CN114958155A - Silane-containing chromium-free roll priming paint - Google Patents
Silane-containing chromium-free roll priming paint Download PDFInfo
- Publication number
- CN114958155A CN114958155A CN202210503766.6A CN202210503766A CN114958155A CN 114958155 A CN114958155 A CN 114958155A CN 202210503766 A CN202210503766 A CN 202210503766A CN 114958155 A CN114958155 A CN 114958155A
- Authority
- CN
- China
- Prior art keywords
- parts
- primer
- silane
- free coil
- chrome
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 22
- 239000003973 paint Substances 0.000 title claims description 5
- 230000037452 priming Effects 0.000 title claims description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 238000005260 corrosion Methods 0.000 claims abstract description 33
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 15
- 229920001225 polyester resin Polymers 0.000 claims abstract description 15
- 239000004645 polyester resin Substances 0.000 claims abstract description 15
- 229920003180 amino resin Polymers 0.000 claims abstract description 14
- 239000000049 pigment Substances 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 3
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000013022 formulation composition Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical class O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The application relates to a silane-containing chromium-free coil coating primer which comprises the following components in parts by mass: polyester resin: 20-60 parts of amino resin: 5-20 parts of bis [3- (triethoxysilyl) propyl ] tetrasulfide: 0.1-10 parts of ion exchange anticorrosive pigment: 1-15 parts of catalyst: 0.3-1 part of auxiliary agent: 1-5 parts of solvent: 30-60 parts. In the application, the primer component is added with bis [3- (triethoxysilyl) propyl ] tetrasulfide and an ion exchange corrosion resistant pigment, and the synergistic use of the two can further improve the corrosion resistance and the metal adhesion performance of the primer. According to the primer, the anionic conductive polymer is further added into the primer component, so that the metal adhesion of the primer can be further improved, and the generation of electrochemical corrosion can be reduced.
Description
Technical Field
The application relates to the technical field of coatings, in particular to a silane-containing chromium-free coil coating primer.
Background
The coiled material is a precoated coiled material which is prepared by coating a coating on the surface of a steel plate or an aluminum plate by a roller coating operation method and has the advantages of high strength, convenience in processing and forming, attractive appearance, good durability and the like. The large-area rapid coating mode can also effectively control the unorganized emission of VOC, can effectively reduce pollution and improve economy, and is widely applied to the fields of buildings, household appliances, automobiles and the like.
The national standard GB30981-2020 "Limit of harmful substances in Industrial protective coatings" is formally implemented from 1 month and 1 day of 2022 years for the limitation of heavy metals in precoated coil coatings. According to the requirements of the revision manuscript, the content of hexavalent chromium (Cr6+) in the coating must not exceed 1000 mg/kg. This has made china the european union followed by a second country and region in which hexavalent chromium is used, which is a strict overall restriction in industrial coatings.
Previously developed chrome-free primers achieve comparable corrosion performance by replacing strontium chromate with one or more chrome-free corrosion inhibiting pigments; for example, in patent publication No. CN102884141A, calcium ion-exchanged silica, zinc phosphate and one selected from cerium compounds, tungstic acid compounds and molybdic acid compounds are used in combination, and relatively good corrosion resistance can be achieved in a short period of time, but the addition of some metal oxides and inorganic salts has some influence on the adhesion property of the primer.
In view of the above-mentioned related technologies, the inventors believe that the current chromium-free primer has the defects of poor long-term corrosion resistance and poor substrate adhesion, and therefore, it is a promising application prospect to develop a primer composition having good long-term corrosion resistance and excellent metal substrate adhesion.
Disclosure of Invention
In order to improve the corrosion resistance and metal substrate adhesion of the primer, the present application provides a silane-containing, chromium-free coil primer.
The silane-containing chromium-free coil priming paint adopts the following technical scheme:
the silane-containing chrome-free roll priming paint comprises the following components in parts by mass:
polyester resin: 20-60 parts of
Amino resin: 5-20 parts of
Bis [3- (triethoxysilyl) propyl ] tetrasulfide: 0.1 to 10 portions
Ion-exchange corrosion-resistant pigment: 1-15 parts of
Catalyst: 0.3 to 1 portion
Auxiliary agent: 1-5 parts of
Solvent: 30-60 parts.
By adopting the technical scheme, the bis [3- (triethoxysilyl) propyl ] tetrasulfide is a special silane coupling agent, the tetrasulfide bond and the silane structure contained in the tetrasulfide have super-strong affinity to the metal surface, and the adhesion between the coating and the metal substrate can be enhanced by adding the tetrasulfide bond and the silane structure into the primer component; and the tetrasulfide bond in the bis [3- (triethoxysilyl) propyl ] tetrasulfide can promote the combination of the cation in the ion exchange anticorrosive pigment and the corrosion product to form a compact insoluble substance, thereby blocking the continuation of corrosion.
Preferably, the silane-containing chromium-free coil primer comprises the following components in parts by mass:
polyester resin: 30-50 parts of
Amino resin: 8 to 12 portions of
Bis [3- (triethoxysilyl) propyl ] tetrasulfide: 0.5 to 2 portions of
Ion-exchange corrosion-resistant pigment: 7-10 parts of
Catalyst: 0.4 to 0.6 portion
Auxiliary agent: 3-5 parts of
Solvent: 30-40 parts.
By adopting the technical scheme, the proper proportion of the bis [3- (triethoxysilyl) propyl ] tetrasulfide can enhance the corrosion resistance and the metal adhesion of the primer, but the excessive addition can damage the original structure of the primer film and reduce the corrosion resistance of the primer film.
Preferably, the silane-containing chrome-free coil primer further comprises 0.1-1.0 part of anionic conductive polymer.
By adopting the technical scheme, the anionic conductive polymer can ionize anions and associate with cations on the metal surface, so that the metal adhesion of the primer is further increased; and the anionic conductive polymer may further promote the solubility of the ion-exchange anti-corrosive pigment in the solvent.
Preferably, the anionic conductive polymer is one or two of polyethylene dioxythiophene and polystyrene sulfonate.
By adopting the technical scheme, when the metal material is subjected to electrochemical corrosion, the polyethylene dioxythiophene or the polystyrene sulfonate can ionize to generate anions, and the anions react with metal cations generated by ionization on the surface of the metal material to block a current channel, so that the electrochemical corrosion is reduced.
Preferably, the silane-containing chromium-free coil coating primer also comprises 0.1-1.0 part of zinc dialkyl dithiophosphate.
By adopting the technical scheme, the zinc dialkyl dithiophosphate is an oil-soluble zinc salt, can improve the corrosion resistance of the primer after being added, has an antioxidation effect, can slow down the aging of resin and prolongs the service life of the primer.
Preferably, the molecular weight of the polyester resin is 400-10000 Da; the amino resin is methylated amino resin.
By adopting the technical scheme, the methylated amino resin is adopted in the application, has good reactivity, can better improve the crosslinking curing reaction with the polyester resin, and can improve the hardness and the acid and alkali resistance of the polyester resin, so that the corrosion resistance of the polyester resin is improved.
Preferably, the ion-exchange corrosion resistant pigment is calcium ion-exchange silica.
By adopting the technical scheme, calcium ions in the calcium ion exchange type silicon dioxide can be better combined with corrosion products to form insoluble substances, so that the corrosion is blocked; however, the bonding force between the calcium ion exchange type silicon dioxide and the metal surface is not strong, so that the content of the bonding surface between the metal and the primer is low, and the calcium ion exchange type silicon dioxide can be associated to the bonding surface through bis [3- (triethoxysilyl) propyl ] tetrasulfide in the application, so that the corrosion resistance of the calcium ion exchange type silicon dioxide is further improved.
Preferably, the catalyst is a p-methyl benzene sulfonic acid catalyst; the solvent is one or more of No. 100 solvent oil, No. 150 solvent oil, toluene, xylene and ethylene glycol monobutyl ether.
By adopting the technical scheme, the methylbenzenesulfonic acid catalyst is used as a cationic catalyst, so that the crosslinking curing reaction of the resin can be better promoted. The solvents can have good solubility or dispersibility for other components, and can realize phase reaction among the components.
Preferably, the auxiliary agent is one or more of a leveling agent, a dispersing agent and a defoaming agent.
By adopting the technical scheme, the use state of the primer can be better adjusted by adding the auxiliary agent.
Further preferably, the auxiliary agent is titanium dioxide.
By adopting the technical scheme, titanium dioxide is a leveling agent and a dispersing agent with better performance, is used in the primer in the application, and can play a good auxiliary role.
In summary, the present application includes at least one of the following beneficial technical effects:
1. in the application, the primer component is added with bis [3- (triethoxysilyl) propyl ] tetrasulfide and an ion exchange corrosion resistant pigment, and the synergistic use of the two can further improve the corrosion resistance and the metal adhesion performance of the primer.
2. The anionic conductive polymer is added into the primer component, so that the metal adhesion of the primer can be further improved, and the generation of electrochemical corrosion can be reduced.
3. The zinc dialkyl dithiophosphate is added into the primer component, so that the corrosion resistance of the primer is further improved, the antioxidation effect is realized, and the service life of the primer is prolonged.
Detailed Description
The present invention is further illustrated with reference to specific examples, but the scope of the protection parameters of the present invention is not limited thereto.
The primer utilizes the synergistic effect of bis [3- (triethoxysilyl) propyl ] tetrasulfide and an ion exchange corrosion resistant pigment, and further improves the bonding property of the primer and a metal substrate and the corrosion resistance of the primer.
According to different corrosion types, the application further adds an anionic conductive polymer and zinc dialkyl dithiophosphate, so that the corrosion resistance of the product is further improved, and the service life of the primer is prolonged.
The structural formula of bis [3- (triethoxysilyl) propyl ] tetrasulfide used in the examples in this application is shown below:
the polyester resin is produced by Evonik company of Germany with the model number of
LH 820 (molecular weight 5000Da) and
LH 826 (molecular weight 6000Da) polyester resin; or by DSM in the Netherlands
SN 905S 2E5-60 (molecular weight 5000 Da).
Methylated amino resin adopts Allnex
303 or ETERMINO 9603-80 of Taiwan Yongxing, China;
one of Shield C303, Shield AC-3 and Shield C-5 used for the calcium ion-exchange silica;
the catalyst of p-toluenesulfonic acid is NACURE 2500.
In the primer component distribution ratio table in the examples, the components are represented by parts by mass, each part representing 1 g.
Example 1
The composition and proportions of the primers in this example are shown in table 1:
first, a polyester resin (A)
LH 820), methylated amino resins (
303) And a methyl benzene sulfonic acid catalyst (NACURE 2500) are added into a mixed solvent consisting of No. 150 solvent oil and ethylene glycol monobutyl ether, and after stirring and dissolving, the rest other components are added into the mixed solvent, and further stirring and uniformly mixing are carried out, so as to obtain the primer composition.
Example 2
The composition and proportions of the primers in this example are shown in Table 1, and the preparation procedure is identical to that of example 1.
Example 3
The composition and proportions of the primers in this example are shown in Table 1, and the preparation procedure is identical to that of example 1.
Comparative example 1
The composition and proportions of the primers in comparative example 1 are shown in table 1, and the preparation procedure is similar to that of example 1.
Comparative example 2
The composition and proportions of the primers in comparative example 2 are shown in table 1, and the preparation procedure is similar to that of example 1.
Table one: formulation composition of primers for examples 1-3 and comparative examples 1-2
The physical property test of the primers prepared in the examples 1-3 and the comparative examples 1-2 was performed according to the method of GB/T13448-:
table two: comparison of primer Performance in examples 1 to 3 and comparative examples 1 to 2
Results and analysis:
example 1 compared with comparative example 1, in example 1, bis [3- (triethoxysilyl) propyl ] tetrasulfide and shield dex C303 are used instead of strontium chromate, and it can be seen from the performance that the physical properties of the primer in example 1 are equivalent to those of comparative example 1; indicating that a combination of bis [3- (triethoxysilyl) propyl ] tetrasulfide and shield ex C303 can be substituted for strontium chromate; the chromium-free primer material is realized.
Example 1 in comparison with comparative example 2 in which bis [3- (triethoxysilyl) propyl ] tetrasulfide was not added to comparative example 2 but Shieldex C303 component was used instead, comparative example 2 was physically inferior to example 1 in T-bend and neutral salt spray properties, which correspondingly represented a decrease in bonding properties and corrosion resistance to metal substrates. As explained above, the addition of bis [3- (triethoxysilyl) propyl ] tetrasulfide in the present application can act synergistically with the ion-exchange corrosion inhibiting pigment to improve the primer properties.
Examples 4 to 8
The proportion of the primer and the components of examples 4-8 is shown in Table III:
first, a polyester resin (A)
LH 820 or
LH 826), methylated amino resins (
303) Adding methyl benzene sulfonic acid catalyst (NATURE 2500) into mixed solvent composed of No. 150 solvent oil and ethylene glycol monobutyl ether, stirring to dissolve, adding anion conductive polymer (polyethylene dioxythiophene and/or polystyrene sulfonic acid)Acid salt), and after stirring and dissolving, adding the rest other components, and further stirring and uniformly mixing to obtain the primer composition.
Formulation composition of primers in the third example 4-8
The physical property test was performed on the primers in examples 3-8 according to the method in GB/T13448-:
table four: comparison of primer Performance in examples 1 to 3 and comparative examples 1 to 2
The primers of examples 1 and 4 to 8 were coated on the iron sheet, respectively, and all the portions were coated (except for the portions connected to the wires). Taking the iron sheet coated with the primer as a working electrode in a three-electrode system, connecting the iron sheet with the AUTOLAB system through a lead, and measuring the loss of the quality of the working electrode in the corrosive liquid (the test time is 2 h); calculating the metal protection effect of the primer by taking the iron sheet without the primer as a reference; the results are shown in table five:
table five: electrochemical Corrosion resistance Effect of the primers of examples 1 and 4 to 8
It can be seen from table four that the addition of the anionic conductive polymer has no influence on the performance of the primer, mainly because the addition amount of the anionic conductive polymer is relatively small, and the high molecular polymer has good compatibility with the resin in the primer.
It can be seen from table five that the mass loss of the pure iron sheet is relatively large when the pure iron sheet is placed in a hydrochloric acid solution, the primer coated in example 1 shows better corrosion resistance, the protection efficiency can reach more than 95%, and in examples 4 to 8, the conductive polymer added shows super-excellent electrochemical corrosion resistance, the protection efficiency reaches more than 99%, which indicates that the anionic conductive polymer can obviously improve the electrochemical corrosion resistance of the primer.
Examples 9 to 11
The ratios of the primers and components of examples 9-11 are shown in Table six:
first polyester resin (A)
LH 820), methylated amino resins (
303) And a methyl benzene sulfonic acid catalyst (NACURE 2500) is added into a mixed solvent consisting of No. 150 solvent oil and ethylene glycol monobutyl ether, after stirring and dissolving, an anion conducting polymer (polyethylene dioxythiophene) is added into the mixed solvent, after stirring and dissolving, the rest other components are added into the mixed solvent, and the mixture is further stirred and uniformly mixed to obtain the primer composition.
TABLE VI formulation composition of the primers of examples 9-11
The physical properties of the primers prepared in examples 9 to 11 were tested according to the method of GB/T13448-:
TABLE VII: comparison of primer Performance in examples 9-11
After the primers in the embodiments 4 and 9-11 were coated on an iron sheet, the iron sheet was placed in an aging oven at 100 ℃ for 1500 hours, and the condition of the primer layer was observed.
TABLE VIII examples 4 and 9 to 11 resistance to aging
As can be seen from Table VII, the zinc dialkyldithiophosphate has no influence on the performance of the primer, mainly because the zinc dialkyldithiophosphate is oil-soluble zinc salt, has good compatibility with a solvent after being added, and has no influence on the basic performance of the primer because the zinc dialkyldithiophosphate is added in a small amount.
It can be seen from table eight that the primers in examples 4 and 9 to 11 have certain anti-aging performance, and no foaming phenomenon occurs in examples 9 to 11, mainly because the zinc dialkyl dithiophosphate is added in examples 9 to 11, which has an anti-oxidation effect and can slow down the aging of the resin, the anti-aging performance is further improved.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. The silane-containing chromium-free coil coating primer is characterized by comprising the following components in parts by mass:
polyester resin: 20-60 parts of
Amino resin: 5-20 parts of
Bis [3- (triethoxysilyl) propyl ] tetrasulfide: 0.1 to 10 portions
Ion-exchange corrosion-resistant pigment: 1-15 parts of
Catalyst: 0.3 to 1 portion
Auxiliary agent: 1-5 parts of
Solvent: 30-60 parts.
2. The silane-containing chromium-free coil priming paint according to claim 1, which comprises the following components in parts by mass:
polyester resin: 30-50 parts of
Amino resin: 8 to 12 portions of
Bis [3- (triethoxysilyl) propyl ] tetrasulfide: 0.5 to 2 portions of
Ion-exchange corrosion-resistant pigment: 7-10 parts of
Catalyst: 0.4 to 0.6 portion
Auxiliary agent: 3-5 parts of
Solvent: 30-40 parts.
3. The silane-containing chrome-free coil primer according to claim 1 or 2, wherein the silane-containing chrome-free coil primer further comprises 0.1 to 1.0 part of an anionic conductive polymer.
4. The silane-containing, chrome-free coil primer according to claim 3, wherein the anionic conductive polymer is one or both of polyethylene dioxythiophene and polystyrene sulfonate.
5. The silane-containing chromium-free coil primer according to claim 3, wherein said silane-containing chromium-free coil primer further comprises 0.1-1.0 parts of zinc dialkyldithiophosphate.
6. The silane-containing, chrome-free coil primer as recited in claim 1, wherein the polyester resin has a molecular weight of 400-10000 Da; the amino resin is methylated amino resin.
7. The silane-containing, chrome-free coil basecoat of claim 1 wherein the ion-exchange corrosion inhibiting pigment is calcium ion-exchange silica.
8. The silane-containing, chrome-free coil primer of claim 1, wherein the catalyst is a p-toluene sulfonic acid-based catalyst; the solvent is one or more of No. 100 solvent oil, No. 150 solvent oil, toluene, xylene and ethylene glycol monobutyl ether.
9. The silane-containing chrome-free coil primer according to claim 1, wherein the assistant is one or more of a leveling agent, a dispersing agent and an antifoaming agent.
10. The silane-containing, chrome-free coil primer of claim 9, wherein said adjuvant is titanium dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210503766.6A CN114958155A (en) | 2022-05-10 | 2022-05-10 | Silane-containing chromium-free roll priming paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210503766.6A CN114958155A (en) | 2022-05-10 | 2022-05-10 | Silane-containing chromium-free roll priming paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114958155A true CN114958155A (en) | 2022-08-30 |
Family
ID=82982025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210503766.6A Pending CN114958155A (en) | 2022-05-10 | 2022-05-10 | Silane-containing chromium-free roll priming paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114958155A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277068A (en) * | 2011-07-25 | 2011-12-14 | 苏州金近幕墙有限公司 | Primer used for building curtain wall aluminum veneer and preparation method thereof |
| CN105542630A (en) * | 2016-01-22 | 2016-05-04 | 立邦工业涂料(上海)有限公司 | Waterborne coil coating polyester rear face paint and preparation method thereof |
| CN106280921A (en) * | 2016-08-25 | 2017-01-04 | 浙江港流高分子科技有限公司 | A kind of high-temperature wearable coiled material and preparation method thereof |
| CN106497274A (en) * | 2016-11-03 | 2017-03-15 | 马鞍山钢铁股份有限公司 | Silicon steel insulating coating, its preparation method and its using method |
| CN110791183A (en) * | 2019-11-19 | 2020-02-14 | 立邦工业涂料(上海)有限公司 | Matte finish paint composition and application thereof |
| CN111548667A (en) * | 2020-04-14 | 2020-08-18 | 宁波信泰机械有限公司 | Composite polysiloxane protective finish paint for PVD (physical vapor deposition) and preparation method thereof |
-
2022
- 2022-05-10 CN CN202210503766.6A patent/CN114958155A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277068A (en) * | 2011-07-25 | 2011-12-14 | 苏州金近幕墙有限公司 | Primer used for building curtain wall aluminum veneer and preparation method thereof |
| CN105542630A (en) * | 2016-01-22 | 2016-05-04 | 立邦工业涂料(上海)有限公司 | Waterborne coil coating polyester rear face paint and preparation method thereof |
| CN106280921A (en) * | 2016-08-25 | 2017-01-04 | 浙江港流高分子科技有限公司 | A kind of high-temperature wearable coiled material and preparation method thereof |
| CN106497274A (en) * | 2016-11-03 | 2017-03-15 | 马鞍山钢铁股份有限公司 | Silicon steel insulating coating, its preparation method and its using method |
| CN110791183A (en) * | 2019-11-19 | 2020-02-14 | 立邦工业涂料(上海)有限公司 | Matte finish paint composition and application thereof |
| CN111548667A (en) * | 2020-04-14 | 2020-08-18 | 宁波信泰机械有限公司 | Composite polysiloxane protective finish paint for PVD (physical vapor deposition) and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 庄晓彤: "家电卷材涂料的应用与研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101747825B (en) | Environment-friendly solvent-free humidified and rusted anticorrosive paint | |
| CN105838192B (en) | A kind of epoxy polysiloxane coating and preparation method | |
| WO2010018763A1 (en) | Water-base coating composition | |
| CN109181486B (en) | Low-VOC epoxy primer and preparation method thereof | |
| CN101781510A (en) | Bicomponent epoxy resin coating and preparation method thereof | |
| JPH03130141A (en) | Organic coated steel plate excellent in corrosion resistance | |
| CN107400441A (en) | Graphene modified waterborne epoxy anticorrosive paint preparation technology | |
| CN109971313B (en) | Carbon nano material modified epoxy zinc-rich primer and preparation method thereof | |
| CN109880484A (en) | A kind of water-base epoxy thickness slurry anti-decaying paint and its preparation method and application | |
| JPH0713006A (en) | Mirror | |
| US6362255B2 (en) | Cationic electrodeposition coating composition | |
| CN108977043A (en) | Universal single-component water-based metal flash paint of one kind and preparation method thereof | |
| KR20120014426A (en) | Preparing method of 1 component type waterborne epoxy resin | |
| CN110157333A (en) | A kind of water-based anticorrosive paint and preparation method thereof | |
| JPH0651171B2 (en) | Organic composite coated steel sheet with excellent corrosion resistance and weldability | |
| KR100685027B1 (en) | Anticorrosive Coating Composition And Eletro-Galvanized Steel Sheet Coated Therewith | |
| CN114958155A (en) | Silane-containing chromium-free roll priming paint | |
| CN101255303A (en) | Aqueous metal member special-purpose paint and preparation thereof | |
| CN110982385B (en) | Special temperature-resistant coating for corrosion prevention in heat storage tank | |
| CN114592186A (en) | Chromium-free passivation method of zinc powder | |
| EP0420063B1 (en) | Method for forming corrosion resistant coating composition | |
| KR100586454B1 (en) | Anti-corrosion coating composition and zinc-coated steel coated with the composition | |
| CN108690388B (en) | Composite resin and coated base material | |
| CN109111783B (en) | Curing agent for pure polyester powder coating system and preparation method thereof | |
| CN110183932B (en) | Water-based epoxy anticorrosive paint containing composite active salt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220830 |