CN116162383B - Single-component metal protection oil capable of being removed by water and preparation method thereof - Google Patents
Single-component metal protection oil capable of being removed by water and preparation method thereof Download PDFInfo
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- CN116162383B CN116162383B CN202310257776.0A CN202310257776A CN116162383B CN 116162383 B CN116162383 B CN 116162383B CN 202310257776 A CN202310257776 A CN 202310257776A CN 116162383 B CN116162383 B CN 116162383B
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- 239000002184 metal Substances 0.000 title claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000001681 protective effect Effects 0.000 claims abstract description 73
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 67
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 67
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 229920003180 amino resin Polymers 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 5
- 239000008213 purified water Substances 0.000 claims abstract 5
- 238000000034 method Methods 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 27
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 74
- 239000000976 ink Substances 0.000 description 31
- 239000002173 cutting fluid Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 17
- 230000006872 improvement Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a single-component metal protection oil capable of being removed by water and a preparation method thereof. The composition of the protective oil is as follows: 39-73 parts of purified water, 8-20 parts of polyvinyl alcohol, 5-15 parts of aqueous amino resin, 1-5 parts of film forming agent, 0.5-2 parts of defoaming agent, 10-20 parts of filler, 0.5-2 parts of anti-settling agent, 0.5-1 part of antibacterial agent, 0.5-1 part of color paste and 1-3 parts of aqueous adhesive; the preparation method comprises the following steps: (1) Preparing a polyvinyl alcohol solution, injecting water into a container, stirring, adding polyvinyl alcohol, slowly heating to enable the temperature in the container to rise to 95+/-3 ℃ after the polyvinyl alcohol is fully dispersed, preserving heat for 50-70 minutes, continuously stirring until the polyvinyl alcohol is completely dissolved, stirring and cooling to room temperature; (2) And (3) adding the rest components in corresponding parts by weight into the polyvinyl alcohol solution prepared in the step (1) in a certain sequence under the condition of keeping slow stirring, and stirring to obtain a final product.
Description
Technical Field
The invention relates to a metal protection material, in particular to a single-component metal protection oil capable of being removed by water and a preparation method thereof.
Background
When various metals are subjected to fine cutting, a protective ink is often sprayed on the surface of the metal to increase the yield. In order to resist the processing of cutting fluid, the conventional oily protective ink and common water-based protective ink often increase the acid-base resistance and water resistance of the protective oil, and a strong acid or strong alkali deinking agent is often needed for removal after the processing is finished and heating is needed. Most metals other than stainless steel have poor acid and alkali corrosion resistance, such as aluminum alloys, and are often corroded by acid or alkali during removal of the protective oil, resulting in new defects. And the waste liquid after the oily ink or the traditional water-based ink is removed by adopting acid or alkali is not easy to treat, is easy to cause environmental pollution, and is not environment-friendly. Moreover, the traditional water-soluble protective ink has the characteristic of good water solubility at the temperature of 50 ℃, namely, the water-soluble protective ink is instant when meeting water, and can not resist the adverse effects of corrosion, soaking and the like caused by metal cutting fluid in the metal CNC processing process, so that the protective ink is mutually dissolved with the CNC cutting fluid in the metal CNC cutting process, and is separated from the metal surface, so that the protective ink loses efficacy on the metal, the metal is scrapped in the CNC processing process, the processing defective rate of products is obviously increased, and the waste of materials is caused.
Nowadays, along with the general improvement of social environmental awareness, the development of cleaner protective ink has become a necessary trend, and has a huge market application prospect. At present, some of the conventional protective inks commonly used in the market are basically formed by blending strong acid, strong alkali or corresponding solvents, and the conventional protective inks are corrosive to metals or plastics, so that the quality problem is caused by corrosion of the metals by the strong acid or strong alkali ink remover in the process of removing the protective ink from the surface of the processed metal after CNC processing is finished. Moreover, the treatment process of the ink waste liquid generated by removing the strong acid and the strong alkali is more complex, and the ink waste liquid is easy to cause corrosion and other injuries to the environment and production equipment and has adverse effects on the health of workers. For example, in patent CN113307946a, entitled silane modified alkali soluble flexible epoxy acrylic resin, method of preparation and photo-curable glass protective ink containing the same, the protective ink comprises the following components in parts by weight: 30-50 parts of silane modified alkali-soluble flexible epoxy acrylate, 1-5 parts of photoinitiator, 10-30 parts of reactive diluent and 15-40 parts of filler. The ultraviolet light cured glass protective ink has long CNC weak alkaline liquid resistance time, good adhesive force and good scratch resistance. However, after CNC processing, the protective ink needs to be removed by adopting sodium hydroxide strong alkali liquor, the removal condition is harsh, the requirement on equipment is higher, the removal process is easy to corrode the surface of a metal product, and no doubt, the removal process also brings a lot of harm to equipment, environment and worker bodies.
Some conventional inks, which are not resistant to CNC cutting fluids, tend to foam or dissolve or fall off of themselves from the material surface during cutting, resulting in failure or insufficient protection of the metal. For example, in the prior art, a high-performance environment-friendly water-based ink and a preparation method thereof are disclosed in a patent with publication number of CN108976903A, wherein the water-based ink is prepared from the following raw materials in percentage by weight: 40% -60% of connecting material, 15% -20% of pigment, 5% -8% of ethanol, 3% -5% of polyethylene wax, 1% -2.5% of pH regulator, 0.2% -0.5% of bacteriostat, 0.2% -0.5% of defoamer and the balance of deionized water; the connecting material is prepared from the following raw materials in percentage by weight: 95% -99% of polyurethane emulsion and 1% -5% of epoxy resin emulsion, although the VOC emission of the formula is lower, the used waterborne polyurethane has the defects of poor self-thickening property, water resistance and poor glossiness, and particularly cannot resist cutting fluid in the CNC cutting process, and the protection of cut metal is not durable.
When the protective ink is applied and cured, most of the traditional protective ink which is not cured by light is often sprayed on the metal surface, and then needs to be mixed with other reagents and the like, and then sprayed on the metal surface, or both are sprayed on the metal surface at the same time, so that a better adhesion layer is formed on the metal surface, and further the metal is protected from corrosion and other defects in the CNC liquid processing process. However, the addition of the additional agent increases the complexity of the process of operation in the application of the product, and the addition of the additional agent also increases the cost of application of the protective oil significantly.
In the preparation process, at present, most of traditional protective ink has complex preparation process, multiple devices are involved, and the requirements on the devices are high, which undoubtedly increases the preparation and production costs of enterprises and reduces the preparation efficiency.
Therefore, the processing environment of CNC cutting fluid is not required to be removed, no other additives or reagents are required to be added during application, after CNC processing is finished, the ink waste liquid removed from the surface of metal or other materials does not cause environmental pollution, the method is easy to process, reduces adverse effects on the environment and physical injury to operators, has simple preparation process and low equipment requirement, can cooperatively reduce the production and preparation cost of enterprises, and is an actual problem which is in front of the technicians in the field and needs to be solved urgently.
Disclosure of Invention
In order to solve the actual problems in the prior art, the invention aims to provide the single-component metal protection oil capable of being removed by water and the preparation method thereof, wherein the protection oil is of a single-component type, the time for processing the normal-temperature cutting fluid is longer after solidification, and after long-term complete protection is provided for metal, the completely removed protection oil can be realized by pure water only, meanwhile, the protection oil has excellent water resistance and the property of resisting the metal cutting fluid soaking and being difficult to foam and fall under the environment of normal temperature (below 45 ℃), namely under the temperature condition adopted in the CNC processing process, thereby achieving the purpose of completing the long-term protection effect of the whole CNC processing process, and also has strong hydrophilicity under a certain temperature, and the protection oil capable of being quickly dissolved in water from the metal surface in a short time of a few minutes, so that the protection oil can be effectively, quickly and thoroughly removed by using a single aqueous solution, the waste liquid generated after the protection oil removal has little influence on the environment, is more environment-friendly, and the protection oil is reduced, and meanwhile, the protection oil is applied to the surface additives of the metal surface of metal or other enterprises or the production process is simple, and the cost of the production process is reduced, and the production cost is convenient.
The water-removable single-component metal protection oil provided by the application has the following specific scheme:
the single-component metal protection oil capable of being removed by water comprises the following components in parts by weight:
as a further improvement to the above-described aspects, the composition of the metal protective oil satisfies at least one of the following conditions (1) to (4):
(1) The defoamer is selected from octanol, tributyl phosphate TBP, the content of which is 0.05-2 percent,
0.2 to 0.5 percent of at least one of three types of organic silicon;
(2) The anti-settling agent is at least one of fumed silica or bentonite;
(3) The film forming agent is alcohol and/or alcohol ether;
(4) The aqueous adhesive is an epoxy silane coupling agent.
As a further improvement to the above, the polyvinyl alcohol is a polyvinyl alcohol having a degree of polymerization of not more than 3000.
As a further improvement on the scheme, the addition amount of the aqueous amino resin is between 5% and 15%.
As a further improvement to the above-mentioned scheme, the metal protective oil is cured by baking at a temperature of 120 to 150 ℃.
As a further improvement on the scheme, when the metal protective oil needs to be removed from the metal surface at the end of processing, the metal protective oil is soaked or sprayed with hot water at 60-80 ℃ to realize removal.
As a further improvement to the scheme, the filler is talcum powder with the mesh number of 3000-8000.
As a further improvement of the above-mentioned scheme, the ratio of the addition amount of polyvinyl alcohol to the addition amount of the aqueous amino resin is between (8/15) and (20/4).
The application also provides a preparation method of the single-component metal protection oil capable of being removed by water, which comprises the following steps:
(1) Preparing a polyvinyl alcohol solution, injecting water into a container, slowly adding polyvinyl alcohol while stirring, slowly heating until the polyvinyl alcohol is fully dispersed in the water, raising the temperature in the container to 95+/-3 ℃, preserving the heat for 50-70 minutes, continuously stirring until the polyvinyl alcohol powder is completely dissolved in the heat preservation process, stirring and cooling to room temperature;
(2) And sequentially adding the film forming agent, the aqueous amino resin, the defoaming agent, the filler, the anti-settling agent, the antibacterial agent and the color paste into the prepared polyvinyl alcohol solution under the slow stirring state, stirring to uniformly disperse the materials, and continuing stirring for 1.5-3 hours to obtain a final product.
As a further improvement to the above-described scheme, the operation condition of the step (1) is required to satisfy at least one of the following conditions:
A. the temperature of the water injected in the container is lower than 25 ℃;
B. the feeding speed of the polyvinyl alcohol is specifically as follows: in 1L of water, the stirring speed was
Under the condition of 400r/min, the feeding speed is 200-300 g/min;
C. after the addition of the polyvinyl alcohol is finished, the polyvinyl alcohol is fully stirred for 10 to 15 minutes, and then the temperature is raised, and the stirring is kept in the heating process.
Advantageous technical effects
The invention creatively provides a single-component metal protection oil capable of being removed by water and a preparation method thereof, the metal protection oil is simple in components, is mainly prepared from the common wagons raw materials in the field, is convenient to purchase and prepare, but the components defined and preferred by the invention are obtained through creative combination of the conventional raw materials and creative improvement of the proportion, in a system formed by the components, aqueous amino resin can react with hydroxyl groups in polyvinyl alcohol to form certain crosslinking when baked and solidified at the high temperature of 120-150 ℃, so that the purpose of durable protection of the metal is achieved by cutting fluid resistance at normal temperature, and meanwhile, the optimal auxiliary effect is obtained through the optimal proportion of the two components, namely the ratio of the adding amount of the polyvinyl alcohol to the adding amount of the aqueous amino resin is between (8/15) - (20/4), the best and balanced between the subsequent solidification efficiency and the removal efficiency are taken into consideration while the protection against the corrosion of CNC cutting fluid is provided for the metal to the maximum extent.
The protective oil disclosed by the invention not only can form complete and durable protective force on the metal surface in CNC cutting fluid at the temperature below 45 ℃, but also can be completely removed from the metal surface without leaving any residue and completely clean after CNC metal processing is completed because the protective oil has very strong hydrophilicity in the temperature range of 60-80 ℃. Therefore, compared with the traditional protective oil which needs strong acid and strong alkali to remove, the metal oil with limited components and proportions is more environment-friendly, the removal procedure is simpler, the equipment requirement is low, the production cost of enterprises is reduced, the protective oil belongs to the water-based protective oil, and the pure water removal process is more friendly to workers and has lower body harm to workers compared with the non-water-based protective oil and the strong acid and strong alkali removal process. In addition, compared with the traditional protective oil, the components of the curing oil provided by the invention are simpler, and when the curing oil is applied, only the protective oil is sprayed on the metal surface, and other or additional materials such as curing agents and the like are not required to be additionally added, so that the application process is simpler. The protective oil provided by the invention has the advantages of good fluidity, smooth spraying process, difficult blockage or precipitation, uniform thickness of the protective film formed on the metal surface, good consistency of the appearance of the coating, and capability of providing a durable and optimal protective effect on the metal in a cooperative manner. Meanwhile, compared with the traditional preparation method of the protective ink, the preparation method of the metal protective oil provided by the application has only two steps in total, the raw materials of each step are simple, the process is simpler and easier to operate, the requirements on equipment are low, and the preparation are easy to realize, so that the preparation cost and investment of enterprises are greatly reduced.
Detailed Description
The technical solutions of the various embodiments of the present invention will be clearly and completely described below in connection with different embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are all commercially available.
The invention relates to a single-component metal protection oil capable of being removed by water, which comprises the following components in parts by mass:
as a preferable scheme, the above scheme comprises the following components in parts by weight:
for the above composition, where polyvinyl alcohol is a polymer linked by CH2 and polyvinyl alcohol is a repeating chain with one hydroxyl group on each carbon atom on the hydrocarbon chain side:
-CH2-CH (OH) -. Different polyvinyl alcohol structures, different natural characteristics and different purposes. Since polyvinyl alcohol contains a large number of hydroxyl groups, which have strong hydrophilicity, polyvinyl alcohol is generally characterized as a water-soluble polymer and can be melted in water. The solubility of polyvinyl alcohol in water is greatly affected by the degree of alcoholysis. The lower the alcoholysis, the higher the solids it dissolves in water; the higher the alcoholysis degree of polyvinyl alcohol, the more insoluble the water is, therefore, the polyvinyl alcohol with the alcoholysis degree of 70-90 is preferable, and the dissolution effect and the efficiency are found to be better. The aim of high temperature water solubility is achieved by utilizing the characteristic that polyvinyl alcohol is quickly dissolved in hot water. The protective oil with high solid content can be sprayed out to have thick film thickness, and the thicker the film thickness of the protective oil is, the better the product protection effect is. In order to be able to increase the protective oil protective effect, polyvinyl alcohol is specifically selected to have a degree of polymerization of not more than 3000, specifically, the degree of polymerization here may be 3000, 2900, 2800, 2600, 2200, 2000, 1800, 1600, 1400, 1200, 1000, 800, 600, or the like. Such as colali PVA-203, PVA-205, PVA-403, PVA-L-9, etc. And the alcoholysis degree of the polyvinyl alcohol may be specifically selected from 70, 73, 76, 79, 80, 82, 84, 86, 88, 90, etc.
The film forming agent mainly aims at reducing the film forming temperature, and the variety of film forming auxiliary agents is many: examples of alcohols and alcohol ethers are 1, 5-pentanediol and propylene glycol methyl ether (PM) dipropylene glycol methyl ether DPM, ethylene glycol phenyl ether alcohol ester Ten, etc.
The water-based amino resin has the function of reacting with hydroxyl groups in the polyvinyl alcohol to form certain crosslinking under the condition of baking at a high temperature of 150 ℃, so that the aims of resisting cutting fluid at normal temperature and protecting metal for a long time are fulfilled.
The defoaming agent is mainly used for eliminating foam generated in the process of producing and constructing the printing ink on the metal surface, the product is not easy to foam when the defoaming agent is added into a prepared aqueous solution, but a small amount of foam can be generated when the solution concentration is high and the rotating speed is high, and 0.05-2% of octanol, tributyl phosphate TBP or 0.2-0.5% of organic silicon defoaming agent such as Di-high tego-810 can be added for inhibiting the foam. Specifically, the octanol added may be specifically 0.05%, 0.1%, 0.15%, 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2% and the like octanol; the silicone defoamer to be added is specifically 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5% or the like.
The filler is used to adjust the ink adhesion and tinting strength. Too much filler can lead to reduced adhesion and if no filler is added the protective oil does not develop colour, which is detrimental to controlling the film thickness when applied to metal surfaces. The filler is preferably talc. The talc is preferably 3000 to 8000 mesh talc, and the preferable mesh may be 3000, 3500, 4000, 4500, 5000, 6000, 6500, 7000, 7500, 8000 mesh. Since talc powder having a too low mesh number is liable to precipitate, and if the mesh number is too high, the oil absorption is too large, and the fluidity of the protective oil is lowered, resulting in poor spraying in subsequent applications. The talcum powder with the preferable range can reduce precipitation to the greatest extent, and balance the output efficiency of the protective oil, and the simplicity, smoothness and spraying efficiency in the subsequent spraying process.
The anti-settling agent mainly aims at preventing the filler from settling and caking, and fumed silica or bentonite, such as cabot M5, wake N20 and the like, can be selected.
The antibacterial agent mainly has the effect of preventing mildew and odor of protective oil during storage, and can be selected from ceramic SKANE M-8 type antibacterial agent.
The color paste is water-based blue color paste, which is convenient for distinguishing and observing in the application and subsequent removal processes.
The aqueous adhesive can well increase the adhesive force between the protective oil layer and the base material, and the aqueous adhesive adopts epoxy silane coupling agents, such as A-187 of American Union carbon company, KBM-403 of Japanese Xinyue, dow Corning Z-6040 and the like.
As a further improvement on the scheme, the addition amount of the aqueous amino resin is between 5% and 15%. Specifically, 5%, 8%, 10%, 12%, 13%, 15%, etc. are possible. The preferable addition amount of the aqueous polyurethane is 5% -15%, and the crosslinking density is insufficient when the addition amount is insufficient, so that the effect of the cutting fluid resistance is not achieved, the aqueous polyurethane is easily corroded by the cutting fluid in the CNC process, and the meaning of losing protection of oil is lost. However, if the additive is excessively added, the too high crosslinking density can cause that the protective oil is difficult to remove or even impossible to remove at all when the high temperature water is removed after the workpiece is processed, so that the cut metal material cannot be normally applied. Here, in order to avoid the difficulty in removal of the protective oil-water due to the too high crosslink density, the preferable ratio is: according to the addition amount, PVA: the amino resin is just suitable in the range of 8/15-20/4, and can not only resist cutting fluid, but also remove protective oil in water at 70 ℃ within 5 minutes. Because the inventors found that when PVA: the addition amount of the amino resin is more than 20: and 5, the protective oil cannot resist the corrosion of the cutting fluid, and cannot protect metals. And when PVA: the addition amount of the amino resin is less than 8:15, the protective oil is removed by adopting high-temperature water very slowly, the efficiency is very low, when the PVA: the addition amount of the amino resin is less than 8: at 20, the protective oil cannot be removed from the metal surface with hot water. For the amino group, a partially methylated amino group such as cyanotegymel 325, CYMEL385 and the like can be selected.
As a further improvement to the above, the composition of the metal protective oil is required to satisfy at least one of the following conditions:
(1) The defoaming agent is at least one selected from octanol, tributyl phosphate TBP and organosilicon in 0.05-2 wt%;
(2) The anti-settling agent is at least one of fumed silica or bentonite;
(3) The film forming agent is alcohol and/or alcohol ether;
(4) The aqueous adhesive is an epoxy silane coupling agent.
Of the above conditions, the above four conditions are all satisfied at the same time as the most preferable mode, and then three conditions are satisfied, and then two conditions are satisfied, and then one condition is satisfied.
As a further improvement to the above, the protective oil is cured by baking at a temperature of 120 to 150 ℃. The temperature may be 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃. When the product is coated with the protective oil and baked at a high temperature of 120-150 ℃, the hydroxyl in the polyvinyl alcohol can be ensured to react with the amino resin to crosslink, so that the purpose of protecting the product in CNC is achieved, and the sufficiency and the high efficiency of curing are ensured.
As a further improvement to the scheme, when the protective oil needs to be removed from the metal surface at the end of processing, the protective oil is soaked or sprayed with hot water at 60-80 ℃ to realize removal. The water may be at 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, etc. The temperature of the hot water is selected according to comprehensive evaluation of the thickness of the protective oil formed on the metal surface, the hydrophilicity of the protective oil after being solidified on the metal surface and the like, and the temperature of the hot water can be properly reduced when the thickness of the protective oil is thinner or the hydrophilicity is higher, and the temperature of the hot water needs to be increased when the thickness of the protective oil is thicker or the hydrophilicity is lower.
As a further improvement of the scheme, when the protective oil needs to be removed from the metal surface, the protective oil is soaked or sprayed with hot water at 70 ℃ for 30-80 seconds, specifically, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds and the like. The above time range may be more preferably 30 to 55 seconds.
Meanwhile, the application also provides a preparation method of the single-component metal protection oil capable of removing water, which specifically comprises the following steps:
(1) Preparing a polyvinyl alcohol solution, injecting water into a container, slowly adding polyvinyl alcohol while stirring, slowly heating until the polyvinyl alcohol is fully dispersed in the water, raising the temperature in the container to 95+/-3 ℃, preserving the heat for 50-70 minutes, continuously stirring until the polyvinyl alcohol powder is completely dissolved in the heat preservation process, stirring and cooling to room temperature; the incubation time may be specifically 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, or the like. The reasonable heat preservation time can better promote the sufficient dissolution of the polyvinyl alcohol.
(2) And sequentially adding the film forming agent, the aqueous amino resin, the defoaming agent, the filler, the anti-settling agent, the antibacterial agent and the color paste into the prepared polyvinyl alcohol solution under the slow stirring state, stirring to uniformly disperse the materials, and continuing stirring for 1.5-3 hours to obtain a final product. The stirring time can be specifically 1.5, 2, 2.5 and 3 hours, and the stirring is continued for a certain time, so that the full dissolution of all components and the stabilization of the whole system are facilitated.
As a further improvement to the scheme, the operating conditions of step (1) are required to satisfy at least one of the following conditions:
A. the temperature of the water injected in the container is lower than 25 ℃;
B. the feeding speed of the polyvinyl alcohol is specifically as follows: in 1L of water, the stirring speed was 400r/min, and the charging speed was 200 to 300g/min. The feeding speed can be 200g/min, 210g/min, 220g/min, 230g/min, 240g/min, 250g/min, 260g/min, 270g/min, 280g/min, 290g/min, 300g/min and the like, and the feeding speed is as slow as possible on the premise of maintaining the working efficiency of preparation so as to reduce the generation of floccules in the dissolving process of the polyvinyl alcohol and ensure and promote the sufficient dissolving of the floccules.
C. After the addition of the polyvinyl alcohol is finished, the polyvinyl alcohol is fully stirred for 10 to 15 minutes, and then the temperature is raised, and the stirring is kept in the heating process.
By satisfying at least one, two or all of the three conditions, the method can reduce the flocculent or block-shaped substances generated by the polyvinyl alcohol during dissolution to different degrees, promote the dissolution of the polyvinyl alcohol and reduce the occurrence of precipitation and subsequent adverse reaction. The utilization rate of the raw materials is also improved. When the above three conditions are satisfied simultaneously, the optimal dissolution effect of polyvinyl alcohol can be obtained, and precipitation can be minimized.
Examples 1 to 7
Referring to Table 1 below, the components and parts by weight, curing, removal conditions and respective results for the water-removable one-component protective oils of examples 1-7 are shown.
The preparation method of each water-removable single-component protective oil in examples 1-7 comprises the following steps:
(1) Preparing a polyvinyl alcohol solution, injecting water into a container, slowly adding polyvinyl alcohol while stirring, and slowly heating to enable the temperature in the container to rise to 95+/-3 ℃ after the polyvinyl alcohol is fully dispersed in the water, preserving the heat for 50-70 minutes, continuously stirring until the polyvinyl alcohol powder is completely dissolved in the heat preservation process, stirring and cooling to room temperature.
(2) And sequentially adding the film forming agent, the aqueous amino resin, the defoaming agent, the filler, the anti-settling agent, the antibacterial agent and the color paste into the prepared polyvinyl alcohol solution under the slow stirring state, stirring to uniformly disperse the materials, and continuing stirring for 1.5-3 hours to obtain a final product.
Wherein the operating conditions in step (1) satisfy the following three conditions simultaneously:
A. the temperature of the water injected in the container is lower than 25 ℃;
B. the feeding speed of the polyvinyl alcohol is specifically as follows: in 1L of water, the stirring speed was 400r/min, and the charging speed was 200 to 300g/min.
C. After the addition of the polyvinyl alcohol is finished, the polyvinyl alcohol is fully stirred for 10 to 15 minutes, and then the temperature is raised, and the stirring at 400r/min is maintained in the heating process.
The measurement of the relevant properties in the present invention was performed by the following method.
(1) CNC (computer numerical control) cutting fluid
And (3) after the metal base material coated with the protective oil is thermally cured, soaking the metal base material in CNC cutting fluid for 60min at the temperature lower than 50 ℃. Observing whether the ink coating foams or falls off.
(2) Removal performance
And (3) after thermally curing the metal substrate coated with the protective oil, immersing the metal substrate in hot water at 70 ℃ for a protective oil removal experiment, observing whether removal can be performed or not, and recording whether residues exist after removal.
TABLE 1 Components of examples 1-7 and comparative examples 1-4 parts by mass and results of Performance test
As can be seen from the table, the comprehensive properties of the protection oil to be protected in the application are better than those in the comparative examples 1 to 4, and in the examples 1 to 7, the protection oil is not fallen off or dissolved in the cutting process, after CNC processing is finished, the complete and rapid removal can be realized by adopting hot water at 70 ℃, the removal time is the fastest for 30 seconds, the slowest only needs 80 seconds, and no residue exists on the metal surface after the removal. The technical scheme effect that illustrates this application provided can water desorption monocomponent formula protection oil is better, but wide application in CNC cutting metal's protection, because this application curing in-process need not to add extra curing agent, and in the follow-up desorption process, need not to use strong base or strong acid solution to come desorption protection oil, consequently, the waste liquid pollution nature after the protection oil desorption also reduces with it, and is more environmental protection, also reduces the requirement and the corrosion level of equipment, more practices thrift the cost.
The above examples represent only 7 embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A single-component metal protection oil capable of being removed by water is characterized in that: the composition comprises the following components in parts by mass:
wherein, when the protective oil needs to be removed from the metal surface, the protective oil is soaked or sprayed with hot water at 60-80 ℃ for removal.
2. The water-removable one-component type metal shielding oil according to claim 1, wherein the composition of the metal shielding oil satisfies at least one of the following conditions (1) to (4):
(1) The defoaming agent is at least one selected from octanol, tributyl phosphate TBP and organosilicon in 0.05-2 wt%;
(2) The anti-settling agent is at least one of fumed silica or bentonite;
(3) The film forming agent is alcohol and/or alcohol ether;
(4) The aqueous adhesive is an epoxy silane coupling agent.
3. The one-component metal protecting oil of claim 1, wherein the polyvinyl alcohol has a polymerization degree of not more than 3000.
4. The water-removable single-component metal protection oil according to claim 1, wherein the addition amount of the aqueous amino resin is between 5% and 15%.
5. The one-component type metal protecting oil capable of removing water according to claim 1, wherein the metal protecting oil is cured by baking at a temperature of 120-150 ℃.
6. The one-component type metal protecting oil capable of being removed by water according to claim 1, wherein when the protecting oil needs to be removed from the metal surface, the protecting oil is soaked or sprayed with hot water at 70 ℃ for 30-80 seconds.
7. The one-component metal protecting oil capable of being removed by water as claimed in claim 1, wherein the filler is talcum powder with a mesh number of 3000-8000.
8. The one-component metal protecting oil capable of removing water according to claim 1, wherein the addition amount of the polyvinyl alcohol and the addition amount of the aqueous amino resin are between (8/15) and (20/4).
9. A process for the preparation of a water-removable one-component metal protection oil according to any one of claims 1 to 8, comprising in particular the steps of:
(1) Preparing a polyvinyl alcohol solution, injecting purified water into a container, slowly adding polyvinyl alcohol while stirring, and slowly heating until the polyvinyl alcohol is fully dispersed in the purified water to ensure that the temperature in the container is raised to 95+/-3 ℃, preserving the heat for 50-70 minutes, continuously stirring until the polyvinyl alcohol powder is completely dissolved in the heat preservation process, stirring and cooling to room temperature;
(2) And (3) sequentially adding the film forming agent, the aqueous amino resin, the defoaming agent, the filler, the anti-settling agent, the antibacterial agent and the color paste into the polyvinyl alcohol solution prepared in the step (1) under the slow stirring state, stirring to uniformly disperse the aqueous adhesive, and continuing stirring for 1.5-3 hours to obtain a final product.
10. The method of manufacturing according to claim 9, wherein: the operating conditions of step (1) need to satisfy at least one of the following three conditions:
A. the temperature of the purified water injected into the container is lower than 25 ℃;
B. the feeding speed of the polyvinyl alcohol is specifically as follows: in 1L of purified water, under the condition that the stirring speed is 400r/min, the feeding speed is 200-300 g/min;
C. after the addition of the polyvinyl alcohol is finished, the polyvinyl alcohol is fully stirred for 10 to 15 minutes, and then the temperature is raised, and the stirring is kept in the heating process.
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| CN110183921A (en) * | 2019-06-21 | 2019-08-30 | 东莞大宝化工制品有限公司 | A kind of aqueous polishes of salt spray resistance of metal erosion material and preparation method thereof |
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| CN110183921A (en) * | 2019-06-21 | 2019-08-30 | 东莞大宝化工制品有限公司 | A kind of aqueous polishes of salt spray resistance of metal erosion material and preparation method thereof |
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