CN103319975A - Epoxy powder coating composition with high pulverization resistance - Google Patents
Epoxy powder coating composition with high pulverization resistance Download PDFInfo
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- CN103319975A CN103319975A CN2013102447636A CN201310244763A CN103319975A CN 103319975 A CN103319975 A CN 103319975A CN 2013102447636 A CN2013102447636 A CN 2013102447636A CN 201310244763 A CN201310244763 A CN 201310244763A CN 103319975 A CN103319975 A CN 103319975A
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Abstract
The invention discloses an epoxy powder coating composition with high pulverization resistance. The epoxy powder coating composition comprises the following components in percentage by mass: 35-60% of novolac epoxy resin, 5-12% of a phenol curing agent, 0-10% of a latent amine curing agent, 0.01-2% of a curing accelerator, 25-45% of padding, 0.5-1% of pigment, 0.5-1% of benzoin, 0.4-1% of a flatting agent, 1-50% of assistant resin and 0.3-1% of fumed silica. The epoxy powder coating composition with high pulverization resistance has the test effects that the outdoor exposure resistance time is up to 18 months, the bonding strength loss is smaller than 30%, a coating is free of bubbles and has the first-level adhesive force after put in a sodium chloride solution high-pressure autoclave at the temperature of 110 DEG C and the pressure of 20MPa for7d; after soaked by using 2% sodium hypochlorite at the temperature of 95 DEG C for 28d, the coating is free of bubbles on the surface and has the gloss loss rate smaller than 50%.
Description
Technical field
The present invention relates to a kind of epoxy powder coating composition of high resistance efflorescence, be mainly used in solving the open air problem such as wet adhesion (95 ℃) under the oxidation efflorescence, high temperature of hypochlorite in loss of gloss, the cathodic disbonding process of being exposed to the sun.Background technology
In order to guarantee the reliably and with long-term operation of buried metal pipeline under severe environment, normal anticathode pipeline carries out galvanic protection, even corrosive pipeline also corrodes first plug-in sacrificial metal anode, so that metallic conduit is avoided corrosion.Therefore, to combine with cathode protection measure be the heavy anticorrosion main method that adopts of buried pipeline up to now to organic coating.More than 2,000 kilometer of external heavy construction such as Queensland's water conveyance pipeline project first phase of construction, the engineering time length is a year and a half at least, and pipeline is piled up on-the-spot coating meeting because begin degraded sunshine, the coating machine performance is (such as impact property, bending property etc.) descend, antiseptic property descends, therefore developing high resistance efflorescence coating becomes a kind of demand, for powder coating systems, only have polyester powder fast light degraded relative to polyurethane powder coating, but because the reason of coating formation mechanism, coating can not thickly be coated with, otherwise can be because the solidification process small molecular be overflowed and to be caused pin-hole phenomena, and after the Nap gard7-2610 finish paint open air of heavy anticorrosion general epoxide powder coating such as Du Pont was exposed to the sun 6 months, impact property descended 30%, coating is down to 6～7Mpa to the cohesive strength of base material by 40～60Mpa, loss of gloss rate 90%.Be exposed to the sun the time for the open air that surpasses a year, the epoxide powder coating coating does not have product to address the above problem at present.
Need to experience cathode protection measure for heavy anti-corrosion pipeline with powder coating; pipeline delivery medium temperature is higher; coated cathode is peeled off probe temperature and is also therefore improved; the anti-efflorescence of coating becomes the problem of a sternness more than 85 ℃ the time for delivery temperature; even if otherwise coating has good sticking power; under the hypochlorite high temperature in the cathodic disbonding process to the oxidation of coating so that the big area degraded appears in coating; cause coating to lose efficacy; under 85 ℃/28d/-1.5V condition; during 400 microns of conventional bisphenol-A epoxy coating original thicknesses; the coating that the coating efflorescence was lost efficacy after the test cathodic disbonding is about about 300 microns; the actual net thickness of coating is reduced to about 100 microns, seriously is lower than the primary demand of at least 120 microns of corrosion protection coatings.
Based on above two aspect difficult points, solving the epoxide powder coating pulverizing problem becomes that restriction anticorrosion coating on pipeline trend is more extensive, the difficult problem of high-end applications more.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of existing powdered epoxy coating technology, provide a kind of high resistance chalking paint, the substantially constant cathodic disbonding efflorescence that also can resist under the hot environment of retention under the environment that can tan by the sun out of doors.Concrete technical scheme is as follows:
A kind of epoxy powder coating composition of high resistance efflorescence comprises following component by mass percentage:
Novolac epoxy: 35～60%;
Phenols curing agent: 5～12%;
The amine curing agent of hiding: 0～10%;
Curing catalyst: 0.01～2%;
Filler: 25～45%;
Pigment: 0.5～1%;
St-yrax: 0.5～1%;
Flow agent: 0.4～1%;
Auxiliary agent type resin: 1～50%;
Aerosil: 0.3～1%.
The softening temperature of described Resins, epoxy is 85～95 ℃, and Resins, epoxy comprises the solid epoxy resins such as bisphenol A epoxide resin, DCPD-containing epoxy resin, oxazolidone Resins, epoxy, phenolic aldehyde epoxy.
The hydroxyl equivalent of described phenols curing agent is 200～210,82～100 ℃ of softening temperatures.
The described amine curing agent of hiding has the similar solid-state amines such as Dyhard RU 100, solid-state azanol, SA two hydrazides, isophthalic dihydrazide, and fusing point is greater than 100 ℃.
Described curing catalyst be generally imidazoles, modified imidazole, ureas,, boron trifluoride-amine complex, triphenyl phosphorus, 2-benzothiazolyl mercaptan, thiocarbamide and modifier, modified imidazoline etc. have strong nucleophilic promotor.
Described filler is selected from one or more in process white, silicon powder, mica powder, the iron oxide red, and the order number is 400～800 orders, and the order number is preferably 800 orders.
Described pigment can select phthalocyanine blue, phthalocyanine blue, iron oxide yellow etc. to have the filler of certain tinting strength and water insoluble and alkali, and does not have photolytic activity.
Described flow agent is polyacrylic ester, can select the South Sea, Ningbo chemistry 503, the PF-67 of ESTRON, the BYK3900P of Bi Ke chemistry, BYK3951P etc.
Described auxiliary agent type resin can be selected steady chemical structure, be difficult for photodegradative resin, the resin that serial such as silicone resin (epoxide group or amino group and nonreactive functional groups are arranged), cellaburate ester such as Yi Siman CAB381 and CAB551, as to contain phosphorous acid ester structure modified resin etc. does not contain phenyl ring or has the oxidation inhibitor functional structure.
Described aerosil is high-specific surface area (〉=100m
2/ g, the BET method records) and hydrophilic soft silica, tamped density is about 30～80g/l.
Aerosil can be selected the A200 of Degussa, and watt N20 that digests etc. has the strong soft silica of high-specific surface area wetting ability.
Conventional bisphenol A epoxide resin system or the bisphenol A modified resin of adopting of double antiseptic powder coating coating, contain a large amount of polar groups in the resin, has wetting ability, the while structure of bisphenol A contains phenyl ring and is very easily excited by high-octane light wave, cause producing free radical cracking or produced free radical by the hypochlorite oxidation and cause degraded, the generation powder phenomenon-tion.Therefore will change this phenomenon and splice silicone resin and organic-silicon-modified resin in Resins, epoxy, can effectively utilize silicone resin to free radical and high energy light wave, to contain the benzene ring structure epoxy more stable than common.
The epoxy powder anti-corrosion coating test effect of a kind of high resistance efflorescence of the present invention is: anti-outdoor exposure 18 months, loss of bond strength＜30%, impact property descends＜30%, non-foaming and the adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate＜50%.
Description of drawings
Fig. 1 is the coating preparation schema of embodiment 1.
Embodiment
Below, further specify content of the present invention with embodiment, but protection scope of the present invention is not limited in embodiment.Those skilled in the art in the situation that do not deviate from other variation and the modification that the present invention spirit and protection domain are made, still is included within the protection domain of the present invention.
Embodiment 1
| Raw material | Consumption/% |
| Resins, epoxy | 35 |
| Phenols curing agent | 5 |
| Curing catalyst | 0.1 |
| Filler | 45 |
| Pigment | 0.5 |
| Flow agent | 0.4 |
[0033]?
| St-yrax | 0.5 |
| Aerosil | 0.5 |
| Silicone resin | 13 |
1, during the weighing weighing, only need be accurate to 0.1 to measuring large resin, solidifying agent, filler etc., and need to be accurate to 0.01 to pigment, auxiliary agent etc.;
2, the batch mixing batch mixing need to be with three roller mixers, and about half hour of time, stirring velocity is 80r/min;
3, during twin-screw extrusion, the first paragraph temperature is 40 ℃, and the second segment temperature is 100 ℃, and the 3rd section temperature is 105 ℃;
4, the compressing tablet process need has refrigerating unit;
5, after the fragmentation, tablet is of moderate size, can not be too large, and thickness＜3mm.
6, with the print after the fragmentation, aerosil;
7, behind the abrasive dust, need regularly equipment to be guaranteed to keep in good repair;
8, sieve, need to filter with 120 eye mesh screens;
9, the every case of charging 25KG.
Coating process:
At 10mm * 10mm * 6mm, the upper 200 ℃/2min of iron plate solidified after the powder coating preparation was finished, 350 ± 50 microns of coat-thicknesses, and preparation flow is as shown in Figure 1.
Coating performance: anti-outdoor exposure is after 18 months, loss of bond strength 40%, impact property descend 40%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 48%.
Embodiment 2
| Raw material | Consumption/% |
| Resins, epoxy | 35 |
| Dyhard RU 100 | 2.5 |
| Boron trifluoride-amine | 0.1 |
| Filler | 45 |
| Pigment | 0.5 |
| Flow agent | 0.4 |
| St-yrax | 0.5 |
[0048]?
| Aerosil | 0.5 |
| The cellaburate ester | 15.5 |
1, during the weighing weighing, only need be accurate to 0.1 to measuring large resin, solidifying agent, filler etc., and need to be accurate to 0.01 to pigment, auxiliary agent etc.;
2, the batch mixing batch mixing need to be with three roller mixers, and about half hour of time, stirring velocity is 80r/min;
3, during twin-screw extrusion, the first paragraph temperature is 40 ℃, and the second segment temperature is 100 ℃, and the 3rd section temperature is 105 ℃;
4, the compressing tablet process need has refrigerating unit;
5, after the fragmentation, tablet is of moderate size, can not be too large, and thickness＜3mm;
6, with the print after the fragmentation, aerosil;
7, behind the abrasive dust, need regularly equipment to be guaranteed to keep in good repair;
8, sieve, need to filter with 120 eye mesh screens;
9, the every case of charging 25KG.
Coating process:
At 10mm * 10mm * 6mm, the upper 200 ℃/2min of iron plate solidified 350 ± 50 microns of coat-thicknesses after the powder coating preparation was finished.
Coating performance: anti-outdoor exposure is after 18 months, loss of bond strength 38%, impact property descend 36%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 45%.
Embodiment 3
| Raw material | Consumption/% |
| Resins, epoxy | 30 |
| Phenols curing agent | 4 |
| Imidazoles | 0.1 |
| Triphenyl phosphorus | 0.1 |
| Filler | 40 |
| Pigment | 0.5 |
| Flow agent | 0.4 |
[0063]?
| St-yrax | 0.5 |
| Aerosil | 0.5 |
| Silicone resin | 23.8 |
1, during the weighing weighing, only need be accurate to 0.1 to measuring large resin, solidifying agent, filler etc., and need to be accurate to 0.01 to pigment, auxiliary agent etc.;
2, the batch mixing batch mixing need to be with three roller mixers, and about half hour of time, stirring velocity is 80r/min;
3, during twin-screw extrusion, the first paragraph temperature is 40 ℃, and the second segment temperature is 100 ℃, and the 3rd section temperature is 105 ℃;
4, the compressing tablet process need has refrigerating unit;
5, after the fragmentation, tablet is of moderate size, can not be too large, and thickness＜3mm;
6, with the print after the fragmentation, aerosil;
7, behind the abrasive dust, need regularly equipment to be guaranteed to keep in good repair;
8, sieve, need to filter with 120 eye mesh screens;
9, the every case of charging 25KG.
Coating process:
At 10mm * 10mm * 6mm, the upper 190 ℃/2min of iron plate solidified 350 ± 50 microns of coat-thicknesses after the powder coating preparation was finished.
Coating performance: anti-outdoor exposure 18 months, loss of bond strength 25%, impact property descend 27%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 27%.
Embodiment 4
Coating process:
At 10mm * 10mm * 6mm, the upper 190 ℃/2min of iron plate solidified 350 ± 50 microns of coat-thicknesses after the powder coating preparation was finished.
Coating performance: anti-outdoor exposure is after 18 months, loss of bond strength 20%, impact property descend 25%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 15%.
Embodiment 5
| Raw material | Consumption/% |
| Resins, epoxy | 30 |
| Phenols curing agent | 3 |
| Dyhard RU 100 | 0.5 |
| Curing catalyst | 0.2 |
| Filler | 30 |
| Pigment | 0.5 |
| Flow agent | 0.4 |
| St-yrax | 0.5 |
| Aerosil | 0.5 |
| The cellaburate ester | 33.3 |
Coating process:
At 10mm * 10mm * 6mm, the upper 190 ℃/2min of iron plate solidified 350 ± 50 microns of coat-thicknesses after the powder coating preparation was finished.
Coating performance: anti-outdoor exposure is after 18 months, loss of bond strength 15%, impact property descend 20%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 20%.
Embodiment 6
| Raw material | Consumption/% |
| Resins, epoxy | 30 |
| Phenols curing agent | 3 |
| Azanol | 2 |
| Curing catalyst | 0.2 |
| Filler | 30 |
| Pigment | 0.5 |
| Flow agent | 0.4 |
| St-yrax | 0.5 |
| Aerosil | 0.5 |
| Silicone resin | 31.8 |
Coating process:
At 10mm * 10mm * 6mm, the upper 190 ℃/2min of iron plate solidified 350 ± 50 microns of coat-thicknesses after the powder coating preparation was finished.
Coating performance: anti-outdoor exposure is after 18 months, loss of bond strength 18%, impact property descend 23%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 15%.
Embodiment 7
Coating process:
At 10mm * 10mm * 6mm, the upper 190 ℃/2min of iron plate solidified 350 ± 50 microns of coat-thicknesses after the powder coating preparation was finished.
Coating performance: anti-outdoor exposure is after 18 months, loss of bond strength 18%, impact property descend 23%, the non-foaming and adhesion 1 grade of 110 ℃/20Mpa/7d of sodium chloride solution autoclave coating, coatingsurface was non-foaming after 2% clorox soaked 95 ℃/28d, loss of gloss rate 10%.
Claims (10)
1. the epoxy powder coating composition of a high resistance efflorescence is characterized in that, described coating composition comprises following component by mass percentage:
Novolac epoxy: 35～60%;
Phenols curing agent: 5～12%;
The amine curing agent of hiding: 0～10%;
Curing catalyst: 0.01～2%;
Filler: 25～45%;
Pigment: 0.5～1%;
St-yrax: 0.5～1%;
Flow agent: 0.4～1%;
Auxiliary agent type resin: 1～50%;
Aerosil: 0.3～1%.
2. coating composition according to claim 1 is characterized in that, the softening temperature of described novolac epoxy is 85～95 ℃, is selected from bisphenol A epoxide resin, DCPD-containing epoxy resin, oxazolidone Resins, epoxy, novolac epoxy.
3. coating composition according to claim 1 is characterized in that, the hydroxyl equivalent of described phenols curing agent is 200～210, and softening temperature is 82～100 ℃.
4. coating composition according to claim 1 is characterized in that, the described amine curing agent of hiding is selected from Dyhard RU 100, solid-state azanol, SA two hydrazides, isophthalic dihydrazide.
5. coating composition according to claim 1, it is characterized in that, described curing catalyst be selected from imidazoles, modified imidazole, ureas,, boron trifluoride-amine complex, triphenyl phosphorus, 2-benzothiazolyl mercaptan, thiocarbamide and modifier thereof, modified imidazoline.
6. coating composition according to claim 1 is characterized in that, described filler is selected from process white, silicon powder, mica powder, iron oxide red, and the order number is 400～800 orders.
7. coating composition according to claim 1 is characterized in that, described pigment is selected from phthalocyanine blue, phthalocyanine blue, iron oxide yellow.
8. coating composition according to claim 1 is characterized in that, described flow agent is polyacrylic ester.
9. coating composition according to claim 1 is characterized in that, described auxiliary agent type resin is silicone resin, cellaburate ester or the modified resin that contains the phosphorous acid ester structure.
10. coating composition according to claim 1 is characterized in that, described aerosil is high-specific surface area and hydrophilic soft silica, and tamped density is about 30～80g/l.
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Cited By (11)
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| CN104177984A (en) * | 2014-08-28 | 2014-12-03 | 苏州洛特兰新材料科技有限公司 | Epoxy resin flat powder coating for ceramics |
| CN104962172A (en) * | 2015-07-08 | 2015-10-07 | 安庆联泰电子科技有限公司 | Novel low-temperature curing epoxy powder paint |
| CN106519898A (en) * | 2016-10-28 | 2017-03-22 | 福建万安实业集团有限公司 | Imitated gold thermosetting powder coating and preparation method thereof |
| CN107502150A (en) * | 2017-09-28 | 2017-12-22 | 深圳市兴鸿昌电器有限公司 | A kind of high-temp. electro-heating coating and preparation method thereof |
| CN108753101A (en) * | 2018-05-07 | 2018-11-06 | 张建洲 | A kind of epoxide powder coating and its application |
| CN109054632A (en) * | 2018-06-13 | 2018-12-21 | 宁波双人新材料有限公司 | A kind of water-fast weather-proof composite powder coatings and preparation method thereof |
| CN109266214A (en) * | 2018-09-19 | 2019-01-25 | 江苏三木化工股份有限公司 | Heat Resistant Powder Coatings of high adhesion force and preparation method thereof |
| CN109554065A (en) * | 2018-10-17 | 2019-04-02 | 广州擎天材料科技有限公司 | A kind of primary coat powdery paints of resistance to marine climate and preparation method thereof |
| CN109762452A (en) * | 2018-12-29 | 2019-05-17 | 山东千江粉末科技有限公司 | A kind of high temperature resistant grit powder coating and preparation method thereof |
| CN111187560A (en) * | 2020-04-01 | 2020-05-22 | 江苏江南绝缘粉末有限公司 | Ultrahigh-voltage flame-retardant insulating powder for outdoor busbar and preparation method thereof |
| CN112341908A (en) * | 2020-11-27 | 2021-02-09 | 海隆石油产品技术服务（上海）有限公司 | High-wear-resistance powder coating for gas well oil pipe |
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| CN104177984A (en) * | 2014-08-28 | 2014-12-03 | 苏州洛特兰新材料科技有限公司 | Epoxy resin flat powder coating for ceramics |
| CN104962172A (en) * | 2015-07-08 | 2015-10-07 | 安庆联泰电子科技有限公司 | Novel low-temperature curing epoxy powder paint |
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| CN108753101A (en) * | 2018-05-07 | 2018-11-06 | 张建洲 | A kind of epoxide powder coating and its application |
| CN108753101B (en) * | 2018-05-07 | 2021-02-26 | 江门市新会区新日旭电子材料有限公司 | Epoxy powder coating and application thereof |
| CN109054632B (en) * | 2018-06-13 | 2020-11-27 | 宁波双人新材料有限公司 | Water-resistant weather-resistant composite powder coating and preparation method thereof |
| CN109054632A (en) * | 2018-06-13 | 2018-12-21 | 宁波双人新材料有限公司 | A kind of water-fast weather-proof composite powder coatings and preparation method thereof |
| CN109266214A (en) * | 2018-09-19 | 2019-01-25 | 江苏三木化工股份有限公司 | Heat Resistant Powder Coatings of high adhesion force and preparation method thereof |
| CN109554065A (en) * | 2018-10-17 | 2019-04-02 | 广州擎天材料科技有限公司 | A kind of primary coat powdery paints of resistance to marine climate and preparation method thereof |
| CN109554065B (en) * | 2018-10-17 | 2021-07-13 | 擎天材料科技有限公司 | Marine climate resistant primary coating powder coating and preparation method thereof |
| CN109762452A (en) * | 2018-12-29 | 2019-05-17 | 山东千江粉末科技有限公司 | A kind of high temperature resistant grit powder coating and preparation method thereof |
| CN109762452B (en) * | 2018-12-29 | 2021-09-21 | 山东千江粉末科技有限公司 | High-temperature-resistant sand-streak powder coating and preparation method thereof |
| CN111187560A (en) * | 2020-04-01 | 2020-05-22 | 江苏江南绝缘粉末有限公司 | Ultrahigh-voltage flame-retardant insulating powder for outdoor busbar and preparation method thereof |
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| CN112341908B (en) * | 2020-11-27 | 2022-03-22 | 海隆石油产品技术服务（上海）有限公司 | High-wear-resistance powder coating for gas well oil pipe |
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Application publication date: 20130925 |