WO2018036465A1

WO2018036465A1 - Inorganic surface-treated galvanized steel sheet, preparation method therefor, and aqueous inorganic surface treatment agent thereof

Info

Publication number: WO2018036465A1
Application number: PCT/CN2017/098430
Authority: WO
Inventors: 张剑萍; 张文麒; 戴毅刚
Original assignee: 宝山钢铁股份有限公司
Priority date: 2016-08-24
Filing date: 2017-08-22
Publication date: 2018-03-01
Also published as: EP3505655B1; EP3505655A4; EP3505655A1; CN107779853A; JP2019525007A; CN107779853B; JP6839755B2

Abstract

An environmentally-friendly inorganic surface-treated galvanized steel sheet, a preparation method therefor and an aqueous inorganic surface treatment agent thereof, capable of satisfying requirements of rapid deep-drawing treatment of progressive dies in the field of micromotors, and providing excellent red rust resistance performance and excellent surface conductivity for parts and components. An aqueous inorganic surface treatment agent comprising a single organic silane cross-linking agent containing hydrophobic groups, a system cross-linking agent, water-soluble nano sol, surface modified high-density polyethylene particles, tetraethyl orthosilicate modified oxidized graphene, a water-soluble fluorinated compound, a water-soluble phosphorous compound and a water-soluble metal salt compound are coated and cured on the surface of a galvanized steel sheet; the obtained inorganic surface-treated galvanized steel sheet has excellent red rust resistance performance, excellent surface conductivity, surface lubricating performance and excellent blackening resistance performance, and can satisfy requirements of rapid deep-drawing treatment and bare service of progressive dies, and the inorganic surface-treated galvanized steel sheet is especially applicable to the field of micromotors.

Description

Inorganic surface treatment galvanized steel sheet, preparation method thereof and aqueous inorganic surface treatment agent

Technical field

The invention belongs to the technical field of surface treatment of galvanized steel sheets, in particular to an inorganic surface treatment galvanized steel sheet, a preparation method thereof and an aqueous inorganic surface treatment agent, the inorganic surface treatment galvanized steel sheet according to the invention and a preparation method thereof The surface-treated galvanized steel sheet and the preparation method thereof can satisfy the rapid deep-drawing processing of the progressive die in the field of micro-motors, and at the same time have excellent red rust resistance and surface conductivity of the parts.

Background technique

Galvanized steel sheets are widely used in various fields such as automobiles, home appliances, and construction, and are often used as parts for automobiles, household appliances, and micro-motors. At the same time, the degree of mechanical automation has increased, making various types of micro-motors widely used in automobiles, processing machinery or electrical equipment.

However, due to the special requirements of micro-motor processing and service, there are several key issues in the process of warehousing, processing and service of galvanized steel sheets for micro-motors:

In order to prevent rust of galvanized steel sheet during transportation and storage, white rust is generated, and anti-rust oil should be applied when producing steel plate. In the process of stamping processing in micro-motor field, the rapid deep drawing process intensifies the mold and metal sheet. Friction and wear between the two, in order to prevent cracking of the sheet and scratches on the surface of the zinc layer, the parts should be lubricated to the mold during stamping and forming, and then degreased and cleaned after molding. In the service process of micro-motors, in order to ensure the service life, grounding safety and electromagnetic characteristics of micro-motors, the red rust resistance and surface conductivity of stamped parts are very high. The anti-red rust performance corresponds to the service life of the micro-motor, and the surface conductivity corresponds to the grounding safety and electromagnetic characteristics of the micro-motor. First of all, the use of anti-rust oil, lubricating oil and degreasing agent in the entire storage, transportation and stamping process of galvanized steel sheets is unfavorable to the environment and production costs.

In order to improve corrosion resistance and formability, the past method mainly involves chromic acid passivation surface treatment of galvanized steel sheets, which can improve the corrosion resistance of steel sheets, but has limited improvement in processing formability and other resistance. Can not meet the requirements of rapid deep drawing processing of micro-motor field progressive die; or coated with solid lubricating additives (usually low surface energy polymers such as polyolefin and poly four) based on chromate passivation The organic resin of vinyl fluoride) has both corrosion resistance and lubrication effect, but this type of organic film usually has low cohesive energy. When the micro-motor field is advanced deep-drawing, the organic film rubs against the surface of the mold, which easily leads to organic The film peels off between layers, which causes black chips or organic film peeling on the surface of the part, which not only affects the appearance of the stamped parts, but also the organic film debris that falls off adheres to the parts or molds, causing frequent cleaning of the mold many times, affecting Production efficiency of the stamping line. At the same time, in order to improve the surface conductivity of the part, a conductive auxiliary agent such as a strong polar compound, a metal powder or a carbon powder is usually added to the film. However, these conductive additives are detrimental to the corrosion resistance of the film, which greatly reduces the corrosion resistance of the film and thus affects the service life of the parts. At the same time, with the continuous promulgation of environmental protection directives, chromium-containing galvanized steel sheets have gradually been replaced by environmentally friendly products that do not contain chromium.

At present, chromium-free environmentally friendly products can be roughly classified into inorganic type and organic/inorganic composite type according to the type of surface treatment. The inorganic lubricating film is mainly a film containing inorganic compounds such as silicon, manganese, phosphorus, etc., and the inorganic film has high cohesive energy, and the inorganic lubricating film is not likely to be delaminated and the film is peeled off due to friction of the mold during the pressing process. Therefore, this type of product can also obtain a good appearance after deep drawing processing, but the inorganic lubricating film can not significantly improve the corrosion resistance of the galvanized steel sheet, and does not have good surface conductivity, and cannot Used in areas where the grounding safety and electromagnetic characteristics of parts are required. The organic/inorganic composite lubricating film is a composite film of a resin, a corrosion inhibitor, a silane coupling agent, a silica colloid, and a solid lubricating agent, and has excellent lubricity and corrosion resistance, and Various chemical media have good resistance such as fingerprint resistance and alkali resistance. However, the content of organic resin in the organic/inorganic composite lubricating film is high, and the low cohesive energy of the organic resin tends to cause interlayer peeling of the organic film in the rapid deep drawing process of the micro-motor field, which leads to the surface of the part. The black shavings or organic film peeling off not only affects the appearance of the stamped parts, but also the organic polymer debris that falls off adheres to the parts or molds, causing frequent cleaning of the mold and affecting the efficiency of the stamping line. At the same time, the organic/inorganic composite lubricating film usually does not have excellent surface electrical conductivity, and cannot be used in a field where the grounding safety and electromagnetic characteristics of parts are required to be high. Therefore, the current chromium-free environmentally friendly products (including inorganic and organic/inorganic composite types) cannot meet the requirements of high-speed deep-drawing characteristics, red rust resistance and surface conductivity of the micro-motor field.

Chinese Patent Publication No. CN 101376859A discloses the use of an inorganic treating agent containing manganese, nickel, phosphate ions and silane to form a thin transparent inorganic solid film on the surface of a galvanized steel sheet, which can improve the stamping forming property of the galvanized steel sheet. Eliminate or reduce the viscous zinc in galvanized steel sheets during stamping With the phenomenon of powdered shedding. Chinese Patent Publication No. CN 1177020A China Authorized Patent is a lubricating steel sheet containing a protective film containing silicic acid or silicate on a steel sheet having fine irregularities on its surface, and its film coverage is about 60%, which has phosphatability and good properties. Lubricity. All of the above patents give the steel plate good lubricity, but the corrosion resistance is not as good as that of the chromium-containing passivation product, and it cannot meet the requirements of the micro-motor for the red rust resistance of the material.

Chinese Patent Publication No. CN 101787527A provides a galvanized steel sheet having excellent processability and alkali resistance and solvent resistance, the surface of which is covered with an organic/inorganic composite protective film containing an aqueous cationic polyurethane resin, one or one. More than one organosilane coupling agent, as well as corrosion inhibitors and oxidized polyethylene particles. The protective film imparts excellent press formability, solvent resistance, and alkali resistance to the surface of the galvanized steel sheet, and at the same time, the galvanized steel sheet has excellent corrosion resistance and coating adhesion. However, in fact, the micro-motor has high requirements on the surface conductivity. The organic/inorganic composite protective film does not have excellent surface electrical conductivity, and cannot be used in a field where the grounding safety and electromagnetic characteristics of parts are required to be high.

The Chinese Patent Publication No. CN 101394998A patent provides a coated steel sheet excellent in bending workability, press formability, solvent resistance, chemical resistance, corrosion resistance, and having a good surface appearance and sufficient coating film hardness. However, the steel plate is a single-layer thick coating product with a film thickness of 2-10 micrometers, and the manufacturing process is a two-step process, first forming a chemical conversion film containing no chromium, and then coating a polyester resin, that is, a post-treatment film needs to pass Two coatings, two baking, usually the second baking is required to be heated at a steel plate temperature of 170-250 ° C. The patent requires relatively high production equipment, and does not have surface conductivity, not suitable for micro The field of motors.

Summary of the invention

In view of the above situation, the present invention aims to provide an inorganic surface-treated galvanized steel sheet, a preparation method thereof and an aqueous inorganic surface treatment agent thereof, wherein the inorganic surface-treated galvanized steel sheet and an aqueous inorganic surface treatment agent thereof are environmentally friendly and chrome-free It can meet the rapid deep-drawing processing of micro-motor field progressive die, and at the same time, it has excellent red rust resistance and surface conductivity to meet the environmental protection, surface conductivity and red rust resistance of galvanized steel sheets for users in the field of micro-motors. And fast stamping processability requirements.

In order to solve the problems existing in the prior art, it has been painstakingly found that by coating a surface of a galvanized steel sheet, a single organosiloxane containing a specific hydrophobic group, a plurality of orthosilicates used as a system crosslinking agent, or a plurality of diorganosiloxanes having a bridging structure, one or more aqueous nanosols, one or The inorganic surface-treated galvanized steel sheet formed by various solid lubricating particles, orthosilicate-modified graphene oxide, fluorine-containing compound, phosphoric acid compound and metal salt compound having specific structure has excellent press processing performance and can satisfy The invention is completed by the requirement of rapid deep drawing processing of the progressive die, and at the same time, excellent surface electrical conductivity and red rust resistance of the parts, thereby solving the problems of the prior art.

Meanwhile, the present invention also provides an environmentally-friendly aqueous inorganic surface treatment agent for producing the above surface-treated galvanized steel sheet.

The technical scheme of an inorganic surface-treated galvanized steel sheet of the present invention is as follows:

An inorganic surface-treated galvanized steel sheet is coated on the surface of a galvanized steel sheet with a single-layer inorganic film having a thickness of 0.3-1.0 μm, wherein

The inorganic film contains:

A) one or more hydrophobic monoorganosilane coupling agents in an amount of 40-60 parts by weight in the inorganic film;

The hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;

B) the system cross-linking agent, the weight fraction in the inorganic film is 10-30 parts;

The system crosslinking agent is one or more of orthosilicate, titanate or a diorganosilane coupling agent having a bridging structure;

C) a water-soluble nano sol in an amount of 5-15 parts by weight in the inorganic film;

The water-soluble nano sol has a mass fraction of 20-30%;

D) surface-modified high-density polyethylene particles in the inorganic film in parts by weight of 10-25 parts;

E) orthosilicate-modified graphene oxide, wherein the weight fraction of graphene oxide in the inorganic film is 0.05-0.5 parts;

The orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%.

An inorganic surface-treated galvanized steel sheet according to the present invention, characterized in that

The inorganic film further contains:

F) a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;

G) a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;

H) A water-soluble metal salt compound in which the metal element is contained in an amount of 0.1 to 2.5 parts by weight in the inorganic film.

According to the invention, it is preferred that

According to the invention, the hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) is selected from the group consisting of -CH ₃ (methyl), -C ₂ H ₅ (ethyl), -C ₃ H ₇ (propyl) ), -C ₆ H ₅ (phenyl), -CF ₃ (perfluoromethyl), -C ₂ F ₅ (perfluoroethyl), -C ₃ F ₇ (perfluoropropyl), -C ₅ F One or two of ₁₁ (perfluoropentyl), -C ₇ F ₁₅ (perfluoroheptyl) or -C ₉ F ₁₉ (perfluorodecyl);

According to the present invention, the reactive group in the hydrophobic monoorganosilane coupling agent is selected from the group consisting of -OCH ₃ (methoxy), -OC ₂ H ₅ (ethoxy), vinyl, propenyl, epoxy One to three of an amino group, a hydroxyl group, a carboxyl group, an amide group or a 2,3-epoxypropoxy group;

According to the present invention,

The sum of the number of hydrophobic groups and the number of reactive groups in the hydrophobic monoorganosilane coupling agent is equal to four;

The hydrophobic monoorganic silane coupling agent is contained in the inorganic film in an amount of 40 to 60 parts by weight, preferably 45 to 55 parts by weight.

According to the invention, it is preferred that

The system cross-linking agent (B) may be a tetrasilicate having 4 reactive groups, a titanate having 4 reactive groups, or a double-bridged structure having 6 reactive groups. One or more of organosilane coupling agents;

The reactive group in the orthosilicate is selected from any one of a methoxy group, an ethoxy group, a propoxy group or a butoxy group;

The reactive group in the titanate is selected from one or more of an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl ester group;

The bridging structure of the bis-organosilane coupling agent is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups;

The reactive group of the bis-organosilane coupling agent is selected from any one of a methoxy group, an ethoxy group or a propoxy group.

According to the invention, it is preferred that

The aqueous nanosol (C) is an aqueous inorganic oxide or a metal oxide sol;

The aqueous nanosol is selected from one or more of an aqueous silica sol, an aqueous titanium dioxide sol, an aqueous zirconia sol or an aqueous alumina sol.

According to the invention, it is preferred that

The surface-modified high-density polyethylene particles (D) have a particle diameter of between 0.1 and 0.5 μm; the surface-modifying group is reactive, and is specifically selected from an amino group, a hydroxyl group, a carboxyl group, an epoxy group or a urethane. One or more of the bases;

According to the invention, it is preferred that

The number of layers of the orthosilicate-modified graphene oxide (E) layer is between 1-5 layers (thickness is between 0.35 nm and 1.75 nm); the size of the orthosilicate-modified graphene oxide is Between 2-5 microns, the aspect ratio of graphene is between 1100-14000.

According to the present invention, the orthosilicate in the orthosilicate-modified graphene oxide is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or butyl orthosilicate. Species

The orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of <3 and a silicon element content of 5-12%.

According to the invention, it is preferred that

The water-soluble fluorine-containing compound (F) is a fluorine-containing metal salt or a fluorine-containing acid, and is selected from the group consisting of sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate, hexafluorotitanate, and fluorosilicic acid. Kind or more.

According to the invention, it is preferred that

The water-soluble phosphorus-containing compound (G) is a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid. One or more of aluminum and ammonium polyphosphate.

According to the invention, it is preferred that

The water-soluble metal salt compound (H) is one or more of a titanium salt, a phosphonium salt, a phosphonium salt, a molybdenum salt, a tungsten salt, a cobalt salt, and a zirconium salt.

Specifically, the titanium salt is selected from one or more of ammonium fluorotitanate, hexafluorotitanate, titanium orthosulfate, titanium oxysulfate or titanium chloride.

Specifically, the onium salt is selected from one or more of cerium nitrate, barium sulfate, a fluorine-containing phosphonium salt, and a cerium ammonium complex salt.

Specifically, the onium salt may be one or more of barium chloride, barium sulfate, and barium nitrate.

Specifically, the molybdenum salt is selected from one or more of ammonium molybdate, magnesium molybdate or sodium molybdate.

Specifically, the tungsten salt is selected from one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate.

Specifically, the cobalt salt may be an inorganic cobalt salt such as cobalt nitrate, cobalt sulfate or cobalt chloride, or may be one or more of cobalt naphthenate, cobalt oxalate or cobalt stearate.

The zirconium salt may be one or more of potassium zirconium fluorophosphate, zirconium nitrate, and zirconium sulfate.

The above inorganic surface-treated galvanized steel prepared according to the invention has environmentally friendly chromium-free steel, can meet the rapid deep-drawing processing of the progressive die in the field of micro-motors, and has excellent red rust resistance and surface electrical conductivity at the same time.

The object of the present invention is also to provide a method for preparing an inorganic surface-treated galvanized steel sheet, which can satisfy the rapid deep-drawing processing of the progressive die in the field of micro-motors, and at the same time has excellent red rust resistance and surface conductivity of the parts, and the technology thereof The plan is as follows:

Method for preparing inorganic surface treated galvanized steel sheet, characterized in that

Dissolving or dispersing a component of an aqueous inorganic surface treatment agent in water to form an aqueous inorganic surface treatment agent, and applying the aqueous inorganic surface treatment agent to the surface of the galvanized steel sheet by one-time roll coating, and at 60-100 Drying between °C, so that the dry film thickness of the inorganic film is 0.3-1.0 microns,

The inorganic film contains:

The system crosslinking agent is selected from one or more of a orthosilicate, a titanate or a diorganosilane coupling agent having a bridging structure;

The water-soluble nano sol has a mass fraction of 20-30%;

A method for preparing an inorganic surface-treated galvanized steel sheet according to the present invention, characterized in that

The inorganic film further contains:

According to the method for producing an inorganic surface-treated galvanized steel sheet according to the present invention, it is preferred that

The hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) may be -CH ₃ (methyl), -C ₂ H ₅ (ethyl), -C ₃ H ₇ (propyl), -C ₆ H ₅ (phenyl), -CF ₃ (perfluoromethyl), -C ₂ F ₅ (perfluoroethyl), -C ₃ F ₇ (perfluoropropyl), -C ₅ F ₁₁ (perfluoro One or two of pentyl), -C ₇ F ₁₅ (perfluoroheptyl) or -C ₉ F ₁₉ (perfluorodecyl); a reactive group in the hydrophobic monoorganosilane coupling agent It may be -OCH ₃ (methoxy), -OC ₂ H ₅ (ethoxy), vinyl, propenyl, epoxy, amino, hydroxy, carboxyl, amide or 2,3-epoxypropoxy Up to three of them; the sum of the number of hydrophobic groups and the number of reactive groups in the hydrophobic monoorganosilane coupling agent is equal to four; the weight fraction of the hydrophobic monoorganosilane coupling agent in the inorganic film is 40-60 parts, preferably 45-55 parts.

According to the invention, it is preferred that

The system cross-linking agent (B) may be an orthosilicate having 4 reactive groups, and has 4 reactivity. a titanate of a group or one or more of a biorganosilane coupling agent having a bridging structure having 6 reactive groups; the reactive group in the orthosilicate may be methoxy Any one of a group, an ethoxy group, a propoxy group or a butoxy group; the reactive group in the titanate may be an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl group One or more of the ester groups; the bridging structure of the bis-organosilane coupling agent is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups; the double organosilane coupling agent The reactive group may be any one of a methoxy group, an ethoxy group or a propoxy group.

According to the invention, it is preferred that

The aqueous nanosol (C) is an aqueous inorganic oxide or metal oxide sol; the aqueous nanosol is selected from one of an aqueous silica sol, an aqueous titanium oxide sol, an aqueous zirconia sol or an aqueous alumina sol or A variety.

According to the invention, it is preferred that

The surface-modified high-density polyethylene particles (D) have a particle diameter of between 0.1 and 0.5 μm; the surface-modifying group has reactivity, specifically selected from amino, hydroxyl, carboxyl, epoxy or carbamic acid. One or more of the ester groups.

According to the invention, it is preferred that

According to the present invention, the orthosilicate in the orthosilicate-modified graphene oxide is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or butyl orthosilicate. Kind.

According to the invention, it is preferred that

The above inorganic surface-treated galvanized steel prepared by the method of the invention has the advantages of environmentally friendly and chrome-free, can meet the rapid deep drawing processing of the progressive die of the micro-motor field, and has excellent red rust resistance and surface conductivity of the parts at the same time.

The invention further provides an aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet, wherein the aqueous inorganic surface treatment agent can satisfy the rapid deep drawing processing of the progressive die in the micro-motor field, and at the same time, has excellent red rust resistance and surface conduction of the parts. Performance for galvanized steel sheets.

An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet for coating onto a surface of a galvanized steel sheet to form an inorganic film according to the present invention, characterized in that

The total solids in its aqueous solution contain the following ingredients:

The water-soluble nano sol has a mass fraction of 20-30%;

The orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%;

An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention, characterized in that

The aqueous nanosol (C) is an aqueous inorganic oxide or a metal oxide sol; the aqueous nanosol may be one of an aqueous silica sol, an aqueous titania sol, an aqueous zirconia sol or an aqueous alumina sol or A variety.

The surface-modified high-density polyethylene particles (D) have a particle diameter of between 0.1 and 0.5 μm; the surface-modifying group has reactivity, specifically an amino group, a hydroxyl group, a carboxyl group, an epoxy group or a urethane group. One or more of them;

The number of layers of the orthosilicate-modified graphene oxide (E) layer is between 1-5 layers (thickness is between 0.35 nm and 1.75 nm); the size of the orthosilicate-modified graphene oxide is Between 2-5 microns, the aspect ratio of graphene is between 1100-14000; the orthosilicate in the orthosilicate-modified graphene oxide may be methyl orthosilicate, tetraethyl orthosilicate, positive One or more of propyl silicate or butyl orthosilicate; the orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of <3 and a silicon element content of 5-12%.

The water-soluble fluorine-containing compound (F) is a fluorine-containing metal salt or a fluorine-containing acid. For example, the water-soluble fluorine-containing compound may be sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate or hexafluorocarbon. One or more of titanic acid and fluorosilicic acid.

The water-soluble phosphorus-containing compound (G) is a phosphate or a phosphoric acid. For example, the water-soluble phosphorus-containing compound may be orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, or the like. One or more of aluminum polyphosphate and ammonium polyphosphate.

The water-soluble metal salt compound (H) is one or more of a titanium salt, a cerium salt, a cerium salt, a molybdenum salt, a tungsten salt, a cobalt salt and a zirconium salt. For example, the titanium salt may be fluorine. One or more of ammonium titanate, hexafluorotitanate, titanium orthosulfate, titanium oxysulfate or titanium chloride; the cerium salt may be cerium nitrate, cerium sulfate, or a fluorinated cerium salt, or cerium ammonium One or more of the composite salts; the cerium salt may be one or more of cerium chloride, cerium sulfate and cerium nitrate; the molybdenum salt may be one of ammonium molybdate, magnesium molybdate or sodium molybdate Or a plurality of; the tungsten salt may be one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate; the cobalt salt may be an inorganic cobalt salt such as cobalt nitrate, cobalt sulfate or cobalt chloride, or It may be one or more of cobalt naphthenate, cobalt oxalate or cobalt stearate; the zirconium salt may be one or more of potassium zirconium fluorophosphate, zirconium nitrate and zirconium sulfate.

An inorganic surface-treated galvanized steel sheet according to the present invention, a preparation method thereof and an aqueous inorganic surface treatment agent,

The hydrophobic monoorganosilane coupling agent (A) in the aqueous inorganic surface treatment agent may be a mixture of one or more of the above monoorganosilanes, and is a main film-forming substance of the aqueous inorganic surface treatment agent of the present invention. In the present invention, the inorganic film formed by using the hydrophobic monoorganosilane coupling agent (A) as a main component has strong cohesive energy, and the cohesive effect of the inorganic film is remarkable. In the micro-motor field, when the die-feeding method is deep deep-drawing, the strong cohesive inorganic film can maintain the integrity of the film when the mold is severely rubbed, and prevent the inorganic film from peeling off or falling off, thus ensuring the parts are in the grade. The die has a good appearance after multiple stamping, and can also reduce the number of clearing lines of the stamping line and improve the production efficiency of the stamping line. However, the hydrophobic monoorganosilane coupling agent (A) in the present invention itself has remarkable hydrophobic properties, but the reactive group contained in the monoorganosiloxane may react with water to form an excellent hydrophilic property. a hydrophilic group such as a hydroxyl group, a carboxyl group or an amino group; or capable of reacting with a system crosslinking agent in an aqueous inorganic surface treatment agent to enter an aqueous system, so that the hydrophobic monoorganosilane coupling agent (A) can be in an aqueous system Stable dissolution or dispersion.

In order for the formed inorganic film to have excellent corrosion resistance, it is required that the inorganic film has a high degree of crosslinking. The main film-forming substance in the inorganic film, the hydrophobic monoorganosilane coupling agent (A) needs to be cross-linkable with other components in the film such as the system crosslinking agent (B) and the aqueous nano-sol (C), thereby Increase the crosslink density of the film. Therefore, in order to ensure excellent reactivity of the hydrophobic monoorganosilane coupling agent (A) used in the present invention, the hydrophobic monoorganosilane coupling agent (A) must contain two or more. Reactive group. The reactive group may be one or more of -OCH ₃ (methoxy) and -OC ₂ H ₅ (ethoxy) which are first reacted with water to form a hydroxyl group and then reacted with other substances (B and C). Or one or more of an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an amide group, and a 2,3-epoxypropoxy group capable of directly reacting with other substances (B and C); One or more of a vinyl group and a propenyl group in which polymerization occurs.

In order to ensure that the surface of the part after the rapid blasting of the progressive die is white, the non-broken inorganic film or zinc powder adheres to the surface of the part, that is, the surface of the part is required to have "non-stick" characteristics, corresponding to the surface of the steel plate and only the inorganic film exists. The possibility of "non-stick" features. After painstaking research and many attempts, it was found that the hydrophobic monoorganosilane coupling agent was formed by introducing a hydrophobic group into a conventional monoorganosilane coupling agent to form a hydrophobic monoorganosilane coupling agent (A). The hydrophobic group in (A) can migrate to the surface of the film during the curing process of the film, forming a very thin hydrophobic layer on the surface of the inorganic film, thereby reducing the surface polarity and Gibbs free energy of the inorganic film, and reducing the inorganic film pair. The adhesion of zinc powder, impurities and broken film makes the surface of the inorganic film have "non-stick" characteristics, so as to ensure that the surface of the part is cleaned after rapid deep drawing of the progressive die, and no broken inorganic film or zinc powder adheres to the surface of the part.

Considered synthetically, an inorganic surface-treated galvanized steel sheet according to the present invention, a preparation method thereof and an aqueous inorganic surface treatment agent,

In the present invention, the hydrophobic monoorganic silane coupling agent (A) should have both a reactive group and a hydrophobic group, and the sum of the number of reactive groups and the number of hydrophobic groups should be 4. In order to ensure that the hydrophobic monoorganosilane coupling agent (A) of the present invention has sufficient reactivity to achieve a certain crosslinking density after baking and curing, the number of reactive groups should be greater than or equal to two (ie, Is available for two or three). Therefore, the number of hydrophobic groups capable of providing "non-stick" characteristics to the hydrophobic monoorganosilane coupling agent (A) is (the number of 4-reactive groups), which is indicative of the hydrophobic monoorganosilane of the present invention. The number of hydrophobic groups in the coupling agent (A) may be one or two. The hydrophobic group in the above hydrophobic monoorganosilane coupling agent (A) may be a short-chain hydrocarbon group such as -CH ₃ (methyl), -C ₂ H ₅ (ethyl), -C ₃ H ₇ (propyl) Or -C ₆ H ₅ (phenyl); may also be a fluorine-containing hydrophobic group such as -CF ₃ (perfluoromethyl), -C ₂ F ₅ (perfluoroethyl), -C ₃ F ₇ ( Perfluoropropyl), -C ₅ F ₁₁ (perfluoropentyl), -C ₇ F ₁₅ (perfluoroheptyl) or -C ₉ F ₁₉ (perfluorodecyl). The hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) in the present invention may be any one or any two of the above groups.

In summary, the inorganic surface-treated galvanized steel sheet according to the present invention, the preparation method thereof and the aqueous inorganic surface treatment agent,

In the present invention, the hydrophobic monoorganosilane coupling agent (A) structure should have both a reactive group (two or three) and a hydrophobic group (one or two), and the number of reactive groups and hydrophobicity The sum of the number of groups is 4. For example, a trimethoxymethylsilane coupling agent, a triethoxymethylsilane coupling agent, a tripropoxymethylsilane coupling agent, a trimethoxyethylsilane coupling agent, and a triethoxy group are mentioned. Ethylsilane coupling agent, tripropoxyethylsilane coupling agent, trimethoxypropylsilane coupling agent, triethoxypropylsilane coupling agent, tripropoxypropylsilane coupling agent, 3-aminopropyl-ethoxy-methylsilane coupling agent, N-(2-aminoethyl)-aminopropylmethyldimethoxysilane coupling agent, 1H, 1H, 2H, 2H-all Fluorinated trimethoxysilane coupling agent, 1H, 1H, 2H, 2H-perfluorodecyl triethoxysilane coupling agent, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane coupling Agent, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane coupling agent, methylphenyldiethoxysilane, diphenyldiethoxysilane, fluoromethyltrimethoxysilane, Fluoromethyltriethoxysilane, fluoromethylethoxydimethoxysilane, fluoroethyltrimethoxysilane, fluoroethyltriethoxysilane, 3-fluoropropylmethyldimethoxysilane , 3-fluoropropylmethyldiethoxysilane, 3-fluoropropyl Diethoxy silane. One type or two or more types of the above silane coupling agents can be used arbitrarily for the hydrophobic monoorganic silane coupling agent (A).

In the present invention, the hydrophobic monoorganosilane coupling agent (A) is contained in an amount of 40 to 60 parts by weight in the inorganic film. If it is less than 40 parts, the corrosion resistance and "non-stick" characteristics of the inorganic film are poor, and the poor corrosion resistance of the inorganic film may affect the red rust resistance of the stamped parts; the "non-stick" characteristics may cause the surface adhesion of the parts after punching. More impurities, affecting the appearance of parts after stamping. If it is more than 60 parts, the ductility of the inorganic film is deteriorated, and the inorganic film is liable to be cracked and peeled off during the molding process, resulting in a decrease in film formability.

The system cross-linking agent (B) used in the present invention has a large number of reactive groups which can be chemically bonded to the metal substrate and other components in the inorganic film, which can not only improve the inorganic film and the metal substrate. Adhesion, at the same time, can enhance the crosslink density of the inorganic film to enhance the corrosion resistance and stamping formability of the inorganic film, so that the parts after stamping have excellent red rust resistance and surface appearance.

The system crosslinking agent (B) in the present invention may be one or more of a orthosilicate, a titanate or a diorganosilane coupling agent having a bridging structure; and 4 of the orthosilicates a reactive group, wherein the reactive group may be any one of a methoxy group, an ethoxy group, a propoxy group or a n-butoxy group; the titanate has four reactive groups, and the reaction thereof The group may be one or more of an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl ester group; the double organosilane coupling agent means two in the same molecular structure The silane structure has 6 reactive groups on one molecule, and the number of reactive groups is larger than that of the conventional monoorganosilane coupling agent. The bis-organosilane coupling agent of the invention has a bridging structure, and the bridging structure is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups; the reactive group of the bis-organosilane coupling agent may be Any one of a methoxy group, an ethoxy group or a propoxy group.

The orthosilicate used in the system cross-linking agent (B) in the present invention may be methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate or isopropyl orthosilicate. One or more; the titanate used in the system cross-linking agent (B) in the present invention may be tetraisopropyl orthotitanate, isopropyl tris(dioctylphosphoryloxy) titanate, Isopropyl trioleic acid oxy titanate, tetraisopropyl bis(dioctylphosphite oxy) titanate, bis(dioctyloxypyrophosphate) ethylene titanate, different One or more of propyl tris(dodecylbenzenesulfonyl) titanate, tetra-tert-butyl orthotitanate or diisopropyl bis(triethanolamine)titanate; system crosslinker in the present invention (B) The diorganosilane coupling agent used may be 1,2-bistrimethoxysilylethane, 1,2-bisethoxysilylethane, bis-(γ-triethoxy) One or more of silyl propyl) tetrasulfide, bis-[γ-(triethoxysilyl)propyl]-disulfide, bis-(γ-trimethoxysilylpropyl)amine . The system crosslinking agent (B) used in the present invention may be any one or any of the above-mentioned orthosilicates, titanates and diorganosilane coupling agents.

In the present invention, the system crosslinking agent (B) is contained in an amount of 10 to 30 parts by weight in the inorganic film. If it is less than 10 parts, the crosslinking density of the inorganic film will be greatly reduced, thereby affecting the corrosion resistance of the inorganic film, and finally The red rust resistance of the stamped parts is poor. If it is higher than 30 parts, due to the compatibility of the selected system cross-linking agent with water, more system cross-linking agents will affect the stability of the aqueous inorganic surface treatment agent, which will result in obvious treatment agent after a long time. The stratification phenomenon causes a large decrease in the overall performance of the aqueous inorganic surface treatment agent.

The water-soluble nano sol (C) used in the present invention is preferably a water-soluble colloid having a particle diameter of 5 to 50 nm, and the kind thereof may be an aqueous inorganic oxide or a metal oxide sol, and specifically may be aqueous two. One or more of a silica sol, an aqueous titania sol, an aqueous zirconia sol or an aqueous alumina sol. The crosslinking density of the inorganic film can be further increased by a large number of reactive groups in the aqueous nanosol, thereby enhancing the corrosion resistance of the inorganic film. At the same time, the fine particles formed by baking and solidifying the aqueous nano-sol have higher hardness, which can effectively improve the scratch resistance of the inorganic film and avoid surface scratches on the parts after stamping.

The water-soluble nano sol (C) used in the present invention may be an aqueous silica sol such as SNOWTEX-40, SNOWTEX-50, SNOWTEX-C, SNOWTEX-N, SNOWTEX-O, SNOWTEX-OL, SNOWTEX of Nissan Chemical Co., Ltd. -ZL and SNOWTEX-UP; LUDOX-AM, LUDOX-AS, LUDOX-CL, LUDOX-DF, LUDOX-HS, LUDOX-LS, LUDOX-SK, LUDOX-SM, LUDOX-TM and LUDOX-TMA ADELITE AT-20N or ADELITE AT-20A of Asahi Chemical Co., Ltd.; the water-soluble nano sol (C) used in the present invention may also be an aqueous titanium dioxide sol, such as Shenzhen Yoshida Chemical MTI-2080; Shanghai EFUT- GY01, EFUT-GY02, EFUT-GY03, etc.; the water-soluble nano sol (C) used in the present invention may also be an aqueous zirconia sol, such as VK-RJ80 of Xuancheng Jingrui, GT-360 of Yizheng Technology, UG03W, UG-R10W and UR-R30W of Suzhou Zirconium; the water-soluble nanosol (C) used in the present invention may be an aqueous alumina sol, such as SH-33 of Qingdao Shankehaitai, LA of Jinan Fujing -20, Shanghai Yifu's EFUAL-Y10C, EFUAL-Y10S, EFUAL-Y20C, EFUAL-Y20S, EFUAL-Y30C and EFUAL-Y30S. Aqueous nano-solutions used in the present invention As the gum (C), any one or any of the above aqueous silica sol, aqueous titania sol, aqueous zirconia sol or aqueous alumina sol can be used.

The aqueous nanosol (C) in the present invention accounts for 5 to 15 parts by weight in the inorganic film. If it is less than 5 parts, the surface hardness of the inorganic film is greatly lowered, thereby affecting the scratch resistance of the inorganic film, resulting in the inorganic film being easily damaged during the press forming process. If it is more than 15 parts, the nanotechnology in the inorganic film is too much, and the ductility of the film is deteriorated, resulting in a decrease in film formability.

The surface-modified high-density polyethylene particles (D) used in the present invention are commercially available solid lubricating particles. This type of lubricating agent has the characteristics of low surface energy, high lubricity and high surface hardness. It can form a hard lubricating layer on the surface of the inorganic film, which not only improves the scratch resistance of the inorganic film, but also enhances the inorganic film. The surface is smooth, and the purpose of strengthening the stamping formability of the inorganic film is achieved, so that it can meet the requirements of rapid deep drawing processing of the progressive die in the field of micro-motors. In the field of micro-motors, progressive die stamping usually exceeds 10 passes, and each pass of stamping causes frictional wear on the inorganic film of the present invention. To ensure the appearance and corrosion resistance of the stamped parts, the inorganic film of the present invention is required. It should have strong scratch resistance and ensure the integrity and excellent appearance of the film during the multi-pass stamping process. Through arduous research and trial, it has been found that, if it is necessary to ensure that the inorganic film of the present invention has the above properties, it is necessary to precisely control the distribution state of the composite lubricating particles used in the present invention in the inorganic film, so that the solid lubricating particles can be not only in the inorganic film. A small amount of surface aggregation also needs to be uniformly dispersed inside the inorganic film, so that the inorganic film has excellent scratch resistance in the entire thickness direction, thereby ensuring that the inorganic film can meet the multi-pass stamping requirements of the progressive die.

The surface-modified high-density polyethylene particles (D) used in the present invention are solid lubricating particles having a reactive group grafted on the surface, specifically one of an amino group, a hydroxyl group, a carboxyl group, an epoxy group or a urethane group. One or more, wherein the hydroxyl group and the carboxyl group can be obtained by immersing the high-density polyethylene particles in a strong oxidizing solution; the amino group and the urethane group can be passed through ethylenediamine, hexamethylenediamine or urethane with a high density The surface of the polyethylene particles is grafted; the epoxy group can be obtained by surface grafting of glycidyl methacrylate or allyl glycidyl ether with high density polyethylene particles. The above reactive group can react with the organosilane coupling agent in the treatment liquid to form a covalent bond, which not only strengthens the bonding strength between the high-density polyethylene particles and the inorganic film, but also binds the high-density polyethylene particles, thereby ensuring The high-density polyethylene particles can be uniformly dispersed in the inorganic film, and can provide excellent anti-wear properties in the entire thickness direction of the inorganic film, and improve the press workability and scratch resistance of the inorganic film. At the same time, chemical bonding between the high-density polyethylene particles and the film can delay the penetration of the corrosive medium along the surface of the high-density polyethylene particles into the film, and reduce the negative influence of the addition of the high-density polyethylene particles on the corrosion resistance of the inorganic film.

The surface-modified high-density polyethylene particles (D) used in the present invention have a particle diameter in the range of 0.1 to 0.5 μm, and if less than 0.1 μm, the surface-modified high-density polyethylene particles (D) do not occur in the inorganic film. To enhance the anti-scratch effect of the inorganic film; if it is higher than 0.5 μm, the surface-modified high-density polyethylene particles (D) are too large, and most of the particles are exposed on the surface of the film, and when subjected to punching friction, large particles are easily detached As a result, the press workability of the film is drastically lowered.

The surface-modified high-density polyethylene particles (D) used in the present invention are 10-25 parts by weight in the inorganic film. If less than 10 parts, the surface of the inorganic film is insufficient in lubricity and scratch resistance; if more than 25 parts, too much surface-modified high-density polyethylene particles (D) are present in the inorganic film, and the corrosive medium may be along the surface. The modified high-density polyethylene particles (D) interface penetrates into the inorganic film to reduce the corrosion resistance of the inorganic film.

The inorganic surface-treated galvanized steel sheet of the invention needs to have good surface electrical conductivity, and can discharge the static electricity generated during the actual operation of the stamped and formed parts through the surface thereof, thereby preventing a large amount of static electricity from being zero. The surface area of the piece is concentrated, which affects the safety and electromagnetic properties of the part and affects the normal use of the part. Through painstaking research and experimentation, it was found that by using the excellent electrical conductivity of the graphene sheet, adding an appropriate amount of graphene sheets to the inorganic film of the galvanized steel sheet can significantly improve the surface conductivity of the inorganic surface-treated galvanized steel sheet of the present invention.

Further, the above graphene sheet layer needs to be stably present in the aqueous inorganic surface treatment agent for a long period of time, and no agglomeration, precipitation, and precipitation occur. However, due to the large van der Waals force between the sheets, the graphene sheets are particularly prone to agglomeration between the graphene sheets, and are not easily dispersed uniformly in the aqueous inorganic surface treatment agent. Therefore, it is necessary to modify the surface of the above graphene sheets. By introducing other substances to destroy the surface van der Waals force, the graphene sheets are peeled off from each other, so that they can be stably present in the aqueous inorganic surface treatment agent for a long time. In order for the graphene sheet layer to be stably present in the aqueous inorganic surface treatment agent in the present invention for a long period of time, the graphene surface-modified substance is further limited. In view of the fact that the main component of the aqueous inorganic surface treatment agent of the present invention is mostly a silicon-containing substance such as a hydrophobic monoorganosilane coupling agent (A), a system crosslinking agent (B), and a water-soluble nano sol (C), Further improving the dispersibility of the graphene sheet layer and strengthening the compatibility of the graphene sheet layer and the aqueous inorganic surface treatment agent, the present invention uses the orthosilicate as a modifying substance and propanol as a solvent to surface the graphene sheet layer. modified.

The graphene sheet layer used in the present invention has a sheet structure and may be a single layer or a plurality of layers. When the graphene is a plurality of layers, the number of sheets is preferably 5 or less (the thickness of the sheet is between 0.35 and 1.75 nm). Further, the graphene sheet layer used in the present invention has a sheet diameter of 2 to 5 μm and a graphene diameter to thickness ratio of 1100 to 14,000. By controlling the number of graphene oxide layers to 5 or less and the sheet diameter to 2 to 5 μm, graphene can maintain excellent electrical conductivity and easily form a conductive network in the inorganic film, thereby improving the surface conductivity of the inorganic film.

The surface of the graphene sheet layer used in the present invention is modified with orthosilicate, and a method known for its use can be used. For example, first, the graphite oxide can be ultrasonically dispersed for 1 hour by immersing the graphite oxide in a strong oxidizing solution (such as a concentrated sulfuric acid/potassium permanganate mixed solution, a concentrated sulfuric acid/concentrated nitric acid mixed solution) at 70-80 ° C, and then filtered. And washed with a large amount of deionized water to neutral, to obtain a graphene oxide sheet; further, the graphene oxide sheet, orthosilicate and propanol were stirred and mixed at 100 ° C for 24 h and then filtered. The silicate-modified graphene oxide is obtained; secondly, propanol is used, and the orthosilicate-modified graphene oxide is diluted to a mass fraction of 1-5%.

The orthosilicate-modified graphene oxide used in the present invention may be a tetrasilicate orthosilicate, a tetraethyl orthosilicate or a butyl orthosilicate. One or more. In the present invention, the orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of <3, and the silicon element content is between 5-12%.

The orthosilicate-modified graphene oxide surface grafted orthosilicate of the invention not only can improve the dispersion stability coefficient of graphene oxide in the aqueous inorganic surface treatment agent system, prevent agglomeration or precipitation thereof, and can also enhance graphite oxide. The chemical bonding reaction between the olefin and the hydrophobic monoorganosilane coupling agent (A), the system crosslinking agent (B) and the water-soluble nano sol (C), so that the graphene oxide is more likely to form a conductive network in the inorganic film. Enhance the effect of graphene oxide on the surface conductivity of inorganic membranes. Further, the sheet-structured graphene oxide is uniformly dispersed inside the inorganic film, and when the corrosive medium penetrates into the inorganic film, the graphene oxide sheet layer can increase the permeation path of the corrosive medium, thereby providing excellent physical protection. Greatly improve the corrosion resistance of the film. At the same time, the graphene oxide sheet is carbon-carbon covalently bonded between the atoms, has excellent mechanical properties, and has good resistance to wear and damage of external objects, thereby improving the scratch resistance of the inorganic film. effect.

The orthosilicate-modified graphene oxide used in the present invention is calculated by using graphene oxide in an amount of 0.05 to 0.5 parts by weight in the inorganic film. If less than 0.05 parts, that is, when the graphene oxide is less, the graphene oxide has no obvious improvement on the surface conductivity of the inorganic film; if it is higher than 0.5 part, that is, when the graphene oxide is more, the inorganic film is affected by the graphene oxide. Dark, affecting the appearance. At the same time, a large amount of graphene oxide is also prone to agglomeration, which reduces the surface quality of the inorganic film.

The fluorine-containing compound used in the present invention is water-soluble, and may be a fluorine-containing metal salt or a fluorine-containing acid. For example, the fluorine-containing compound may be one or more of sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate, hexafluorotitanate, and fluorosilicic acid. The mass fraction in the inorganic film is from 1 to 4 parts, calculated as the fluorine element in the fluorine-containing compound. If the mass fraction of fluorine is less than 1 part, that is, when the fluorine content is small, the corrosion resistance of the inorganic film may decrease; if the mass fraction of fluorine is more than 4 parts, that is, the fluorine compound When more, the stability of the aqueous inorganic surface treatment agent may be deteriorated.

The phosphorus-containing compound used in the present invention is water-soluble, and may be a phosphate or a phosphoric acid. For example, the phosphorus-containing compound may be one or more of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, three-way metaphosphoric acid, ammonium phosphate, aluminum tripolyphosphate, and ammonium polyphosphate. The amount of the mass fraction in the inorganic film is from 0.5 to 4 parts, calculated as the phosphorus element in the phosphorus-containing compound. If the mass fraction of phosphorus is less than 0.5 parts, that is, when there are less phosphorus compounds, there is no effect of addition, and the corrosion resistance of the inorganic film may decrease; if the mass fraction of phosphorus is more than 4 parts, That is to say, when there are many phosphorus-containing compounds, the adhesion of the inorganic film may be deteriorated.

The metal salt compound used in the present invention is a water-soluble salt, and may be one or more of a titanium salt, a phosphonium salt, a phosphonium salt, a molybdenum salt, a tungsten salt, a cobalt salt, and a zirconium salt. For example, the titanium salt may be one or more of ammonium fluorotitanate, hexafluorotitanate, titanium orthosulfate, titanium oxysulfate or titanium chloride; the cerium salt may be cerium nitrate, cerium sulfate, or a fluorine-containing cerium salt or one or more of cerium ammonium composite salts; the cerium salt may be one or more of cerium chloride, cerium sulfate and cerium nitrate; the molybdenum salt may be ammonium molybdate or molybdic acid One or more of magnesium or sodium molybdate; the tungsten salt may be one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate; the cobalt salt may be cobalt nitrate, cobalt sulfate or chlorine The inorganic cobalt salt such as cobalt may also be one or more of cobalt naphthenate, cobalt oxalate or cobalt stearate; the zirconium salt may be one or more of potassium zirconium fluorophosphate, zirconium nitrate and zirconium sulfate. Kind. The metal salt compound can react with the galvanic layer on the surface of the galvanized steel sheet and the hydroxyl groups of other components in the aqueous inorganic surface treatment agent to form a metal bond having a high bond energy, forming a thin structure dense metal on the surface of the galvanized layer. The salt conversion film physically shields the direct contact between the steel plate and the corrosive medium, reduces the possibility of corrosion of the steel plate, and significantly improves the anti-film erosion resistance of the steel plate. The amount of the mass in the film is 0.1 to 2.5 parts, calculated as the metal element. If the mass fraction of the rare earth element is less than 0.1 part, that is, when the metal salt compound is small, there is no effect of addition, and the corrosion resistance and adhesion of the inorganic film may be lowered; if the mass fraction of the rare earth element is more than 2.5 parts When the metal salt-containing compound is contained, the stability of the aqueous inorganic surface treatment agent may be deteriorated, which may affect the quality of the inorganic surface-treated galvanized steel sheet.

The invention provides a method for manufacturing an environmentally-friendly inorganic surface-treated galvanized steel sheet which can satisfy the rapid deep-drawing processing of the progressive die in the micro-motor field and has excellent red rust resistance and surface electrical conductivity. The drying temperature of the steel plate is between 60-120 °C. If it is lower than 60 °C, the crosslinking reaction of the inorganic film is insufficient, which may cause the properties of the inorganic film to decrease. If it is higher than 120 °C, the middle part of the aqueous inorganic surface treatment agent is grouped. Sub-performance changes may affect the film formation effect.

The water inorganic surface treatment agent of the invention is applied on the surface of a galvanized steel sheet, and the dry film thickness thereof is between 0.3 and 1 micrometer. When the thickness is less than 0.3 micrometer, the inorganic film may be thinned, which may cause the stamping processability of the inorganic film. The red rust resistance is reduced, and when the inorganic film thickness exceeds 1 micrometer, the surface treatment cost per unit area is increased.

The heat drying method of the aqueous inorganic surface treatment agent applied to the surface of the galvanized steel sheet is not particularly limited, and may be hot air heating, induction heating, infrared heating or the like. The size, shape, and the like of the galvanized steel sheet are not particularly limited in the present invention. The galvanized steel sheet which can be used in the present invention may be an electroplated pure zinc steel sheet, a hot dip galvanized pure steel sheet, a hot dip galvanized aluminum steel sheet, or an alloyed hot dip galvanized steel sheet.

In an open environment, the aqueous inorganic surface treatment agent of the present invention can form an inorganic film on the surface of the galvanized steel sheet by coating and low temperature rapid curing (less than 100 ° C), and the galvanized steel sheet coated with the inorganic film It is required to meet the requirements of rapid die-cutting of the progressive die, such as non-clamping, part appearance, dimensional accuracy and surface cleanliness, as well as excellent red rust resistance, surface conductivity and non-adhesive properties of the film. . Specifically, stamping without clamping requires that the parts can be naturally separated from the die by gravity after rapid stamping (the stamping parts cannot be naturally detached if the stamped parts are stuck on the die of a certain stage of the progressive die), Therefore, the parts that are naturally detached automatically enter the next stamping station under the tapping traction; the appearance of the parts after stamping requires no surface defects such as stamping blackening, stamping and brightening, stamping and scratching, and black dot stripping on the surface of the stamped part. The surface of the parts is white, no broken film or zinc powder is attached to the surface; the red rust resistance of the parts mainly refers to the red rust on the surface of the stamped parts to evaluate the corrosion resistance of the parts. The excellent red rust resistance ensures that the materials can be used barely. Post-coating; surface conductivity mainly means that the surface of the galvanized steel sheet coated with the inorganic film should have certain electrical conductivity to ensure the grounding safety and electromagnetic characteristics of the molded part.

Compared with the prior art, the beneficial effects of the present invention:

1) The present invention uses a hydrophobic monoorganosilane coupling agent having both a hydrophobic group and a reactive group as a main film-forming substance, and the inorganic film further has a hydrophobic and low surface on the basis of excellent red rust resistance. The ability to achieve the "non-stick" nature of the inorganic film allows it to maintain excellent surface cleanliness after rapid deep drawing of the progressive die.

2) The invention adopts a system cross-linking agent having a plurality of reactive groups and a water-soluble nano sol, further strengthens the degree of cross-linking of the inorganic film in three dimensions, thereby making the inorganic film resistant to red rust, hardness and abrasion resistance. The performance has been greatly improved.

3) The reactive group in the surface-modified high-density polyethylene particles of the present invention can react with various main components in the treatment liquid to form a covalent bond, which can not only strengthen the bonding strength between the high-density polyethylene particles and the inorganic film. It is also capable of restraining high-density polyethylene particles, thereby ensuring that high-density polyethylene particles can be uniformly dispersed in the inorganic film, providing excellent wear resistance in the entire thickness direction of the inorganic film, improving the punching processability and scratch resistance of the inorganic film. performance.

4) The present invention uses a graphitic structure of 5 layers or less of graphene oxide, and grafts orthosilicate on the surface thereof, improves the dispersion stability of graphene oxide in an aqueous inorganic surface treatment agent system, and enhances graphene oxide and water. Chemical bonding reaction of hydrophobic monoorganic silane coupling agent (A), system crosslinking agent (B) and water-soluble nano sol (C) in inorganic surface treatment system, so that graphene oxide is more easily formed in inorganic film The conductive network enhances the effect of graphene oxide on the surface conductivity of the inorganic film.

5) The aqueous inorganic surface treatment agent of the invention does not contain chromium, and is an environmentally-friendly surface treatment agent. After surface treatment of the galvanized steel sheet, the galvanized steel sheet can satisfy the rapid deep-drawing processing of the progressive die in the field of micro-motors, and at the same time Excellent parts with red rust resistance and surface conductivity.

Specific implementation

The present invention will be further described below in conjunction with the embodiments. However, the scope of the invention is not limited by the embodiments. In the following examples and comparative examples, the galvanizing materials used, the surface cleaning method, and the aqueous inorganic surface treatment agent were described below.

Example

(1) Substrate

The types of substrates used are shown in Table 1. As the substrate coated with the inorganic film, mild steel having a thickness of 0.5 mm was used. Use an alkaline degreaser with a mass fraction of 2% for the substrate in Table 1 (brand: FC-364S, Shanghai Paka 濑 fine production) aqueous solution for spray cleaning. Aqueous solution temperature: 50 ° C; spray time: 60 seconds. Then, it was washed with industrial pure water to remove the alkaline component remaining on the surface, and dried by a blower for use.

Table 1 substrate

序号Serial number	样板种类Sample type	备注Remarks
S1S1	电镀纯锌钢板Electroplated pure zinc plate	镀层重量20/20g/m² Coating weight 20/20g/m ²
S2S2	热浸镀纯锌钢板Hot dip galvanized steel plate	镀层重量60/60g/m² Coating weight 60/60g/m ²
S3S3	热浸镀锌铝钢板Hot dip galvanized aluminum plate	镀层中Al：5wt％；镀层重量60/60g/m² Al: 5wt% in the coating; coating weight 60/60g/m ²
S4S4	合金化热浸镀锌钢板Alloyed hot dip galvanized steel sheet	镀层中Fe：10wt％；镀层重量45/45g/m² Fe: 10wt% in the coating; coating weight 45/45g/m ²

(2) Aqueous inorganic surface treatment agent

The aqueous inorganic surface treatment agent for forming an inorganic film is a hydrophobic type monoorganosilane coupling agent (Table 2), a system crosslinking agent (Table 3), a water-soluble nano sol (Table 4), and a surface-modified high-density polymerization. Ethylene particles (Table 5), orthosilicate-modified graphene oxide (Table 6), water-soluble fluoride (Table 7), water-soluble phosphide (Table 8), and water-soluble metal salt compounds (Table 9) were The blending amounts shown in Table 10 were blended, and the samples were prepared in accordance with the sample types and sample preparation conditions shown in Table 10.

Table 2 single organosilane coupling agent

序号Serial number	单有机硅烷偶联剂Monoorganosilane coupling agent
A1A1	三甲氧基甲基硅烷偶联剂Trimethoxymethylsilane coupling agent
A2A2	三乙氧基甲基硅烷偶联剂Triethoxymethylsilane coupling agent
A3A3	三丙氧基甲基硅烷偶联剂Tripropoxymethylsilane coupling agent
A4A4	三甲氧基乙基硅烷偶联剂Trimethoxyethylsilane coupling agent
A5A5	三乙氧基乙基硅烷偶联剂Triethoxyethylsilane coupling agent
A6A6	三甲氧基丙基硅烷偶联剂Trimethoxypropyl silane coupling agent
A7A7	三乙氧基丙基硅烷偶联剂Triethoxypropylsilane coupling agent
A8A8	3-氨丙基-乙氧基-甲基硅烷偶联剂3-aminopropyl-ethoxy-methylsilane coupling agent
A9A9	N-(2-氨乙基)-氨丙基甲基二甲氧基硅烷偶联剂N-(2-aminoethyl)-aminopropylmethyldimethoxysilane coupling agent
A10A10	1H，1H，2H，2H-全氟癸基三甲氧基硅烷偶联剂1H,1H,2H,2H-perfluorodecyltrimethoxysilane coupling agent

A11A11	1H，1H，2H，2H-全氟癸基三乙氧基硅烷偶联剂1H,1H,2H,2H-perfluorodecyltriethoxysilane coupling agent
A12A12	1H，1H，2H，2H-全氟辛基三甲氧基硅烷偶联剂1H,1H,2H,2H-perfluorooctyltrimethoxysilane coupling agent
A13A13	1H，1H，2H，2H-全氟辛基三乙氧基硅烷偶联剂1H,1H,2H,2H-perfluorooctyltriethoxysilane coupling agent
A14A14	甲基苯基二乙氧基硅烷Methylphenyldiethoxysilane
A15A15	氟甲基乙氧基二甲氧基硅烷Fluoromethylethoxydimethoxysilane
A16A16	氟乙基三乙氧基硅烷Fluoroethyltriethoxysilane
A17A17	3-氟丙基甲基二乙氧基硅烷3-fluoropropylmethyldiethoxysilane

Table 3 system crosslinker

序号Serial number	体系交联剂System crosslinker
B1B1	正硅酸乙酯Ethyl orthosilicate
B2B2	正硅酸丙酯Propyl orthosilicate
B3B3	正硅酸丁酯Butyl silicate
B4B4	正钛酸四异丙酯Tetraisopropyl titanate
B5B5	异丙基三(二辛基磷酸酰氧基)钛酸酯Isopropyl tris(dioctylphosphoryloxy) titanate
B6B6	异丙基三(十二烷基苯磺酰基)钛酸酯Isopropyl tris(dodecylbenzenesulfonyl) titanate
B7B7	1，2-双乙甲氧基硅基乙烷1,2-bisethoxysilylethane
B8B8	双-(γ-三乙氧基硅基丙基)四硫化物Bis-(γ-triethoxysilylpropyl) tetrasulfide
B9B9	双-(γ-三甲氧基硅基丙基)胺Bis-(γ-trimethoxysilylpropyl)amine

Table 4 Water-soluble nanosol

序号Serial number	水溶性纳米溶胶Water soluble nanosol
C1C1	水溶性纳米硅溶胶SNOWTEX-OWater-soluble nano silica sol SNOWTEX-O
C2C2	水溶性纳米硅溶胶SNOWTEX-40Water soluble nano silica sol SNOWTEX-40
C3C3	水溶性纳米硅溶胶LUDOX-ASWater soluble nano silica sol LUDOX-AS
C4C4	水溶性纳米硅溶胶ADELITE AT-20NWater soluble nano silica sol ADELITE AT-20N
C5C5	水溶性二氧化钛溶胶EFUT-GY01Water soluble titanium dioxide sol EFUT-GY01
C6C6	水溶性氧化锆溶胶UG-R10WWater-soluble zirconia sol UG-R10W

C7C7	水溶性氧化锆溶胶VK-RJ80Water-soluble zirconia sol VK-RJ80
C8C8	水溶性氧化铝溶胶EFUAL-Y10CWater soluble alumina sol EFUAL-Y10C

Table 5 Surface modified high density polyethylene particles

序号Serial number	表面改性高密度聚乙烯粒子Surface modified high density polyethylene particles
D1D1	表面氨基改性高密度聚乙烯粒子：粒径0.1微米Surface amino modified high density polyethylene particles: particle size 0.1 micron
D2D2	表面氨基改性高密度聚乙烯粒子：粒径0.3微米Surface amino modified high density polyethylene particles: particle size 0.3 microns
D3D3	表面氨基改性高密度聚乙烯粒子：粒径0.5微米Surface amino modified high density polyethylene particles: particle size 0.5 microns
D4D4	表面羧基改性高密度聚乙烯粒子：粒径0.1微米Surface carboxyl modified high density polyethylene particles: particle size 0.1 micron
D5D5	表面羧基改性高密度聚乙烯粒子：粒径0.3微米Surface carboxyl modified high density polyethylene particles: particle size 0.3 microns
D6D6	表面羧基改性高密度聚乙烯粒子：粒径0.5微米Surface carboxyl modified high density polyethylene particles: particle size 0.5 microns

Table 6 orthosilicate modified graphene oxide

序号Serial number	正硅酸酯改性氧化石墨烯Orthosilicate modified graphene oxide
E1E1	正硅酸甲酯改性氧化石墨烯：片层数1-3层，片径2-3微米Methyl orthosilicate modified graphene oxide: 1-3 layers, with a diameter of 2-3 microns
E2E2	正硅酸甲酯改性氧化石墨烯：片层数4-5层，片径2-5微米Methyl orthosilicate modified graphene oxide: 4-5 layers, 2-5 micron
E3E3	正硅酸乙酯改性氧化石墨烯：片层数1-3层，片径2-3微米Ethyl orthosilicate modified graphene oxide: 1-3 layers, with a diameter of 2-3 microns
E4E4	正硅酸乙酯改性氧化石墨烯：片层数4-5层，片径2-5微米Ethyl orthosilicate modified graphene oxide: 4-5 layers, 2-5 micron
E5E5	正硅酸丙酯改性氧化石墨烯：片层数1-3层，片径2-3微米Propyl silicate-modified graphene oxide: 1-3 layers, 2-3 micrometers
E6E6	正硅酸丙酯改性氧化石墨烯：片层数4-5层，片径2-5微米Propyl silicate-modified graphene oxide: 4-5 layers, 2-5 micrometers

Table 7 Water-soluble fluorine-containing compounds

序号Serial number	水溶性含氟化合物Water-soluble fluorochemical
F1F1	氟化钠Sodium fluoride
F2F2	氟钛酸铵Ammonium fluorotitanate
F3F3	氟硅酸钠Sodium fluorosilicate
F4F4	六氟钛酸Hexafluorotitanate

Table 8 Water-soluble phosphorus compounds

序号Serial number	水溶性含磷化合物Water-soluble phosphorus-containing compound
G1G1	正磷酸Orthophosphate
G2G2	三聚磷酸Tripolyphosphate
G3G3	磷酸铵Ammonium phosphate
G4G4	多聚磷酸铵Ammonium polyphosphate

Table 9 Water-soluble metal salts

序号Serial number	水溶性金属盐类物Water soluble metal salt
H1H1	硫酸氧钛Titanium sulfate
H2H2	硝酸铈Barium nitrate
H3H3	硝酸镧Barium nitrate
H4H4	钼酸铵Ammonium molybdate
H5H5	仲钨酸铵Ammonium paratungstate
H6H6	硝酸钴Cobalt nitrate
H7H7	锆氟酸钾Potassium zirconium fluorolate

(3) Evaluation test

After the aqueous inorganic surface treatment agent for the test sample in the above Examples 1-100 and Comparative Examples 1-15 was coated, the test sample was sampled and tested according to the following test methods, thereby obtaining the evaluation obtained. The test data for each property is listed in Table 11. Among them, the test to evaluate its performance parameters is as follows:

1) Flat corrosion resistance:

The salt spray test was carried out on the flat plate. The test standard was ASTMB117, and the test time was 120 hours. The evaluation criteria were:

◎: white rust area ratio is less than 5%

○: White rust area ratio is greater than 5% and less than 10%

△: white rust area ratio is greater than 10% and less than 50%

×: white rust area ratio is greater than 50%

2) Corrosion resistance after molding:

The Erikson cupping instrument was used to carry out the 8 mm cup process, and the salt spray test was carried out on the cup portion. The test standard was ASTM B117, and the test time was 72 hours. Evaluation criteria:

◎: The area ratio of white rust in the cup is less than 5%.

○: white rust area ratio of cup protrusion is more than 5% and less than 10%

△: The white rust area ratio of the cup portion is greater than 10% and less than 50%.

×: white rust area ratio of cup protrusion is greater than 50%

3) Resistance to red rust and corrosion:

The salt spray test was carried out on the flat plate. The test standard was ASTMB117, and the time when red rust began to appear was recorded. The evaluation criteria were:

◎: S1 steel plate red rust began to appear more than 240 hours; S2-S4 steel plate red rust began to appear more than 288 hours

○: S1 steel plate red rust began to appear more than 196 hours and less than 240 hours; S2-S4 steel plate red rust began to appear more than 240 hours and less than 288 hours

△: S1 steel plate red rust began to appear more than 168 hours and less than 196 hours; S2-S4 steel plate red rust began to appear 196 hours and less than 240 hours

×: S1 steel plate red rust began to appear less than 168 hours; S2-S4 steel plate red rust began to appear time Less than 196 hours

4) Stamping formability:

Use the drawbead method to prepare samples. Experimental conditions: fixed bead pressure 3KN, indenter diameter 9.6mm, drawing speed 200mm/min, evaluation criteria:

◎: no change in appearance

○: a small amount of black spots

△: Appearance is more obvious black stripes

×: The appearance is completely black

5) "non-stick" on the surface of the film:

The sample was prepared by the drawbead method. The experimental conditions were as follows: the pressure under the fixed bead was 7 KN, the diameter of the indenter was 9.6 mm, and the drawing speed was 200 mm/min. After the drawing test was completed, the surface of the sample was cleaned by blowing the surface of the sample with a hair dryer for 5 seconds. evaluation standard:

◎: no surface film and zinc powder adhered to the surface

○: There is trace film crumb and zinc powder adhesion on the surface.

△: Some film debris and zinc powder adhered on the surface

×: There is a large amount of film debris and zinc powder adhesion on the surface.

6) Wear resistance:

Using rubber wear method, load 500g, stroke distance 20mm, speed 300mm/min, repeated wear 50 times, evaluation criteria:

◎: no change in the film

○: a small amount of scratches on the film

△: multiple scratches on the membrane

×: The film completely falls off

7) Surface conductivity:

The surface resistance of the upper and lower surfaces was measured by the four-needle method, and 10 points were measured on the upper and lower surfaces, and the average surface resistance at 20 points was calculated. evaluation standard:

◎: The average surface resistance is less than 0.1 milliohms

○: The average surface resistance is greater than 0.1 milliohms and less than 0.5 milliohms

△: The average surface resistance is greater than 0.5 milliohms and less than 1 milliohm

×: The average surface resistance is greater than 1 milliohm

8) Paintability:

After the surface-treated galvanized steel sheet was coated according to the following conditions, the coating adhesion test was carried out, and the test conditions were as follows:

Ink (Japan Seiko Ink), 14# rod coating, baking conditions: baking at 120 ° C for 20 minutes;

After coating the above two coatings, a utility knife is used to draw 100 small cells on the surface of the coating film, the size is 1 mm ² , and the depth should be smoothed through the paint film layer to reach the surface of the steel plate. After peeling off with a glass tape, the residual number of the paint film was observed, and the more the residual number, the better the coatability of the steel plate to the ink.

Table 11 test sample performance

序号Serial number	平板耐蚀性Plate corrosion resistance	成型耐蚀性Molding corrosion resistance	抗红锈性Red rust resistance	冲压成型性Stamping formability	表面“不粘”性Surface "non-stick"	耐磨损性Wear resistance	表面导电性Surface conductivity	涂装性Paintability
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实施例97Example 97	◎◎	◎◎	◎◎	○○	○○	◎◎	◎◎	◎◎
实施例98Example 98	◎◎	◎◎	◎◎	◎◎	◎◎	◎◎	◎◎	○○
实施例99Example 99	◎◎	◎◎	◎◎	◎◎	◎◎	◎◎	◎◎	△△
实施例100Example 100	◎◎	◎◎	◎◎	◎◎	◎◎	◎◎	◎◎	△△
对比例1Comparative example 1	△△	△△	△△	◎◎	○○	◎◎	○○	◎◎
对比例2Comparative example 2	△△	△△	△△	◎◎	○○	◎◎	◎◎	○○
对比例3Comparative example 3	◎◎	◎◎	◎◎	××	◎◎	××	◎◎	◎◎
对比例4Comparative example 4	○○	○○	○○	○○	◎◎	○○	××	△△
对比例5Comparative example 5	○○	○○	△△	○○	◎◎	○○	◎◎	◎◎
对比例6Comparative example 6	△△	△△	△△	○○	○○	○○	◎◎	◎◎
对比例7Comparative example 7	○○	○○	△△	○○	○○	△△	○○	○○
对比例8Comparative example 8	◎◎	◎◎	◎◎	××	○○	××	◎◎	○○
对比例9Comparative example 9	△△	△△	△△	◎◎	◎◎	◎◎	××	○○
对比例10Comparative example 10	△△	△△	△△	◎◎	◎◎	◎◎	○○	○○
对比例11Comparative Example 11	△△	△△	××	××	○○	××	◎◎	◎◎
对比例12Comparative example 12	△△	△△	××	××	○○	××	○○	△△
对比例13Comparative example 13	◎◎	◎◎	◎◎	○○	◎◎	○○	××	△△
对比例14Comparative example 14	△△	△△	△△	△△	◎◎	△△	△△	△△
对比例15Comparative example 15	○○	○○	◎◎	○○	◎◎	◎◎	××	△△

Table 11 lists the performance parameters of the test panels after application of the aqueous inorganic surface treatment agents in Examples 1-100 and Comparative Examples 1-15.

It can be seen from Table 11 that after the test sample coated by the aqueous inorganic surface treatment agent of Example 1-100 was tested, except for a certain evaluation result of a small number of examples, "△" appeared, and most of the other implementations were carried out. The evaluation results of all the examples are "?" and "○", indicating that the galvanized steel sheets coated with the aqueous inorganic surface treatment agent of the present invention have excellent red rust resistance, surface electrical conductivity, surface lubricating properties and anti-stamping. Blackening performance, able to meet the requirements of fast deep drawing and bare service for progressive die.

As can be seen from the combination of Tables 10 and 11, there is no system crosslinking agent (C) in the aqueous inorganic surface treatment agent in Comparative Example 1, Comparative Example 2, Comparative Example 6, and Comparative Example 7 as compared with Example 1-100. Or the water-soluble nano sol (C) results in a lower crosslinking density of the inorganic film, so that the corrosion resistance of the inorganic film is inferior.

The surface-modified high-density polyethylene particles (D) were not contained in the aqueous inorganic surface treatment agent of Comparative Example 3 and Comparative Example 8, and therefore, the press formability of the inorganic film of the galvanized steel sheet coated with the aqueous inorganic surface treatment agent And wear resistance is poor.

In the aqueous inorganic surface treatment agent of Comparative Example 4 and Comparative Example 9, there was no orthosilicate-modified graphene oxide (E), and a conductive network could not be formed in the inorganic film, and therefore, the coating was carried out by the aqueous inorganic surface treatment agent. The conductive properties of galvanized steel sheets are poor. In addition, since the inorganic film thicknesses of Comparative Example 13 and Comparative Example 15 were large, the surface conductivity was also poor.

In the aqueous inorganic surface treatment agents of Comparative Example 5 and Comparative Example 10, there were no water-soluble fluorine-containing compound (F) or water-soluble phosphorus-containing compound (G), so that the corrosion resistance of the inorganic film was inferior.

The inorganic film in Comparative Example 11 was low in thickness, resulting in poor overall performance. In Comparative Example 12, the baking curing temperature was low, resulting in the inorganic film not being completely cured, so that the inorganic film was inferior in overall performance.

It is to be noted that the above are only specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, and many similar variations are possible. All modifications that are directly derived or associated by those of ordinary skill in the art are intended to be within the scope of the invention.

Claims

An inorganic surface-treated galvanized steel sheet is coated on the surface of a galvanized steel sheet with a single-layer inorganic film having a thickness of 0.3-1.0 μm, wherein

The inorganic film contains:

A) one or more hydrophobic monoorganosilane coupling agents in an amount of 40-60 parts by weight in the inorganic film;

The hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;

B) the system cross-linking agent, the weight fraction in the inorganic film is 10-30 parts;

The system crosslinking agent is one or more of orthosilicate, titanate or a diorganosilane coupling agent having a bridging structure;

C) a water-soluble nano sol in an amount of 5-15 parts by weight in the inorganic film;

The water-soluble nano sol has a mass fraction of 20-30%;

D) surface-modified high-density polyethylene particles in the inorganic film in parts by weight of 10-25 parts;

E) orthosilicate-modified graphene oxide, wherein the weight fraction of graphene oxide in the inorganic film is 0.05-0.5 parts;

The orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%.
An inorganic surface-treated galvanized steel sheet according to claim 1, wherein

The inorganic film further contains:

F) a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;

G) a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;

H) A water-soluble metal salt compound in which the metal element is contained in an amount of 0.1 to 2.5 parts by weight in the inorganic film.
An inorganic surface-treated galvanized steel sheet according to claim 1, wherein

The hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) is selected from the group consisting of -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl), -C 6 H 5 (phenyl), -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 (perfluoropropyl), -C 5 F 11 (perfluoro One or both of pentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl).
An inorganic surface-treated galvanized steel sheet according to claim 1, wherein

The reactive group in the hydrophobic monoorganosilane coupling agent is selected from the group consisting of -OCH 3 (methoxy), -OC 2 H 5 (ethoxy), vinyl, propenyl, epoxy, amino, hydroxy One of three, a carboxyl group, an amide group or a 2,3-epoxypropoxy group.
An inorganic surface-treated galvanized steel sheet according to claim 1, wherein

The sum of the number of hydrophobic groups and the number of reactive groups in the hydrophobic monoorganosilane coupling agent is equal to four;

The hydrophobic monoorganic silane coupling agent is contained in the inorganic film in an amount of 40 to 60 parts by weight, preferably 45 to 55 parts by weight.
A method of producing an inorganic surface-treated galvanized steel sheet according to any one of claims 1 to 5, characterized in that

Dissolving or dispersing a component of an aqueous inorganic surface treatment agent in water to form an aqueous inorganic surface treatment agent, and applying the aqueous inorganic surface treatment agent to the surface of the galvanized steel sheet by one-time roll coating, and at 60-100 Drying between °C, so that the dry film thickness of the inorganic film is 0.3-1.0 microns,

The inorganic film contains:

A) one or more hydrophobic monoorganosilane coupling agents in an amount of 40-60 parts by weight in the inorganic film;

The hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;

B) the system cross-linking agent, the weight fraction in the inorganic film is 10-30 parts;

The system crosslinking agent is selected from one or more of a orthosilicate, a titanate or a diorganosilane coupling agent having a bridging structure;

C) a water-soluble nano sol in an amount of 5-15 parts by weight in the inorganic film;

The water-soluble nano sol has a mass fraction of 20-30%;

D) surface-modified high-density polyethylene particles in the inorganic film in parts by weight of 10-25 parts;

E) orthosilicate-modified graphene oxide, wherein the weight fraction of graphene oxide in the inorganic film is 0.05-0.5 parts;

The orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%.
A method of preparing an inorganic surface-treated galvanized steel sheet according to claim 6, wherein

The inorganic film further contains:

F) a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;

G) a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;

H) A water-soluble metal salt compound in which the metal element is contained in an amount of 0.1 to 2.5 parts by weight in the inorganic film.
A method of preparing an inorganic surface-treated galvanized steel sheet according to claim 6, wherein

The hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) may be -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl), -C 6 H 5 (phenyl), -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 (perfluoropropyl), -C 5 F 11 (perfluoro One or two of pentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl); a reactive group in the hydrophobic monoorganosilane coupling agent It may be -OCH 3 (methoxy), -OC 2 H 5 (ethoxy), vinyl, propenyl, epoxy, amino, hydroxy, carboxyl, amide or 2,3-epoxypropoxy Up to three of them; the sum of the number of hydrophobic groups and the number of reactive groups in the hydrophobic monoorganosilane coupling agent is equal to four; the weight fraction of the hydrophobic monoorganosilane coupling agent in the inorganic film is 40-60 parts, preferably 45-55 parts.
A method of preparing an inorganic surface-treated galvanized steel sheet according to claim 6, wherein

The system cross-linking agent (B) may be a tetrasilicate having 4 reactive groups, a titanate having 4 reactive groups, or a double-bridged structure having 6 reactive groups. One or more of an organosilane coupling agent; the reactive group in the orthosilicate may be any one of a methoxy group, an ethoxy group, a propoxy group or a butoxy group; The reactive group in the titanate may be one or more of an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl ester group; the framework of the double organosilane coupling agent The bridge structure is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups; the reactive group of the bis-organosilane coupling agent may be any one of methoxy, ethoxy or propoxy groups. Kind.
An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet coated on the surface of a galvanized steel sheet and formed into an inorganic film according to any one of claims 6-9, wherein

The total solids in its aqueous solution contain the following ingredients:

A) one or more hydrophobic monoorganosilane coupling agents in the inorganic film in parts by weight 40-60 Share

The hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;

B) the system cross-linking agent, the weight fraction in the inorganic film is 10-30 parts;

The system crosslinking agent is one or more of orthosilicate, titanate or a diorganosilane coupling agent having a bridging structure;

C) a water-soluble nano sol in an amount of 5-15 parts by weight in the inorganic film;

The water-soluble nano sol has a mass fraction of 20-30%;

D) surface-modified high-density polyethylene particles in the inorganic film in parts by weight of 10-25 parts;

E) orthosilicate-modified graphene oxide, wherein the weight fraction of graphene oxide in the inorganic film is 0.05-0.5 parts;

The orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%;

F) a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;

G) a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;

H) A water-soluble metal salt compound in which the metal element is contained in an amount of 0.1 to 2.5 parts by weight in the inorganic film.
An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to claim 10, wherein

The hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) may be -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl), -C 6 H 5 (phenyl), -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 (perfluoropropyl), -C 5 F 11 (perfluoro One or two of pentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl); a reactive group in the hydrophobic monoorganosilane coupling agent It may be -OCH 3 (methoxy), -OC 2 H 5 (ethoxy), vinyl, propenyl, epoxy, amino, hydroxy, carboxyl, amide or 2,3-epoxypropoxy Up to three of them; the sum of the number of hydrophobic groups and the number of reactive groups in the hydrophobic monoorganosilane coupling agent is equal to four; the weight fraction of the hydrophobic monoorganosilane coupling agent in the inorganic film is 40-60 parts, preferably 45-55 parts.
An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to claim 10, wherein

The system crosslinker (B) is selected from the group consisting of orthosilicates having 4 reactive groups, titanates having 4 reactive groups, or double bridges having 6 reactive groups One or more of an organosilane coupling agent; the reactive group in the orthosilicate is selected from any one of a methoxy group, an ethoxy group, a propoxy group or a butoxy group; The reactive group in the titanate is selected from one or more of an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl ester group; the frame of the double organosilane coupling agent The bridge structure is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups; the reactive group of the bis-organosilane coupling agent is selected from any one of methoxy, ethoxy or propoxy groups. Kind.