent is a silane coupling agent containing double bonds; the leveling agent is polyether modified organosilicon compound; the antistatic agent is at least one of sodium dodecyl sulfonate, lithium dodecyl sulfonate and potassium dodecyl sulfonate.
Preferred examples seven
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 5.0-12%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:2.0-1:3.8.
The organosilicon modified epoxy emulsion is prepared by mixing epoxy polyether organosilicon serving as an emulsifier with epoxy resin and uniformly dispersing the mixture in water; the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol S epoxy resin and bisphenol F epoxy resin; the epoxy equivalent of the epoxy resin is 600-3300 g/eq.
Wherein, the quick-soaking unsaturated polyester emulsion is obtained by carrying out polycondensation reaction on maleic anhydride doped with phthalic anhydride and propylene glycol, and uniformly dispersing the product in water; the molecular weight of the fast-saturated unsaturated polyester is 4000-15000 Da.
Preferred example eight
The glass fiber impregnating compound for the coloring-level SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 5.0-12%; wherein, the solid mass of each component of the effective components accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified; the film forming agent is a mixture of a first film forming agent and a second film forming agent, and the first film forming agent is organosilicon modified epoxy emulsion; the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:2.0-1:3.8.
Wherein the coupling agent is a silane coupling agent containing double bonds; the leveling agent is polyether modified organosilicon compound; the antistatic agent is at least one of sodium dodecyl sulfonate, lithium dodecyl sulfonate and potassium dodecyl sulfonate.
The organosilicon modified epoxy emulsion is prepared by mixing epoxy polyether organosilicon serving as an emulsifier with epoxy resin and uniformly dispersing the mixture in water; the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol S epoxy resin and bisphenol F epoxy resin; the epoxy equivalent of the epoxy resin is 600-3300 g/eq. Wherein, the quick-soaking unsaturated polyester emulsion is obtained by carrying out polycondensation reaction on maleic anhydride doped with phthalic anhydride and propylene glycol, and uniformly dispersing the product in water; the molecular weight of the fast-saturated unsaturated polyester is 4000-15000 Da.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below in conjunction with 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.
Some specific examples of the glass fiber sizing for SMC of the present application are set forth below.
Examples
The solid mass of each component in the examples of the glass fiber sizing agent for the coloring grade SMC of the present application is shown in the table 1.
TABLE 1 glass fiber sizing example formulation for color grade SMC
TABLE 1 example formulation of fiberglass sizing for (continuous) color grade SMC
The preparation methods of examples 1 to 12 are as follows:
s1: adding a coupling agent and a handfeel agent into water respectively for pre-dispersing to prepare a coupling agent solution and a handfeel agent solution respectively, and then uniformly mixing the two solutions;
s2: pre-dissolving an antistatic agent, and then adding the pre-dissolved antistatic agent into the solution obtained in the step S1;
s3: diluting the first film forming agent with 6-12 times of water; diluting the second film forming agent with water 3-9 times the volume of the second film forming agent, sequentially adding the second film forming agent into the solution obtained in the step S2, and uniformly mixing and stirring the second film forming agent;
s4: and (3) pre-dissolving the leveling agent, adding the pre-dissolved leveling agent into the solution obtained in the step (S3), and mixing and stirring uniformly to obtain the sizing agent.
To further illustrate the benefits of the present application, two glass fiber sizing agents (comparative example 1 and comparative example 2) commonly used at present and sizing agents with different content ratios are selected as comparative examples (comparative example 3 and comparative example 4), wherein the handfeel agents of comparative examples 3-4 are selected from the handfeel agent types of the present application, the percentage of the solid content of each effective component in comparative examples 1-4 to the total solid content of the sizing agent is expressed as follows, and the balance is water:
comparative example 1
Comparative example 2
Comparative example 3
Comparative example 4
Table 2 shows the results of performance tests of the glass fiber ply yarn products produced with the sizing agents described in examples 1 to 12 and comparative examples 1 to 4, in order to ensure comparability of the test results, it was ensured that the combustible content of the glass fibers prepared in each example and comparative example was substantially the same (control range 1.15 to 1.35, center value 1.25), namely: in the examples and comparative examples, the percentage of the solid mass of the sizing agent over the surface of the glass fiber was substantially uniform. In addition, it was ensured that the glass fibers prepared in each of the examples and comparative examples were consistent with other raw materials and production process parameters, etc. used in the mechanical property test, so as to compare the properties of the glass fibers in parallel.
Table 2 results of testing the performance of glass fibers coated with the sizing described in examples and comparative examples
TABLE 2 results of testing the performance of glass fibers produced by the sizing coatings described in examples and comparative examples
Note that:
wherein, the sample plate of the glass fiber reinforced unsaturated polyester resin for testing mechanical properties (comprising bending strength and side pressure strength) is prepared by molding by SMC (sheet molding compound).
From the test results of the above examples, we can see that the glass fiber texture condition on the surface of the glass fiber coated by the impregnating compound has obvious advantages, and the mechanical properties of the prepared fiber reinforced unsaturated polyester resin are obviously better than those of the glass fiber prepared by the comparative examples, such as examples 6 and 7, and the performances are particularly outstanding; in addition, the fiber has the advantages of high stiffness, good surface smoothness, less hairiness in the production and use processes, and the like.
Therefore, the formula and the process of the glass fiber sizing agent provided by the application are scientific and reasonable, the glass fiber coated with the sizing agent has better compatibility with unsaturated polyester resin, stronger interface bonding can be formed, and the surface performance of the product is improved.
Finally, it should be noted that: in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
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 (10)
1. A glass fiber sizing agent for a coloring-grade SMC, which is characterized by comprising an effective component and water; the solid content of the impregnating compound is 3.8-13.8%; the effective components comprise a coupling agent, a film forming agent, an antistatic agent, a leveling agent and a handfeel agent; the solid mass of each effective component of the impregnating compound is expressed as follows:
wherein, the hand feeling agent is a high molecular polymer polymerized by silicone oil containing long-chain alkyl and end-capped and modified;
wherein the film forming agent is a mixture of a first film forming agent and a second film forming agent; the first film forming agent is organic silicon modified epoxy emulsion, and the second film forming agent is unsaturated polyester emulsion which is quickly soaked; the mass ratio of the first film forming agent to the second film forming agent is 1:1-1:5.
2. The glass fiber sizing for color grade SMC of claim 1, wherein the weight percent solids of each active component of said sizing to the total weight of sizing solids is expressed as follows:
wherein the coupling agent is a silane coupling agent containing unsaturated bonds.
3. The glass fiber sizing for color grade SMC of claim 1 or 2, characterized in that said leveling agent is a polyether modified organosilicon compound.
4. The glass fiber sizing for color grade SMC according to claim 1 or 2, characterized in that said antistatic agent is at least one of sodium dodecyl sulfonate, lithium dodecyl sulfonate and potassium dodecyl sulfonate.
5. The glass fiber sizing agent for coloring-grade SMC according to claim 1 or 2, wherein said silicone modified epoxy emulsion is obtained by uniformly dispersing epoxy resin in water after mixing epoxy-terminated polyether silicone as an emulsifier.
6. The glass fiber sizing for color grade SMC of claim 5, wherein said epoxy resin is at least one of bisphenol a type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; the epoxy equivalent of the epoxy resin is 600-3300 g/eq.
7. The glass fiber sizing agent for coloring-grade SMC according to claim 1 or 2, characterized in that said fast-impregnating unsaturated polyester emulsion is obtained by polycondensation of maleic anhydride doped with phthalic anhydride and propylene glycol, the product being uniformly dispersed in water; the molecular weight of the fast-saturated unsaturated polyester is 4000-15000 Da.
8. A method of preparing a glass fiber sizing for a coloring grade SMC according to any of claims 1 to 7, comprising the steps of:
s1: adding a coupling agent and a handfeel agent into water respectively for pre-dispersing to prepare a coupling agent solution and a handfeel agent solution respectively, and then uniformly mixing the two solutions;
s2: pre-dissolving an antistatic agent, and then adding the pre-dissolved antistatic agent into the solution obtained in the step S1;
s3: diluting the first film forming agent with 6-12 times of water; diluting the second film forming agent with water 3-9 times the volume of the second film forming agent, sequentially adding the second film forming agent into the solution obtained in the step S2, and uniformly mixing and stirring the second film forming agent;
s4: and (3) pre-dissolving the leveling agent, adding the pre-dissolved leveling agent into the solution obtained in the step (S3), and mixing and stirring uniformly.
9. A glass fiber product produced by coating a coloring grade SMC according to any of claims 1 to 8 with a glass fiber sizing agent.
10. Use of the glass fiber product according to claim 9 in the construction field.
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