CN116875160A - Pearly-lustre paint for aircraft skin and preparation method thereof - Google Patents
Pearly-lustre paint for aircraft skin and preparation method thereof Download PDFInfo
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- CN116875160A CN116875160A CN202310984336.5A CN202310984336A CN116875160A CN 116875160 A CN116875160 A CN 116875160A CN 202310984336 A CN202310984336 A CN 202310984336A CN 116875160 A CN116875160 A CN 116875160A
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- polyaspartic acid
- aircraft skin
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- 239000003973 paint Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 94
- 229920005989 resin Polymers 0.000 claims abstract description 94
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 54
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 54
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 150000002148 esters Chemical class 0.000 claims description 33
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 16
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 15
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 15
- -1 aliphatic isocyanate Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 238000004040 coloring Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 5
- 239000002966 varnish Substances 0.000 claims description 5
- 230000033444 hydroxylation Effects 0.000 claims description 4
- 238000005805 hydroxylation reaction Methods 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 30
- 235000013877 carbamide Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000007665 sagging Methods 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N aspartic acid group Chemical group N[C@@H](CC(=O)O)C(=O)O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- ODEHMIGXGLNAKK-OESPXIITSA-N 6-kestotriose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)O1 ODEHMIGXGLNAKK-OESPXIITSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the field of paint chemical industry, and particularly relates to a pearl paint for aircraft skin and a preparation method thereof, wherein the pearl paint for aircraft skin comprises a paint component and a curing agent component, and the paint component comprises the following components in percentage by weight of 20-35: 5-15 parts of urea-based resin dispersion and pearl powder, wherein the urea-based resin dispersion comprises, by weight, 40-60 parts of linear polyester polyol, 15-30 parts of hydroxylated polyaspartic acid resin dispersion, 15-20 parts of dispersing solvent, 3-7 parts of benzylamine and 2-5 parts of hexamethylene diisocyanate for carrying out urea modification on the benzylamine.
Description
Technical Field
The invention belongs to the field of paint chemical industry, and particularly relates to a pearly-lustre paint for aircraft skins and a preparation method thereof.
Background
In recent years, the China aviation industry rapidly develops, civil aircrafts such as ARJ-21 branch airliners, C919 large airliners, AG600 amphibious aircrafts and the like are densely and brightly phased, and gradually enter a mass production stage, and high-quality aircraft matched coating materials are urgently needed for decoration and protection. The civil aircraft often meets the aesthetic requirements of the masses through personalized coating, attracts passenger flows, and gives people a new and fresh feel with beautiful patterns and striking colors on the coating. It is expected that there will be an increasing number of civil aircraft coated with pearlescent paint having a special appearance effect.
The pearling paint is prepared by adding mica base materials coated with titanium dioxide or ferric oxide into a paint base, namely pearling pigment, and after light irradiates on pearling particles, the light has multiple refraction, reflection and interference effects among the titanium dioxide, the ferric oxide and a mica base layer due to different refractive indexes of the coating layer and the mica base material, so that different colors are presented at different observation angles, and the pearling paint has an effect of 'flop'; in addition, unlike aluminum paint, the pearlescent paint has the glittering effect of metal pigment, and the paint film of the pearlescent paint also tends to have pearl-like soft luster, so that the pearlescent paint has wide application in automobile paint and high-grade package printing paint.
However, since the mica substrate in the pearlescent paint is transparent or semitransparent, the hiding power is low, and a three-coating process of adding a basic color primer and a pearlescent base color primer and a varnish is needed. For the coating of civil aircrafts, the primary coating usually needs tens of people, takes a few weeks to finish, and some large aircrafts with complex patterns have a coating period of even one month. The pearlescent paint adopting the three-coating process can greatly improve the coating period of the aircraft, so that the pearlescent paint which can be coated by adopting the conventional process, does not increase the coating time and has good appearance effect is required to meet the coating requirement of the large-scale aircraft. The thickness of the transparent paint film layer is increased, so that the covering power to the base material can be correspondingly improved, and the covering power requirement cannot be met because the thickness of one film forming of a plurality of pearlescent paints is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides the pearly-lustre paint for the aircraft skin, which has the advantages of thick coating, strong covering power, good medium resistance and excellent color and gloss retention, comprises a coating component and a curing agent component,
the coating comprises the following components in percentage by weight: 5 to 15 parts of urea-based resin dispersion and pearl powder, wherein the urea-based resin dispersion comprises, by weight, 40 to 60 parts of linear polyester polyol, 15 to 30 parts of hydroxylated polyaspartic acid resin dispersion, 15 to 20 parts of dispersing solvent, 3 to 7 parts of benzylamine, 2 to 5 parts of hexamethylene diisocyanate for carrying out urea modification on the benzylamine,
wherein the number average molecular weight of the linear polyester polyol is 500-2500.
As preferable: the hydroxylated polyaspartic acid resin dispersion comprises n mole parts of polyaspartic acid ester resin, n+1 to n+1.3 mole parts of hexamethylene diisocyanate for carbamide modification of the polyaspartic acid ester resin, and 2 mole parts of polyol resin for hydroxylation end capping of the carbamide modified polyaspartic acid ester resin, wherein n is an integer of 4 to 8,
the number average molecular weight of the polyaspartic acid ester resin is 500-600, and the polyol resin is pentanediol and/or hexanediol.
As preferable: the paint component also comprises 20 to 35 weight percent of coloring pigment, 0 to 15 weight percent of dispersing agent, 0 to 3 weight percent of dispersing agent, 0 to 1 weight percent of drier, 0 to 1 weight percent of leveling agent and 30 to 45 weight percent of first solvent according to the weight percent of the ureido-containing resin dispersoid,
further: the dispersant is BYK-P104 and/or TEGODispers655.
Further: the drier is one or a combination of a plurality of dibutyl tin dilaurate, stannous octoate and organic bismuth.
Further: the leveling agent is one or a combination of more of EFKA-3777, BYK-358 and EFKA-3772.
Further: the first solvent is one or a combination of a plurality of dimethylbenzene, butyl acetate, propylene glycol methyl ether acetate, 2-heptanone and diethylene glycol butyl ether acetate.
As preferable: the curing agent component comprises aliphatic isocyanate dispersed in a second solvent at a weight concentration of 65-75%.
Further: the aliphatic isocyanate is one or a combination of several of DesmodurN75, desmodurN3390, desmodurN3300 or DesmodurZ 4470.
Further: the second solvent is butyl acetate.
As preferable: the weight part usage ratio of the coating component to the curing agent component is 10:1 to 3.
The invention also provides a preparation method of the pearly-lustre paint for the aircraft skin, which comprises the following steps:
(1) Preparation of hydroxylated polyaspartic acid resin dispersion
Dispersing polyaspartic acid ester resin in a reaction solvent, dropwise adding hexamethylene diisocyanate into the reaction solvent at 40-60 ℃, and after the dropwise adding is finished, adding polyol resin into the reaction solvent and continuing to react for a period of time;
(2) Preparation of ureido-containing resin dispersions
Adding linear polyester polyol and a dispersing solvent into the reaction system obtained in the step (1), fully mixing, cooling the mixed system to below 10 ℃ and keeping the flow state, respectively and simultaneously dropwise adding benzylamine and hexamethylene diisocyanate into the mixed system, and keeping the mixed system to continuously react for a period of time below 10 ℃ after the dropwise adding is finished;
(3) And (3) mixing the reaction system obtained in the step (2) with the rest components to form a coating component, and preparing a curing agent component for standby.
In the invention, diisocyanate is firstly connected with secondary amine groups of polyaspartic acid ester resin in a chemical reaction way to generate substituted urea group structures of-RN-CO-NH-, after hydroxylation, the substituted urea groups are distributed in a paint film after film forming and crosslinking of the polyaspartic acid ester resin, and wet film flowing is controlled through hydrogen bonding, so that sagging phenomenon of paint components in film coating construction is inhibited; however, the hydrogen bonding effect of the part of substituted ureido is relatively weak, and for this purpose, a-NH-CO-NH-ureido structure generated by chemical reaction connection of benzylamine and diisocyanate is also added in the scheme, and the part of urea structure which does not participate in crosslinking effectively supplements the substituted ureido structure crosslinked in the paint film, and meanwhile, the oil resistance and the medium resistance of the paint film are not affected because the number of chain segments which do not participate in crosslinking is limited.
According to the scheme, no sagging resistant components such as directional wax are required to be added into the paint, so that the paint of the scheme obtains higher construction solid content, the thickness of a film layer of a primary coating film in the film forming construction process is effectively improved, meanwhile, a three-dimensional network is formed by hydrogen bonds between urea groups under the mutual coordination of the two urea-based structures, sagging is effectively inhibited to realize thick coating orientation of the pearly-luster paint, and the cured colored transparent paint film obtains ideal hiding power; meanwhile, the displacement of the pearlescent pigment is controlled and reduced, and a good pearlescent effect can be maintained;
meanwhile, in the scheme, on the basis of taking high weather-resistant flexible polyester resin as a resin main body, the mechanical property of the coating is improved by adding the hydroxylated polyaspartic acid resin, and the requirement on the flexibility of low-temperature impact is still met on the premise of improving the coating thickness;
wherein, the polyaspartic acid ester resin which is connected with diisocyanate through reaction is subjected to hydroxylation modification by the polyol resin, so that the polyaspartic acid ester resin and the main resin linear polyester polyol also have hydroxyl functional groups, and when the film forming and curing are performed, the polyaspartic acid ester resin and the linear polyester polyol can form crosslinking,
the defect of uneven crosslinking caused by too slow reaction rate of secondary amino groups on the polyaspartic acid ester and isocyanate groups compared with alcoholic hydroxyl groups when the polyaspartic acid ester is directly mixed with linear polyester polyol and crosslinked by adding an isocyanate curing agent is avoided;
in the scheme, in the step (2), benzyl amine and hexamethylene diisocyanate react preferentially to generate an ureido structure, but in consideration of the reaction speed between the active amino group on the benzyl amine and isocyanate, the reaction is severe, in the scheme, at a lower temperature, benzyl amine and hexamethylene diisocyanate are respectively added into a dispersion system containing a hydroxylated polyaspartic acid resin dispersion and linear polyester polyol at the same time for reaction, so that the concentration of reactants is reduced, and matrix resin imparts larger viscosity to the reaction system, so that the reaction rate is effectively controlled by reducing the activity of the reactants after dripping.
In conclusion, the pearlescence paint for the aircraft skin has the performances of thick coating, strong covering power, good medium resistance, excellent color retention, light retention and the like, is used as a primer to be matched with the varnish for the aircraft skin, and has ideal prospect as an aerospace coating material.
Detailed Description
The preparation method of the pearly-lustre paint for the aircraft skin comprises the following steps:
(1) Preparation of hydroxylated polyaspartic acid resin dispersion
Dispersing n mole parts of polyaspartic acid ester resin in a reaction solvent, dropwise adding n+1 to n+1.3 mole parts of hexamethylene diisocyanate into the reaction solvent at the temperature of 40-60 ℃, adding 2 mole parts of polyol resin into the reaction solvent after the dropwise adding is finished, keeping the temperature of 40-60 ℃ for continuous reaction for a period of time, wherein n is an integer of 4-8,
wherein the polyol resin is pentanediol and/or hexanediol;
(2) Preparation of ureido-containing resin dispersions
Adding 40-60 parts by weight of linear polyester polyol and 15-20 parts by weight of dispersing solvent into 15-30 parts by weight of the reaction system obtained in the step (1), fully mixing, cooling the mixed system to below 10 ℃ and keeping the flow state, simultaneously dropwise adding 3-7 parts by weight of benzylamine and 2-5 parts by weight of hexamethylene diisocyanate into the mixed system respectively, and keeping the mixed system to react for a period of time below 10 ℃ after the dropwise adding is finished;
(3) Mixing 20-35 parts by weight of the reaction system obtained in the step (2) with 5-15 parts by weight of pearl powder, 0-15 parts by weight of coloring pigment, 0-3 parts by weight of dispersing agent, 0-1 part by weight of drier, 0-1 part by weight of leveling agent and 30-45 parts by weight of first solvent to form a coating component, dispersing aliphatic isocyanate in a second solvent to form a curing agent component at a weight concentration of 65-75%, and mixing the coating component and the curing agent component according to a weight ratio of 10:1 to 3 of the material is used for standby,
wherein the dispersing agent is BYK-P104 and/or TEGODispers655,
the drier is one or the combination of a plurality of dibutyl tin dilaurate, stannous octoate and organic bismuth,
the leveling agent is one or the combination of more of EFKA-3777, BYK-358 and EFKA-3772,
the first solvent is one or the combination of a plurality of dimethylbenzene, butyl acetate, propylene glycol methyl ether acetate, 2-heptanone and diethylene glycol butyl ether acetate,
the aliphatic isocyanate is one or a combination of several of DesmodurN75, desmodurN3390, desmodurN3300 or DesmodurZ4470,
the second solvent is butyl acetate.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Preparation of hydroxylated polyaspartic acid resin dispersion
Adding 1420650g of the polyaspartic acid ester resin DesmophenNH and 72.3g of dimethylbenzene into a reaction vessel provided with a condensing pipe, a stirrer, a thermometer and a dropping funnel, uniformly mixing, heating to 50 ℃, uniformly dropping 250g of HDI monomer into the reaction vessel, continuously dropping 61.2g of 1, 5-pentanediol into the reaction vessel at a uniform speed for 0.5 hour, continuously reacting for 1 hour at 50 ℃, discharging to obtain a hydroxylated polyaspartic acid resin dispersoid, wherein the solid content of the hydroxylated polyaspartic acid resin dispersoid is about 93wt%,
after conversion, the molar part ratio of the polyaspartic acid ester resin to the hexamethylene diisocyanate HDI monomer is 4:5.05 (n: n+1.05, n=4),
wherein DesmophenNH1420 is a kestose polyaspartic acid ester having a molecular weight of about 552;
(2) Preparation of ureido-containing resin dispersions
Into a reaction vessel equipped with a condenser, a stirrer, a thermometer and a dropping funnel, a linear polyester resin was added1606BA-80710g (solid content is 80 wt%), 426g (solid content is 93 wt%) of the hydroxylated polyaspartic acid resin dispersoid prepared in the step (1), 90g of dimethylbenzene, uniformly stirring, cooling to 8 ℃, simultaneously and uniformly dropwise adding 53g of benzylamine and 42g of HDI into the mixture, simultaneously and completely dripping for 1 hour, continuously preserving heat at 8 ℃ for 0.5 hour, discharging to obtain the urea-group-containing resin dispersoid, wherein the solid content is about 80wt%,
wherein, the liquid crystal display device comprises a liquid crystal display device,1606BA-80 is a Zhan Xin linear polyester product, the solid content is 80wt%, and the solvent is butyl acetate;
(3) Mixing the ureido-containing resin dispersoid obtained in the step (2) with pearl powder, coloring pigment, dispersing agent, drier, leveling agent and first solvent according to the following table to form a coating component,
in addition, an aliphatic isocyanate curing agent Desmodur 3300 (Bayer, germany) was dispersed in butyl acetate at a concentration of 75% by weight to form a curing agent component, and the coating component and the curing agent component were mixed in a weight ratio of 10:2, standby.
Example 2
(1) Preparation of hydroxylated polyaspartic acid resin dispersion
Adding 520650g of polyaspartic acid ester resin F and 95g of dimethylbenzene into a reaction vessel provided with a condensing tube, a stirrer, a thermometer and a dropping funnel, uniformly mixing, heating to 43 ℃, uniformly dropping 212g of HDI monomer into the reaction vessel, continuously dropping 33g of 1, 6-hexanediol into the reaction vessel for 0.5 hour, continuously reacting for 1 hour at 43 ℃, discharging to obtain a hydroxylated polyaspartic acid resin dispersoid, wherein the solid content of the hydroxylated polyaspartic acid resin dispersoid is about 90wt%,
after conversion, the mole fraction ratio of the polyaspartic acid ester resin to the hexamethylene diisocyanate HDI monomer is 8:9.04 (n: n+1.04, n=8),
wherein F520 is polyaspartic acid ester of Shenzhen Feiyuang Jun research New Material Co., ltd, and has a molecular weight of about 582;
(2) Preparation of ureido-containing resin dispersions
Adding 424g (solid content is 72 wt%) of the hydroxylated polyaspartic acid resin dispersoid prepared in the step (1) (the solid content is 90 wt%) of the linear polyester resin Setal1715VX-74690g, the dimethylbenzene is 74g, uniformly stirring, cooling to 10 ℃, simultaneously and uniformly dropwise adding 65g of benzylamine and 51g of HDI into the reaction vessel, simultaneously and completely dripping for 1 hour, continuously preserving heat for 0.5 hour at 10 ℃ after the completion of dripping, discharging to obtain the urea-group-containing resin dispersoid, wherein the solid content is about 76.3wt%,
wherein Setal1715VX-74 is a skillful new linear polyester product, the solid content is 72 weight percent, and the solvent is butyl acetate;
(3) Mixing the ureido-containing resin dispersoid obtained in the step (2) with pearl powder, coloring pigment, dispersing agent, drier, leveling agent and first solvent according to the following table to form a coating component,
in addition, an aliphatic isocyanate curing agent was dispersed in butyl acetate at a weight concentration of 69% [ 40+40 x 0.9)/110 ] to form a curing agent component, and the coating component and the curing agent component were combined at a weight ratio of 10:2 standby (40 parts by weight of aliphatic isocyanate curing agent Desmodur 3300 (Bayer, germany, solid content 100 wt.%) 40 parts by weight of aliphatic isocyanate curing agent Desmodur 3390 (Bayer, germany, solid content 90 wt.%) 30 parts by weight of butyl acetate).
Comparative example 1
The commercial sag prevention resin CTR-6736 (product of Changzhou coating chemical institute of China) was used in place of the urea-based resin dispersion of example 1, and the remaining components were the same as in example 1, with the specific components shown in the following table:
in addition, an aliphatic isocyanate curing agent Desmodur 3300 (Bayer, germany) was dispersed in butyl acetate at a concentration of 75% by weight to form a curing agent component, and the coating component and the curing agent component were mixed in a weight ratio of 10:2, standby.
Comparative example 2
After the traditional sagging prevention component (oriented wax, CAB resin) is compounded with the linear polyester resin and the commercial sagging prevention resin CTR-6725, the urea-based resin dispersion in the example 1 is replaced, and the other components are the same as the urea-based resin dispersion in the example 1, and the specific components are shown in the following table (the use amount is larger during replacement due to the low solid content of the oriented wax and the CAB resin), and the total solid content of the pearlescent paint is lower):
in addition, an aliphatic isocyanate curing agent Desmodur 3300 (Bayer, germany) was dispersed in butyl acetate at a concentration of 75% by weight to form a curing agent component, and the coating component and the curing agent component were mixed in a weight ratio of 10:2, standby.
Comparative example 3
The substitution of the urea groups converted by the benzylamine reaction in example 1 with urea groups converted by the secondary amine reaction on the polyaspartic acid ester resin (theoretically equimolar) simultaneously allows for an increase in the amount of polyaspartic acid ester resin and a corresponding decrease in the mass of the linear polyester resin in step (2), the remaining components and operations being the same as in example 1:
(1) Preparation of hydroxylated polyaspartic acid resin dispersion
Adding 1420650g of the polyaspartic acid ester resin DesmophenNH and 72.3g of dimethylbenzene into a reaction vessel provided with a condensing pipe, a stirrer, a thermometer and a dropping funnel, uniformly mixing, heating to 50 ℃, uniformly dropping 250g of HDI monomer into the reaction vessel, continuously dropping 61.2g of 1, 5-pentanediol into the reaction vessel at a uniform speed for 0.5 hour, continuously reacting for 1 hour at 50 ℃, discharging to obtain a hydroxylated polyaspartic acid resin dispersoid, wherein the solid content of the hydroxylated polyaspartic acid resin dispersoid is about 93wt%,
after conversion, the molar part ratio of the polyaspartic acid ester resin to the hexamethylene diisocyanate HDI monomer is 4:5.05 (n: n+1.05, n=4),
wherein DesmophenNH1420 is a kestose polyaspartic acid ester having a molecular weight of about 552;
(2) Preparation of ureido-containing resin dispersions
Adding linear polyester resin to a dosage vessel1606BA-80405g (solid content 80 wt%), 640g (solid content 93 wt%) of the hydroxylated polyaspartic acid resin dispersion obtained in step (1), stirring uniformly, its solid content is about 88wt%,
wherein, the liquid crystal display device comprises a liquid crystal display device,1606BA-80 is a Zhan Xin linear polyester product, the solid content is 80%, and the solvent is butyl acetate;
(3) Mixing the ureido-containing resin dispersoid obtained in the step (2) with pearl powder, coloring pigment, dispersing agent, drier, leveling agent and first solvent according to the following table to form a coating component,
in addition, an aliphatic isocyanate curing agent Desmodur 3300 (Bayer, germany) was dispersed in butyl acetate at a concentration of 75% by weight to form a curing agent component, and the coating component and the curing agent component were mixed in a weight ratio of 10:2, standby.
Comparative example 4
The substitution of the urea groups converted by the reaction of secondary amine groups on the polyaspartic acid ester resin in example 1 with urea groups converted by the reaction of benzylamine (theoretically equimolar) and the substitution of the linear polyester resin for the missing polyaspartic acid ester resin were carried out in the same way as in example 1:
(1) Preparation of ureido-containing resin dispersions
Into a reaction vessel equipped with a condenser, a stirrer, a thermometer and a dropping funnel, a linear polyester resin was added1606BA-801200g (solid content is 80 wt%) and 70g of dimethylbenzene, uniformly stirring, cooling to 8 ℃, respectively and uniformly dripping 155g of benzylamine and 125g of HDI into the mixture, simultaneously dripping the mixture for 3 hours, continuously preserving heat at 8 ℃ for 0.5 hour after dripping, discharging to obtain the urea-based resin dispersoid with solid content of about 80wt%,
wherein, the liquid crystal display device comprises a liquid crystal display device,1606BA-80 is a high and novel linear polyester product with a solid content of 80wt% and a solvent of butyl acetateAn ester;
(2) Mixing the ureido-containing resin dispersoid obtained in the step (1) with pearl powder, coloring pigment, dispersing agent, drier, leveling agent and first solvent according to the following table to form a coating component,
in addition, an aliphatic isocyanate curing agent Desmodur 3300 (Bayer, germany) was dispersed in butyl acetate at a concentration of 75% by weight to form a curing agent component, and the coating component and the curing agent component were mixed in a weight ratio of 10:2, standby.
The coating compositions obtained in the examples and comparative examples above were thoroughly mixed with the corresponding hardener composition, and construction and performance tests were carried out after adjusting the solids content (different resins and formulations, which resulted in different upper limits of the solids content of the coating (construction solids content), and when the upper limits of the construction solids content were exceeded, the viscosity of the coating was too high to facilitate smooth spraying during construction:
TABLE 1
In the above table, "low temperature bending" performance was measured according to GB/T1731-2020, and "flash index (dynamic color index FI)" was measured by SGY-A flash index measuring instrument, and hydraulic oil resistance was measured according to GB/T9274-1988.
In table 1, the bead varnish prepared in comparative example 1 based on the commercial sagging-preventing resin CTR-6736 as the main resin, although the sagging resistance and the pearlescence orientation capability during thick coating are also improved, the low-temperature flexibility after film formation is insufficient due to the fact that the aspartic acid structure is not involved, and the requirements of the aircraft skin varnish cannot be fully met;
in comparative example 2, the sagging resistance of the coating is improved by adding the oriented wax and the CAB resin, but because the molecular weights of the oriented wax and the CAB resin are larger, a large amount of solvent is needed to realize dispersion and dissolution, so that the prepared coating has lower solid content and construction solid content, one-time thick coating cannot be realized during construction, the covering power after one-time coating is obviously insufficient, and the covering of the base coat can be realized by repeatedly spraying to reach a preset thickness; meanwhile, the introduction of an aspartic acid structure is not involved, so that the low-temperature flexibility after film formation is insufficient, and the requirements of the aircraft skin paint cannot be comprehensively met;
the urea group structure in the comparative example 3 is formed by the reaction of secondary amine groups on the polyaspartic acid ester resin and isocyanate groups, compared with the urea group formed by the reaction of amine groups provided by the polyaspartic acid ester resin and benzylamine in the scheme, under the condition that the number of urea groups is not greatly different, the sagging prevention control capability and the pearl orientation of a wet film in the comparative example 3 are obviously reduced, and under the condition of high solid content of the coating, the effective thickness cannot be formed by one film forming, so that the covering power is insufficient;
the ureido structures in the comparative example 4 are all generated by the reaction of benzylamine and diisocyanate, and the compound chain segments to which the ureido groups belong do not participate in crosslinking polymerization, and although the ureido groups are close to the example 1 in the theoretical quantity, the sagging prevention effect in the example 1 is not achieved, meanwhile, the low-temperature flexibility after film formation is insufficient due to the fact that the introduction of an aspartic acid structure is not involved, and the requirements of the aircraft skin paint cannot be fully met; and the compound chain segments of the ureido groups do not participate in cross-linking polymerization, and the excessive chain segments which do not participate in cross-linking exist, so that the oil resistance and the medium resistance of the paint film are also influenced.
From the above comparison examples 3 and 4, it is known that the reasonable distribution of chemical connection relationship of ureido groups in paint film is beneficial to the hydrogen bonding between the ureido groups to be exerted to a greater extent, so as to achieve better sagging prevention effect.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. An aircraft skin is with pearl finish, its characterized in that: the pearlescent paint comprises a coating component and a curing agent component,
the coating comprises the following components in percentage by weight: 5 to 15 of urea-based resin dispersion and pearl powder,
the urea-based resin dispersion comprises, by weight, 40-60 parts of linear polyester polyol, 15-30 parts of hydroxylated polyaspartic acid resin dispersion, 15-20 parts of dispersing solvent, 3-7 parts of benzylamine and 2-5 parts of hexamethylene diisocyanate for carrying out urea modification on benzylamine.
2. The aircraft skin bead paint of claim 1, wherein: the hydroxylated polyaspartic acid resin dispersion comprises n mole parts of polyaspartic acid ester resin, n+1 to n+1.3 mole parts of hexamethylene diisocyanate used for carrying out urea modification on the polyaspartic acid ester resin, and 2 mole parts of polyol resin for carrying out hydroxylation end capping on the urea modified polyaspartic acid ester resin, wherein n is an integer of 4 to 8.
3. The aircraft skin bead paint of claim 1, wherein: the paint component also comprises coloring pigment, dispersing agent, drier, leveling agent and first solvent,
wherein the weight percentage of the urea-based resin dispersion is 20 to 35 percent, the weight percentage of the pearl powder is 5 to 15 percent, the weight percentage of the coloring pigment is 0 to 15 percent, the weight percentage of the dispersing agent is 0 to 3 percent, the weight percentage of the drier is 0 to 1 percent, the weight percentage of the leveling agent is 0 to 1 percent, and the weight percentage of the first solvent is 30 to 45 percent.
4. A pearlescent paint for aircraft skin according to claim 3, wherein: the dispersant is BYK-P104 and/or TEGO Dispers655.
5. A pearlescent paint for aircraft skin according to claim 3, wherein: the drier is one or a combination of a plurality of dibutyl tin dilaurate, stannous octoate and organic bismuth.
6. A pearlescent paint for aircraft skin according to claim 3, wherein: the leveling agent is one or a combination of more of EFKA-3777, BYK-358 and EFKA-3772.
7. A pearlescent paint for aircraft skin according to claim 3, wherein: the first solvent is one or a combination of a plurality of dimethylbenzene, butyl acetate, propylene glycol methyl ether acetate, 2-heptanone and diethylene glycol butyl ether acetate.
8. The aircraft skin bead paint of claim 1, wherein: the curing agent component comprises aliphatic isocyanate dispersed in a second solvent at a weight concentration of 65-75%.
9. The aircraft skin bead paint of claim 8, wherein: the aliphatic isocyanate is one or a combination of several of Desmodur N75, desmodur N3390, desmodur N3300 and Desmodur Z4470.
10. A process for the preparation of an aircraft skin pearl varnish according to any of claims 1 to 9, wherein: the preparation method is that,
(1) Preparation of hydroxylated polyaspartic acid resin dispersion
Dispersing polyaspartic acid ester resin in a reaction solvent, dropwise adding hexamethylene diisocyanate into the reaction solvent at 40-60 ℃, and after the dropwise adding is finished, adding polyol resin into the reaction solvent and continuing to react for a period of time;
(2) Preparation of ureido-containing resin dispersions
Adding linear polyester polyol and a dispersing solvent into the reaction system obtained in the step (1), fully mixing, cooling the mixed system to below 10 ℃ and keeping the flow state, respectively and simultaneously dropwise adding benzylamine and hexamethylene diisocyanate into the mixed system, and keeping the mixed system to continuously react for a period of time below 10 ℃ after the dropwise adding is finished;
(3) And (3) mixing the reaction system obtained in the step (2) with the rest components to form a coating component, and preparing a curing agent component for standby.
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