CN102464937B - Powder coating for polyurethane-modified polyester automobile finish and preparation method thereof - Google Patents
Powder coating for polyurethane-modified polyester automobile finish and preparation method thereof Download PDFInfo
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- CN102464937B CN102464937B CN 201110206872 CN201110206872A CN102464937B CN 102464937 B CN102464937 B CN 102464937B CN 201110206872 CN201110206872 CN 201110206872 CN 201110206872 A CN201110206872 A CN 201110206872A CN 102464937 B CN102464937 B CN 102464937B
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Abstract
The invention relates to a powder coating for a polyurethane-modified polyester automobile finish and a preparation method thereof, which are used for solving the problems of poor elasticity, poor softness, poor wear resistance and strength insufficient to meet the technical requirements of the automobile finish caused by the use of triglycidyl isocyanurate (TGIC) as a curing agent in a pure polyester powder coating in a powder coating. The invention provides a powder coating for a polyurethane-modified polyester automobile finish and a preparation method thereof. The powder coating for the polyurethane-modified polyester automobile finish is prepared from the following components in percentage by weight: 6-16 percent of a polyether ester, 40-50 percent of a polyester resin, 0.3-0.6 percent of dibutyltin dilaurate, 0.4-0.6 percent of benzoin, 1.4-1.6 percent of a flatting agent, 27-29 percent of titanium pigment and 10-15 percent of epsilon-caprolactam enclosed isophorone diisocyanate. According to the invention, the modified powder coating has the advantages of higher softness, elasticity, higher strength, porous coating layer, higher moisture permeability and higher air permeability; and a coating layer has higher wear resistance and higher moisture resistance.
Description
Technical field
The present invention relates to the chemistry painting industry technical field, relate in particular to powder coating of a kind of polyurethane-modified polyester for automobile finish and preparation method thereof.
Background technology
Powder coating is a kind of novel solvent 100% solid powdery coating that do not contain.Powder coating is by special resin, color stuffing, solidifying agent and other auxiliary agent, mixes in certain proportion, then is prepared from by hot extrusion and the technique such as pulverize and sieve.They at normal temperatures, shelf-stable through electrostatic spraying or fluidized bed dipping, reheats the baking melting and solidification, makes to form the permanent of smooth and film, and reaches and decorates and etch-proof purpose.Simultaneously, the utilization ratio of powder coating is near 100%, and the powder after spraying can be recycled, usually than the easy construction of liquid coating, and the good endurance of filming of formation, product advantage is remarkable.
Powder coating has very large application aspect automobile finish, existing powder coating is divided into pure epoxy powder coating, epoxy-polyester mixed type powder paint, pure polyester powdery paints and acrylic powder coating.Pure epoxy powder coating and epoxy-polyester mixed type powder paint can not be as the outdoor automobile finishs because weathering resistance is poor; The acrylic powder coating price is high, uses cost larger; Pure polyester powdery paints, the polyester powder coating of particularly making solidifying agent with triglycidyl isocyanurate (TGIC) is the weathering resistance powder that has comparative advantage on the domestic market, it has following characteristics: the good weatherability of filming is applicable to the application of outdoor product; The good heat resistance of filming, filming when baking-curing is difficult for yellowing; The physicalies such as impact strength, snappiness, the hardness of filming are excellent, chemical-resistant resistance and water-fast etc. functional; The coating performance of coating is good, can use the method applications such as air spray finishing and electrostatic powder coating method, but pure polyester powdery paints is owing to making solidifying agent with poly-triglycidyl isocyanurate (TGIC), its elasticity, flexibility, ventilation property, wear resistance are slightly poor, and intensity can not satisfy the automobile finish technical requirements.
Application number is 200710162058.6 Chinese patent, a kind of air permeable pure polyester powdery paints is disclosed, this disclosure of the invention a kind of air permeable pure polyester powdery paints, outdoor vibrin, the solidifying agent of 3-5%, 0.8-5% flow agent, 1-20% pigment, the air release agent of 0.1-0.8%, other auxiliary agent by weight part 50-60%, and the clout filler adopts existing powder coating production technique to make, although this powder coating has solved the ventilation property of pure polyester powdery paints, do not solve as the needed wear resistance of automobile finish, flexibility and intensity.
Summary of the invention
In order to solve in powder coating pure polyester powdery paints owing to using poly-triglycidyl isocyanurate (TGIC) to make solidifying agent, cause its elasticity, flexibility, wear resistance slightly poor, intensity can not satisfy the problem of automobile finish technical requirements, the present invention proposes a kind of powder coating for polyurethane-modified polyester automobile finish and preparation method thereof, thereby make the powder coating after modification have better flexibility and elasticity; Has higher intensity; The coating porous has better wet and ventilation property thoroughly; Coating has higher wear-resisting and wet fastness.
Technical scheme of the present invention is: a kind of powder coating for polyurethane-modified polyester automobile finish is prepared from by following each component, and the weight percent of each component is:
Polyether ester 6 ~ 16%
Vibrin 40 ~ 50%,
Dibutyl tin laurate 0.3 ~ 0.6%,
St-yrax 0.4 ~ 0.6%,
Flow agent 1.4 ~ 1.6%,
Titanium dioxide 27 ~ 29%,
ε-caprolactam sealing isophorone diisocyanate 10 ~ 15%;
Wherein, polyether ester is prepared from by following each component, and the weight percent of each component is:
Terephthalic acid 29 ~ 39%
Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid 10 ~ 20%
BDO 23 ~ 33%
Polyoxy methylene glycol 17 ~ 27 %
Photostabilizer 0.1 ~ 0.3%
Butyl stannonic acid 0.05 ~ 0.15%
As preferably, vibrin is selected unsaturated polyester resin.Unsaturated polyester resin has thermotolerance, has higher stretching, bending, compression equal strength and resistance to chemical corrosion.
The preparation method of powder coating for polyurethane-modified polyester automobile finish is following steps:
(1) with terephthalic acid, 1,4-cyclohexane dicarboxylic acid, BDO, polyoxy methylene glycol, photostabilizer, butyl stannonic acid drop in reactor, are heated to 245 ~ 255 ℃ under the protection of inert nitrogen gas, then keep 2.5 ~ 3.5h under 77 ~ 83KPa, obtain polyether ester;
(2) polyether ester that step (1) is obtained and vibrin, dibutyl tin laurate, st-yrax, flow agent, titanium dioxide, ε-caprolactam sealing isophorone diisocyanate drop in blender and carry out pre-mixing, twin screw extruder is warming up to 75 ~ 85 ℃, material extrusion moulding in twin screw extruder that premix is got togather, clay into power in grinding machine after moulding is cooling, namely obtain powder coating of the present invention.
During the synthesizing polyester resin, if introduce some other compositions by chemical reaction, can have the performance that vibrin does not possess originally, reach and improve and outstanding certain performance purpose, reach special application performance requirement, so the present invention adopts urethane modified polyester resin.
In this reaction, polyether ester and the reaction of ε-caprolactam sealing isophorone diisocyanate generate urethane.Vibrin contains terminal hydroxy group functional group, by with isocyanate-crosslinked film-forming.Urethane has the advantages such as good physicals, excellent winter hardiness, elasticity, high gloss, organic solvent-resistant.
Urethane (PU) is widely used in many fields because of its remarkable performance.Polyurethane coating agent is the main species of Developing, and its advantage is: coating is soft and flexible; Strength of coating is good, can be used for very thin coating; The coating porousness has wet and venting capability; Wear-resisting, moisture-proof.Urethane (PU) powder is suitable for outdoor application.
Urethane and vibrin consistency are good, make under suitable condition both form inierpeneirating network structure or half interpenetrating network structure, improve vibrin toughness thereby reach, and do not reduce its intensity, stable on heating purpose simultaneously.In coating vibrin used be low-molecular-weight, unsaturated, contain side chain, can be crosslinked polymkeric substance.
In the urethane colored paint, under the effect of light, oxygen, all DeR can occur due to any coating.Coating after degraded shows the forfeiture of loss of gloss, xanthochromia, efflorescence and defencive function.Many pigment can be used for protecting polymkeric substance to avoid photoaging, and as iron oxides pigment, chromic oxide, zinc oxide etc., in addition, nano titanium oxide also is used as inorganic UV light absorber and is widely used in car paint in recent years.Titanium dioxide is more stable, and optical activity is little, thereby good weatherability, and higher opacifying power is arranged simultaneously, and reducing power belongs to inert pigment, is considered at present the best a kind of white pigment of performance in the world.Flow agent increases the intermiscibility of slurry and solvent, reduces the interface brute force, prevents that " flake " produces, and has anlistatig effect simultaneously.
Dibutyl tin laurate participates in the synthetic of urethane, can improve product thermostability, the transparency, with the consistency of resin, and the performance such as shock strength.
Compared with prior art, the invention has the beneficial effects as follows, use powder coating of the present invention that compound coating is had the following advantages:
1, better flexibility and elasticity;
2, has higher intensity;
3, coating porous has better wet and ventilation property thoroughly;
4, coating has higher wear-resisting and wet fastness.
Embodiment
In conjunction with the embodiments the present invention is described in further detail.
Embodiment 1
(1) with terephthalic acid 34%, 1,4-cyclohexane dicarboxylic acid 15%, 1,4-butyleneglycol 28%, polyoxy methylene glycol 22.7%, photostabilizer 770 types 0.2%, butyl stannonic acid 0.1% drop in reactor, be heated to 250 ℃ under the protection of inert nitrogen gas, then keep 3h under 80KPa, obtain polyether ester;
(2) polyether ester 11% that step 1 is obtained, unsaturated polyester 45.5%, dibutyl tin laurate 0.5%, st-yrax 0.5%, flow agent P588 type 1.5%, titanium dioxide 28%, ε-caprolactam sealing isophorone diisocyanate 13%, drop in blender and carry out pre-mixing, twin screw extruder is warming up to 80 ℃, material extrusion moulding in twin screw extruder that premix is got togather, in the form of sheets, test piece namely obtains powder coating at the cooling rear powder of wearing into required particle diameter in grinding machine.
Embodiment 2
(1) with terephthalic acid 39%, 1,4-cyclohexane dicarboxylic acid 20%, 1,4-butyleneglycol 23%, polyoxy methylene glycol 17.75%, photostabilizer 770 types 0.1%, butyl stannonic acid 0.15% drop in reactor, be heated to 245 ℃ under the protection of inert nitrogen gas, then keep 2.5h under 83KPa, obtain polyether ester;
(2) polyether ester 16% that step 1 is obtained, unsaturated polyester 44.7%, dibutyl tin laurate 0.3%, st-yrax 0.4%, flow agent P588 type 1.6%, titanium dioxide 27%, ε-caprolactam sealing isophorone diisocyanate 10%, drop in blender and carry out pre-mixing, twin screw extruder is warming up to 75 ℃, material extrusion moulding in twin screw extruder that premix is got togather, the moulding test piece namely obtains powder coating at the cooling rear powder of wearing into required particle diameter in grinding machine.
Embodiment 3
(1) with terephthalic acid 29%, 1,4-cyclohexane dicarboxylic acid 11%, 1,4-butyleneglycol 33%, polyoxy methylene glycol 26.65%, photostabilizer 770 types 0.3%, butyl stannonic acid 0.05% drop in reactor, be heated to 255 ℃ under the protection of inert nitrogen gas, then keep 3.5h at 77KPa, obtain polyether ester;
(2) polyether ester 7% that step 1 is obtained, unsaturated polyester 50%, dibutyl tin laurate 0.6%, st-yrax 0.6%, flow agent P588 type 1.4%, titanium dioxide 29%, ε-caprolactam sealing isophorone diisocyanate 11.4%, drop in blender and carry out pre-mixing, twin screw extruder is warming up to 85 ℃, material extrusion moulding in twin screw extruder that premix is got togather, the moulding test piece namely obtains powder coating at the cooling rear powder of wearing into required particle diameter in grinding machine.
Embodiment 4
(1) with terephthalic acid 29%, 1,4-cyclohexane dicarboxylic acid 20%, 1,4-butyleneglycol 24%, polyoxy methylene glycol 26.7%, photostabilizer 770 types 0.2%, butyl stannonic acid 0.1% drop in reactor, be heated to 250 ℃ under the protection of inert nitrogen gas, then keep 3h under 80KPa, obtain polyether ester;
(2) polyether ester 15.6% that step 1 is obtained, unsaturated polyester 40%, dibutyl tin laurate 0.6%, st-yrax 0.4%, flow agent P588 type 1.4%, titanium dioxide 27%, ε-caprolactam sealing isophorone diisocyanate 15%, drop in blender and carry out pre-mixing, twin screw extruder is warming up to 80 ℃, material extrusion moulding in twin screw extruder that premix is got togather, the moulding test piece namely obtains powder coating at the cooling rear powder of wearing into required particle diameter in grinding machine.
Embodiment 5
(1) with terephthalic acid 39%, 1,4-cyclohexane dicarboxylic acid 10%, 1,4-butyleneglycol 33%, polyoxy methylene glycol 17.7%, photostabilizer 770 types 0.2%, butyl stannonic acid 0.1% drop in reactor, be heated to 250 ℃ under the protection of inert nitrogen gas, then keep 3.5h under 80KPa, obtain polyether ester;
(2) polyether ester 14.7% that step 1 is obtained, unsaturated polyester 40%, dibutyl tin laurate 0.3%, st-yrax 0.5%, flow agent P588 type 1.5%, titanium dioxide 28%, ε-caprolactam sealing isophorone diisocyanate 15%, drop in blender and carry out pre-mixing, twin screw extruder is warming up to 80 ℃, material extrusion moulding in twin screw extruder that premix is got togather, the moulding test piece namely obtains powder coating at the cooling rear powder of wearing into required particle diameter in grinding machine.
Powder coating snappiness≤the 0.8mm that obtains; Resistance to impact shock 〉=60kg.cm; Hardness 〉=2H; Wet fastness: in temperature (47 ± 1) ℃, under the condition of humidity (96 ± 2) %, paint film was without considerable change in 〉=120 hours.
Claims (2)
1. powder coating for polyurethane-modified polyester automobile finish, it is characterized in that: described powder coating for polyurethane-modified polyester automobile finish is prepared from by following each component, and the weight percent of each component is:
Polyether ester 6 ~ 16%
Vibrin 40 ~ 50%,
Dibutyl tin laurate 0.3 ~ 0.6%,
St-yrax 0.4 ~ 0.6%,
Flow agent 1.4 ~ 1.6%,
Titanium dioxide 27 ~ 29%,
ε-caprolactam sealing isophorone diisocyanate 10 ~ 15%;
Described polyether ester is prepared from by following each component, and the weight percent of each component is:
Terephthalic acid 29 ~ 39%
Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid 10 ~ 20%
BDO 23 ~ 33%
Polyoxy methylene glycol 17 ~ 27 %
Photostabilizer 0.1 ~ 0.3%
Butyl stannonic acid 0.05 ~ 0.15%;
The preparation method of described powder coating for polyurethane-modified polyester automobile finish is following steps:
(1) with terephthalic acid, 1,4-cyclohexane dicarboxylic acid, BDO, polyoxy methylene glycol, photostabilizer, butyl stannonic acid drop in reactor, are heated to 245 ~ 255 ℃ under the protection of inert nitrogen gas, then keep 2.5 ~ 3.5h under 77 ~ 83KPa, obtain polyether ester;
(2) polyether ester that step (1) is obtained and vibrin, dibutyl tin laurate, st-yrax, flow agent, titanium dioxide, ε-caprolactam sealing isophorone diisocyanate drop in blender and carry out pre-mixing, twin screw extruder is warming up to 75 ~ 85 ℃, material extrusion moulding in twin screw extruder that premix is got togather, clay into power in grinding machine after moulding is cooling, namely obtain powder coating of the present invention.
2. a kind of powder coating for polyurethane-modified polyester automobile finish according to claim 1, it is characterized in that: vibrin is selected unsaturated polyester resin.
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| CN 201110206872 CN102464937B (en) | 2011-05-20 | 2011-07-22 | Powder coating for polyurethane-modified polyester automobile finish and preparation method thereof |
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| CN201110130920.1 | 2011-05-20 | ||
| CN201110130920 | 2011-05-20 | ||
| CN 201110206872 CN102464937B (en) | 2011-05-20 | 2011-07-22 | Powder coating for polyurethane-modified polyester automobile finish and preparation method thereof |
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| CN102464937B true CN102464937B (en) | 2013-11-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103289543B (en) * | 2013-05-28 | 2016-01-20 | 宁波派特勒新材料股份有限公司 | A kind of automobile finish powder coating |
| CN103289544B (en) * | 2013-05-28 | 2016-04-20 | 宁波派特勒新材料股份有限公司 | A kind of automobile finish powder coating and preparation method thereof |
| CN104231191B (en) * | 2014-09-16 | 2018-04-24 | 上海金力泰化工股份有限公司 | The preparation method for the polyester that water-based non-isocyanate polyurethane is modified |
| CN107254249B (en) * | 2017-07-26 | 2020-03-17 | 立邦涂料（天津）有限公司 | High-hardness powder coating, preparation method and application thereof |
| WO2021120001A1 (en) * | 2019-12-17 | 2021-06-24 | 江苏凯伦建材股份有限公司 | Single-component solvent-free anti-sagging polyurethane waterproof coating, production system, and production method thereof |
| CN112341591B (en) * | 2020-10-27 | 2023-03-24 | 上海伊纯实业有限公司 | Polyurethane material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365371A (en) * | 1999-06-03 | 2002-08-21 | 伊斯曼化学公司 | Low melt viscosity amorphous copolymers with enhanced glass transition temperatures |
| CN101124283A (en) * | 2004-12-01 | 2008-02-13 | 杜邦强力涂料斯堪的纳维股份公司 | Powder coating composition for coating surfaces of heat-sensitive substrates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365371A (en) * | 1999-06-03 | 2002-08-21 | 伊斯曼化学公司 | Low melt viscosity amorphous copolymers with enhanced glass transition temperatures |
| CN101124283A (en) * | 2004-12-01 | 2008-02-13 | 杜邦强力涂料斯堪的纳维股份公司 | Powder coating composition for coating surfaces of heat-sensitive substrates |
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