CN112390542A - Glass fiber antistatic impregnating compound and preparation method thereof - Google Patents
Glass fiber antistatic impregnating compound and preparation method thereof Download PDFInfo
- Publication number
- CN112390542A CN112390542A CN202010314047.0A CN202010314047A CN112390542A CN 112390542 A CN112390542 A CN 112390542A CN 202010314047 A CN202010314047 A CN 202010314047A CN 112390542 A CN112390542 A CN 112390542A
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- Prior art keywords
- grease
- cationic
- starch
- fatty acid
- emulsifier
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000004519 grease Substances 0.000 claims abstract description 64
- 229920002472 Starch Polymers 0.000 claims abstract description 48
- 235000019698 starch Nutrition 0.000 claims abstract description 48
- 239000008107 starch Substances 0.000 claims abstract description 48
- -1 polyol ester Chemical class 0.000 claims abstract description 45
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000194 fatty acid Substances 0.000 claims abstract description 32
- 239000002752 cationic softener Substances 0.000 claims abstract description 31
- 239000002216 antistatic agent Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 125000002091 cationic group Chemical group 0.000 claims abstract description 25
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 25
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 24
- 229940100486 rice starch Drugs 0.000 claims abstract description 24
- 239000003755 preservative agent Substances 0.000 claims abstract description 20
- 230000002335 preservative effect Effects 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 230000002829 reductive effect Effects 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 26
- 229930195729 fatty acid Natural products 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000004513 sizing Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 10
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000010513 hydrogenated corn oil Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 235000019482 Palm oil Nutrition 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000002540 palm oil Substances 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- 229950004959 sorbitan oleate Drugs 0.000 claims description 4
- 229950011392 sorbitan stearate Drugs 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003240 coconut oil Substances 0.000 claims description 3
- 235000019864 coconut oil Nutrition 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 239000004902 Softening Agent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 206010020112 Hirsutism Diseases 0.000 abstract description 17
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000005611 electricity Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- VWYIWOYBERNXLX-KTKRTIGZSA-N Glycidyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC1CO1 VWYIWOYBERNXLX-KTKRTIGZSA-N 0.000 description 4
- OUQGOXCIUOCDNN-UHFFFAOYSA-N Glycidyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC1CO1 OUQGOXCIUOCDNN-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical group CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical group CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000008172 hydrogenated vegetable oil Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 239000002759 woven fabric 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
-
- 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
- C03C25/25—Non-macromolecular compounds
-
- 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
- C03C25/255—Oils, waxes, fats or derivatives thereof
-
- 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
-
- 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
- C03C25/321—Starch; Starch derivatives
-
- 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
- C03C25/42—Coatings containing inorganic materials
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)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of glass fiber, in particular to an antistatic impregnating compound for glass fiber and a preparation method thereof, wherein the impregnating compound comprises the following raw materials in percentage by weight: 1.5-3% of modified rice starch, 1.8-3.8% of cationic starch, 0.3-1.4% of grease A, 0.2-0.35% of grease B, 0.1-0.25% of emulsifier, 0.3-0.8% of cationic softener and antioxidant0.3-1% of electrostatic agent, 0.3-0.9% of modified epoxy resin, 0.01-0.1% of preservative and the balance of water; the solubility of the modified rice starch is less than or equal to 30 percent; the solubility of the cationic starch is more than or equal to 90 percent; the grease A is polyol ester; the grease B is C18‑C30Fatty acid esters of (a); the antistatic agent is a mixture of a cationic surfactant and a nonionic surfactant, wherein the mass ratio of the cationic surfactant to the nonionic surfactant is (3.5-4.5): 1. the antistatic impregnating compound is obtained by compounding the cationic surfactant and the nonionic surfactant, and can meet the requirements of production workshops in different environments, so that the yarn hairiness amount is reduced, and the yarn bundling property is improved.
Description
Technical Field
The invention relates to the technical field of glass fibers, in particular to an antistatic impregnating compound for glass fibers and a preparation method thereof.
Background
With the wide application of the glass fiber composite material in the fields of aerospace, transportation, civil construction, biomedical use, sports equipment and the like, the composite material is required to have high damage tolerance and reliability, and the requirements on the structural integrity and the shape of a reinforcing material are also stricter. Woven fabrics and knitted fabrics are reinforced structures of traditional textile composite materials, but in recent years, knitted fabrics receive more and more attention due to the advantages of flexible structural design, impact resistance, easiness in forming and manufacturing components with complex shapes and the like.
The glass fiber yarn generally refers to a glass fiber yarn product formed by drawing glass into a spinning cake and then degrading the glass fiber yarn product, and is usually used as a reinforcing material in a composite material. Glass fibers are classified into rovings and spun yarns depending on their fiber diameter and use, and glass spun yarns are more suitable for making woven structural reinforcements because spun yarns have smaller diameter of individual fibers and generally have better damage resistance than fibers having larger diameter.
At present, static electricity is easily generated due to friction in glass fiber production and weaving, and the static electricity can cause oil stains and hairiness to be generated on cop yarns in the twisting process. Meanwhile, in the weaving process of downstream customers, static electricity can enable the grey cloth to adsorb floating fibers or dust, and further the smoothness and the hairiness of the grey cloth are affected. Therefore, the antistatic impregnating compound is a vital production material in the production process of the glass fiber and directly plays a decisive role in the performance of the glass fiber.
The existing antistatic impregnating compound only contains one type of antistatic agent, and cannot meet the requirements of production workshops in different environments. Therefore, developing a sizing agent capable of improving the antistatic property of glass fiber yarns in different production environments is a technical problem to be solved in the field.
Disclosure of Invention
The first purpose of the invention is to provide a sizing agent for antistatic glass fiber, which can improve the antistatic property of glass fiber yarns in different production environments.
The second purpose of the invention is to provide a method for preparing an antistatic impregnating compound for glass fibers, and the invention aims to provide a method for preparing an antistatic impregnating compound which can meet the requirements of different production environments.
The invention provides an antistatic impregnating compound for glass fibers, which comprises the following raw materials in percentage by weight:
1.5-3% of modified rice starch, 1.8-3.8% of cationic starch, 0.3-1.4% of grease A, 0.2-0.35% of grease B, 0.1-0.25% of emulsifier, 0.3-0.8% of cationic softener, 0.3-1% of antistatic agent, 0.3-0.9% of modified epoxy resin, 0.01-0.1% of preservative and the balance of water;
the solubility of the modified rice starch is less than or equal to 30 percent;
the solubility of the cationic starch is more than or equal to 90 percent;
the grease A is polyol ester;
the grease B is C18-C30Fatty acid esters of (a);
the antistatic agent is a mixture of a cationic surfactant and a nonionic surfactant, wherein the mass ratio of the cationic surfactant to the nonionic surfactant is (3.5-4.5): 1.
the starch is the main component of the starch type impregnating compound, and the starch can form a protective film on the surface of the fiber in the high-speed wire drawing process, and the glass fiber has moderate hardness, low hairiness and higher breaking strength by selecting a starch system in which modified rice starch (the solubility is less than or equal to 30%) and cationic starch (the solubility is more than or equal to 90%); with polyhydric alcohol and C18-C30The grease composed of the fatty acid ester can play a certain lubricating role on the sizing agent and provide toughness of a starch film, so that the hairiness amount of the glass fiber yarn is reduced; in addition, the impregnating compound of the invention adopts the positiveThe mixture of the ionic surfactant and the nonionic surfactant is used as the antistatic agent, so that the prepared impregnating compound has excellent antistatic effect, because the cationic surfactant can play an antistatic role by neutralizing the negative charge on the surface of the glass fiber, and the nonionic surfactant absorbs moisture in the environment through hydrophilic functional groups so as to form a conductive path to eliminate static electricity. Also, studies have shown that when the cationic surfactant and the nonionic surfactant are present in a ratio of (3.5-4.5): 1, the prepared impregnating compound has the best antistatic performance and can meet the requirements of production workshops in different environments.
Further, the cationic surfactant is a composition prepared by mixing one or more of quaternary ammonium salts, amido ammonium salts, ether-containing ammonium salts, ester-containing ammonium salts, imidazoline quaternary ammonium salts or pyridine quaternary ammonium salts in any proportion;
the nonionic surfactant is a composition prepared by mixing one or more of fatty alcohol-polyoxyethylene ether, fatty alcohol-polyoxyethylene ester or fatty acid polyol ester in any proportion.
The cationic surfactant in the invention can be selected from one or more of quaternary ammonium salts, amido ammonium salts, ether-containing ammonium salts, ester-containing ammonium salts, imidazoline quaternary ammonium salts or pyridine quaternary ammonium salts; the nonionic surfactant can be one or more of fatty alcohol-polyoxyethylene ether, fatty alcohol-polyoxyethylene ester or fatty acid polyol ester. The negative charges on the surface of the glass fiber and the moisture in the environment can be effectively eliminated by compounding the cationic surfactant and the nonionic surfactant of the type, so that static electricity is eliminated.
Further, the emulsifier is any one group of glycidyl oleate and polyoxyethylene glycidyl oleate, polyoxyethylene polyoxypropylene ether and fatty acid polyoxyethylene amide, glycidyl stearate and polyoxyethylene ether glycidyl stearate, glycerol stearate and polyoxyethylene ether fatty acid ester;
the grease A is any one of glyceride, hydrogenated palm oil, hydrogenated corn oil or hydrogenated coconut oil;
the grease B is C12-C18A mixture of fatty acid esters.
The emulsifier provided by the invention mainly plays a role in emulsifying the grease A and the grease B. The invention uses any one group of glycidyl oleate and polyoxyethylene glycidyl oleate, polyoxyethylene polyoxypropylene ether and fatty acid polyoxyethylene amide, glycidyl stearate and polyoxyethylene ether glycidyl stearate, glycerol stearate and polyoxyethylene ether fatty acid ester as emulsifier to be matched with grease A and grease B for use, wherein the grease B is C12-C18C consisting of fatty acid esters18-C30Fatty acid esters of (a). Wherein the mass ratio of the emulsifier to the grease A to the grease B is (0.1-0.25): (0.3-1.4): (0.2-0.35), the optimal hydrophilic-lipophilic balance value can be obtained, and in addition, the HLB value of the emulsifier can be adjusted by the composite emulsifier, so that the emulsifying efficiency is improved, and the stability of the emulsion is increased. Further, it has been found that when hydrogenated vegetable oil such as hydrogenated palm oil, hydrogenated corn oil and hydrogenated coconut oil is used as the fat a, the effect of using sorbitan oleate and polyoxyethylene sorbitan oleate as the composite emulsifier is most excellent.
Further, the cationic softener is a reactant of fatty acid and polyethylene polyamine;
wherein the carbon number of the fatty acid is C8-C18The polyethylene polyamine is a composition compounded by any one or more of hydroxyethyl ethylenediamine, diethylenetriamine or tetraethylenepentamine in any proportion.
The cationic softening agent can effectively reduce the coefficient of dynamic friction, reduce the generation of hairiness in production links such as wire drawing and twisting, and enhance the bundling property of the glass fiber. The invention adopts the reaction product of fatty acid and polyethylene polyamine as the cation softener, and the usage amount is 0.3-0.8%, which can effectively reduce the generation amount of hairiness without affecting the convergence of fiber strands.
Further, the modified epoxy resin is amine modified epoxy resin.
The modified epoxy resin has good effect of protecting the surface of the glass fiber, has good film forming property, and can ensure that the fiber has certain bundling property and is not easy to slide. According to the invention, the amine modified epoxy resin is used in combination with the modified rice starch, the cationic softener and the antistatic agent, so that the antistatic property of the glass fiber yarn in different production environments and the problems of oil stain and hairiness generated on the surface of the cop due to the electrostatic action can be effectively improved.
Further, the preservative is any one of organic nitrogen sulfur compounds, nitrites, sulfites, formaldehyde or phenol.
In order to prevent starch and oil from being deteriorated and putrefactive due to the action of microorganisms, the present invention uses any one of organic nitrogen-sulfur compounds, nitrites, sulfites, formaldehyde or phenol as an antibacterial preservative.
The invention also discloses a preparation method of the impregnating compound, which comprises the following steps:
s1, adding the modified rice starch and the cationic starch into water, and pasting the starch;
s2, adding the grease A, the grease B, the emulsifier and the cationic softener into a mixing container, and adding water for emulsification treatment to obtain emulsion;
s3, adding the emulsion, the antistatic agent, the modified epoxy resin, the preservative and water into the gelatinized starch, and adjusting the solid content to 4.5-8% to obtain the impregnating compound;
wherein, the step S1 and the step S2 have no sequential limitation.
The preparation method of the impregnating compound comprises the following steps: firstly, calculating the dosage of each required starch raw material, adding deionized water into a preparation kettle, adding weighed modified rice starch and cationic starch into the preparation kettle, and carrying out gelatinization treatment on the starch. Meanwhile, the oil A, the oil B and the cationic softener are emulsified by using an emulsifier to obtain emulsion. And finally, adding the emulsion, the antistatic agent, the modified epoxy resin and the preservative into the gelatinized starch, and finally adding deionized water to adjust the solid content to 4.5-8% to obtain the impregnating compound. The impregnating compound prepared by the method has excellent antistatic property due to the specific formula and the preparation process, and effectively solves the problems of oil stains and filoplume generated on the surface of the cop in the twisting process due to static electricity.
Further, step S1 specifically includes: adding modified rice starch and cationic starch into water 50-65% of the total amount, stirring, heating to 85-100 deg.C, and treating at constant temperature for 30-50 min.
And S1, adding normal-temperature deionized water accounting for 50-65% of the total amount of the impregnating compound to be prepared into a preparation kettle, adding the prepared modified rice starch and cationic starch, starting stirring, gelatinizing the starch when the temperature is raised to 85-100 ℃, and keeping the temperature for 30-50min to completely gelatinize the cationic starch, wherein the gelatinizing amount of the modified rice starch is less than 40%.
Further, step S2 specifically includes: mixing and stirring the grease A, the grease B, the emulsifier and the cationic softener after the preheating treatment, heating to 60-70 ℃, and then adding water at 60-70 ℃ accounting for 50-60% of the total amount of the grease A, the grease B, the emulsifier and the cationic softener until the emulsification is finished to obtain the emulsion.
The emulsifier is used for emulsifying the grease A and the grease B and comprises the following specific steps: firstly, preheating oil A, oil B, an emulsifier and a cationic softener until the oil A, the oil B, the emulsifier and the cationic softener are completely melted, then adding the melted oil A, the melted oil B, the emulsifier and the cationic softener into an emulsification tank according to a preset proportion, starting shearing and stirring and slowly heating, wherein the stirring speed is controlled to be 55-75Hz, the emulsifier can emulsify the oil A, the oil B and the cationic softener to emulsion drops with proper size at the stirring speed, and when the temperature is raised to 60-70 ℃, slowly adding 60-70 ℃ deionized water accounting for 50-60% of the total amount of the oil A, the oil B, the emulsifier and the cationic softener until emulsification is completed to form stable oil-water emulsion.
Further, step S3 specifically includes: and adding water with the temperature of 20-35 ℃ into the gelatinized starch until the temperature of the system is reduced to 60-75 ℃, then adding the emulsion, the antistatic agent, the modified epoxy resin and the preservative, and finally adding water to adjust the solid content to 4.5-8% to obtain the impregnating compound.
Step S3 specifically includes: and (3) cooling the starch system after gelatinization to 60-75 ℃ by using deionized water at 20-35 ℃ through a spraying pipeline arranged in the preparation kettle, then adding the emulsion prepared in the step S2, the antistatic agent, the modified epoxy resin and the preservative, and finally adding deionized water to adjust the solid content to 4.5-8% to finally obtain the glass fiber antistatic impregnating compound.
Compared with the prior art, the glass fiber antistatic impregnating compound has the following advantages:
in the glass fiber drawing process, starch can form a protective film on the surface of the glass fiber, so that the requirements of drawing and subsequent processing processes are met; the emulsion formed by the grease A, the grease B, the emulsifier and the cationic softener in a specific ratio has a certain lubricating effect, can improve the toughness of the starch film and reduce yarn hairiness, and can promote the loss and volatilization of the starch film in the later heat treatment process, thereby facilitating the post-treatment of the glass fiber cloth; the addition of 0.3-0.8% of cationic softener can reduce the surface tension of the sizing agent, facilitate the drawing operation of glass fiber yarns and reduce hairiness and broken ends during twisting; the antistatic wetting agent is obtained by compounding the cationic surfactant and the nonionic surfactant, the cationic surfactant can achieve an antistatic effect by neutralizing negative charges on the surface of the glass fiber, the nonionic surfactant can adsorb moisture in the environment through hydrophilic functional groups so as to form a conductive path to eliminate static electricity, and the antistatic wetting agent is obtained by compounding the cationic surfactant and the nonionic surfactant, so that the requirements of production workshops in different environments can be met, the hairiness amount of the glass fiber yarns, especially the low-dielectric glass fiber yarns, is reduced, and the yarn convergence is improved.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1, adding the modified rice starch and the cationic starch into water accounting for 50% of the total amount of the preparation, stirring, simultaneously heating to 85 ℃, and carrying out constant-temperature treatment for 30 min; wherein the solubility of the modified rice starch is 30 percent, and the solubility of the cationic starch is 100 percent.
S2, mixing and stirring the grease A, the grease B, the emulsifier and the cationic softener after preheating treatment, heating to 60 ℃, and adding 65 ℃ water accounting for 50% of the total amount of the grease A, the grease B, the emulsifier and the cationic softener until emulsification is completed to obtain emulsion; wherein the grease A is glyceride; the grease B is C12And C18C consisting of fatty acid esters30A fatty acid ester mixture of (a); the emulsifier is a composite emulsifier composed of polyoxyethylene polyoxypropylene ether and fatty acid polyoxyethylene amide in a mass ratio of 1: 1; the cationic softener is C12Fatty acid and hydroxyethyl ethylenediamine.
S3, adding water of 20 ℃ into the gelatinized starch until the system temperature is reduced to 60 ℃, then adding an emulsion, an antistatic agent, a modified epoxy resin and a preservative, and finally adding water to adjust the solid content to 5% to obtain the impregnating compound, wherein the antistatic agent is a mixture obtained by compounding an ester quaternary ammonium salt (a cationic surfactant) and fatty alcohol-polyoxyethylene ether (a nonionic surfactant) in a ratio of 1: 1; the modified epoxy resin is diethanolamine modified epoxy resin; the preservative is an organic nitrogen-sulfur compound.
Wherein, the step S1 and the step S2 have no sequential limitation.
Example 2
S1, adding the modified rice starch and the cationic starch into water accounting for 55% of the total preparation amount, stirring, simultaneously heating to 95 ℃, and carrying out constant-temperature treatment for 40min, wherein the solubility of the modified rice starch is 20%, and the solubility of the cationic starch is 100%.
S2, mixing and stirring the grease A, the grease B, the emulsifier and the cationic softener after preheating, heating to 65 ℃, adding water at 60 ℃ accounting for 55% of the total amount of the grease A, the grease B, the emulsifier and the cationic softener until emulsification is completed to obtain emulsion, wherein the grease A is hydrogenated corn oil; the grease B is C18A fatty acid ester; the emulsifier is a composite emulsifier composed of glycidyl sorbitol oleate and polyoxyethylene glycidyl sorbitol oleate in a mass ratio of 1: 1; the cationic softener is C18Fatty acid and diethylenetriamine.
S3, adding water of 30 ℃ into the gelatinized starch until the system temperature is reduced to 65 ℃, then adding an emulsion, an antistatic agent, a modified epoxy resin and a preservative, and finally adding water to adjust the solid content to 5% to obtain the impregnating compound, wherein the antistatic agent is a mixture obtained by compounding pyridine quaternary ammonium salt (cationic surfactant) and fatty alcohol-polyoxyethylene ether (nonionic surfactant) in a ratio of 2: 1; the modified epoxy resin is diethanolamine modified epoxy resin; the preservative is formaldehyde.
Wherein, the step S1 and the step S2 have no sequential limitation.
Example 3
S1, adding the modified rice starch and the cationic starch into water accounting for 65% of the total amount of the preparation, stirring, simultaneously heating to 100 ℃, and carrying out constant-temperature treatment for 50min, wherein the solubility of the modified rice starch is 30%, and the solubility of the cationic starch is 100%.
S2, mixing and stirring the grease A, the grease B, the emulsifier and the cationic softener after preheating, heating to 70 ℃, adding 70 ℃ water accounting for 60% of the total amount of the grease A, the grease B, the emulsifier and the cationic softener until emulsification is completed to obtain emulsion, wherein the grease A is hydrogenated palm oil; the grease B is C12C consisting of fatty acid esters24Fatty acid esters of (a); the emulsifier is a composite emulsifier composed of sorbitan stearate and polyoxyethylene ether sorbitan stearate in a mass ratio of 1: 1; the cationic softener is C12Fatty acid with tetraethylenepentamine.
S3, adding 35 ℃ water into the gelatinized starch until the system temperature is reduced to 65 ℃, then adding an emulsion, an antistatic agent, a modified epoxy resin and a preservative, and finally adding water to adjust the solid content to 5% to obtain the impregnating compound, wherein the antistatic agent is a mixture obtained by compounding amide ammonium salts (cationic surfactant) and fatty alcohol-polyoxyethylene ether (nonionic surfactant) in a ratio of 1: 1; the modified epoxy resin is diethanolamine modified epoxy resin; the preservative is phenol.
Wherein, the step S1 and the step S2 have no sequential limitation.
Example 4
S1, adding the modified rice starch and the cationic starch into water accounting for 65% of the total amount of the preparation, stirring, simultaneously heating to 100 ℃, and carrying out constant-temperature treatment for 50min, wherein the solubility of the modified rice starch is 30%, and the solubility of the cationic starch is 100%.
S2, mixing and stirring the grease A, the grease B, the emulsifier and the cationic softener after preheating treatment, heating to 70 ℃, adding 70 ℃ water accounting for 60% of the total amount of the grease A, the grease B, the emulsifier and the cationic softener until emulsification is completed to obtain emulsion, wherein the grease A is hydrogenated corn oil; the grease B is C30A fatty acid ester; the emulsifier is glycerin hardThe composite emulsifier consists of fatty acid ester and polyoxyethylene ether fatty acid ester in a mass ratio of 1: 1; the cationic softener is C16Fatty acid with tetraethylenepentamine.
S3, adding 35 ℃ water into the gelatinized starch until the system temperature is reduced to 65 ℃, then adding an emulsion, an antistatic agent, a modified epoxy resin and a preservative, and finally adding water to adjust the solid content to 5% to obtain the impregnating compound, wherein the antistatic agent is a mixture obtained by compounding an amido ammonium salt (a cationic surfactant) and fatty alcohol-polyoxyethylene ether (a nonionic surfactant) in a ratio of 3: 1; the modified epoxy resin is triethanolamine modified epoxy resin; the preservative is nitrite.
Wherein, the step S1 and the step S2 have no sequential limitation.
Comparative example 1
The antistatic agent used in comparative example 1 was only a cationic surfactant, and the rest was the same as in example 1.
Comparative example 2
The antistatic agent used in comparative example 2 was only a nonionic surfactant, and the rest was the same as in example 1.
The formulations of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 component formulas of examples 1-4 and comparative examples 1-2 (wherein the values are percentages by mass of solids in the sizing agent)
The effects of the wetting agents prepared in examples 1 to 4 and comparative examples 1 to 2 were evaluated by measuring the number of hairiness (0 to 5 pieces representing "pass", 6 to 10 pieces representing "poor", and 11 or more pieces representing "fail") and the number of oily soil yarns (0 to 2 pieces representing "pass", 2 to 3 pieces representing "poor", and 3 or more pieces representing "fail") of the glass fiber yarns within 0.5mm, and the evaluation results are shown in Table 2.
TABLE 2 evaluation results of the effects of impregnating agent
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Number of hairs | Qualified | Qualified | Qualified | Qualified | Is poor | Fail to be qualified |
| Number of greasy dirt | Qualified | Qualified | Qualified | Qualified | Is poor | Fail to be qualified |
It can be known from the formulas of the impregnating agents and the evaluation results of the using effects of the prepared impregnating agents in table 1 that the cationic surfactant and the nonionic surfactant are compounded as the antistatic agents of the impregnating agents in examples 1 to 4, the corresponding hairiness numbers are lower than 5, the oil stain numbers are lower than 2, the evaluation results are all qualified, while the comparative example 1 only uses the cationic surfactant as the antistatic agent to prepare the impregnating agent, the antistatic effect is poorer than that of the examples 1 to 4, the hairiness numbers and the oil stain numbers are relatively more, and the evaluation results are all "poorer"; similarly, in comparative example 2, only the nonionic surfactant was used as the antistatic agent for preparing the impregnating compound, the antistatic effect was the worst, the number of hairiness and the number of oily stains were the most, and the corresponding evaluation result was "failed". Therefore, the invention uses the mixed starch system of the modified rice starch and the cationic starch to endow the glass fiber yarn with moderate softness, low hairiness and higher breaking strength, and the cationic surfactant and the nonionic surfactant are compounded to be used as the antistatic agent, so that the requirements of production workshops in different environments can be met, the hairiness amount of the yarn is reduced, and the bundling property of the yarn is improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The antistatic impregnating compound for the glass fiber is characterized by comprising the following raw materials in percentage by weight:
1.5-3% of modified rice starch, 1.8-3.8% of cationic starch, 0.3-1.4% of grease A, 0.2-0.35% of grease B, 0.1-0.25% of emulsifier, 0.3-0.8% of cationic softener, 0.3-1% of antistatic agent, 0.3-0.9% of modified epoxy resin, 0.01-0.1% of preservative and the balance of water;
the solubility of the modified rice starch is less than or equal to 30 percent;
the solubility of the cationic starch is more than or equal to 90 percent;
the grease A is polyol ester;
the grease B is C18-C30Fatty acid esters of (a);
the antistatic agent is a mixture of a cationic surfactant and a nonionic surfactant, wherein the mass ratio of the cationic surfactant to the nonionic surfactant is (3.5-4.5): 1.
2. the sizing agent according to claim 1, wherein said cationic surfactant is a composition prepared by compounding one or more of quaternary ammonium salts, amido ammonium salts, ether ammonium salts, ester ammonium salts, imidazoline quaternary ammonium salts and pyridinium quaternary ammonium salts in any proportion;
the nonionic surfactant is a composition prepared by mixing one or more of fatty alcohol-polyoxyethylene ether, fatty alcohol-polyoxyethylene ester or fatty acid polyol ester in any proportion.
3. The sizing agent according to claim 1, wherein said emulsifier is any one of the group consisting of sorbitan oleate and polyoxyethylene sorbitan oleate, polyoxyethylene polyoxypropylene ether and fatty acid polyoxyethylene amide, sorbitan stearate and polyoxyethylene ether sorbitan stearate, glycerol stearate and polyoxyethylene ether fatty acid ester;
the grease A is any one of glyceride, hydrogenated palm oil, hydrogenated corn oil or hydrogenated coconut oil;
the grease B is C12-C18A mixture of fatty acid esters.
4. The sizing agent according to claim 1, wherein said cationic softening agent is a reaction product of a fatty acid and a polyethylene polyamine;
wherein the carbon number of the fatty acid is C8-C18The polyethylene polyamine is a composition compounded by any one or more of hydroxyethyl ethylenediamine, diethylenetriamine or tetraethylenepentamine in any proportion.
5. The sizing agent according to claim 1, wherein said modified epoxy resin is an amine-based modified epoxy resin.
6. The sizing agent according to claim 1, wherein said preservative is any one of an organic nitrogen-sulfur compound, a nitrite, a sulfite, formaldehyde or phenol.
7. A method for producing the sizing agent as set forth in any one of claims 1 to 6, characterized by comprising the steps of:
s1, adding the modified rice starch and the cationic starch into water, and pasting the starch;
s2, adding the grease A, the grease B, the emulsifier and the cationic softener into a mixing container, and adding water for emulsification treatment to obtain emulsion;
s3, adding the emulsion, the antistatic agent, the modified epoxy resin, the preservative and water into the gelatinized starch, and adjusting the solid content to 4.5-8% to obtain the impregnating compound;
wherein, the step S1 and the step S2 have no sequential limitation.
8. The method according to claim 7, wherein step S1 specifically includes: adding modified rice starch and cationic starch into water 50-65% of the total amount, stirring, heating to 85-100 deg.C, and treating at constant temperature for 30-50 min.
9. The method according to claim 7, wherein step S2 specifically includes: mixing and stirring the grease A, the grease B, the emulsifier and the cationic softener after the preheating treatment, heating to 60-70 ℃, and then adding water at 60-70 ℃ accounting for 50-60% of the total amount of the grease A, the grease B, the emulsifier and the cationic softener until the emulsification is finished to obtain the emulsion.
10. The method according to any one of claims 7 to 8, wherein step S3 specifically includes: and adding water with the temperature of 20-35 ℃ into the gelatinized starch until the temperature of the system is reduced to 60-75 ℃, then adding the emulsion, the antistatic agent, the modified epoxy resin and the preservative, and finally adding water to adjust the solid content to 4.5-8% to obtain the impregnating compound.
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