CN114635128A - Ultraviolet-curable surface passivator, metal product and application - Google Patents

Ultraviolet-curable surface passivator, metal product and application Download PDF

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CN114635128A
CN114635128A CN202011493929.4A CN202011493929A CN114635128A CN 114635128 A CN114635128 A CN 114635128A CN 202011493929 A CN202011493929 A CN 202011493929A CN 114635128 A CN114635128 A CN 114635128A
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passivator
parts
curable surface
oxetane resin
curable
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钱晓春
张学龙
金晓蓓
马春雨
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent

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Abstract

The invention provides an ultraviolet-curable surface passivator, a metal product and application. The surface passivator capable of being cured by ultraviolet light comprises the following components in parts by weight: 20-40 parts of oxetane resin, 40-60 parts of reactive diluent, 4-8 parts of photoinitiator and 1-15 parts of auxiliary agent. The passivator with the composition does not contain solvent, and VOCs is discharged little or even not during use; meanwhile, the passivator can be cured under ultraviolet light, so that the energy consumption is lower compared with the existing passivator. In addition, under the specific composition, the passivation layer formed by the passivator also has the advantages of better corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like, so that the passivation layer can be directly coated on the surface of a hot-dip aluminum-zinc plate for use. The ultraviolet-curable surface passivator has the advantages of good environmental protection, low curing energy consumption, corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like.

Description

Ultraviolet-curable surface passivator, metal product and application
Technical Field
The invention relates to the field of chromium-free passivation of metal products, in particular to an ultraviolet-curable surface passivator, a metal product and application.
Background
The hot-dip aluminum-zinc plate has the advantages of both hot-dip galvanizing and hot-dip aluminum plates, and has the quality performance characteristics of excellent corrosion resistance, high-temperature oxidation resistance, good appearance decoration and the like. During the transportation and storage processes, white rust or black spots are generated on the surface of the aluminum-zinc alloy coating due to the corrosion of the aluminum-zinc alloy coating caused by the humid environment, and the surface quality and the corrosion resistance of the aluminum-zinc alloy coating are influenced. In order to further improve the corrosion resistance of the hot-dip aluminum-zinc plate, the surface of the hot-dip aluminum-zinc plate is usually passivated.
The traditional hot-dip aluminum-zinc plating plate passivation adopts chromate passivation, and a chromate passivation film has excellent corrosion resistance and self-repairing function. Hexavalent chromium, however, is carcinogenic, and thus legislation has been banned in recent years by countries around the world to prohibit the use of chromate in the passivation of steel sheets. In recent years, the research on chromium-free passivation in the field is mainly divided into three general directions, namely inorganic passivation, organic passivation and organic-inorganic composite passivation.
Inorganic passivation includes molybdate passivation, phosphate passivation, zirconate passivation, silicate passivation, rare earth metal salt passivation, and the like.
The organic passivation is mainly that the water-based acrylic resin or epoxy resin is matched with a silane coupling agent for use, the silane coupling agent is hydrolyzed into silanol in water, and hydroxyl in the silanol can react with hydroxyl on the surface of the steel plate to form a Si-O-Me covalent bond, so that the bonding force between a passivation film and the steel plate is enhanced; meanwhile, unsaturated resins in the passivating agent are also crosslinked to form a compact network structure, and the structure can prevent oxygen and water from contacting with plating metal, so that the corrosion resistance of the steel plate is improved.
The organic-inorganic composite passivation is to add an inorganic corrosion inhibitor into an organic passivator, and the inorganic corrosion inhibitor and the organic component have good synergistic effect, so that the corrosion resistance of a passivation film can be further improved. The effect of organic-inorganic composite passivation is close to or even exceeds that of chromate passivation at present.
The passivation technology of the coating steel plate in China at present is mainly an organic-inorganic composite passivation technology, the passivation effect is excellent, the production efficiency is high, and the fastest online passivation and curing speed can reach 150 m/min. At present, all passivators used by large steel enterprises are water-based passivators, and films are formed mainly by drying surface moisture through high-frequency heating or blast heating. The passive film formed by the film forming mode has excellent performance but higher energy consumption, however, some micromolecular organic matters in the passivator can volatilize into the air in the heating process, so that the discharge of VOCs exceeds the standard, the national requirements on environmental protection cannot be met, and meanwhile, the body of field operators can be damaged.
Therefore, the surface passivator capable of simultaneously solving the problems of high energy consumption, excessive discharge of VOCs (volatile organic compounds), unfavorable health of operators and the like is needed.
Disclosure of Invention
The invention mainly aims to provide an ultraviolet-curable surface passivator, a metal product and application thereof, and aims to solve the problems of high energy consumption, excessive discharge of VOCs (volatile organic compounds), unfavorable health of operators and the like of the conventional surface passivator.
In order to achieve the above object, in one aspect, the present invention provides a uv-curable surface passivating agent, including, by weight: 20-40 parts of oxetane resin, 40-60 parts of reactive diluent, 4-8 parts of photoinitiator and 1-15 parts of auxiliary agent.
Further, the ultraviolet light curable surface passivating agent comprises the following components in parts by weight: 30-35 parts of oxetane resin, 50-53 parts of reactive diluent, 6-8 parts of photoinitiator and 10-11 parts of auxiliary agent.
Further, the photoinitiator is selected from one or more of the group consisting of aryldiazonium salts, iodonium salts, sulfonium salts, and arylferrocenium salts.
Further, the photoinitiator is selected from compounds having a structure represented by formula (I) and/or (II):
Figure BDA0002841496910000021
wherein R is1And R2Each independently selected from hydrogen, C1～C20Straight or branched chain ofChain alkyl radical, C4～C20Cycloalkylalkyl or alkylcycloalkyl of (A), and the acyclic-CH in the above-mentioned group2-optionally substituted by-O-, -S-or 1, 4-phenylene; r3And R4Each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl of (A), and the acyclic-CH in the above-mentioned group2-optionally substituted by-O-, -S-or 1, 4-phenylene; r is5Is selected from C6～C20Aryl of (C)1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl, substituted or unsubstituted phenylthiophenyl, and the acyclic-CH in the above groups2-optionally substituted by-O-, -S-or 1, 4-phenylene; g1 -And G2 -Each independently selected from PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、SO2C4F9 -Or B (C)6M5)4And M is selected from H, F, Cl or Br.
Further, the oxetane resin is one or more selected from the group consisting of a bisphenol a oxetane resin, an organosilicon-modified oxetane resin, a bisphenol F oxetane resin, a polyester-modified oxetane resin and an organofluorine-modified oxetane resin.
Further, the reactive diluent is one or more selected from the group consisting of 3, 4-epoxycyclohexylmethyl 3 ', 4' -epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 2-epoxy-4-vinylcyclohexane, 3-benzyloxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-ethyl-3- ((oxyethylene-2-methoxy) methyl) oxetane and 1- (3-ethyloxetane-3-methoxy) -2-propanol-3-methyl ether.
Further, the auxiliary agent is one or more selected from the group consisting of a defoaming agent, a leveling agent, a dispersing agent, an inorganic filler and an adhesion promoter.
In another aspect, the present application further provides a metal product, which includes a passivation layer formed by coating and curing the uv-curable surface passivating agent provided in the present application.
Further, the metal product is a hot-dip galvanized plate or a hot-dip aluminized zinc plate.
In yet another aspect, the present application provides a use of the uv-curable surface passivating agent provided in the present application in the field of surface treatment of metal, plastic, glass, paper or wood.
By applying the technical scheme of the invention, the passivator with the composition does not contain solvent, and VOCs are discharged little or even not during the use process; meanwhile, the passivator can be cured under ultraviolet light, so that the energy consumption is lower compared with the existing passivator. In addition, under the specific composition, the passivation layer formed by the passivator also has the advantages of better corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like, so that the passivation layer can be directly coated on the surface of the hot-dip aluminum zinc plate for use. In conclusion, the surface passivating agent capable of being cured by ultraviolet light has the advantages of being good in environmental protection performance, low in curing energy consumption, corrosion-resistant, fingerprint-resistant, high-temperature yellowing-resistant and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing surface passivator has the problems of high energy consumption, excessive discharge of VOCs, unfavorable health of operators and the like. In order to solve the technical problem, the application provides an ultraviolet-curable surface passivator, which comprises the following components in parts by weight: 20-40 parts of oxetane resin, 40-60 parts of reactive diluent, 4-8 parts of photoinitiator and 1-15 parts of auxiliary agent.
The passivator with the composition does not contain solvent, and VOCs is discharged little or even not during use; meanwhile, the passivator can be cured under ultraviolet light, so that the energy consumption is lower compared with the conventional passivator. In addition, under the specific composition, the passivation layer formed by the passivator also has the advantages of better corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like, so that the passivation layer can be directly coated on the surface of a hot-dip aluminum-zinc plate for use. In summary, the ultraviolet-curable surface passivator provided by the application has the advantages of good environmental protection, low curing energy consumption, corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like of a formed passivation layer.
In order to further improve the overall performance of the uv-curable surface passivating agent provided herein, preferably, the uv-curable surface passivating agent comprises, by weight: 30-35 parts of oxetane resin, 50-53 parts of reactive diluent, 6-8 parts of photoinitiator and 10-11 parts of auxiliary agent.
The photoinitiator used in the above-described uv-curable surface passivating agent may be of the kind commonly used in the art. In a preferred embodiment, the photoinitiator includes, but is not limited to, one or more of the group consisting of aryldiazonium salts, iodonium salts, sulfonium salts, and arylferrocenium salts. The cationic photoinitiators have higher photoinitiation activity and stability, so that the curing efficiency of the surface passivator is improved, and the application range of the surface passivator can be widened. More preferably, the photoinitiator includes, but is not limited to, compounds having the structure represented by formula (i) and/or (ii):
Figure BDA0002841496910000031
wherein R is1And R2Each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl of (a), and acyclic-CH in the above-mentioned group2-optionally substituted by-O-, -S-or 1, 4-phenylene; r3And R4Each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl of (A) to (B)acyclic-CH in the radicals mentioned2-optionally substituted by-O-, -S-or 1, 4-phenylene; r5Including but not limited to C6～C20Aryl of (C)1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl, substituted or unsubstituted phenylthiophenyl, and the acyclic-CH in the above groups2-optionally substituted by-O-, -S-or 1, 4-phenylene; g1 -And G2 -Each independently selected from PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、SO2C4F9 -Or B (C)6M5)4M includes but is not limited to H, F, Cl or Br.
In a preferred embodiment, the oxetane resin includes, but is not limited to, one or more of the group consisting of bisphenol a oxetane resin, silicone modified oxetane resin, bisphenol F oxetane resin, polyester modified oxetane resin, and organofluorine modified oxetane resin.
In a preferred embodiment, the reactive diluent includes, but is not limited to, one or more of the group consisting of 3, 4-epoxycyclohexylcarboxylic acid-3 ', 4' -epoxycyclohexylmethyl ester (UVR6110), bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 2-epoxy-4-vinylcyclohexane, 3-benzyloxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-ethyloxetane (TMPO), 3-ethyl-3- ((oxyethylene-2-methoxy) methyl) oxetane, and 1- (3-ethyloxetan-3-methoxy) -2-propanol-3-methyl ether. The addition of the reactive diluent can adjust the viscosity of the ultraviolet-curable surface passivator provided by the application, and improve the construction convenience of the ultraviolet-curable surface passivator; and simultaneously, the reactivity and the curing time can be adjusted.
In order to further improve the overall performance of the surface passivating agent, the auxiliary agents include, but are not limited to, one or more of the group consisting of antifoaming agents, leveling agents, dispersing agents, inorganic fillers, and adhesion promoters.
Preferably, the inorganic filler includes, but is not limited to, one or more of the group consisting of nano kaolin, nano silica and nano alumina; adhesion promoters include, but are not limited to, one or more of the group consisting of 6105 phosphate adhesion promoter, JSC-567 adhesion promoter, JSC-1005 adhesion promoter, JSC-1008 adhesion promoter, JSC-1009 adhesion promoter, AS-1601 adhesion promoter, AS-1603 adhesion promoter.
In another aspect, the present application further provides a metal product, which includes a passivation layer formed by coating and curing the uv-curable surface passivation agent provided herein.
The passivator with the composition does not contain solvent, and VOCs is discharged little or even not during use; meanwhile, the passivator can be cured under ultraviolet light, so that the energy consumption is lower compared with the existing passivator. In addition, under the specific composition, the passivation layer formed by the passivator also has the advantages of better corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like, so that the passivation layer can be directly coated on the surface of a hot-dip aluminum-zinc plate for use. Therefore, the passivation layer formed by the passivating agent is beneficial to greatly improving the protection effect of the passivation layer on metal products. More preferably, the metal product is a hot-dip galvanized sheet or a hot-dip aluminum-zinc sheet.
The invention also provides a preparation method of the preferred hot-dip aluminum-zinc plate passivating agent, which comprises the following steps: uniformly stirring the photoinitiator, the oxetane resin, the reactive diluent and the auxiliary agent according to a preset weight ratio, and measuring the viscosity for later use.
Preferably, the above preparation method further comprises: dissolving a photoinitiator in a propylene carbonate solution (weight ratio is 1:1), mixing the photoinitiator with an oxetane resin, a reactive diluent and an auxiliary agent after the photoinitiator is completely dissolved, stirring uniformly, and measuring viscosity for later use.
The fourth aspect of the invention also provides a preparation method of the hot-dip aluminum-zinc passivation plate, which comprises the following steps:
(1) pretreatment of hot-dip aluminum-zinc plate: firstly, polishing burrs at the edge of a steel plate by using sand paper, then putting the steel plate polished to be smooth into a 2% medium-alkali degreasing agent aqueous solution for soaking for 10 minutes, taking out the steel plate, washing the steel plate with deionized water (taking the surface without water drops as clean), putting the steel plate into a 100 ℃ oven for drying the surface moisture of the steel plate, and finally wiping the surface of the steel plate with acetone;
(2) and (3) curing the coating film: the prepared passivator is uniformly coated on the surface of a hot-dip aluminum-zinc plate by a 1-micron wire rod, then a steel plate is placed at one end of a UV exposure machine, and the steel plate is conveyed out from the tail part of the exposure machine to obtain the hot-dip aluminum-zinc passivated plate.
Preferably, the linear velocity of the exposure machine is 150m/min, the exposure time is 0.0083s, and the exposure energy is 150mJ/cm2。
Preferably, the chemical composition of the coating of the hot-dip aluminum-zinc plate is 55% of Al, 43.4% of Zn and 1.6% of Si in percentage by weight.
Preferably, the thickness of the coating of the passivating agent coating of the hot-dip aluminum-zinc chromium-free passivated plate is 1.0-1.5 g/m2。
In yet another aspect, the present application provides a use of the uv-curable surface passivator provided herein in the field of surface treatment of metal, plastic, glass, paper or wood.
The passivator with the composition does not contain solvent, and VOCs is discharged little or even not during use; meanwhile, the passivator can be cured under ultraviolet light, so that the energy consumption is lower compared with the existing passivator. In addition, under the specific composition, the passivation layer formed by the passivator also has the advantages of better corrosion resistance, fingerprint resistance, high-temperature yellowing resistance and the like, so that the passivation layer can be directly coated on the surface of the hot-dip aluminum zinc plate for use. On the basis of the advantages of the passivator, the passivator has good application prospect in the field of surface treatment of metal, plastic, glass, paper or wood.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Examples 1 to 15 and comparative examples 1 to 2 were prepared according to the formulations listed in Table 1, and the manufacturers of the respective raw materials are shown in Table 2. The effects of the combination of different photoinitiators and inorganic fillers on the curing speed and corrosion resistance of the coating are compared, wherein the photoinitiators A1-A3 in examples 1-15 and comparative examples 1-2 have the following structures:
Figure BDA0002841496910000051
TABLE 1
Figure BDA0002841496910000061
Figure BDA0002841496910000071
TABLE 2
Figure BDA0002841496910000072
Performance test
Performance tests were performed on examples 1 to 15 and comparative examples 1 to 2 and a current chromium-free passivator for waterborne hot-dip aluminum zinc plates (CT-E360, tradesman, shanghai corp.).
And (3) stability testing: the prepared UV photocuring chromium-free passivator is placed in a dark place for storage, and the storage stability of the liquid is observed, namely, the time of phenomena such as color change precipitation, large viscosity rise (the viscosity is increased by more than 50cP) and the like does not appear, and the result is shown in Table 3. The shelf life of the currently common chromium-free passivator for the hot-dip aluminized zinc sheet is 90 days.
Viscosity: the test was performed using a rotational viscometer. And 3 parts of the newly prepared UV passivator is taken, viscosity is measured by a viscometer and then is put into three black vials with the same material, the three parts of the passivator are placed in a dark environment and are kept in a dark place, and the viscosity change of the passivator is measured after the passivator is respectively kept for 7 days, 14 days and 30 days. The viscosity change of the currently commonly used chromium-free passivator for the hot-dip aluminized zinc sheet is less than 10 cP.
The thickness, curing speed, adhesion, corrosion resistance, high temperature yellowing resistance, acid and alkali resistance, solvent resistance and fingerprint resistance of the coating of the UV-cured hot-dip aluminum-zinc passivated plates (examples 1 to 15 and comparative examples 1 to 2) were tested, and the results are shown in Table 4.
Thickness: and (4) carrying out evaluation test by adopting a weighing method. Firstly, a cleaned hot-dip aluminum-zinc plated plate is placed on an electronic balance to obtain the mass m of the plate1Then coating and curing the steel plate, and weighing the steel plate to obtain the mass m2And measuring the surface area S of the steel plate, and finally calculating the weight of the coating film, wherein the calculation formula is as follows:
Figure BDA0002841496910000081
curing speed: the degree of curing is evaluated by a finger touch method for testing, and the higher the grade is, the higher the degree of curing is, the higher the curing speed is. The curing degree is mainly 5 grades, the surface of the coating is oiled, and the degree of no change before and after exposure is 1 grade; curing the surface oil and bottom layer of the coating to 2 levels; the surface of the coating is sticky, and the finger print is seriously grade 3 after the finger touch; the slightly astringent surface with light fingerprint is grade 4 after the surface is basically dry; the coating is completely cured, the surface is smooth, and no fingerprint is grade 5 after the coating is touched by fingers.
Adhesion force: the test was performed by the cross-hatch method. And (3) using a scriber to draw a grid on the surface of the passive film until the depth reaches the surface of a coating, sticking the grid on a working area for 5 minutes by using a ScOYCH-600 transparent adhesive tape of 3M company, tearing the grid by force, observing the proportion of the peeled area of the surface of the paint film, and grading the test result according to GB/T9286-1998 after peeling. The adsorption force of the coating formed by the chromium-free passivator for the currently common water-based hot-dip aluminum zinc plate is 0 grade.
Corrosion resistance: performing a neutral salt spray test on the passive film according to GB10125-1997 standard, wherein the corrosion solution is 50g/L NaCl solution, the solution is neutral, the temperature in a salt spray box is 35 +/-2 ℃, and the sedimentation amount is 1-2 mL/80cm2And h, placing the sample at an angle of 30 degrees with the vertical direction of the salt spray frame, and evaluating the corrosion resistance of the passivation film layer obtained by different treatment processes by the percentage of the white rust area generated by the sample after continuously spraying for 72 hours. At present, the corrosion resistance of the hot-dip aluminum zinc plate coating generally requires that the corrosion area is less than or equal to 5 percent within 72 hours。
High temperature yellowing resistance: the test is carried out by adopting a mode of measuring the color difference of the coating after baking for 20min at 200 ℃. And placing the cured steel plate on a color difference meter to test the L, a and b values of the passivation film before high-temperature baking, selecting at least three points for testing, marking test point positions on the back surface of the steel plate, then placing the steel plate in a 200 ℃ oven for baking for 20min, testing the color difference of the same point positions, and then recording the test result delta E. At present, the requirement of delta E for high-temperature yellowing resistance of a hot-dip aluminum zinc plate coating is less than or equal to 3.0.
Acid/alkali resistance: the color change of the coating was judged by soaking the sample in 1% HCl/NaOH solution at room temperature for 1 h. The acid/alkali resistance requirement delta E of the current hot dip aluminum zinc plate coating is less than or equal to 3.0.
Solvent resistance: the ethanol resistance of the passive film is mainly tested by adopting a manual wiping method: wrapping four layers of medical cotton gauze on an index finger, taking out after soaking in a specified solvent, forming an angle of 45 degrees between the index finger and a test surface of the sample, applying pressure of about 500g, wiping the surface of the sample back and forth for 20 times, and carrying out visual rating according to the following evaluation standard: the surface has no damage to 5 grades; the surface is not damaged when the observation is carried out on the front side, and the side light subcutaneous skin is slightly damaged by 4 grades; the slight damage of the skin membrane on the front surface is grade 3; the damage of the involucra is serious, but the unexposed substrate is grade 2; the complete peel-off of the skin was grade 1. At present, the solvent resistance of the hot-dip aluminum zinc plate coating is more than or equal to 3 grades.
Fingerprint resistance: and (3) judging according to the change of the color difference value before and after the surface of the sample is coated with the vaseline, uniformly coating the vaseline on the surface of the passive film, standing for 1 hour at room temperature, and then testing the color difference of the passive film. The fingerprint resistance requirement delta E of the prior hot-dip aluminum zinc plate coating is less than or equal to 2.0.
TABLE 3
Figure BDA0002841496910000101
Figure BDA0002841496910000111
TABLE 4
Figure BDA0002841496910000112
The data in tables 3 and 4 show that the high-performance UV-curable chromium-free passivator for hot-dip aluminum-zinc plates provided by the invention has good storage stability (storage in a dark place) and extremely high curing speed. Meanwhile, because no solvent is added into the passivator, the passivator does not volatilize the solvent in the using process, and is an excellent environment-friendly coating. The passive film formed after coating and curing has excellent adhesion, corrosion resistance, high temperature yellowing resistance, acid and alkali resistance, fingerprint resistance and other performances.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An ultraviolet-curable surface passivator, characterized in that, by weight, the ultraviolet-curable surface passivator comprises: 20-40 parts of oxetane resin, 40-60 parts of reactive diluent, 4-8 parts of photoinitiator and 1-15 parts of auxiliary agent.
2. The uv-curable surface passivator according to claim 1, wherein the uv-curable surface passivator comprises, in parts by weight: 30-35 parts of the oxetane resin, 50-53 parts of the reactive diluent, 6-8 parts of the photoinitiator and 10-11 parts of the auxiliary agent.
3. The uv-curable surface passivating agent according to claim 1 or 2, wherein the photoinitiator is selected from one or more of the group consisting of aryldiazonium salts, iodonium salts, sulfonium salts, and arylferrocenium salts.
4. The UV-curable surface passivator of claim 3, wherein the photoinitiator is selected from compounds having the structure of formula (I) and/or (II):
Figure FDA0002841496900000011
wherein, R is1And said R2Each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl of (A), and the acyclic-CH in the above-mentioned group2-optionally substituted by-O-, -S-or 1, 4-phenylene;
the R is3And said R4Each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl of (a), and acyclic-CH in the above-mentioned group2-optionally substituted by-O-, -S-or 1, 4-phenylene;
the R is5Is selected from C6～C20Aryl of (C)1～C20Straight or branched alkyl of (2), C4～C20Cycloalkylalkyl or alkylcycloalkyl, substituted or unsubstituted phenylthiophenyl, and the acyclic-CH in the above groups2-optionally substituted by-O-, -S-or 1, 4-phenylene;
the G is1 -And said G2 -Each independently selected from PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、SO2C4F9 -Or B (C)6M5)4And M is selected from H, F, Cl or Br.
5. The uv-curable surface passivator according to any one of claims 1 to 4, wherein the oxetane resin is selected from one or more of the group consisting of bisphenol-a oxetane resin, silicone-modified oxetane resin, bisphenol-F oxetane resin, polyester-modified oxetane resin and organofluorine-modified oxetane resin.
6. The UV-curable surface-passivating agent according to claim 5, the reactive diluent is selected from one or more of the group consisting of 3, 4-epoxycyclohexylmethyl 3 ', 4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 1, 2-epoxy-4-vinylcyclohexane, 3-benzyloxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-ethyl-3- ((ethylene oxide-2-methoxy) methyl) oxetane and 1- (3-ethyloxetane-3-methoxy) -2-propanol-3-methyl ether.
7. The uv-curable surface passivating agent according to claim 6, wherein the auxiliary agent is selected from one or more of the group consisting of an antifoaming agent, a leveling agent, a dispersing agent, an inorganic filler and an adhesion promoter.
8. A metal article comprising a passivation layer, wherein the passivation layer is formed by coating and curing the uv-curable surface passivating agent of any of claims 1 to 7.
9. The metal product according to claim 8, wherein the metal product is a hot-dip galvanized sheet or a hot-dip aluminized zinc sheet.
10. Use of a uv-curable surface-passivating agent according to any of claims 1 to 7 in the field of surface treatment of metal, plastic, glass, paper or wood.
CN202011493929.4A 2020-12-16 2020-12-16 Ultraviolet-curable surface passivator, metal product and application Pending CN114635128A (en)

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CN108314911A (en) * 2017-01-17 2018-07-24 常州格林感光新材料有限公司 A kind of UVLED curable wood coatings
CN108303851A (en) * 2018-01-05 2018-07-20 湖北固润科技股份有限公司 Include photoetching compositions of the poly(4-hydroxystyrene) class oxetane resin as film-forming resin

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