CN117050627B - Polyaspartic acid ester polyurea coating for SMC (sheet molding compound) substrate and preparation method thereof - Google Patents
Polyaspartic acid ester polyurea coating for SMC (sheet molding compound) substrate and preparation method thereofInfo
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- CN117050627B CN117050627B CN202311170686.4A CN202311170686A CN117050627B CN 117050627 B CN117050627 B CN 117050627B CN 202311170686 A CN202311170686 A CN 202311170686A CN 117050627 B CN117050627 B CN 117050627B
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
- C08G18/287—Imine compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
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Abstract
The application belongs to the field of coating processing, and particularly relates to a polyaspartic acid ester polyurea coating for an SMC (sheet molding compound) substrate and a preparation method thereof. The polyaspartic acid ester polyurea coating for the SMC substrate comprises, by weight, 18-32 parts of polyaspartic acid ester resin, 18-32 parts of ketimine modified polyaspartic acid ester resin, 3-12 parts of resin additive, 2-2.5 parts of pigment, 4-22 parts of functional filler, 1-1.5 parts of auxiliary agent and 15-31.5 parts of solvent, and a curing agent, wherein the curing agent comprises 41.2-43.5 parts of isocyanate trimer, 2.3-4.6 parts of polyester modified elastic isocyanate prepolymer, 3-4 parts of solvent and 0.3-0.4 part of water absorbent. The application improves the adhesive force of the polyaspartic acid ester polyurea coating and the SMC substrate, and the coating has excellent ageing resistance, wear resistance and scratch resistance.
Description
Technical Field
The invention belongs to the field of coating processing, and particularly relates to a polyaspartic acid ester polyurea coating for an SMC (sheet molding compound) substrate and a preparation method thereof.
Background
SMC is a composite material, belonging to a glass fiber reinforced plastic, and the main raw materials comprise GF (special yarn), MD (filler) and various auxiliary agents. The SMC material has very excellent performance characteristics, and in practical application, the material is often made into common parts, and has absolute sealing waterproof performance, corrosion resistance, electrical insulation, attractive appearance and long service life. The SMC composite material for the automobile industry is molded at one step at high temperature and high pressure, has high deformation resistance and high temperature resistance, and can meet the requirements of the automobile industry.
The SMC composite material adopts high-temperature single-component paint baking paint abroad, and needs baking at 120-140 ℃ and baking resin at lower than 120-140 ℃ without crosslinking and drying. In the design of some production lines in China, the problems of energy consumption, carbon emission, coating line engineering cost and the like are considered, and low-temperature two-component coating is adopted for baking at 80 ℃, but the low-temperature baking is not suitable for a single-coating process.
Disclosure of Invention
In order to overcome the defect that low-temperature baking is not suitable for a single-coating process, the application provides a polyaspartic acid ester polyurea coating for an SMC (sheet molding compound) substrate and a preparation method thereof.
In a first aspect, the application provides a polyaspartic acid ester polyurea coating for an SMC substrate, which is realized by adopting the following technical scheme:
The polyaspartic acid ester polyurea coating for the SMC substrate comprises, by weight, 18-32 parts of polyaspartic acid ester resin, 18-32 parts of ketimine modified polyaspartic acid ester resin, 3-12 parts of resin additive, 2-2.5 parts of pigment, 4-22 parts of functional filler, 1-1.5 parts of auxiliary agent and 15-31.5 parts of solvent, and a curing agent, wherein the curing agent comprises 41.2-43.5 parts of isocyanate trimer, 2.3-4.6 parts of polyester modified elastic isocyanate prepolymer, 3-4 parts of solvent and 0.3-0.4 part of water absorbent, and the mass ratio of the main agent to the curing agent is 100 (44.39-57.75).
Through adopting above-mentioned technical scheme, the addition of ketimine modified polyaspartic acid ester resin makes polyaspartic acid ester polyurea coating spraying after, can accelerate hydrolytic reaction rate, reduces the production line baking temperature, and it can to toast 30min at 80 ℃, can reach consumption reduction energy-conserving and improve SMC substrate work piece chain speed's effect.
The ketimine modified polyaspartic acid ester resin has lower viscosity, prolongs the pot life, delays the viscosity increase rate and improves the wettability to the SMC substrate. The compound use of the polyaspartic acid ester resin and the ketimine modified polyaspartic acid ester resin can form a compact three-dimensional network structure through crosslinking with isocyanate trimer and polyester modified elastic isocyanate prepolymer, so that the adhesive force of the polyaspartic acid ester polyurea coating and an SMC substrate is improved, and the ageing resistance, the wear resistance and the high-low temperature alternation resistance of the polyaspartic acid ester polyurea coating can also be improved.
The addition of the resin additive can effectively reduce the internal stress of the coating while forming high crosslinking density, thereby being beneficial to the adhesive force of the polyaspartic acid ester polyurea coating.
The polyester modified elastic isocyanate prepolymer is added into the curing agent, so that the coating has good toughness, and meanwhile, the adhesive force between the polyaspartic acid ester polyurea coating and the SMC substrate is further improved, so that the comprehensive performance of the coating is greatly improved.
The polyaspartic acid ester polyurea coating for the SMC substrate provided by the application has the advantages that the high crosslinking density of the polyaspartic acid ester polyurea coating is utilized, and the high wear resistance and the high scratch resistance of the coating are improved. The polyaspartic acid ester polyurea has high weather resistance and high decoration, so that the coating achieves the bottom surface integration, and the coating has excellent adhesion and protection and excellent decoration.
Preferably, the ketimine modified polyaspartic acid ester resin has a structural formula ofWherein R 1 is alkyl of 1 to 8 carbon atoms, R 2 is a divalent hydrocarbon radical, R 3 and R 4 are independently of one another represented as monovalent aliphatic, cycloaliphatic or araliphatic residues, and R 3 and R 4 do not have tertiary amine nitrogen.
By adopting the technical scheme, the imine group is introduced into the ketimine modified polyaspartic acid ester resin, so that the reaction speed of the polyaspartic acid ester resin and isocyanate is reduced, the hydrolysis resistance and the storage stability of the polyaspartic acid ester polyurea coating are improved, the polyaspartic acid ester polyurea coating has an excellent wetting effect on an SMC substrate, and the adhesive force of the polyaspartic acid ester polyurea coating and the SMC substrate is improved.
Preferably, the preparation step of the ketimine modified polyaspartic acid ester resin comprises the following steps:
firstly, dropwise adding maleic acid ester into fatty amine, and controlling the temperature to be 60-70 ℃ for reaction for 12-48 hours to obtain a reaction liquid;
Then adding ketone compounds into the reaction solution, controlling the temperature to be 80-150 ℃ for reaction for 2-12 hours, and obtaining ketimine modified polyaspartic acid ester resin after the reaction is completed;
the ratio of the fatty amine to the substances of the maleate and ketone compounds is 1 (1-1.4): 0.7-1.1.
Preferably, the ratio of the amounts of the fatty amine to the maleate and ketone compounds is 1:1.4:0.7.
In the present application, the aliphatic amine is selected from one of 4,4' -diaminodicyclohexylmethane, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, 2-methylpentanediamine, isophoronediamine, methylcyclohexanediamine and polyetheramine D230, and preferably, the aliphatic amine is 4,4' -diaminodicyclohexylmethane.
In the application, the maleic acid ester is selected from one of dimethyl maleate, diethyl maleate, dipropyl maleate and dibutyl maleate, and preferably, the maleic acid ester is diethyl maleate.
In the application, the ketone compound is selected from one of butanone, methyl isopropyl ketone and methyl isobutyl ketone, and preferably, the ketone compound is methyl isobutyl ketone.
Preferably, the mass ratio of the polyaspartic acid ester resin to the ketimine modified polyaspartic acid ester resin is 1:1.5.
By adopting the technical scheme, the polyaspartic acid ester polyurea coating has excellent ageing resistance, wear resistance and scratch resistance, and the polyaspartic acid ester polyurea coating has good adhesive force with the SMC substrate.
Preferably, the polyaspartic acid ester polyurea coating for the SMC substrate comprises 20 parts of polyaspartic acid ester resin, 30 parts of ketimine modified polyaspartic acid ester resin, 6.5 parts of resin additive, 2.5 parts of pigment, 14.5 parts of functional filler, 1.4 parts of auxiliary agent and 21.3 parts of solvent, and a curing agent comprising 43.5 parts of isocyanate trimer, 2.3 parts of polyester modified elastic isocyanate prepolymer, 3.7 parts of solvent and 0.3 part of water absorbent, wherein the mass ratio of the main agent to the curing agent is 100:49.59.
Preferably, the resin additive is selected from one or more of a silane coupling agent, a polyester polyol resin, and a hydroxy acrylic resin.
By adopting the technical scheme, the silane coupling agent, the polyester polyol resin and the hydroxy acrylic resin are used as resin additives, so that the adhesive force of a paint film is improved, the internal stress of a coating is reduced while the high crosslinking density is formed, and the adhesive force of the polyaspartic acid ester polyurea coating is further improved, and the salt spray resistance, the moist heat resistance and the high-low temperature alternation resistance of the polyaspartic acid ester polyurea coating are improved.
In the application, the silane coupling agent is selected from one or more of KH-560, KH-550 and KH-570, and preferably, the silane coupling agent is KH-560.
In the present application, the polyester polyol resin is selected from the group consisting of polyester polyol resin 168SS-80, polyester polyol resinAddBond LTH polyester polyol resinAddBond LTW, one of polyester polyol resins XCP-1000H, polyester polyol resins XCP-2000H and polyester polyol resins XCP-3000H, preferably the polyester polyol resin is selected from the group consisting of polyester polyol resins 168SS-80, polyester polyol resinsAddBond LTH and polyester polyol resinsAddBond LTW, one or more of the following.
In the application, the hydroxyl acrylic resin is selected from one or more of hydroxyl acrylic resin CFU2450B, hydroxyl acrylic resin BS526 and hydroxyl acrylic resin BS5766, and preferably, the hydroxyl acrylic resin is hydroxyl acrylic resin BS5766.
Preferably, the resin additive is formed by mixing (3-10) silane coupling agent, polyester polyol resin and hydroxy acrylic resin according to the mass ratio of (5-20).
By adopting the technical scheme, the resin additive compounded by the silane coupling agent, the polyester polyol resin and the hydroxy acrylic resin has better compatibility, and can effectively reduce the internal stress of the coating while forming high crosslinking density, thereby further improving the adhesive force of the polyaspartic acid ester polyurea coating and the SMC substrate.
More preferably, the mass ratio of the silane coupling agent, the polyester polyol resin and the hydroxy acrylic resin is 1:7:13.
By adopting the technical scheme, the polyaspartic acid ester polyurea coating has higher adhesive force with the SMC substrate and better adhesive force stability.
Preferably, the functional filler is a mixture of polyurethane microspheres and ED30 matting powder.
By adopting the technical scheme, the polyurethane microsphere is resin and has excellent weather resistance and scratch resistance. The ED30 matting powder is silicon dioxide subjected to surface treatment, and has excellent matting, wear-resisting, scratch-resisting and weather-resisting effects. Compared with common fillers, the functional filler compounded by the polyurethane microspheres and the ED30 matting powder improves the weather resistance and the wear resistance of the polyaspartic acid ester polyurea coating, and a paint film has no scratch.
Preferably, the mass ratio of the polyurethane microsphere to the ED30 matting powder is 1 (0.4-0.5), and more preferably, the mass ratio of the polyurethane microsphere to the ED30 matting powder is 1:0.45.
Preferably, the main agent further comprises 3.5-4 parts by weight of precipitated barium sulfate.
In the application, the precipitated barium sulfate is a common filler, and the chemical resistance is good and stable when the filler is added. The paint film skeleton is achieved, and the paint film is plump.
Preferably, the auxiliary agent comprises a dispersing agent, a defoaming agent and a leveling agent.
In the application, the mass ratio of the dispersing agent to the defoaming agent to the leveling agent is (0.7-0.9): 0.2-0.4, and preferably, the mass ratio of the dispersing agent to the defoaming agent to the leveling agent is 0.8:0.3:0.3.
In the application, the dispersing agent is one or more of dispersing agents BYK-163, dispersing agents EFKA4061 and Hunsted Mich 207 dispersing agents.
Preferably, the dispersant is dispersant BYK-163 or dispersant EFKA4061.
In the application, the defoamer is selected from defoamer BYK-054 and Yingchangdi Gao Tuopao agentsAirex900 and a Xipu defoamer 100N.
Preferably, the defoamer is defoamer BYK-054 and win-win high-foam-removing agentAirex900, 900.
Preferably, the defoamer BYK-054 and the Yingchangdi Gao Tuopao agentAirex900 is (0.15-0.25) 0.1, more preferably, the defoamer BYK-054 and Yingchangdi Gao TuopaoAirex900 to 900 was 0.2:0.1 by mass.
In the application, the leveling agent is one or more selected from the group consisting of leveling agents BYK-300, BYK-306, BYK-307, BYK-333, BYK-342, BYK-358 and BYK-378.
Preferably, the leveling agent is a leveling agent BYK-300.
In the present application, the polyaspartate resin is selected from one or more of the flying jun-grinding aspartyl resin F420, the flying jun-grinding aspartyl resin F421 and the flying jun-grinding aspartyl resin F520.
Preferably, the polyaspartate resin is F421 and/or F520.
In the application, the pigment is carbon black or titanium dioxide.
In the application, the solvent in the main agent is a mixture of dimethylbenzene, butyl ester and propylene glycol methyl ether acetate.
Preferably, the solvent in the main agent is formed by mixing dimethylbenzene, butyl ester and propylene glycol methyl ether acetate according to a volume ratio of 4:4:2.
In the application, the isocyanate trimer is an HDI trimer and/or an IPDI trimer.
Preferably, the isocyanate trimer is an HDI trimer.
Preferably, the HDI trimer is HT-100 or TPA-100.
In the application, the polyester modified elastic isocyanate prepolymer is Feiyuan GB905A-85.
By introducing the polyester modified elastic isocyanate prepolymer, the coating has good toughness, and meanwhile, the adhesive force of the polyaspartic acid ester polyurea coating and the SMC substrate is further improved, so that the comprehensive performance of the coating is greatly improved.
In the application, the solvent in the curing agent is a mixture of butyl ester and propylene glycol methyl ether acetate.
Preferably, the solvent in the curing agent is formed by mixing butyl ester and propylene glycol methyl ether acetate according to a volume ratio of 7:3.
In the application, the water absorbing agent is water absorbing agent TI or Sylosiv A 3 powder.
Preferably, the water absorbing agent is water absorbing agent TI.
In a second aspect, the application provides a preparation method of an SMC substrate polyaspartic acid ester polyurea coating, which is realized by adopting the following technical scheme:
a method for preparing a polyaspartic acid ester polyurea coating for an SMC substrate, comprising the following steps:
the preparation of the main agent comprises the steps of mixing polyaspartic acid ester resin, ketimine modified polyaspartic acid ester resin, a resin additive, pigment, a dispersing agent and a solvent, uniformly stirring, grinding, adding functional filler, a defoaming agent and a leveling agent, uniformly mixing, and stirring to obtain the main agent;
The preparation of the curing agent comprises the steps of mixing isocyanate trimer, polyester modified elastic isocyanate prepolymer, solvent and water absorbent, and uniformly stirring to obtain the curing agent;
The main agent and the curing agent are mixed for the SMC substrate polyaspartic acid ester polyurea coating.
In summary, the application has the following beneficial effects:
1. The ketimine modified polyaspartic acid ester resin adopted by the application has lower viscosity, prolongs the applicable period, delays the viscosity increase rate and improves the wettability to the SMC substrate. The compound use of the polyaspartic acid ester resin and the ketimine modified polyaspartic acid ester resin improves the adhesive force of the polyaspartic acid ester polyurea coating and the SMC substrate, can also improve the ageing resistance, the wear resistance and the high-low temperature alternation resistance of the polyaspartic acid ester polyurea coating, can also reduce the baking temperature of a production line, and achieves the effects of reducing consumption, saving energy and improving the chain speed of SMC substrate workpieces.
2. The application adopts the resin additive compounded by the silane coupling agent, the polyester polyol resin and the hydroxy acrylic resin, has better compatibility between the resins, can effectively reduce the internal stress of the coating while forming high crosslinking density, and further improves the adhesive force of the polyaspartic acid ester polyurea coating, thereby improving the salt spray resistance, the moist heat resistance and the high-low temperature alternation resistance of the polyaspartic acid ester polyurea coating.
3. Compared with the common filler, the functional filler compounded by the polyurethane microsphere and the ED30 matting powder improves the weather resistance and the wear resistance of the polyaspartic acid ester polyurea coating, and a paint film has no scratch.
4. The application adopts the curing agent containing the polyester modified elastic isocyanate prepolymer, so that the coating has good toughness, and the adhesive force between the polyaspartic acid ester polyurea coating and the SMC substrate is further improved, so that the comprehensive performance of the coating is greatly improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example
Preparation example 1 provides a ketimine modified polyaspartic acid ester resin, which comprises the following preparation steps:
A 1L four-necked glass flask was taken, 238g (1 mol) of 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane was added thereto, 240.8g (1.4 mol) of diethyl maleate was added dropwise thereto, and the temperature was raised to 60℃for 24 hours to obtain a reaction solution;
70g (0.7 mol) of methyl isobutyl ketone is weighed and added into the reaction solution, the temperature is raised to 130 ℃ for reaction for 6 hours, after the reaction is finished, the temperature is reduced to 100 ℃ for reduced pressure distillation, and the excessive methyl isobutyl ketone is extracted, so that the ketimine modified polyaspartic acid ester resin 1 is obtained.
Preparation example 2 provides a ketimine modified polyaspartic acid ester resin, which comprises the following preparation steps:
A 1L four-necked glass flask was taken, 210g (1 mol) of 4,4' -diaminodicyclohexylmethane was added thereto, 172g (1.0 mol) of diethyl maleate was added dropwise thereto, and the mixture was heated to 60℃to react for 24 hours to obtain a reaction solution;
Then 110g (1.1 mol) of methyl isobutyl ketone is weighed and added into the reaction solution, the temperature is raised to 120 ℃ for reaction for 2 hours, after the reaction is finished, the temperature is reduced to 100 ℃ for reduced pressure distillation, and the excessive methyl isobutyl ketone is extracted, thus obtaining the ketimine modified polyaspartic acid ester resin 2.
Examples
Examples 1-21 provide a polyaspartic acid ester polyurea coating for an SMC substrate, as exemplified in example 1 below.
Example 1 provides a polyaspartic acid ester polyurea coating for an SMC substrate, which is prepared by the following steps:
S1, preparing a main agent, namely mixing 200g of Feiyang jun grinding asparagus resin F421, 300g of ketimine modified polyaspartic acid ester resin 1 prepared in preparation example 1, 65g of polyester polyol resin 168SS-80, 20g of carbon black, 35g of precipitated barium sulfate, 6g of dispersing agent BYK-163 and 150g of solvent (prepared by mixing xylene, butyl ester and propylene glycol methyl ether acetate according to a volume ratio of 4:4:2), uniformly stirring, grinding until the fineness is less than 20 mu m, and then adding 70g of ED30 matting powder, 150g of polyurethane microspheres, 1g of defoaming agent BYK-054 and 1g of Yingzhuang high-foaming agent defoaming agent Mixing with 2g of flatting agent BYK-300, and uniformly stirring to obtain a main agent;
s2, preparing a curing agent, namely mixing 435g of Asahi into TPA-100, 23g of Feiyangjun Ji GB905A-85, 40g of solvent (prepared by mixing butyl ester and propylene glycol methyl ether acetate according to a volume ratio of 7:3) and 4g of water absorbent TI, and uniformly stirring to obtain the curing agent;
s3, mixing the main agent prepared in the step S1 and the curing agent prepared in the step S2 according to the mass ratio of 100:49.98 to obtain the polyaspartic acid ester polyurea coating for the SMC substrate;
Wherein the polyester polyol resin 168SS-80 is available from Newpesi;
ED30 matting powder was purchased from Graves, inc. of America;
polyurethane microspheres, available from german waffle;
water absorbent TI was purchased from Hao-based trade Inc. of Guangzhou.
Examples 2 to 6 differ from example 1 only in the composition of the individual preparation starting materials, in particular from Table 1.
TABLE 1 examples 1-6 Components of the preparation starting materials
Examples 7-12 differ from example 3 only in the composition of the individual preparation starting materials, see in particular Table 2.
TABLE 2 Components of the preparation starting materials for examples 7 to 12
Example 13 differs from example 12 only in that the equivalent mass of the ketimine-modified polyaspartic acid ester resin 1 is replaced with the ketimine-modified polyaspartic acid ester resin 2 (derived from preparation example 2).
Examples 14-21 differ from example 12 only in the composition of the resin additives, see in particular Table 3.
TABLE 3 compositions of resin additives of examples 12, 14-21
Among them, the hydroxy acrylic resin BS5766 was purchased from Jiangsu sea Yao chemical industry Co.
Comparative example
Comparative example 1 differs from example 5 only in that the quality of the flying jun ground asparate resin F421 is replaced by a ketimine modified polyaspartate resin 1.
Comparative example 2 differs from example 5 only in that the mass of the ketimine-modified polyaspartate resin 1 is replaced with the flying jun-ground asparate resin F421.
Performance test
The following performance tests were performed on the polyaspartic acid ester polyurea coatings prepared in examples 1-21 and comparative examples 1-2 of the present application.
1. Adhesion was measured according to GB/T9286-1998 Standard of the cross-hatch test for color paint and varnish films, the test results being shown in Table 4.
2. Pencil hardness was measured according to GB/T6739-2006 Standard for measuring paint film hardness by the paint and varnish pencil method, and the test results are shown in Table 4.
3. Abrasion resistance was measured according to GB/T1768-2006 Standard of method for measuring abrasion resistance of Rotary rubber grinding wheel for color paint and varnish, and the measurement results are shown in Table 4.
4. The wet heat resistance was measured according to the GB/T1740-2007 paint film wet heat resistance measurement method, and the test results are shown in Table 4.
5. Salt spray resistance was measured according to GB/T1771-1991 test for neutral salt spray resistance of paints and varnishes, and the test results are shown in Table 4.
6. Ageing resistance testing was performed according to GB T1865-2009, "Artificial weathering for paints and varnishes and Artificial radiation exposure filtered xenon arc radiation", and the test results are shown in Table 4.
7. The high-low temperature alternation test was carried out by uniformly coating the polyaspartic acid ester polyurea coatings prepared in examples 1 to 21 and comparative examples 1 to 2 on SMC substrates to form 50 μm paint films, and carrying out the high-low temperature alternation test on SMC containing the paint films under the specific conditions of (23+ -2) ° C1h→ (80+ -2) ° C3h→ (23+ -2) ° C, RH (50+ -5)% 1h→ (-40+ -2) ° C3h→ (23+ -2) ° C, RH (50+ -5)% 1h→ (38+ -2) ° C, RH (95-98)% 14h as one cycle, and recording the number of cycles without foaming, without cracking, without change in appearance or light loss, and the test results are shown in Table 4.
8. Scratch resistance polyaspartic acid ester polyurea coatings prepared in examples 1-21 and comparative examples 1-2 were uniformly coated on SMC substrates to form 50 μm paint films, the paint films were rubbed with chamois, the presence or absence of scratches was observed, the good score was less, the difference was more, and the test results are shown in Table 4.
Table 4 test results
The present application is described in detail below with respect to the test data of table 4.
From the test data of example 5 and comparative examples 1-2, it is known that the composite use of the polyaspartic acid ester resin and the ketimine modified polyaspartic acid ester resin significantly improves the adhesion of the polyaspartic acid ester polyurea coating to the SMC substrate, and also improves the aging resistance, wear resistance and high-low temperature alternation resistance of the polyaspartic acid ester polyurea coating.
From the test data of examples 3-7, it is seen that increasing the amount of ketimine modified polyaspartate resin increases the high and low temperature alternation resistance of the polyaspartate polyurea coating, which is followed by a decrease, and also increases the wet heat resistance of the polyaspartate polyurea coating.
From the test data of examples 3 and 8-11, it is understood that the increased content of the polyester polyol resin can improve the adhesion of the polyaspartic acid ester polyurea coating, and simultaneously the moisture-heat resistance and the high-low temperature alternation resistance are improved and then reduced. The content of the polyester polyol resin has little influence on the salt spray resistance and aging resistance of the polyaspartic acid ester polyurea coating.
From the test data of examples 3 and 12, it is understood that the increase in the amount of the flying jun research GB905A-85 reduces the hardness of the poly-aspartic acid ester polyurea coating and improves the wear resistance, salt spray resistance, moist heat resistance and high-low temperature alternation resistance of the poly-aspartic acid ester polyurea coating.
From the test data of examples 12 and 14-21, it is known that the resin additive compounded by the silane coupling agent, the polyester polyol resin and the hydroxy acrylic resin can more effectively reduce the internal stress of the coating while forming high crosslinking density, and further improve the adhesive force of the polyaspartate polyurea coating, thereby improving the salt spray resistance, the moist heat resistance and the high-low temperature alternation resistance of the polyaspartate polyurea coating.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (8)
1. The polyaspartic acid ester polyurea coating for the SMC substrate consists of a main agent and a curing agent, and is characterized in that the main agent comprises, by weight, 18-32 parts of polyaspartic acid ester resin, 18-32 parts of ketimine modified polyaspartic acid ester resin, 3-12 parts of resin additive, 2-2.5 parts of pigment, 4-22 parts of functional filler, 1-1.5 parts of auxiliary agent and 15-31.5 parts of solvent, the curing agent comprises 41.2-43.5 parts of isocyanate trimer, 2.3-4.6 parts of polyester modified elastic isocyanate prepolymer, 3-4 parts of solvent and 0.3-0.4 part of water absorbent, and the mass ratio of the main agent to the curing agent is 100 (44.39-57.75);
The structural formula of the ketimine modified polyaspartic acid ester resin is as follows Wherein R 1 is alkyl of 1 to 8 carbon atoms, R 2 is a divalent hydrocarbon radical, R 3 and R 4 are independently of each other represented as monovalent aliphatic, cycloaliphatic or araliphatic residues, and R 3 and R 4 do not have tertiary amine nitrogen;
The resin additive is formed by mixing a silane coupling agent, polyester polyol resin and hydroxy acrylic resin according to the mass ratio of 1 (3-10) to 5-20.
2. The polyaspartic acid ester polyurea coating for an SMC substrate according to claim 1, wherein said ketimine modified polyaspartic acid ester resin preparation step comprises the steps of:
firstly, dropwise adding maleic acid ester into fatty amine, and controlling the temperature to be 60-70 ℃ for reaction for 12-48 hours to obtain a reaction liquid;
Then adding ketone compounds into the reaction solution, controlling the temperature to be 80-150 ℃ for reaction for 2-12 hours, and obtaining ketimine modified polyaspartic acid ester resin after the reaction is completed;
the ratio of the fatty amine to the substances of the maleate and ketone compounds is 1 (1-1.4): 0.7-1.1.
3. A polyaspartic acid ester polyurea coating for SMC substrates according to any of claims 1-2, characterized in that the mass ratio of polyaspartic acid ester resin to ketimine modified polyaspartic acid ester resin is 1:1.5.
4. A polyaspartic acid ester polyurea coating for SMC substrates according to claim 1, characterized in that said resin additive is selected from one or more of silane coupling agents, polyester polyol resins and hydroxy acrylic resins.
5. The polyaspartic acid ester polyurea coating for the SMC substrate according to claim 1, wherein the mass ratio of the silane coupling agent, the polyester polyol resin and the hydroxy acrylic resin is 1:7:13.
6. A polyaspartic acid ester polyurea coating for SMC substrates according to claim 1, characterized in that said functional filler is a mixture of polyurethane microspheres and ED30 matting powder.
7. A polyaspartic acid ester polyurea coating for SMC substrates according to claim 1, characterized in that said adjuvants comprise dispersants, defoamers and leveling agents.
8. A process for preparing a polyaspartic acid ester polyurea coating for SMC substrates according to claim 7,
The method comprises the following steps:
the preparation of the main agent comprises the steps of mixing polyaspartic acid ester resin, ketimine modified polyaspartic acid ester resin, a resin additive, pigment, a dispersing agent and a solvent, uniformly stirring, grinding, adding functional filler, a defoaming agent and a leveling agent, uniformly mixing, and stirring to obtain the main agent;
The preparation of the curing agent comprises the steps of mixing isocyanate trimer, polyester modified elastic isocyanate prepolymer, solvent and water absorbent, and uniformly stirring to obtain the curing agent;
The main agent and the curing agent are mixed for the SMC substrate polyaspartic acid ester polyurea coating.
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