CN102212305B - Method for improving pinholes and levelling property of hydroxyalkylamide/polyester powder paint - Google Patents
Method for improving pinholes and levelling property of hydroxyalkylamide/polyester powder paint Download PDFInfo
- Publication number
- CN102212305B CN102212305B CN 201110112793 CN201110112793A CN102212305B CN 102212305 B CN102212305 B CN 102212305B CN 201110112793 CN201110112793 CN 201110112793 CN 201110112793 A CN201110112793 A CN 201110112793A CN 102212305 B CN102212305 B CN 102212305B
- Authority
- CN
- China
- Prior art keywords
- powder coating
- polyester
- hydroxyalkyl amide
- polyester powder
- hbpu
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a method for improving the pinholes and levelling property of hydroxyalkylamide/polyester powder paint. After the existing hydroxyalkylamide/polyester powder paint is cured, pinholes are generated on the surface of the paint. The method comprises the following steps: firstly, adopting the highly branched polymer synthesis method and using isocyanate monomer and polyfunctional monomer to synthesize highly branched polyurethane solution; secondly, using water to precipitate the solution, performing suction filtering, drying to obtain highly branched polyurethane powder, mixing the highly branched polyurethane powder with hydroxyalkylamide/polyester powder paint according to a ratio, using a double-screw extruder to melt, extrude and tablet the mixture and obtain sheet, grinding the sheet to fine powder, and sieving to obtain the modified hydroxyalkylamide/polyester powder paint. By adopting the method, the problem that as the viscosity of the powder paint is increased too fast in the curing process, pinholes are generated, can be obviously improved, the curing speed can be reduced, the effect of high levelling can be realized and high thickness coating of the powder paint is easy to realize.
Description
Technical field
The invention belongs to the powder coating technical field, relate to a kind of method of improving the pin hole and the levelling property of hydroxyalkyl amide/polyester powder coating.
Background technology
Powder coating is developed rapidly at coatings industry circle with its energy-conserving and environment-protective.Especially the outdoor powder coating is used extensive day by day.At present, hydroxyalkyl amide/polyester powder coating is the latest developments of weathering resistance art of powder coatings, as topmost substitute in TGIG (three-glycidyl based isocyanate)/polyester system coating, it is that a class is nontoxic, the powder coating that weather resistance is more excellent.But, also there is certain defective in hydroxyalkyl amide/polyester powder coating, having water molecules in the solidified process overflows, can produce pin hole in film coated surface, not only influence outward appearance but also can cause water tolerance, chemical-resistant descends, so needs increase the degasifying effect of curing system, produce sublimation simultaneously in the change surface tension, make that water molecules is easier to be overflowed, st-yrax is a kind of of the most normal use, though add the pin hole that st-yrax can significantly be eliminated film coated surface,, benzoic adding makes to film and is easy to generate xanthochromia, has brought negative impact for the final performance of powder coating.At present, a lot of additives develop successively, solve this problem, but still are benzoic degasifying effect the best at present.Additive and st-yrax be used to increase degasifying effect and reduce xanthochromia be a good selection, but incidental xanthochromia problem has increased new problem for again the application of powder coating, therefore, develop some new materials, can good consistency be arranged with coating resin, can increase the levelling property of powder coating, improve bubble and remove threshold value, reduce the appearance of pin hole, have market outlook and using value.
Highly-branched polymers is because its novel structure, unique properties has also caused widely at coating circle to be paid close attention to, highly-branched polymers has spherical compacted molecular structure, unique cavity and a large amount of branching units make highly-branched polymers have lower viscosity, high resolution, multifunctionality and film-forming properties etc. are the very potential coating resins of a class.Highly-branched polymers is used for powder coating, utilize its cavity and branched structure, can help small molecules from system, to remove, significantly improve in the powder coating solidification process producing the pin hole problem too soon because viscosity rises, and, because a large amount of terminal end groups can also part use as solidifying agent through the design modification, reduce solidified speed, improve bubble and remove threshold value, play the effect that improves the levelling effect, help the thick of powder coating to be coated with.
Summary of the invention
The objective of the invention is to the deficiency that exists in existing hydroxyalkyl amide/polyester powder coating, a kind of method of improving powder coating pin hole and levelling property is provided.
The inventive method is to add highly branched urethane in the hydroxyalkyl amide powder coating, the levelling property of the powder systems when increasing hydroxyalkyl amide/polyester powder coating and solidifying, improve bubble and remove threshold value, reduce the appearance of pin hole, avoid adding the phenomenon of the flavescence of filming that st-yrax and other levelling additive cause simultaneously.
The concrete steps of the inventive method are as follows:
Step (1). adopt the highly-branched polymers synthetic method with isocyanate-monomer and the synthetic highly branched polyurethane solution of polyfunctionality monomer.The highly-branched polymers synthetic method is sophisticated prior art.
The degree of branching DB of the highly branched urethane of synthetic is 0.3～0.7, and number-average molecular weight is 2000～60000; DB is preferably 0.4～0.6, and number-average molecular weight is preferably 6000～40000.
Described isocyanate-monomer is vulcabond or polyisocyanates, it specifically is isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, dimer (fatty acid) yl diisocyanate, 2,2,4-trimethylammonium hexamethylene diisocyanate, 2, the 4-tolylene diisocyanate, 4, the 4-diphenylmethanediisocyanate, naphthalene-1, the 5-vulcabond, tetramethylxylylene diisocyanate, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, triphenylmethane triisocyanate, 2,2 '-dimethyl-3,3 ', 5,5 '-a kind of in the triphenyl methane tetraisocyanate.
Described polyfunctionality monomer is polyvalent alcohol or polyamine, specifically is TriMethylolPropane(TMP), trimethylolethane, glycerol, 1,2,4-trihydroxybutane, 1,2, a kind of in 6-hexanetriol, tetramethylolmethane, the polyetheramine.
Can add chainextender in the building-up process, described chainextender is 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2,3-butyleneglycol, trimethylammonium butyleneglycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 1,3-pentanediol, 1,3-encircles pentanediol, 1,6-hexylene glycol, 2-ethyl-1,3-hexylene glycol, 1,2-hexylene glycol, cyclohexanedimethanol, 1,2-propylene diamine, 1,4-butanediamine, 1, one or both in the 6-hexanediamine.
Can also add end-capping reagent in the building-up process, described end-capping reagent is a kind of in stearic acid, oleic acid, Succinic anhydried, Tetra hydro Phthalic anhydride, Pyroglutaric acid, R-GLYCIDOL, the Resins, epoxy.
Step (2). with the highly branched polyurethane solution water precipitation of synthetic, throw out is carried out suction filtration and drying, obtain highly branched polyurethane powder.
Step (3). highly branched polyurethane powder is proportionally mixed with hydroxyalkyl amide/polyester powder coating, and the weight ratio of contained carboxy(l)polyester is 0.01～0.2:1 in mixture camber branched polyurethanes powder and the hydroxyalkyl amide/polyester powder coating; Utilize twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material; One district's temperature of twin screw extruder is that 90～100 ℃, two district's temperature are 100～110 ℃;
Step (4). sheet material is ground to form fine powder with colloid mill, and fine powder is with 160～200 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
The present invention is used for powder coating with highly branched urethane, utilize its cavity and branched structure, can help small molecules from system, to remove, significantly improve in the powder coating solidification process and produce the pin hole problem too soon because viscosity rises, reduce solidified speed, play the effect that improves the levelling effect, help the thick of powder coating to be coated with.
Embodiment
Embodiment 1
Isophorone diisocyanate is dissolved in the solvent, is added drop-wise to the highly branched urethane of prepared in reaction (HBPU-1) in the TriMethylolPropane(TMP), the molecular weight of the HBPU-1 that makes is 2000, and the degree of branching is 0.7; With the HBPU-1 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-1 powder; The HBPU-1 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-1 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.01:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 90 ℃, 100 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 124mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 2
With isophorone diisocyanate, 1, the 4-butanediol is carried out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in solvent.Then performed polymer is added drop-wise in the TriMethylolPropane(TMP) reaction and makes highly branched urethane (HBPU-2), the molecular weight of the HBPU-2 that makes is 6000, the degree of branching 0.6.With the HBPU-2 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-2 powder; The HBPU-2 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-2 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.02:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 90 ℃, 100 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 133mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 3
With 2,4 toluene diisocyanate, 1, the 2-propylene glycol is dissolved in and carries out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise to and continues reaction in the trimethylolethane, add the Resins, epoxy reaction at last and make highly branched urethane (HBPU-3), the molecular weight of the HBPU-3 that makes is 12000, the degree of branching 0.52.With the HBPU-3 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-3 powder; The HBPU-3 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-3 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.05:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 95 ℃, 105 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 170 mesh filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 125mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 4
With hexamethylene diisocyanate, 2, the 3-butanediol is carried out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in solvent.Then performed polymer is added drop-wise to and continues reaction in the glycerol, add the stearic acid reaction at last and make highly branched urethane (HBPU-4), the molecular weight of the HBPU-4 that makes is 18000, the degree of branching 0.44.With the HBPU-4 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-4 powder; The HBPU-4 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-4 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.1:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 100 ℃, 110 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 128mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 5
With 2,2,4-trimethylammonium hexamethylene diisocyanate, 1, ammediol are dissolved in and carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise to and continues reaction in the tetramethylolmethane, add the stearic acid reaction at last and make highly branched urethane (HBPU-5), the molecular weight of the HBPU-5 that makes is 22000, the degree of branching 0.43.With the HBPU-5 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-5 powder; The HBPU-5 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-5 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.04:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 95 ℃, 100 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 180 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 118mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 6
With 4,4-diphenylmethanediisocyanate, trimethylammonium butyleneglycol, 1,5-pentanediol are dissolved in and carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise to 1,2, reaction makes highly branched urethane (HBPU-6) in the 4-trihydroxybutane, and the molecular weight of the HBPU-6 that makes is 33500, the degree of branching 0.42.With the HBPU-6 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-6 powder; The HBPU-6 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-6 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.2:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 90 ℃, 110 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 115mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 7
With naphthalene-1,5-vulcabond, 1,3-pentanediol, 1,3-ring pentanediol are dissolved in and carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise to 1,2, continues reaction in the 4-trihydroxybutane, add the Succinic anhydried reaction at last and make highly branched urethane (HBPU-7), the molecular weight of the HBPU-7 that makes is 40000, the degree of branching 0.40.With the HBPU-7 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-7 powder; The HBPU-7 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-7 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.15:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 100 ℃, 110 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 190 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 110mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 8
With dicyclohexyl methane diisocyanate, 2-methyl-2,4-pentanediol, neopentyl glycol are dissolved in carries out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise to 1,2, continues reaction in the 6-hexanetriol, add the Pyroglutaric acid reaction at last and make highly branched urethane (HBPU-8), the molecular weight of the HBPU-8 that makes is 49000, the degree of branching 0.45.With the HBPU-8 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-8 powder; The HBPU-8 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-8 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.16:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 95 ℃, 110 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 116mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 9
With tetramethylxylylene diisocyanate, 2,2,4-trimethylammonium-1,3-pentanediol are dissolved in and carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.With 1, the 2-propylene diamine joins and continues reaction in the performed polymer then, joins at last to react in the TriMethylolPropane(TMP) to make highly branched urethane (HBPU-9), and the molecular weight of the HBPU-9 that makes is 6000, the degree of branching 0.42.With the HBPU-9 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-9 powder; The HBPU-9 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-9 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.06:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 100 ℃, 105 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 200 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 114mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 10
With dimer (fatty acid) yl diisocyanate, 1,6-hexylene glycol, 2-ethyl-1,3-hexylene glycol are dissolved in and carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise in the polyetheramine reaction and makes highly branched urethane (HBPU-10), the molecular weight of the HBPU-10 that makes is 5660, the degree of branching 0.44.With the HBPU-10 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-10 powder; The HBPU-10 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-10 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.01:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 90 ℃, 100 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 98mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 11
With dimethyl diphenyl vulcabond, 1,2-hexylene glycol, cyclohexanedimethanol are dissolved in and carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the solvent.Then performed polymer is added drop-wise in the polyetheramine and reacts, add R-GLYCIDOL continuation reaction at last and make highly branched urethane (HBPU-11), the molecular weight of the HBPU-11 that makes is 60000, the degree of branching 0.46.With the HBPU-11 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-11 powder; The HBPU-11 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-11 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.2:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 92 ℃, 108 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 112mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 12
With Methylcyclohexyl diisocyanate, 1,4-butanediamine, 1, the 6-hexanediamine is dissolved in and carries out pre-polymerization in the solvent, be added drop-wise to then and continue reaction in the TriMethylolPropane(TMP), add phthalic anhydride at last and make highly branched urethane (HBPU-12), the molecular weight of the HBPU-12 that makes is 51000, the degree of branching 0.36.With the HBPU-12 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-12 powder; The HBPU-12 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-12 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.08:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 90 ℃, 100 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 180 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 108mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 13
With 1, the 4-butanediol is added drop-wise to and carries out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the triphenylmethane triisocyanate in solvent.Add the stearic acid reaction then and make highly branched urethane (HBPU-13), the molecular weight of the HBPU-13 that makes is 33200, the degree of branching 0.38.With the HBPU-13 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-13 powder; The HBPU-13 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-13 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.1:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 98 ℃, 106 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 200 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 122mm from 90mm in the oblique flow test, and levelling property improves.
Embodiment 14
With 1, the 4-butanediol in solvent, be added drop-wise to 2,2 '-dimethyl-3,3 ', 5,5 '-carry out the synthetic end capped base polyurethane prepolymer for use as of NCO of pre-polymerization in the triphenyl methane tetraisocyanate.Add elaidin reaction then and make highly branched urethane (HBPU-14), the molecular weight of the HBPU-14 that makes is 25200, the degree of branching 0.3.With the HBPU-14 water precipitation, throw out carries out suction filtration and drying, obtains the HBPU-14 powder; The HBPU-14 powder is mixed with hydroxyalkyl amide/polyester powder coating, in the mixture in HBPU-14 powder and the hydroxyalkyl amide/polyester powder coating weight ratio of contained carboxy(l)polyester be 0.1:1, utilize then twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material, twin screw extruder one district's temperature is 96 ℃, 106 ℃ of the temperature in two districts; Sheet material is ground to form fine powder with colloid mill, and fine powder is with 160 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
On parts, the electric current and voltage of electrostatic spraying is 0.5KV/80UA with the hydroxyalkyl amide after the modification/polyester powder coating electrostatic spraying, and 160 ℃ solidify 20min in baking oven, obtain final filming.The film coated surface surface smoothing, no orange peel is not compared with adding filming of branched polyurethanes of height, and pin hole quantity reduces, and length of flow is increased to 119mm from 90mm in the oblique flow test, and levelling property improves.
With filming of obtaining after powdered sample before the foregoing description 1 to 14 curing and the curing, carry out performance test, the result is as follows:
Claims (5)
1. method of improving hydroxyalkyl amide/polyester powder coating pin hole and levelling property is characterized in that the concrete steps of this method are:
Step (1). adopt the highly-branched polymers synthetic method with isocyanate-monomer and the synthetic highly branched polyurethane solution of polyfunctionality monomer;
The degree of branching DB of the highly branched urethane of synthetic is 0.3～0.7, and number-average molecular weight is 2000～60000;
Described isocyanate-monomer is an isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, dimer (fatty acid) yl diisocyanate, 2,2,4-trimethylammonium hexamethylene diisocyanate, 2, the 4-tolylene diisocyanate, 4, the 4-diphenylmethanediisocyanate, naphthalene-1, the 5-vulcabond, tetramethylxylylene diisocyanate, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, triphenylmethane triisocyanate, 2,2 '-dimethyl-3,3 ', 5,5 '-a kind of in the triphenyl methane tetraisocyanate;
Described polyfunctionality monomer is TriMethylolPropane(TMP), trimethylolethane, glycerol, 1,2,4-trihydroxybutane, 1,2, a kind of in 6-hexanetriol, tetramethylolmethane, the polyetheramine;
Step (2). with the highly branched polyurethane solution water precipitation of synthetic, throw out is carried out suction filtration and drying, obtain highly branched polyurethane powder;
Step (3). highly branched polyurethane powder is proportionally mixed with hydroxyalkyl amide/polyester powder coating, and the weight ratio of contained carboxy(l)polyester is 0.01～0.2:1 in mixture camber branched polyurethanes powder and the hydroxyalkyl amide/polyester powder coating; Utilize twin screw extruder with the mixture fusion, extrude, compressing tablet, become sheet material;
Step (4). sheet material is ground to form fine powder with colloid mill, and fine powder is with 160～200 purpose filter screen sievings, obtains the hydroxyalkyl amide/polyester powder coating after the modification.
2. a kind of method of improving hydroxyalkyl amide/polyester powder coating pin hole and levelling property as claimed in claim 1 is characterized in that: the degree of branching DB of the highly branched urethane of synthetic is 0.4～0.6 in the step (1), and number-average molecular weight is 6000～40000.
3. a kind of method of improving hydroxyalkyl amide/polyester powder coating pin hole and levelling property as claimed in claim 1, it is characterized in that: add chainextender in the building-up process of step (1), described chainextender is 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 2, the 3-butyleneglycol, the trimethylammonium butyleneglycol, 1, the 5-pentanediol, 2-methyl-2, the 4-pentanediol, neopentyl glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 1, the 3-pentanediol, 1,3-encircles pentanediol, 1, the 6-hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, 1, the 2-hexylene glycol, cyclohexanedimethanol, 1, the 2-propylene diamine, 1, the 4-butanediamine, 1, one or both in the 6-hexanediamine.
4. a kind of method of improving hydroxyalkyl amide/polyester powder coating pin hole and levelling property as claimed in claim 1, it is characterized in that: add end-capping reagent in the building-up process of step (1), described end-capping reagent is a kind of in stearic acid, oleic acid, Succinic anhydried, Tetra hydro Phthalic anhydride, Pyroglutaric acid, R-GLYCIDOL, the Resins, epoxy.
5. a kind of method of improving hydroxyalkyl amide/polyester powder coating pin hole and levelling property as claimed in claim 1 is characterized in that: district's temperature of twin screw extruder is that 90～100 ℃, two district's temperature are 100～110 ℃ in step (3) fusion, the extrusion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110112793 CN102212305B (en) | 2011-05-03 | 2011-05-03 | Method for improving pinholes and levelling property of hydroxyalkylamide/polyester powder paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110112793 CN102212305B (en) | 2011-05-03 | 2011-05-03 | Method for improving pinholes and levelling property of hydroxyalkylamide/polyester powder paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102212305A CN102212305A (en) | 2011-10-12 |
| CN102212305B true CN102212305B (en) | 2013-07-31 |
Family
ID=44743855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110112793 Active CN102212305B (en) | 2011-05-03 | 2011-05-03 | Method for improving pinholes and levelling property of hydroxyalkylamide/polyester powder paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102212305B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838718B (en) * | 2012-09-12 | 2015-03-04 | 西安交通大学 | Hyperbranched polyurethane containing isocyanate groups, as well as preparation method and application of hyperbranched polyurethane |
| CN103641737B (en) * | 2013-11-29 | 2016-04-20 | 六安市捷通达化工有限责任公司 | A kind of preparation method of carboxyl acid modified hydroxy alkyl amide curing agents |
| CN105462466B (en) * | 2014-09-26 | 2019-04-26 | 立邦涂料（中国）有限公司 | A kind of aqueous-based coating composition of the high pin hole limit |
| CN105085866A (en) * | 2015-09-02 | 2015-11-25 | 西安交通大学 | Hyperbranched polyurethane containing epoxy groups as well as preparation method and application thereof |
| EP3559317A1 (en) * | 2016-12-20 | 2019-10-30 | Basf Se | Composition for metal plating comprising suppressing agent for void free filling |
| CN109401453A (en) * | 2018-12-13 | 2019-03-01 | 周弛逍 | A kind of heat-resisting phosphatization powdery paints and preparation method thereof |
| CN113527981B (en) * | 2021-08-31 | 2022-02-18 | 江苏江南绝缘粉末有限公司 | Thin-coating high-humidity-resistant heat-insulating powder and preparation method thereof |
| CN114149565B (en) * | 2021-11-30 | 2023-04-25 | 江苏三木化工股份有限公司 | Preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404517A (en) * | 2000-12-21 | 2003-03-19 | Ucb公司 | Powdered thermosetting composition for coatings |
| CN101215442A (en) * | 2008-01-10 | 2008-07-09 | 李新春 | Weather-resisting powder coating composition |
-
2011
- 2011-05-03 CN CN 201110112793 patent/CN102212305B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404517A (en) * | 2000-12-21 | 2003-03-19 | Ucb公司 | Powdered thermosetting composition for coatings |
| CN101215442A (en) * | 2008-01-10 | 2008-07-09 | 李新春 | Weather-resisting powder coating composition |
Non-Patent Citations (1)
| Title |
|---|
| 孙宁等.超支化聚合物在功能材料中的应用.《化工时刊》.2006,第20卷(第8期),61-64. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102212305A (en) | 2011-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102212305B (en) | Method for improving pinholes and levelling property of hydroxyalkylamide/polyester powder paint | |
| CN102220074B (en) | Sagging and blistering preventing overcoat varnish for automobile coating as well as preparation method and coating method thereof | |
| CN102604497B (en) | Water-based metallic flashing paint and preparation method of the flashing paint | |
| JPH01501869A (en) | Dispersion of crosslinked polymer fine particles in an aqueous medium, method for producing this dispersion, and paint containing this dispersion | |
| EP3277756B1 (en) | Coating composition and paint produced from same | |
| CN102977762A (en) | Water-based fluorine-containing polyurethane paint and preparation method thereof | |
| CN110922856A (en) | Powder coating with ultrahigh weather-resistant extinction effect | |
| WO2008148554A1 (en) | Binding agents having high oh number and clear paint composition comprising said agents and having good optical characteristics and good scratch and chemical resistance | |
| CN114369389B (en) | Matte UV ink and preparation method thereof | |
| CN109722157A (en) | A kind of safety-type aqueous double-component bloom finishing coat and preparation method thereof | |
| DE19646640A1 (en) | Organosol polyester paints and a process for their production | |
| CN102666740A (en) | Polyester fluorocarbon mixed powder coating composition and a method for making the same | |
| Kim et al. | Mechanical properties and decomposition performance of peelable coating containing UiO-66 catalyst and waterborne silane-terminated polyurethane dispersions | |
| JP2002506113A5 (en) | ||
| CN111154388A (en) | Safe water-based two-component high-gloss finish paint and preparation method thereof | |
| WO2007128660A2 (en) | Composition with cloudy appearance and improved barrier effect method for production and use thereof | |
| CA1062834A (en) | Thermosetting coating composition of an organic polyisocyanate, a polymer having pendent hydroxyl containing ester groups, and a rheology control agent | |
| CN110183617B (en) | A transparent powder with excellent wear resistance is prepared from (A) 50: 50 polyester resin and preparation method and application thereof | |
| CN116239908B (en) | Insulating sand grain powder coating and preparation method thereof | |
| DE10238349B4 (en) | Polyurethane microgel | |
| CN114806303B (en) | Varnish suitable for one-time spraying film formation of automobile body and preparation method thereof | |
| CN113527997A (en) | Single-component asphalt polyurethane waterproof coating compatible with asphalt-based waterproof coiled material and preparation method thereof | |
| CN102443348A (en) | Process of special high-performance acrylic polyurethane finishing varnish for bus | |
| WO2004069945A1 (en) | Nonaromatic solvent type coating resin composition | |
| TWI531467B (en) | Optical film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |