CN114621656A - Precoated coiled material primer with low VOC (volatile organic compound) emission as well as preparation method and application thereof - Google Patents
Precoated coiled material primer with low VOC (volatile organic compound) emission as well as preparation method and application thereof Download PDFInfo
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- CN114621656A CN114621656A CN202011444286.4A CN202011444286A CN114621656A CN 114621656 A CN114621656 A CN 114621656A CN 202011444286 A CN202011444286 A CN 202011444286A CN 114621656 A CN114621656 A CN 114621656A
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- low voc
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001225 polyester resin Polymers 0.000 claims abstract description 77
- 239000004645 polyester resin Substances 0.000 claims abstract description 77
- 239000000049 pigment Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000945 filler Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 79
- 229920003180 amino resin Polymers 0.000 claims description 49
- 239000003822 epoxy resin Substances 0.000 claims description 36
- 229920000647 polyepoxide Polymers 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002318 adhesion promoter Substances 0.000 claims description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003849 aromatic solvent Substances 0.000 claims description 6
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 32
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 238000000576 coating method Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 239000003377 acid catalyst Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 150000007524 organic acids Chemical group 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical group CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- -1 phosphate ester Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 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
- 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
-
- 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a precoated coiled material primer with low VOC (volatile organic compound) emission and a preparation method and application thereof. The precoated coiled material primer with low VOC emission comprises matrix resin, a curing agent, a pigment filler and a solvent, wherein the matrix resin is polyester resin, the hydroxyl value of the polyester resin is 15-35mg KOH/g, and the acid value of the polyester resin is 6-12 mg KOH/g.
Description
Technical Field
The invention relates to the field of coatings. More particularly, it relates to a low VOC emission pre-coated coil primer, a method for preparing the same and the use of the same in pre-coated coils.
Background
The precoated coiled material is also called organic coating steel plate, color steel plate and plastic composite steel plate. The user can directly machine and mold the coating or directly use the coating without coating. The traditional technology of processing and forming a metal sheet product first and then coating the coating is changed into the technology of pre-coating the coating on the metal sheet first and then processing and forming, thereby greatly simplifying the production technology of the metal sheet product. The coating of the pre-coated coiled material can be divided into a pretreatment layer and a coating layer, wherein the pretreatment layer is used for pretreatment of coiled steel by a coiled material manufacturer, and the coating layer mainly comprises primer, finish paint and back paint. The coil primer is directly coated on the pretreatment layer and mainly has the following functions: 1. the corrosion resistance of the coiled material is improved, and 2, a foundation is provided for finish paint.
Most of precoated coil coatings in the current market are solvent-based, and the proportion of organic solvents in formula components is high, so that two influences can be brought: firstly, the VOC emission of the coating product does not meet the requirement of environmental protection regulations (the VOC of the coating product is less than or equal to 420g/L according to the national regulations), and the products which exceed the standard can be forbidden to be sold or the consumption tax with a certain rate is collected; secondly, most organic solvents have pungent odor, so that the working environment in the product coating construction process is relatively severe, and the physical and psychological health of field workers is not facilitated.
In view of the above, there is a need to provide a green and environmentally friendly pre-coated coil primer with low VOC emission and low odor.
Disclosure of Invention
The invention aims to provide a precoated coil primer which has low VOC emission, small smell and excellent performance. The VOC value of the precoated coil primer with low VOC emission is less than 420g/L by setting parameters such as a proper weight ratio of solid parts in the polyester resin to solid parts in the amino resin (polyester-amino ratio) and a proper weight ratio of the sum of the solid parts in the polyester resin and the solid parts in the amino resin to pigment and filler (pigment ratio). Tests show that after the precoated coiled material primer with low VOC emission is matched with a finish system, the pencil hardness of a pencil test can reach 3H, T bending test, 2T can not peel off, MEK (methyl ethyl ketone) wiping resistance can exceed 100 times, the acid and alkali resistance of the paint surface is good, and the salt spray performance is qualified.
In order to achieve the purpose, the invention adopts the following technical scheme: the precoated coiled material primer with low VOC emission comprises matrix resin, a curing agent, pigment and filler and a solvent; the base resin is polyester resin, the hydroxyl value of the polyester resin is 15-35mg KOH/g, and the acid value of the polyester resin is 6-12 mg KOH/g.
In some embodiments, the polyester resin is a linear polyester resin or a partially branched polyester resin and has a number average molecular weight of 2000 to 3500.
In some embodiments, the polyester resin has a percent solids of 75%.
In the present application, the polyester resin with a large hydroxyl number is selected to increase the crosslink density of the low VOC emission pre-applied coil primer to obtain a better MEK resistance. Therefore, in the application, the linear or partially branched polyester resin with the hydroxyl value of 15-35mg KOH/g, the acid value of 6-12 mg KOH/g and the number average molecular weight of 2000-3500 is selected, so that the precoated coil primer with low VOC emission has high hardness, high flexibility, high processability and high adhesive force.
In some preferred embodiments, the polyester resin may be NSY-9984 from Nippon paint (China) Inc.
In some embodiments, the weight ratio of the solid parts in the polyester resin to the solid parts in the curing agent is (5-10): 1. That is, (parts by weight of polyester resin × solid content of polyester resin)/(parts by weight of curing agent × solid content of curing agent): 1: 5-10.
In some embodiments, the curing agent contains an amino resin.
In some preferred embodiments, the amino resin is hexamethoxymethylmelamine resin. Preferably, the solid content of the amino resin is 95-99%. Preferably, the amino resin may be CYMEL303 from cyanotex, usa, with a solids content of 98%.
In some embodiments, the pre-applied coil primer further comprises an epoxy resin in the composition. The weight ratio of the solid in the epoxy resin to the solid in the amino resin is (0.5-1.5): 1. That is, (part by weight of epoxy resin × solid content of epoxy resin)/(part by weight of amino resin × solid content of amino resin): 1 (0.5 to 1.5).
In some embodiments, the epoxy resin is a bisphenol a epoxy resin. Such as but not limited to EPIKOTE in Vast chemicalTMResin 828EL。
In some embodiments, the solvent is one or more of propylene glycol methyl ether acetate, low naphthalene aromatic solvent, dibasic ester, and ethylene glycol monobutyl ether.
In some embodiments, the weight ratio of the polyester resin to the solvent is (2.0-6.5): 1.
In some embodiments, the pigment and filler is one or a mixture of rutile, anatase titanium dioxide, barium sulfate, an anti-rust pigment and kaolin.
In some embodiments, the weight ratio of the sum of the solids in the polyester resin and the curing agent and the epoxy resin to the pigment filler is (1.0-3.0): 1. That is, (1.0 to 3.0) 1 part by weight of polyester resin × solid content of polyester resin + part by weight of curing agent × solid content of curing agent + part by weight of epoxy resin × solid content of epoxy resin)/1 part by weight of pigment/filler/(1.0 to 3.0 parts by weight of polyester resin × solid content of polyester resin + part by weight of curing agent × solid content of curing agent + part by weight of epoxy resin × solid content of epoxy resin).
In some embodiments, the low VOC emission pre-applied coil primer further comprises an auxiliary agent, the auxiliary agent being at least one of a catalyst, an adhesion promoter, an anti-settling agent, and a matting agent.
In some embodiments, the catalyst is an organic acid catalyst. In some preferred embodiments, the organic acidic catalyst is dinonylnaphthalenesulfonic acid. Such as but not limited to those of the King chemical industry
1051。
In some embodiments, the anti-settling agent is untreated sintered silica gel. Such as, but not limited to, CABOSIL M-5 from cabot corporation.
In some embodiments, the adhesion promoter is a phosphate ester adhesion promoter. Such as, but not limited to, Lumboyant
2063。
In the present application, there is also provided a method of preparing the above-described low VOC emission pre-applied coil primer, the method comprising: mixing and grinding matrix resin, pigment and filler and partial solvent at a grinding temperature not higher than 50 ℃ to obtain slurry; and adding a curing agent and the residual solvent into the slurry, and uniformly mixing to obtain the low VOC emission precoated coil primer.
In the present application, there is also provided the use of the above-mentioned low VOC emission pre-applied coil primer in a pre-applied coil.
The invention has the following beneficial effects:
1. the low VOC emission pre-applied coil primers described herein have Volatile Organic Compounds (VOC) less than 420g/l and low odor;
2. the precoated coil primer with low VOC emission can be quickly cured (more than or equal to 20s) at the temperature of 204-232 ℃ of a metal Plate (PMT);
3. the hardness of the precoated coiled material primer with low VOC emission can reach 3H, the pressure resistance is excellent, and the reverse adhesion of the back paint and the finish paint is avoided;
4. the T-bend of the precoated coil primer with low VOC emission can reach 2T without stripping, the flexibility is good, the adhesive force is excellent, and the paint stripping phenomenon in the processing and processing processes is avoided;
5. the low VOC emission pre-applied coil primers described herein can have more than 20 MEK rubs;
6. the precoated coiled material primer with low VOC emission has the advantages of high solid content, high coating rate and cost saving under the construction viscosity.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
In this embodiment, a precoated coil primer with low VOC emission is provided, which comprises the following components in parts by weight:
the polyester resin is linear polyester resin or partially branched polyester resin, the hydroxyl value is 18mg KOH/g, the acid value is 12mg KOH/g, the number average molecular weight is 2800, and the solid percentage is 75%.
The amino resin is CYMEL303 of Cyanote company in the United states, and the solid content is 98 percent.
The epoxy resin is EPIKOTE in Hansen chemical industryTMResin 828EL, 100% solids.
The pigment and filler is prepared by mixing rutile titanium dioxide, barium sulfate, an anti-rust pigment and kaolin according to the weight ratio of 2:1:2: 1; wherein the titanium dioxide is R-216 titanium dioxide of Zhonghua original titanium dioxide; the barium sulfate is precipitated barium sulfate in Hebei new crystal chemical industry; the rust-proof pigment is 801 lemon strontium chrome yellow of Shanghai Junma chemical industry Co., Ltd; the kaolin is calcined kaolin of inner Mongolia Kaolin powder GmbH.
The mixed solvent is propylene glycol methyl ether acetate, low-naphthalene aromatic solvent, dibasic ester and ethylene glycol monobutyl ether, and the weight ratio of the propylene glycol methyl ether acetate to the low-naphthalene aromatic solvent to the dibasic ester to the ethylene glycol monobutyl ether is 1:1: 1:1.
The organic acid catalyst is in the chemical industry of King
1051。
The anti-settling agent is CABASIL M-5 from Cabot corporation.
The phosphate adhesion promoter is luobu
2063。
The preparation method of the precoated coil primer with low VOC emission comprises the following steps:
1) mixing and grinding 40-50 parts of polyester resin, 20-30 parts of pigment and filler, 0.1-0.3 part of anti-settling agent and 3-7 parts of solvent to obtain slurry; the grinding temperature is not more than 50 ℃;
2) adding 3-4 parts of amino resin, 3-4 parts of epoxy resin, 0.2-0.3 part of organic acid catalyst, 1-2 parts of phosphate adhesion promoter and 5-11 parts of mixed solvent into the slurry, and mixing to obtain the low VOC emission pre-coated coil primer.
In this example, the weight ratio of the solid parts of the polyester resin to the solid parts of the amino resin was 9: 1, the weight ratio of the pigment filler to the sum of the solid components of the polyester resin, the amino resin and the epoxy resin is 0.75: 1.
example 2
In this embodiment, a precoated coil primer with low VOC emission is provided, which comprises the following components in parts by weight:
the matrix resin is polyester resin, particularly linear polyester resin or partially branched polyester resin, the hydroxyl value of the polyester resin is 30mgKOH/g, the acid value of the polyester resin is 10mgKOH/g, the number average molecular weight is 3200, and the solid content is 74-76%.
The pigment and filler is prepared by mixing rutile titanium dioxide, barium sulfate, an anti-rust pigment and kaolin according to the weight ratio of 2:1:2: 1; wherein the titanium dioxide is R-216 titanium dioxide of Zhonghua original titanium dioxide; the barium sulfate is precipitated barium sulfate in Hebei new crystal chemical industry; the rust-proof pigment is 801 lemon strontium chrome yellow of Shanghai Junma chemical industry Co., Ltd; the kaolin is calcined kaolin of inner Mongolia Kaolin powder GmbH.
The mixed solvent is propylene glycol methyl ether acetate, low-naphthalene aromatic solvent, dibasic ester and ethylene glycol monobutyl ether, and the weight ratio of the propylene glycol methyl ether acetate to the low-naphthalene aromatic solvent to the dibasic ester to the ethylene glycol monobutyl ether is 1:1: 1:1.
The amino resin is CYMEL303 of Cyanote company in the United states, and the solid content is 98 percent.
The epoxy resin is EPIKOTE in Hansen chemical industryTMResin 828EL, solids content 100%.
The organic acid catalyst is in the chemical industry of King
1051。
The anti-settling agent is CABASIL M-5 from Cabot corporation.
The phosphate adhesion promoter is luobu
2063。
The weight ratio of the solid parts of the polyester resin to the solid parts of the amino resin is 10: 1, the weight ratio of the pigment filler to the sum of the solid parts of the polyester resin, the amino resin and the epoxy resin is 0.8: 1.
in this embodiment, the preparation method of the pre-coated coil primer with low VOC emission includes the steps of:
mixing and grinding the polyester resin, the pigment and filler, the anti-settling agent and a part of solvent at a grinding temperature of not more than 50 ℃ to obtain slurry; and the number of the first and second groups,
and adding the amino resin, the epoxy resin, the organic acid catalyst, the adhesion promoter and the residual solvent into the slurry, mixing, adding the matting powder under a stirring condition, stirring at a high speed for 30min, adding the residual solvent to adjust the viscosity to 120 s, and measuring at 25 ℃ by using a paint-4 cup to obtain the low VOC emission precoated coil primer.
The low VOC emission precoated coil primer obtained in this example was further subjected to performance tests, and the test items, test methods and test results are listed in table 1.
TABLE 1 test items, test methods and test results for precoated coil primers with low VOC emissions
| Inspection item | Inspection method | Test results |
| VOC | Specific gravity: GB 6750-86; solid content: GB/T6740- | ＜420g/L |
| Hardness of pencil | ASTM D-3363 | ≥3H |
| Bending test | ASTM D-4145 | ≤2T |
| Reverse impact | ASTM D-2794 | ≥9J |
| MEK resistance | GB/T 13448-2006 10 | ≥150 |
| Resistance to 5% HCL | ASTM D-1308 | Without change |
| 5% NaOH resistance | ASTM D-1308 | Without change |
| Neutral salt spray resistance test for 1000h | ASTM B-117 | Unilateral corrosion is less than or equal to 5mm |
In table 1, the inspection item VOC is a volatile organic compound calculated by testing the specific gravity and solid content of the primer.
The test items pencil hardness, bending test, MEK resistance, 5% HCL resistance, 5% NaOH resistance and neutral salt spray resistance were all tested after 1000h of test with the low VOC emission pre-applied coil primer of this example together with a top coat, such as a lippo PCM100 top coat, applied to form a primer top coat system.
Specifically, the method comprises the following steps: the hardness of the pencil is tested by a Mitsubishi pencil, and the surface is required not to be scratched.
Bending test: no flaking is required after testing of primer matched topcoat (e.g., Nippon PCM100 topcoat) systems.
MEK resistance: and (3) testing the primer matched finish (such as Nippon PCM100 finish) system, wherein the number of times of reciprocating is 1 kilogram of force.
Resistance to 5% HCL: and (3) testing a primer matching finish (such as Nippon PCM100 finish) system, and soaking a paint film into hydrochloric acid with the volume concentration of 5%, wherein the test temperature is 25 ℃, and testing for 24 hours.
Resistance to 5% NaOH: and (3) testing a primer matched finish (such as Nippon PCM100 finish) system, wherein a paint film is immersed in sodium hydroxide with the mass concentration of 5%, and the test temperature is 25 ℃ for 24 hours.
Neutral salt spray resistance 1000h experiment: and (3) performing a post-test on a primer matching finish (such as Nippon PCM100 finish) system, manufacturing a plate according to the specification of 150mm in length and 75mm in width, wherein the two long edges are respectively a front cut and a back cut, and the center of the plate surface is scribed.
Through inspection, the precoated coil primer with low VOC emission can be rapidly cured (for not less than 20s) at the temperature of 204-232 ℃ of a metal Plate (PMT). In addition, as shown in table 1, the hardness of the primer of the low-VOC-emission precoated coil reaches 3H, the T-bend reaches 2T after the primer is matched with the finish, peeling does not occur, the MEK wiping resistance exceeds 150 times, the acid and alkali resistance is good, and the salt spray performance is qualified.
Example 3
In this embodiment, a precoated coil primer with low VOC emission is provided, which comprises the following components in parts by weight: 45 parts of polyester resin, 4 parts of amino resin, 3 parts of epoxy resin, 28 parts of pigment and filler, 0.1 part of anti-settling agent, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 18 parts of mixed solvent.
The preparation method of the precoated coil primer with low VOC emission comprises the following steps:
1) mixing 45 parts of polyester resin, 28 parts of pigment and filler, 0.1 part of anti-settling agent and 7 parts of mixed solvent, and grinding to obtain slurry; the grinding temperature is not more than 50 ℃;
2) adding 4 parts of amino resin, 3 parts of epoxy resin, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 11 parts of solvent into the slurry, and mixing to obtain the low-VOC-emission precoated coil primer.
In this example, the selection of the kind of each component was the same as in example 2.
In this example, the percentage of solids of the polyester resin was 75% and the percentage of solids of the amino resin was 98%. The weight ratio of the solid parts in the polyester resin to the solid parts in the amino resin is (9): 1, the weight ratio of the pigment filler to the sum of the solid parts of the polyester resin, the amino resin and the epoxy resin is 0.7: 1. the test results are similar to table 1.
Example 4
In this embodiment, a precoated coil primer with low VOC emission is provided, which comprises the following components in parts by weight: 50 parts of polyester resin, 3.8 parts of amino resin, 3 parts of epoxy resin, 30 parts of pigment and filler, 0.1 part of anti-settling agent, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 18 parts of mixed solvent.
The preparation method of the precoated coil primer with low VOC emission comprises the following steps:
1) mixing and grinding 50 parts of polyester resin, 30 parts of pigment and filler, 0.1 part of anti-settling agent and 7 parts of solvent to obtain slurry; the grinding temperature is not more than 50 ℃;
2) adding 3.8 parts of amino resin, 3 parts of epoxy resin, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 11 parts of solvent into the slurry, and mixing to obtain the low VOC emission precoated coil primer.
In this example, the selection of the kind of each component was the same as in example 2.
In this example, the percentage of solids of the polyester resin was 75% and the percentage of solids of the amino resin was 98%. The weight ratio of the solid parts in the polyester resin to the solid parts in the amino resin is 10: 1, the weight ratio of the pigment filler to the sum of the solid parts of the polyester resin, the amino resin and the epoxy resin is 0.7: 1. the test results were similar to example 1. The test results are similar to table 1.
Example 5
In this embodiment, a precoated coil primer with low VOC emission is provided, which comprises the following components in parts by weight: 40 parts of polyester resin, 3 parts of amino resin, 3 parts of epoxy resin, 30 parts of pigment and filler, 0.1 part of anti-settling agent, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 18 parts of mixed solvent.
The preparation method of the precoated coil primer with low VOC emission comprises the following steps:
1) mixing and grinding 40 parts of polyester resin, 30 parts of pigment and filler, 0.1 part of anti-settling agent and 7 parts of solvent to obtain slurry; the grinding temperature is not more than 50 ℃;
2) adding 3 parts of amino resin, 3 parts of epoxy resin, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 11 parts of solvent into the slurry, and mixing to obtain the low-VOC-emission precoated coil primer.
In this example, the selection of the kind of each component was the same as in example 2.
In this example, the percentage of solids of the polyester resin was 75% and the percentage of solids of the amino resin was 98%. The weight ratio of the solid parts in the polyester resin to the solid parts in the amino resin is 10: 1, the weight ratio of the pigment filler to the sum of the solid components of the polyester resin, the amino resin and the epoxy resin is 0.9: 1. the test results are similar to table 1.
Comparative example 1
In this comparative example, a pre-coil primer was provided, which was prepared by a method comprising the steps of:
1) grinding 45 parts of polyester resin, 28 parts of pigment and filler, 0.1 part of anti-settling agent and 7 parts of solvent to obtain slurry;
2) 8 parts of amino resin, 3 parts of epoxy resin, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 11 parts of mixed solvent are added into the slurry and mixed to obtain the pre-coating coiled material primer.
In this comparative example, the selection of the kind of each component was the same as in example 1.
In this comparative example, the percentage of solids of the polyester resin was 75%, and the percentage of solids of the amino resin was 98%. The weight ratio of the solid parts in the polyester resin to the solid parts in the amino resin is 4.2: 1, the weight ratio of the pigment filler to the sum of the solid parts of the polyester resin, the amino resin and the epoxy resin is 1: 1.57.
Comparative example 2
In this comparative example, a pre-coil primer was provided, which was prepared by a method comprising the steps of:
1) grinding 50 parts of polyester resin, 11.8 parts of pigment and filler, 0.1 part of anti-settling agent and 7 parts of solvent to obtain slurry;
2) adding 3.8 parts of amino resin, 6 parts of epoxy resin, 0.2 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 11 parts of mixed solvent into the slurry, and mixing to obtain the pre-coating coiled material primer.
In this comparative example, the selection of the kind of each component was the same as in example 2.
In this comparative example, the percentage of solids of the polyester resin was 75%, and the percentage of solids of the amino resin was 98%. The weight ratio of the solid parts in the polyester resin to the solid parts in the amino resin is 10: 1, the weight ratio of the pigment filler to the sum of the solid parts of the polyester resin, the amino resin and the epoxy resin is 1: 4.
Comparative example 3
In this comparative example, a pre-coil primer was provided, which was prepared by a method comprising the steps of:
1) 45 parts of polyester resin, 81.1 parts of pigment and filler, 0.1 part of anti-settling agent and 7 parts of solvent are ground to obtain slurry;
2) adding 4 parts of amino resin, 3 parts of epoxy resin, 0.4 part of organic acid catalyst, 2 parts of phosphate adhesion promoter and 11 parts of mixed solvent into the slurry, and mixing to obtain the pre-coated coil primer.
In this comparative example, the selection of the kind of each component was the same as in example 2.
In this comparative example, the percentage of solids of the polyester resin was 75%, and the percentage of solids of the amino resin was 98%. The weight ratio of the solid parts in the polyester resin to the solid parts in the amino resin is 9: 1, the weight ratio of the pigment filler to the sum of the solid parts of the polyester resin, the amino resin and the epoxy resin is 1: 0.5.
The low VOC emission precoated coil primers of comparative examples 1 to 3 were further subjected to performance tests, the test items, test methods and test results are listed in table 2.
Table 2 pre-coated coil primer performance test results of comparative examples
As shown by the data in tables 1 and 2, the low VOC emission pre-applied coil primer of the present application can increase the crosslinking density of the low VOC emission pre-applied coil primer by selecting the polyester resin with a large hydroxyl value, and obtain a better MEK resistance value. And by setting parameters such as a proper weight ratio of the solid in the polyester resin to the solid in the amino resin (polyester-amino ratio), a weight ratio of the sum of the solid in the polyester resin, the solid in the amino resin and the solid in the epoxy resin to the pigment and filler (pigment ratio) and the like, better test results such as pencil hardness, bending test, reverse impact test, 5% HCL resistance, 5% NaOH resistance, neutral salt spray resistance test and the like are obtained.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations and modifications can be made on the basis of the above description, and not exhaustive enumeration of all embodiments, and obvious variations and modifications can be made without departing from the scope of the present invention.
Claims (10)
1. The precoated coil primer with low VOC (volatile organic compound) emission comprises matrix resin, a curing agent, pigment fillers and a solvent, and is characterized in that the matrix resin is polyester resin, the hydroxyl value of the polyester resin is 15-35mg KOH/g, and the acid value of the polyester resin is 6-12 mg KOH/g.
2. The low VOC pre-coated coil primer of claim 1, wherein said polyester resin is a linear polyester resin or a partially branched polyester resin and has a number average molecular weight of 2000-3500.
3. The low VOC pre-applied coil primer according to claim 1, wherein the weight ratio of the solid content of the polyester resin to the solid content of the curing agent is (5-10): 1.
4. The low VOC emission pre-applied coil primer according to claim 1, wherein the curing agent comprises an amino resin; preferably, the amino resin is hexamethoxymethylmelamine resin.
5. The low VOC pre-applied coil primer of claim 4, further comprising an epoxy resin; preferably, the epoxy resin is a bisphenol a epoxy resin; preferably, the weight ratio of the solid parts in the epoxy resin to the solid parts in the amino resin is (0.5-1.5): 1.
6. The low VOC pre-applied coil primer according to claim 1, wherein said solvent is one or a mixture of propylene glycol methyl ether acetate, low naphthalene aromatic solvent, dibasic ester, and ethylene glycol monobutyl ether; preferably, the weight ratio of the polyester resin to the solvent is (2.0-6.5): 1.
7. The low VOC pre-coated coil primer as recited in claim 1, wherein said pigment and filler is one or a mixture of rutile, anatase titanium dioxide, barium sulfate, anti-rust pigment and kaolin; preferably, the weight ratio of the sum of the solid part in the polyester resin, the solid part in the curing agent and the solid part in the epoxy resin to the pigment and filler is (1.0-3.0): 1.
8. The low VOC emission pre-applied coil primer according to claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is at least one of a catalyst, an adhesion promoter, an anti-settling agent, and a matting agent.
9. A method of preparing a low VOC emission pre-applied coil primer according to any one of claims 1 to 8, comprising:
mixing and grinding matrix resin, pigment and filler and partial solvent at a grinding temperature not higher than 50 ℃ to obtain slurry; and the number of the first and second groups,
and adding a curing agent and the residual solvent into the slurry, and uniformly mixing to obtain the precoated coil primer with low VOC (volatile organic compound) emission.
10. Use of a low VOC emission pre-coated web primer according to claim 1 in a pre-coated web.
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| CN202011444286.4A CN114621656A (en) | 2020-12-11 | 2020-12-11 | Precoated coiled material primer with low VOC (volatile organic compound) emission as well as preparation method and application thereof |
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