CN110845941B - TGIC-substituted low-toxicity powder coating and preparation method thereof - Google Patents

TGIC-substituted low-toxicity powder coating and preparation method thereof Download PDF

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CN110845941B
CN110845941B CN201911115153.XA CN201911115153A CN110845941B CN 110845941 B CN110845941 B CN 110845941B CN 201911115153 A CN201911115153 A CN 201911115153A CN 110845941 B CN110845941 B CN 110845941B
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tgic
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toxicity
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CN110845941A (en
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梁超成
李文浩
郭志彬
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Guangdong Yong Tu Le Environmental Protection Technology Co ltd
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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
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Abstract

The invention relates to a TGIC-substituted low-toxicity powder coating and a preparation method thereof, the curing of the powder coating is closely related to the effective components of a coloring pigment and a surfactant of dodecyl benzene sulfonic acid, the effective components of the coloring pigment comprise a compound A and/or a compound B, both the compound A and the compound B comprise two oxazoline structures, can be combined with polyester resin, acid anhydride, epoxy resin, phenolic resin, phenols and the like to form a coating system with quick curing performance, and the compound A and the compound B are both high-temperature-resistant nitrogen-containing heterocyclic compounds, can enhance the physical and mechanical properties of smearing, and the compound with an oxazole ring has biological activity, the epoxy resin powder coating can be used as a substrate coloring pigment of the powder coating and can also be used as a curing agent to prepare an epoxy resin powder coating with good leveling property, excellent chemical resistance, scratch resistance and high mechanical property; in addition, it has excellent storage stability, color retention and weather resistance.

Description

TGIC-substituted low-toxicity powder coating and preparation method thereof
Technical Field
The invention relates to the field of powder coatings, in particular to a TGIC-substituted low-toxicity powder coating and a preparation method thereof.
Background
TGIC is known by chemical name of tris (2, 3-epoxypropane) -s-triazine-2, 4,6(1H,3H,5H) trione, and is known by chemical name of triglycidyl isocyanurate, and has small relative molecular mass and 3 groups available for reaction, so that when used as a curing agent of carboxylic polyester resin, the crosslinking density is high; secondly, the rigid urea ring structure on the TGIC molecular skeleton increases the hardness of the cured coating, has the characteristics of excellent thermal and light stability and weather resistance, has good compatibility with polyester resin, and has good mechanical property and electrical property of the cured product. Therefore, the curing agent is widely applied to the field of coatings.
However, the biological toxicity of TGIC has been a concern of the public, and the european union has identified TGIC as a highly toxic product in 1998, and therefore, there is a need to develop a low-toxicity powder coating which can replace TGIC, does not require TGIC as a curing agent, has a low color stability and biological toxicity, and is effective in improving the safety of the use of the coating.
Disclosure of Invention
The invention provides a TGIC-substituting low-toxicity powder coating and a preparation method thereof, which aim to solve the problem of biological toxicity of TGIC in the above content.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a TGIC-substituting low-toxicity powder coating comprises the following components in percentage by weight: 15-30 parts of novolac epoxy resin; 20-35 parts of epoxy resin; 3-10 parts of seagull stone powder; 5-25 parts of a coloring pigment; 1-8 parts fumed silica; 0.1-3 parts of a defoaming agent; 0.5-5 parts of dodecyl benzene sulfonic acid; 0.1-5 parts of a film-forming assistant; 5-30 parts of extender pigment; 1-5 parts of a polypropylene adhesive; a proper amount of a pH regulator; wherein the coloring pigment comprises at least one of a compound A and a compound B, and the chemical structural formula of the compound A is shown as the formula I:
Figure BDA0002273835010000021
r: hydrocarbyl radical
The chemical structural formula of the compound B is shown as the formula II:
Figure BDA0002273835010000022
preferably, the defoaming agent is at least one of modified polysiloxane, benzil ketone and polypropylene composite micro wax.
Preferably, the film-forming assistant is amide modified polyethylene wax, low molecular weight polyethylene and organosilicon powder, wherein the weight ratio of the polyamide modified polyethylene wax to the organosilicon powder is 1: 2: 1 and mixing.
Preferably, the extender pigment is at least one of silica sol, light calcium carbonate and wollastonite.
Preferably, in the colored pigment, the weight percentage of the compound A and/or the compound B is 10-45%, and the balance is the toner.
Preferably, the toner is at least one of yellow, magenta, cyan, and black four-color toning pigments.
Preferably, the compound A is 8, 18-dichloro-5, 15-diethyl-diindole (3,2-b:3', 2' -m) triphenodioxazine or 8, 18-dichloro-5, 15-dimethyl-diindole (3,2-b:3', 2' -m) triphenodioxazine.
Preferably, the alternative TGIC low toxicity powder coating further comprises 0.5-5 parts of phthalic dihydrazide.
It is understood that, as in the present invention, no curing agent is added, the curing of the whole powder coating is closely related to the effective components of the color pigment and the surfactant dodecylbenzene sulfonic acid, in the present application, the effective components of the color pigment comprise compound A and/or compound B, both compound A and compound B comprise two oxazoline structures, can be combined with polyester resin, acid anhydride, epoxy resin, phenolic resin, phenols and the like to form a coating system with quick curing performance, and the compound A and the compound B are both high-temperature-resistant nitrogen-containing heterocyclic compounds, can enhance the physical and mechanical properties of smearing, and the compound with an oxazole ring has biological activity, the epoxy resin powder coating can be used as a substrate coloring pigment of the powder coating and can also be used as a curing agent to prepare an epoxy resin powder coating with good leveling property, excellent chemical resistance, scratch resistance and high mechanical property; in addition, it has excellent storage stability, color retention and weather resistance.
In addition, the dodecylbenzene sulfonic acid can be used as a curing catalyst in a coating system, and also can be used as a surfactant to improve the grinding efficiency in the coating processing process, avoid the generation of crusting and eliminate foam; the luster is increased in the film forming process, and floating color, flowering and shrinkage cavities are prevented; the adhesive force can be improved in the film coating process, so that the coating is mildew-proof, antifouling and antistatic.
In a second aspect, the invention also provides a preparation method of the alternative TGIC low toxicity powder coating, comprising the following steps:
step S1: adding coloring pigment into a ball mill, adding 50-70 steel balls with the diameter of 6-8mm and 0.1-0.3kg of anhydrous calcium chloride into every 1kg of coloring pigment, performing ball milling for 8h under the condition that the temperature is 65-90 ℃ (preferably 20 ℃), adding dilute hydrochloric acid, boiling for 3-4h, separating dilute acid, filtering, adding water, washing and drying;
step S2: adding the purified coloring pigment obtained in the step S1 into a high-speed stirrer, adding the extender pigment and the polypropylene adhesive, sealing, and then starting stirring, wherein the rotating speed is controlled to be 1000-1500 rpm, the stirring temperature is 50-60 ℃, and the stirring time is 10-15 mins;
step S3: heating the mixture obtained in the step S2 to 120-150 ℃, sequentially adding a defoaming agent, novolac epoxy resin, gull rock powder, fumed silica, dodecyl benzene sulfonic acid and a film-forming aid, and uniformly stirring;
step S3: adjusting the pH of the mixture obtained in the step S2 to 6.8-7.1 by using a pH regulator;
step S4: melting, mixing, extruding, cooling, tabletting, crushing by a crusher, grading and sieving to obtain a finished product with the particle size of 200 meshes.
The preparation method of the TGIC-substituted low-toxicity powder coating obtained according to the steps comprises the following steps of: 15-30 parts of novolac epoxy resin; 20-35 parts of epoxy resin; 3-10 parts of seagull stone powder; 5-25 parts of a coloring pigment; 1-8 parts fumed silica; 0.1-3 parts of a defoaming agent; 0.5-5 parts of dodecyl benzene sulfonic acid; 0.1-5 parts of a film-forming assistant; 5-30 parts of extender pigment; 1-5 parts of a polypropylene adhesive; a proper amount of a pH regulator; wherein the coloring pigment comprises at least one of a compound A and a compound B, and the chemical structural formula of the compound A is shown as the formula I:
Figure BDA0002273835010000041
r: hydrocarbyl radical
The chemical structural formula of the compound B is shown as the formula II:
Figure BDA0002273835010000042
preferably, the defoaming agent is at least one of modified polysiloxane, benzil ketone and polypropylene composite micro wax.
Further preferably, the defoaming agent is a mixture of benzil ketone and polypropylene composite micro powder wax according to a ratio of 3: 1.
Preferably, the film-forming assistant is amide modified polyethylene wax, low molecular weight polyethylene and organosilicon powder, and the weight ratio of the polyamide modified polyethylene wax to the organosilicon powder is 1: 2: 1 and mixing.
Preferably, the extender pigment is at least one of silica sol, light calcium carbonate and wollastonite.
More preferably, the extender pigment is silica sol, light calcium carbonate and wollastonite mixed according to a ratio of 2:3: 1.
Preferably, in the colored pigment, the weight percentage of the compound A and/or the compound B is 10-45%, and the balance is the toner.
Preferably, the toner is at least one of yellow, magenta, cyan, and black four-color toning pigments.
Preferably, the compound A is 8, 18-dichloro-5, 15-diethyl-diindole (3,2-b:3', 2' -m) triphenodioxazine or 8, 18-dichloro-5, 15-dimethyl-diindole (3,2-b:3', 2' -m) triphenodioxazine.
Further preferably, 0.5 to 5 parts of phthalic dihydrazide is further added in step S3.
The invention has the beneficial effects that:
(1) compared with the existing powder coating formula, the curing and coloring method adopts at least one of the compound A and the compound B in the coloring pigment, when the powder coating is used, the coloring example of the powder coating is very high, the powder coating has excellent heat resistance and light fastness, the heat resistance can be more than 200 ℃ even under the condition of very low concentration, the solvent resistance is good, and the powder coating can be used as a curing agent under the action of dodecylbenzene sulfonic acid, so that the epoxy resin powder coating has excellent chemical resistance, scratch resistance and mechanical properties, and also has excellent storage stability, color retention and weather resistance.
(2) The invention can also add phthalic dihydrazide which can be used as a latent curing agent of epoxy resin, and a coating film of the powder coating prepared by using the epoxy resin/phthalic dihydrazide as a binder system has very excellent flexibility, water resistance, weather resistance, corrosion resistance, insulativity and decorativeness.
(3) The powder coating has simple components, can reduce the production cost of the powder coating, is beneficial to producing the powder coating with low toxicity, high benefit and good performance, and replaces TGIC in the application of the powder coating.
(4) The gull rock powder is added, so that the coating has the function of continuously releasing negative ions, can reduce environmental pollution, is environment-friendly, is particularly suitable for occasions such as residential buildings, commercial buildings, public buildings and the like, and has wide application prospect.
Drawings
FIG. 1 is a graph showing the color difference change of the coating layers of the powder coating materials of the test group and the control group of example 1 at different baking temperatures;
FIG. 2 is a graph showing the change in gloss retention at different baking temperatures for the coating layers of the powder coatings of the test group and the control group of example 1;
FIG. 3 is a graph showing the color difference change of the coating layers of the powder coating materials of the test group and the control group of example 1 at different low temperatures;
FIG. 4 is a graph showing the change in gloss retention at different low temperatures for the coatings of the powder coatings of the test group and the control group of example 1;
FIG. 5 is a graph showing the change in color difference between the powder coating coatings of the test group and the control group of example 1 at different aging times;
FIG. 6 is a graph showing the change in gloss retention of the coating of the powder coating of the test group and the control group of example 1 at different aging times;
FIG. 7 is a graph showing the color difference between the coating layers of the powder coating materials of the test group and the control group of example 1 at different boiling times;
FIG. 8 is a graph showing the change in gloss retention of the coating of the powder coating of the test group and the control group of example 1 at different blanching times;
FIG. 9 is a graph of the coating cure curves for the powder coatings of the test and control groups of example 1;
FIG. 10 is a graph of the color difference between the coatings of powder coating A, B, C and TGIC powder coating (KH-R1003A2) of example 2 at different aging times;
FIG. 11 is a graph of gloss retention versus time for coatings of powder coating A, B, C of example 2 and TGIC powder coating (KH-R1003A 2);
FIG. 12 is the color difference change of the coatings of powder coating A, B, C of example 2 and TGIC powder coating (KH-R1003A2) at different boil times;
FIG. 13 is a graph of gloss retention for coatings of powder coating A, B, C and TGIC powder coating (KH-R1003A2) of example 2 at different poaching times;
FIG. 14 is a graph of the cure profile of a coating of powder coating A, B, C of example 2 with TGIC powder coating (KH-R1003A 2).
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) A preparation method of the TGIC-substituted low-toxicity powder coating comprises the following steps:
step S1: adding coloring pigment into a ball mill, adding 65 steel balls with the diameter of 7mm and 0.2kg of anhydrous calcium chloride into 1kg of coloring pigment, ball-milling for 8h at the temperature of 80 ℃, adding dilute hydrochloric acid, boiling for 3.5h, separating out dilute acid, filtering, adding water, washing and drying; wherein the compound A is 8, 18-dichloro-5, 15-diethyl-diindole (3,2-b:3', 2' -m) triphendioxazine (A1) or 8, 18-dichloro-5, 15-dimethyl-diindole (3,2-b:3', 2' -m) triphendioxazine (A2); the compound B is 2, 6-dibenzoyl amide-3, 7-diethoxy-9, 10-diacetyl amino triphendioxazine;
step S2: adding the purified coloring pigment obtained in the step S1 into a high-speed stirrer, adding the extender pigment and the polypropylene adhesive, sealing, and stirring at the rotation speed of 1500 rpm at the stirring temperature of 60 ℃ for 15 mins; wherein the extender pigment is silica sol;
step S3: heating the mixture obtained in the step S2 to 135 ℃, sequentially adding a defoaming agent, novolac epoxy resin, gull rock powder, fumed silica, dodecylbenzene sulfonic acid and a film-forming aid, and uniformly stirring; wherein the defoaming agent is prepared by mixing benzil ketone and polypropylene composite micro powder wax according to the ratio of 3: 1; the film-forming assistant is amide modified polyethylene wax, low molecular weight polyethylene and organosilicon powder, and the weight ratio of the film-forming assistant is 1: 2: 1, mixing;
step S3: adjusting the pH of the mixture obtained in the step S2 to 6.9 by using a pH regulator; wherein the pH regulator is sodium hydroxide;
step S4: melting, mixing, extruding, cooling, tabletting, crushing by a crusher, grading and sieving to obtain a finished product with the particle size of 200 meshes.
The contents of the components in the powder coating are shown in table 1.
TABLE 1 content of ingredients in TGIC-substituted low-toxicity powder coating
Figure BDA0002273835010000071
Figure BDA0002273835010000081
(2) Performance testing
Using a commercially available TGIC powder coating (KH-R1003A2) as a control group and powder coatings of the above-mentioned compositions 1 to 8 as test groups, a high temperature test, an aging test, a low temperature test, a boiling test, a toxicity test, a skin irritation test, and an isothermal curing test were carried out to measure the color difference and the change in gloss of the coating layer of each powder coating under each environment (gloss of the coating layer was measured according to the regulation of GB/T9754 using an incident angle of 60 degrees; according to the regulations of GB/T11186.2, 11186.3).
High temperature test
Selecting 108 metal plates of 5cm multiplied by 5cm, evenly dividing into 9 groups, respectively and evenly spraying the powder coatings corresponding to the control group and the test group on the metal plates of each group, dividing each group into 6 small groups, wherein the two metal plates are one small group, and the metal plates of each small group are respectively placed in an oven to be heated for 15 hours at 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ to test the color difference and the luster of the coating.
② low temperature test
Selecting 108 metal plates of 5cm multiplied by 5cm, evenly dividing into 9 groups, respectively and evenly spraying the powder coatings corresponding to the control group and the test group on the metal plates of each group, dividing each group into 6 small groups, wherein the two metal plates are one small group, and the metal plates of each small group are respectively placed in a freezer and cooled for 30 days at 10 ℃,5 ℃, 0 ℃,5 ℃,10 ℃ and 15 ℃ to test the color difference and the luster of the coating.
③ aging test
The powder coatings of the control group and the test group are respectively sprayed on a metal plate with the thickness of 5cm multiplied by 5cm, and are respectively placed in a test box to be irradiated for 1 month by a UVA-340 fluorescent ultraviolet lamp under the test conditions of irradiance of 0.88W/m2, illumination at 40 ℃ for 12h, condensation at 0 ℃ for 12h, repeated illumination and condensation. After the experiment, the color difference and the gloss of the coating surface were tested.
Water boiling test
Selecting 108 metal plates of 5cm multiplied by 5cm, evenly dividing into 9 groups, respectively and evenly spraying the powder coatings corresponding to the control group and the test group on the metal plates of each group, dividing each group into 6 small groups, wherein the two metal plates are one small group, and the metal plates of each small group are respectively placed in a sterilization type pressure cooker for boiling, and the water is deionized water at the temperature of 100 ℃. After boiling in water for 5.5h, the surface of the metal plate was wiped dry and tested for color difference and gloss.
Toxicological test
Selecting 90 healthy mice with the weight of 30-50g, dividing the mice into 9 groups with half each male and female, diluting the powder coating of 8 groups of test groups and 1 group of control groups, dissolving 5g of the powder coating in each liter of water, feeding the mice for 3 times within 24 hours, feeding for 1 month, and observing the survival rate of the mice.
Skin irritation test
Selecting 90 people from 8-15 years old, 16-35 years old, 36-55 years old and 56-70 years old, dividing each age group into 9 groups, and half each male and female, adding water into the powder coating of 8 groups of test groups and 1 group of control groups, stirring, coating on the inner side of the arm of human body, and observing whether red spots, pruritus, stabbing pain and other conditions appear on the skin.
Isothermal solidification test
Carrying out isothermal curing test on the powder coating by using a Differential Scanning Calorimeter (DSC), wherein the test conditions are that nitrogen is used as shielding gas and the flow is 50 mL/min; the heating rate is 25 ℃/min, and the temperature is rapidly increased to 25 ℃ and kept for 20 min.
(3) Test results
Testing at high temperature: the results of the high temperature resistance test of the powder coating are shown in fig. 1 and fig. 2, wherein fig. 1 shows the color difference change of the coating of the powder coating corresponding to the test group and the control group at different baking temperatures, and fig. 2 shows the gloss retention change of the coating of the powder coating corresponding to the test group and the control group at different baking temperatures, wherein the test group 1-8 respectively correspond to the substitute TGIC low toxicity powder coating with different component contents in table 1, and the control group corresponds to the commercially available TGIC powder coating (KH-R1003a 2). The result shows that with the increase of the baking temperature, the color difference of the coatings of the test group and the control group is gradually increased, the color difference change amplitude of the coatings of the control group 1-8 is smaller than the color difference level of the coatings of the control group, the stability of the surface of the coatings is gradually reduced by heat when the coatings of the control group are at 50-150 ℃ in the baking process, the light retention rate is slightly reduced, the coatings are gradually dissolved by heat at 150-250 ℃, the light retention rate is reduced seriously, and then the light retention rate is rapidly reduced again at 250 ℃, so that the secondary melting phenomenon of the main coatings occurs at 250 ℃, and the surfaces of the coatings have serious orange peels; the light retention of the coatings of the test groups 1-8 is unchanged or slightly reduced under the test conditions, mainly because the molecular structures of the compound A and the compound B are symmetrical and planar, so that the coatings are quite stable, are combined with epoxy resin, have the heat resistance temperature of more than 250 ℃, have very high tinting strength, and have excellent heat resistance and light fastness. Comparing the coatings of the control group and the test groups 1-8, the color and gloss retention of the test groups 1-8 are better than that of the control group.
② low temperature test
The results of the low temperature resistance test of the powder coating are shown in fig. 3 and 4, fig. 3 shows the color difference change of the coating of the powder coating corresponding to the test group and the control group at different low temperatures, and fig. 4 shows the gloss retention change of the coating of the powder coating corresponding to the test group and the control group at different low temperatures, wherein the test groups 1-8 correspond to the substitute TGIC low toxicity powder coating with different component contents in table 1, respectively, and the control group corresponds to the TGIC powder coating (KH-R1003a2) purchased from the market. The result shows that the color difference and the light retention rate of the coatings of the test group and the control group are relatively constant along with the reduction of the temperature, the color difference is maintained within 1 color difference value, and the low-temperature resistance performance is excellent.
③ aging test
The aging resistance test results of the powder coating are shown in fig. 5 and fig. 6, fig. 5 shows the color difference change of the powder coating corresponding to the test group and the control group under the same aging condition and different aging time, fig. 6 shows the gloss retention change of the powder coating corresponding to the test group and the control group under the same aging condition and different aging time, and the test results of the coatings of the control group and the test group under the different aging time, it can be seen that the color difference of the coating of the control group is gradually increased and the gloss retention is gradually decreased along with the increase of the aging time, the color difference of the coatings of the test groups 1 to 8 is also gradually increased and the gloss retention is gradually decreased, and meanwhile, the color difference change amplitude of the coating of the control group is larger than the color difference of the coatings of the test groups 1 to 8 in the same aging time, and the gloss retention of the coatings of the test groups 1 to 8 is higher than the gloss retention of the coating of the control group after the aging time of 10 days, namely, the coating of the powder coating is superior to the coating of a contrast group in the aspect of light and color preservation, namely, the weather resistance is stronger.
Water boiling test
The boiling test results of the powder coatings are shown in fig. 7 and 8, fig. 7 shows the color difference change of the powder coatings corresponding to the test group and the control group under different boiling time, fig. 8 shows the light retention rate change of the powder coatings corresponding to the test group and the control group under different boiling time, and as can be seen from fig. 7 and 8, the color difference of the coatings of the test groups 1-8 and the control group is increased and the light retention rate is reduced along with the increase of the boiling time; the color difference change of the coatings of the test groups 3 and 7 in the initial stage is larger than that of the coatings of the control group, but the color difference change of the subsequent coatings is slowed down and is lower than that of the coatings of the control group, and the light retention rates of the test groups 1 to 8 are higher than that of the coatings of the control group, so that the water resistance of the test groups 1 to 8 is better than that of the control group.
Toxicological test
The toxicological test results of powder coatings containing different concentrations of the ingredients show that: after continuously observing for 1 month, none of the mice in the test groups 1-8 died and no abnormal symptom was found; in the control group, the number of mice died was 2, and some of the mice showed anorexia and listlessness. The test results show that the powder coating in the present application has lower toxicity than the control.
Skin irritation test
Skin irritation test results for different age groups As shown in Table 2, the powder coatings of test groups 1-8 were less irritating to the skin and less damaging to the human skin than the TGIC powder coating (KH-R1003A2) of the control group.
Table 2 irritation test effect of different powder coatings on skin
Figure BDA0002273835010000111
Isothermal solidification test
Referring to fig. 9, the time for the coating of the control group to reach the complete curing in the isothermal curing process is 604s, and in the test groups 1 to 8, the curing time of the test group 5 is the fastest, and the complete curing requires 640s, which means that the powder coating of the control group has a faster curing reaction rate and a higher reaction degree, because the control group contains a large amount of curing accelerator capable of accelerating the reaction of the polyester and TGIC, and the curing accelerator is completed by the surfactant dodecylbenzene sulfonic acid in the present application, but overall, the reaction degrees of the control group and the polyester and the test group 5 are not greatly different, the difference in the comprehensive properties of the coating is less affected, and the reaction rates of the other test groups are slower than that of the control group at the same temperature, but the normal use of the powder coating is still satisfied.
Example 2
To further illustrate the advantageous effects of the present invention, step S1-step S4 of example 1 were repeated, and 0.5-5 parts of phthalic dihydrazide was added in step S3 to obtain powder coating a, powder coating B, and powder coating C, wherein the components and weight percentages thereof are shown in table 3.
FIG. 3 shows the components and their contents in the powder coating
Figure BDA0002273835010000121
According to the performance test of the embodiment 1, the aging test, the boiling test, the toxicity test, the skin irritation test and the isothermal curing test are carried out, and the color difference and the gloss change of the coating of each powder coating under each environment are measured.
Test results
(1) The results of the powder coating aging tests are shown in fig. 10 and fig. 11, fig. 10 shows the color difference change of the powder coating A, B, C and the TGIC powder coating (KH-R1003a2) under the same aging conditions and the color retention of the powder coating A, B, C and the TGIC powder coating (KH-R1003a2) under the same aging conditions and the aging times, and it can be seen that the powder coating A, B, C has enhanced gloss retention and color retention compared with the TGIC powder coating (KH-R1003a2), and the color difference increases with time, but the color difference increases slowly, the aging resistance is enhanced, and the weather resistance is good.
(2) As shown in FIGS. 12 and 13, the color difference between the powder coating A, B, C and the TGIC powder coating (KH-R1003A2) increases and the gloss retention decreases as the boiling time increases, but the water resistance of the powder coating A, B, C is better than that of the control.
(3) Toxicological test results for powder coating A, B, C with TGIC powder coating (KH-R1003A2) show: after continuous observation for 1 month, none of the mice fed with the diluted powder coating A, B, C died and had no abnormal symptoms; the number of dead mice fed with the diluted TGIC powder coating (KH-R1003A2) was 3, and some of them had symptoms of anorexia and listlessness. The results of the tests show that powder coating A, B, C in the present application is less toxic than TGIC powder coating (KH-R1003A 2).
(4) Skin irritation test results for different age groups as shown in table 4, powder coating A, B, C showed less skin irritation and less damage to human skin compared to TGIC powder coating of control group (KH-R1003a2) in powder coating A, B, C.
TABLE 4 irritation test Effect of powder coating A, B, C and TGIC powder coating (KH-R1003A2) on skin
Figure BDA0002273835010000131
(5) Referring to FIG. 14, the time to complete curing of TGIC powder paint (KH-R1003A2) during isothermal curing was 599s, and the time to complete curing of powder paint C, powder paint A, and powder paint B during isothermal curing was 475s, 522s, and 604s, respectively, wherein the curing efficiency of powder paint C and powder paint A was higher than that of TGIC powder paint (KH-R1003A2), and the curing efficiency of powder paint B was close to that of TGIC powder paint (KH-R1003A2), so the addition of phthalic dihydrazide to the powder paint increased the curing efficiency of the powder paint.

Claims (10)

1. A TGIC-substituted low-toxicity powder coating is characterized by comprising the following components in parts by weight: 15-30 parts of novolac epoxy resin; 20-35 parts of epoxy resin; 3-10 parts of seagull stone powder; 5-25 parts of a coloring pigment; 1-8 parts fumed silica; 0.1-3 parts of a defoaming agent; 0.5-5 parts of dodecyl benzene sulfonic acid; 0.1-5 parts of a film-forming assistant; 5-30 parts of extender pigment; 1-5 parts of a polypropylene adhesive; a proper amount of pH regulator; wherein the coloring pigment comprises at least one of a compound A and a compound B, and the chemical structural formula of the compound A is shown as the formula I:
Figure FDA0003163420950000011
r: hydrocarbyl radical
The chemical structural formula of the compound B is shown as the formula II:
Figure FDA0003163420950000012
2. a TGIC-substituting low-toxicity powder coating according to claim 1, characterized in that: the defoaming agent is at least one of modified polysiloxane, benzil ketone and polypropylene composite micro wax.
3. A TGIC-substituting low-toxicity powder coating according to claim 1, characterized in that: the film-forming assistant is amide modified polyethylene wax, low molecular weight polyethylene and organic silicon powder, and the weight ratio of the polyamide modified polyethylene wax to the organic silicon powder is 1: 2: 1 part by weight.
4. A TGIC-substituting low-toxicity powder coating of claim 1, characterized by: the extender pigment is at least one of silica sol, light calcium carbonate and wollastonite.
5. A TGIC-substituting low-toxicity powder coating of claim 1, characterized by: in the coloring pigment, the weight percentage of the compound A and/or the compound B is 10-45%, and the balance is toner.
6. A TGIC-substituting low toxicity powder coating of claim 5, wherein: the toner is at least one of yellow, magenta, cyan and black four-color toning pigments.
7. A TGIC-substituting low-toxicity powder coating of claim 1, characterized by: the compound A is 8, 18-dichloro-5, 15-diethyl-diindole (3,2-b:3', 2' -m) triphendioxazine or 8, 18-dichloro-5, 15-dimethyl-diindole (3,2-b:3', 2' -m) triphendioxazine.
8. A TGIC-substituting low-toxicity powder coating of claim 1, characterized by: also comprises 0.5 to 5 weight portions of phthalic dihydrazide.
9. A method of preparation of alternative TGIC low toxicity powder coatings according to any of claims 1-8, characterized by: the method comprises the following steps:
step S1: adding coloring pigment into a ball mill, adding 50-70 steel balls with the diameter of 6-8mm and 0.1-0.3kg of anhydrous calcium chloride into 1kg of coloring pigment, ball-milling for 8h at the temperature of 65-90 ℃, adding dilute hydrochloric acid, boiling for 3-4h, separating dilute acid, filtering, adding water, washing and drying;
step S2: adding the purified coloring pigment obtained in the step S1 into a high-speed stirrer, adding the extender pigment and the polypropylene adhesive, sealing, and then starting stirring, wherein the rotating speed is controlled to be 1000-1500 rpm, the stirring temperature is 50-60 ℃, and the stirring time is 10-15 mins;
step S3: heating the mixture obtained in the step S2 to 120-150 ℃, sequentially adding a defoaming agent, novolac epoxy resin, gull rock powder, fumed silica, dodecyl benzene sulfonic acid and a film-forming aid, and uniformly stirring;
step S3: adjusting the pH of the mixture obtained in the step S2 to 6.8-7.1 by using a pH regulator;
step S4: melting, mixing, extruding, cooling, tabletting, crushing by a crusher, grading and sieving to obtain a finished product with the particle size of 200 meshes.
10. A method of preparation of TGIC-substituting low-toxicity powder coating according to claim 9, characterized by: 0.5 to 5 parts by weight of phthalic dihydrazide is also added in the step S3.
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