CN113605097A - Secondary sizing slurry for electronic glass fiber cloth and preparation method thereof - Google Patents
Secondary sizing slurry for electronic glass fiber cloth and preparation method thereof Download PDFInfo
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- CN113605097A CN113605097A CN202110974635.1A CN202110974635A CN113605097A CN 113605097 A CN113605097 A CN 113605097A CN 202110974635 A CN202110974635 A CN 202110974635A CN 113605097 A CN113605097 A CN 113605097A
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- 239000004744 fabric Substances 0.000 title claims abstract description 64
- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 239000003365 glass fiber Substances 0.000 title claims abstract description 49
- 238000004513 sizing Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 acetylene glycol Chemical compound 0.000 claims abstract description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 12
- 230000003068 static effect Effects 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002216 antistatic agent Substances 0.000 claims abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 150000003863 ammonium salts Chemical group 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002518 antifoaming agent Substances 0.000 abstract description 6
- 238000005187 foaming Methods 0.000 abstract description 2
- 238000009990 desizing Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 8
- 206010020112 Hirsutism Diseases 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009941 weaving Methods 0.000 description 7
- 238000009987 spinning Methods 0.000 description 4
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JBIGSTYFMNGJGK-UHFFFAOYSA-N 2,4-dimethyldec-5-yn-4-ol Chemical compound CCCCC#CC(C)(O)CC(C)C JBIGSTYFMNGJGK-UHFFFAOYSA-N 0.000 description 1
- JTACNIAVBSQMCU-UHFFFAOYSA-N 2,4-dimethylhex-5-yn-3-ol Chemical compound CC(C)C(O)C(C)C#C JTACNIAVBSQMCU-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- NUYADIDKTLPDGG-UHFFFAOYSA-N 3,6-dimethyloct-4-yne-3,6-diol Chemical compound CCC(C)(O)C#CC(C)(O)CC NUYADIDKTLPDGG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000000528 statistical test Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The invention discloses secondary sizing slurry for electronic glass fiber cloth and a preparation method thereof. The slurry comprises the following components in percentage by mass: 3-15% of polyvinyl alcohol, 0-10% of polyethylene glycol, 0.02-2% of wetting agent, 0-0.5% of antistatic agent and the balance of pure water; the wetting agent is an acetylene glycol surfactant or acetylene alcohol surfactant. The slurry of the invention has a dynamic surface tension and a static surface tension of <30mM/m, even a dynamic surface tension and a static surface tension of <25mM/m, and a viscosity of less than or equal to 35mPa.s, measured at 25 ℃, and can achieve a low foaming effect without adding an antifoaming agent to the slurry.
Description
Technical Field
The invention relates to secondary sizing slurry for electronic glass fiber cloth and a preparation method thereof, belonging to the technical field of electronic glass fiber cloth.
Background
The electronic grade glass fibre yarn is an inorganic non-metal material, and is made up by uniformly pulverizing the minerals of silica sand, limestone and borax, mixing them in high-temp. melting furnace to obtain a eutectic body, high-speed drawing and quick-cooling by means of bushing, and twisting several tens to several hundreds of drawn glass fibre filaments on the spinning cake by means of twisting machine after drying so as to obtain the invented cylindrical yarn for weaving glass fibre cloth. The sizing agent is needed for the last time in the spinning process to prevent broken hairiness of the yarn in the spinning process. The slurry applied during the spinning process is the "primary slurry".
The electronic glass fiber cloth is a plain weave fabric formed by interlacing warp yarns and weft yarns through air-jet weaving, and the yarns are easily damaged to generate hairiness broken ends through repeated bending and rubbing actions at a high speed on a loom. The electronic-grade glass cloth has strict requirements on cloth cover hairiness, and meanwhile, in order to ensure the production efficiency of woven cloth, the sizing agent coated on the yarns during drawing and forming is difficult to meet the high-speed weaving requirement, secondary sizing must be carried out on the warp yarns for woven cloth so as to increase the strength and the wear resistance of the warp yarns and simultaneously coat the hairiness.
After weaving, the sizing agent and the secondary sizing agent on the surface of the raw yarn have no effect, but the thin sizing agent and the thin sizing agent on the surface of the warp yarn can seriously affect the bonding of the electronic cloth and the resin and must be thoroughly removed.
The conventional desizing method of the electronic cloth is to decompose cloth sizing agent by a high-temperature combustion method, and generally comprises twice desizing. Primary desizing, referred to as continuous desizing, utilizes high temperatures to remove most of the slurry. Secondary desizing, batch desizing in batch, is intended to remove all the remaining slurry. After two desizing, the content of the residual organic combustible substances on the cloth surface is required to be not more than a specified value. The two desizing processes are carried out at high temperature, and energy sources are more. To achieve better desizing effect, the desizing temperature must be increased, or the desizing time must be prolonged, and these measures can greatly increase the energy consumption. And the strength loss of the electronic cloth can be caused by prolonging the desizing time or temperature, and the tearing and cloth breaking abnormality is easy to occur in the subsequent production.
At present, the sizing agent adopted for sizing the warp yarn is mainly polyvinyl alcohol sizing agent, the viscosity is stable, the size film is tough, the wear resistance and the bending resistance are good, but the problem that the size is difficult to desize and the size is often burnt insufficiently in the smoldering process causes yellow spots or black spots on the produced glass fiber cloth, the appearance of the product is seriously influenced, the impregnation property of the electronic glass fiber cloth can be influenced by the sizing agent remained on the surface, the combination of the glass fiber and resin is hindered, and the quality of the product is influenced. Meanwhile, in order to achieve a better desizing effect, the using amount of fuel is increased, so that the furnace temperature is increased, and the cost is very high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the secondary sizing agent for the electronic glass fiber cloth and the preparation method thereof, so that the friction resistance and the mechanical impact resistance of the glass fiber yarn in the high-speed weaving process are effectively improved, the finally prepared electronic glass fiber cloth has few fluffing defects, simultaneously, the desizing of the gray cloth is easier, the heat treatment desizing efficiency is higher, the residual fat amount is less, and the surface chemical treatment of the electronic cloth and the infiltration and combination with matrix resin are facilitated.
The invention is realized by the following technical scheme:
the secondary sizing slurry for the electronic glass fiber cloth comprises the following components in percentage by mass: 3-15% of polyvinyl alcohol, 0-10% of polyethylene glycol, 0.02-2% of wetting agent, 0-0.5% of antistatic agent and the balance of pure water.
The secondary sizing slurry for the electronic glass fiber cloth has the alcoholysis degree of 78-89% of polyvinyl alcohol and the polymerization degree of 1700-1900.
The molecular weight of the secondary sizing agent for the electronic glass fiber cloth is 1000-5000-.
The wetting agent is acetylenic ethylene glycol surfactant or mixture of acetylenic alcohol surfactant.
The antistatic agent is ammonium salt of alkyl sulfonic acid, aryl sulfonic acid or alkyl aryl sulfonic acid, and ammonium salt of alkyl phosphoric acid, aryl phosphoric acid or alkyl aryl phosphoric acid.
The secondary sizing slurry for the electronic glass fiber cloth is characterized in that the dynamic surface tension and the static surface tension of the slurry are less than 35 mM/m. Preferably the dynamic and static surface tensions are <25 mM/m; the viscosity is less than or equal to 35mPa.s, measured at 25 ℃.
The preparation method of the secondary sizing slurry for the electronic glass fiber cloth comprises the following steps:
(1) injecting a certain amount of pure water into the container, starting the stirrer, and slowly adding polyvinyl alcohol;
(2) heating to 90 deg.C, stirring for 1 hr, cooling to 70 deg.C, slowly adding polyethylene glycol, stirring for 30min, and observing to obtain clear slurry;
(3) then adding wetting agent, and stirring for 30min at a stirring speed of 150-300 r/mi until a stable milky white dispersion liquid is formed.
(4) And adding the residual pure water to adjust the slurry concentration, keeping the temperature of 30-70 ℃ for stirring at constant temperature, and finally filtering by using a filter element with the aperture of 1 mu to obtain the warp sizing slurry.
The traditional slurry formulation needs defoaming agent or physical methods such as heating, ray irradiation, high-frequency vibration and instantaneous discharge, however, the methods are not practical in industry because it is difficult to eliminate a large amount of foam in a short time, and the chemical defoaming method is generally adopted, so that the method is more practical. The cause of bubble formation is caused by the addition of polyvinyl alcohol and a surface active agent to the slurry, most notably by the agent. Suitable auxiliaries can ameliorate this problem. The wetting agent is selected from acetylene glycol surfactant and acetylene alcohol surfactant, the slurry can effectively reduce dynamic and static surface tension, can also obviously improve fluidity and leveling property, and only generates trace or a small amount of bubbles. The acetylene glycol surfactant and the acetylene alcohol surfactant are insoluble in water, and are dispersed in water in the form of particles under the action of high-speed stirring and polyvinyl alcohol, the dynamic surface tension and the static surface tension of the slurry reach below 30mM/m, even reach below 25mM/m, and the problem that the slurry effectively wets among glass fiber monofilaments and basically does not generate bubbles is solved, so that the problem that the action of a wetting agent is weakened due to the addition of a defoaming agent can be solved without adding a defoaming agent. On the other hand, the high-speed production requirement can be met.
The polyvinyl alcohol mainly plays a role of a film forming agent, can form a relatively complete bonding and coating effect on glass fibers, forms a protective film on the surfaces of the glass fibers, and the formed size film has good elasticity and good tensile property, can effectively improve the wear resistance between yarns and between mechanical parts, and reduces the problems of hairiness, end breakage and powder falling in the weaving process. Polyvinyl alcohol is obtained by partial or complete hydrolysis of polyvinyl acetate. Wherein, the proportion of the molar mass of the polyvinyl alcohol obtained by hydrolysis to the molar mass of the vinyl alcohol orthoacetate is characterized by alcoholysis degree, and the polymerization degree is an index for characterizing the molecular size of the polymer. The performance of the polyvinyl alcohol is directly related to the alcoholysis degree and the polymerization degree of the polyvinyl alcohol, and the larger the alcoholysis degree is, the better the water solubility is; the larger the polymerization degree, the higher the film-forming strength and the poorer the solubility. Through practical research, the polymerization degree is 78-89%, and the polyvinyl alcohol with the polymerization degree of 1700-1900 is suitable for the slurry system.
Polyethylene glycol is also a high molecular compound with good water solubility, and has larger performance difference due to different molecular weights. In the slurry of the present invention, the polyethylene glycol has the functions of a softening agent and a smoothing agent. More importantly, the polyethylene glycol also has the function of promoting the combustion and volatilization of organic residues in the high-temperature desizing process. Polyethylene glycol is stable under normal conditions, but can be oxidized with oxygen in the air at 120 ℃ or higher, and can be cracked or thermally cracked when heated to 300 ℃, and decomposition products thereof are volatile, so that not only residual ash substances are not generated, but also superheated steam released in the desizing process has the effect of promoting combustion and volatilization of organic residues. Through practical research, the applicable molecular weight range of the polyethylene glycol is 1000-5000.
With the increasing production efficiency, the warping speed of the yarn is faster and faster, and the retention time of the yarn in the size box is gradually shortened. Therefore, the size formula needs to be added with a high-efficiency penetrating agent/wetting agent to reduce the surface tension of the size and enable the size to quickly and fully penetrate into the yarn to obtain the sized yarn with the specified sizing rate. The invention selects and uses acetylene glycol surfactant or acetylene alcohol surfactant which can be 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol and alkylene oxide addition product of 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol, and one or more ethylene oxide adducts of 2, 4-dimethyl-5-decyne-4-ol, 3, 6-dimethyl-4-octyne-3, 6-diol, 3, 5-dimethyl-1-hexyne-3-ol, and 2, 4-dimethyl-5-hexyne-3-ol. However, the surfactant may be a commercially available surfactant, and examples thereof include Dynol 604, 360, 607, 800, 810, 960, 980, surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, (all of the above product names are manufactured by Air Products and Chemicals Inc.), Olfin B, Y, P, A, STG, SPC, E1004, E1010, PD-001, EXP4001, EXP4036, EXP4051, AF-107, AF-104, AK-02, SK-14, AE-3 (all of the above Products are manufactured by Nikken chemical industries, Ltd.), AcetylenE 56, Acetylene E6300, 3600, and the above chemical company name 40 (all of the above Products manufactured by chemical industries, Ltd.).
In the production process, the glass fiber has high resistance and low water absorption, so static electricity formed by friction is not easy to eliminate, and static electricity accumulation is easy to generate. The antistatic agent is selected from ammonium salts of alkyl sulfonic acid, aryl sulfonic acid or alkyl aryl sulfonic acid; one or more of ammonium salts of alkyl phosphoric acid, aryl phosphoric acid or alkyl aryl phosphoric acid can play a role in lubrication, and can form ion conduction and antistatic.
The invention achieves the following beneficial effects:
(1) the sizing agent has good adhesion, stable size film formed after being adhered to glass fiber and dried, good wear resistance, less hairiness, no adhesion and no yarn twisting, and can obviously improve the strength of the glass fiber.
(2) The glass fiber cloth slurry has good desizing performance, can reduce the consumption of fuel and cost compared with the conventional slurry, and has less yellow spots and black spots generated in the smoldering process, so that the cloth cover quality of the glass fiber cloth is better.
(3) The invention carries out optimization design through the warp size formula, not only can protect warp and meet the requirements of high-speed weaving process, but also has the performance characteristics of easy desizing, small residual fat amount after high-temperature desizing and the like. The electronic-grade glass fiber cloth surface sizing agent produced by the sizing agent is easier to decompose and gasify, achieves the desizing effect with the lowest content of organic combustible materials on the cloth surface under the same desizing time and desizing temperature, can reduce the desizing time within the allowable range of the organic combustible materials on the electronic-grade glass fiber cloth surface, and saves energy.
(4) The dynamic and static surface tension of the slurry of the invention is <30mM/m, even <25 mM/m; the viscosity is less than or equal to 35mPa.s when measured at 25 ℃, and the low-foaming effect can be achieved without adding a defoaming agent into the slurry.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example l
The novel electronic grade glass fiber cloth slurry is prepared according to the proportion in the table 1.
Example 2
The novel electronic grade glass fiber cloth slurry is prepared according to the proportion in the table 1.
Example 3
The novel electronic grade glass fiber cloth slurry is prepared according to the proportion in the table 1.
The process of preparation of examples 1, 2 and 3, comprising the steps of:
(1) injecting a certain amount of pure water into the container, starting the stirrer, and slowly adding polyvinyl alcohol;
(2) heating to 90 deg.C, stirring for 1 hr, cooling to 70 deg.C, slowly adding polyethylene glycol, stirring for 30min, and observing to obtain clear slurry;
(3) then adding alkynol wetting agent, and stirring for 30min at a stirring speed of 150-300 r/mi until a stable milky white dispersion liquid is formed.
(4) And adding the residual pure water to adjust the slurry concentration, keeping the temperature of 30-70 ℃ for stirring at constant temperature, and finally filtering by using a filter element with the aperture of 1 mu to obtain the warp sizing slurry.
Comparative example 1
Electronic grade glass fiber cloth slurry was prepared according to the proportions in table 1.
Comparative example 2
Electronic grade glass fiber cloth slurry was prepared according to the proportions in table 1.
Comparative example 3
Electronic grade glass fiber cloth slurry was prepared according to the proportions in table 1.
The process of preparation of comparative examples 1, 2 and 3, comprising the steps of:
(1) injecting a certain amount of pure water into the container, starting the stirrer, and slowly adding polyvinyl alcohol;
(2) heating to 90 deg.C, stirring for 1 hr, cooling to 70 deg.C, slowly adding polyethylene glycol, stirring for 30min, and observing to obtain clear slurry;
(3) then adding the needed auxiliary agent into the polyvinyl alcohol water solution, and stirring for 30 min.
(4) And adding the residual pure water to adjust the slurry concentration, keeping the temperature of 30-70 ℃ for stirring at constant temperature, and finally filtering by using a filter element with the aperture of 1 mu to obtain the warp sizing slurry.
TABLE 1 slurry formulations of examples and comparative examples (wherein each raw material is in mass percentage, and the balance is pure water)
The electronic glass fiber cloth was sized using a conventional sizing method for the sizes prepared in examples and comparative examples, and the obtained glass fiber cloth was subjected to a performance test, the results of which are shown in table 2.
Table 2 results of performance test of examples and comparative examples
The above test data were tested according to the general statistical test method for electronic grade glass fiber products. The breaking strength was tested according to standard GB/T3923.1 using a model YG02B electronic fabric tensile machine. The method for measuring the residual amount of the cloth cover sizing agent comprises the following steps: taking cloth with a specified area, firstly placing the cloth in a 110 ℃ oven for 60 minutes, then placing the cloth in a dryer for 30 minutes, weighing W1, then placing the cloth in a 625 ℃ high-temperature furnace for 45 minutes, placing the cloth in the 110 ℃ oven for 15 minutes, cooling the cloth, placing the cloth in the dryer for 60 minutes, and then weighing W2. Residual amount = (W1-W2)/W1 × 100%.
As can be seen from the test results of the above examples and comparative examples, the electronic-grade glass fiber cloth prepared by the secondary sizing agent provided by the invention has better residual fat content after secondary desizing of the gray cloth than that of the comparative example, and the breaking strength is basically close to that of the comparative example.
Compared with the comparative example 1, the comparative example 2 and the comparative example 3, in the electronic-grade glass fiber cloth slurry used in the examples 1, 2 and 3, the addition amount of polyvinyl alcohol is reduced, and simultaneously, no defoaming agent is needed to be added, but the prepared slurry is thick for sizing the electronic glass fiber cloth, the hairiness of the electronic glass fiber cloth is small, the cloth cover quality is good, the desizing is easy, and the BH furnace smoldering time is reduced, so that the consumption of fossil fuel is reduced, the production energy consumption is reduced, and the production cost is saved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The secondary sizing slurry for the electronic glass fiber cloth is characterized by comprising the following components in percentage by mass: 3-15% of polyvinyl alcohol, 0-10% of polyethylene glycol, 0.02-2% of wetting agent, 0-0.5% of antistatic agent and the balance of pure water; the wetting agent is an acetylene glycol surfactant or acetylene alcohol surfactant.
2. The secondary sizing agent for electronic glass fiber cloth as recited in claim 1, wherein the alcoholysis degree of the polyvinyl alcohol is 78% -89%, and the polymerization degree is 1700-1900.
3. The secondary sizing agent for electronic glass fiber cloth as recited in claim 1, wherein the molecular weight of the polyethylene glycol is 1000-5000.
4. The secondary sizing agent for electronic glass fiber cloth according to claim 1, wherein the antistatic agent is an ammonium salt of an alkyl sulfonic acid, an aryl sulfonic acid or an alkyl aryl sulfonic acid, an ammonium salt of an alkyl phosphoric acid, an aryl phosphoric acid or an alkyl aryl phosphoric acid.
5. The secondary sizing slurry for electronic glass fiber cloth according to claim 1, wherein the dynamic and static surface tensions of the slurry are <35 mM/m.
6. The method for preparing the secondary sizing agent for the electronic glass fiber cloth according to any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) injecting a certain amount of pure water into the container, starting the stirrer, and slowly adding polyvinyl alcohol;
(2) heating to 90 deg.C, stirring for 1 hr, cooling to 70 deg.C, slowly adding polyethylene glycol, stirring for 30min, and observing to obtain clear slurry;
(3) then adding wetting agent, and stirring for 30min at a stirring speed of 150-300 r/mi until a stable milky white dispersion liquid is formed.
(4) And adding the residual pure water to adjust the slurry concentration, keeping the temperature of 30-70 ℃ for stirring at constant temperature, and finally filtering by using a filter element with the aperture of 1 mu to obtain the warp sizing slurry.
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| JP2023088244A (en) * | 2021-12-14 | 2023-06-26 | 日本エイアンドエル株式会社 | Composition for fiber sizing, and resin-impregnated fiber using the same, and molding |
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