CN113402975B - High-weather-resistance polysiloxane type luminous paint and preparation method thereof - Google Patents

High-weather-resistance polysiloxane type luminous paint and preparation method thereof Download PDF

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CN113402975B
CN113402975B CN202110696882.XA CN202110696882A CN113402975B CN 113402975 B CN113402975 B CN 113402975B CN 202110696882 A CN202110696882 A CN 202110696882A CN 113402975 B CN113402975 B CN 113402975B
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noctilucent
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CN113402975A (en
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杨锐
欧菊花
吴长永
孔振兴
戴子林
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22Luminous paints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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Abstract

The invention discloses a polysiloxane type luminous paint with high weather resistance and a preparation method thereof. A polysiloxane type luminous coating with high weather resistance comprises the following components in parts by weight: 100 parts of methyl vinyl silicone oil, 10-20 parts of methyl hydrogen-containing silicone oil, 30-60 parts of methyl MQ resin, 5-10 parts of vinyl MQ resin, 5-15 parts of noctilucent powder, 0.01-0.06 part of inhibitor and 0.1-0.2 part of curing agent. The polysiloxane matrix selected by the noctilucent paint prepared by the invention has moderate viscosity, and can effectively prevent noctilucent powder from settling after the viscosity is too low, thereby achieving the uniform distribution of the noctilucent powder in a coating layer and ensuring the consistency of the luminous intensity of the formed noctilucent paint film.

Description

High-weather-resistance polysiloxane type luminous paint and preparation method thereof
Technical Field
The invention relates to the technical field of luminous paint, in particular to polysiloxane type luminous paint with high weather resistance and a preparation method thereof.
Background
The luminous powder is aluminate activated by various rare earth ions, can continuously emit light for a long time in the dark after being excited by illumination, is added into a polymer to prepare the luminous coating, has bright color, long luminous time and high brightness, and is widely applied to the fields of architectural decoration, artificial landscape, outdoor identification and the like. The luminous paint at present is generally divided into oil paint and water paint, wherein the luminous paint is prepared by dispersing luminous powder and a polymer matrix in an organic solvent, the solvent is volatilized during construction to form a paint film, and the process pollutes the environment, so the luminous paint is limited in many occasions and is gradually replaced by the water luminous paint without the organic solvent. However, polymer matrixes used by the two are carbon-based polymer materials such as polyacrylate, polyurethane, epoxy resin and the like, and after a paint film is formed by the prepared noctilucent paint, the paint film is seriously aged and degraded under long-term use and particularly in an outdoor environment, and the phenomena of color change, brittleness and the like occur, so that the luminous brightness of the noctilucent paint film is reduced and the luminous time is shortened. And the polymer matrix begins to soften at 90-100 ℃ generally, and is directly converted into viscous state at 140-160 ℃, so that the paint film is seriously stripped in a scene of a higher-temperature use environment, and meanwhile, the thermal-oxidative aging degradation degree is rapidly deepened, so that the luminous brightness of the noctilucent paint film is reduced and the luminous time is shortened. Therefore, the prepared environment-friendly high-weather-resistance and high-temperature-resistance luminous paint has wide market application prospect.
Disclosure of Invention
The invention solves the problems in the prior art, and aims to provide the polysiloxane type luminous paint with high weather resistance and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a polysiloxane type luminous coating with high weather resistance comprises the following components in parts by weight: 100 parts of methyl vinyl silicone oil, 10-20 parts of methyl hydrogen-containing silicone oil, 30-60 parts of methyl MQ resin, 5-10 parts of vinyl MQ resin, 5-15 parts of noctilucent powder, 0.01-0.06 part of inhibitor and 0.1-0.2 part of curing agent.
Preferably, the methyl vinyl silicone oil has a vinyl content of 1.2-2.0 wt% and a viscosity of 3000-30000 MPa.S; the methyl hydrogen-containing silicone oil contains 0.3 to 1.0 weight percent of hydrogen and has the viscosity of 50 to 500 MPa.S.
Preferably, the molecular weight of the methyl MQ resin is 6000-; the molecular weight of the vinyl MQ resin is 6000-8000 and the vinyl content is 1.0 to 3.0 weight percent.
Preferably, the noctilucent powder is rare earth aluminate oxide, and is selected from one of the tradenames GL-4A, GL-8C, BL-2A, HL-730 and HL-825.
Preferably, the curing agent is a mixture of a platinum-based catalyst and azobisisobutyronitrile, the platinum-based catalyst is 5000ppm of vinyl siloxane solution of a platinum-vinyl siloxane complex, and the mass ratio of the platinum-based catalyst to the azobisisobutyronitrile is 1: 1.
Preferably, the inhibitor is ethynylcyclohexanol or methylbutynol.
The invention also provides a preparation method of the high weather resistance polysiloxane type luminous paint, which comprises the steps of uniformly mixing 100 parts by mass of methyl vinyl silicone oil, 10-20 parts by mass of methyl hydrogen-containing silicone oil, 30-60 parts by mass of methyl MQ resin, 5-10 parts by mass of vinyl MQ resin, 5-15 parts by mass of luminous powder, 0.01-0.06 part by mass of inhibitor and 0.1-0.2 part by mass of curing agent in 30-40 parts by mass of solvent, and removing the solvent through vacuum defoaming to obtain the high weather resistance polysiloxane type luminous paint.
Preferably, the solvent is cyclohexane or petroleum ether.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polysiloxane matrix selected for preparing the noctilucent paint has moderate viscosity, and can effectively prevent noctilucent powder from settling after the viscosity is too low, so that the noctilucent powder is uniformly distributed in a coating layer, and the luminous intensity of a formed noctilucent paint film is consistent.
(2) The noctilucent paint does not need to use a solvent in the using and constructing process, is nontoxic and harmless, and is environment-friendly.
(3) Because polysiloxane has high weather resistance, the formed noctilucent paint film can be used for a long time in the outdoor environment, the aging degree of the paint film is reduced, and the brightness is kept.
(4) Because polysiloxane has high thermal stability, the formed noctilucent paint film can be used in the high-temperature environment of not higher than 250 ℃.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. Unless otherwise specified, the examples were carried out under the conventional conditions or conditions recommended by the manufacturer without specifying the conditions. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The molecular weight of the methyl MQ resin is 6000-; the molecular weight of the vinyl MQ resin is 6000-.
Example 1
100g of methyl vinyl silicone oil (the viscosity is 30000 MPa.S) with the vinyl content of 1.2wt%, 10g of methyl hydrogen-containing silicone oil (the viscosity is 500 MPa.S) with the hydrogen content of 0.3wt% and 0.01g of ethynl cyclohexanol are dissolved in 30g of cyclohexane, after uniform mixing, 30g of methyl MQ resin, 5g of vinyl MQ resin with the vinyl content of 3.0wt%, 5g of noctilucent powder BL-2A, 0.05g of vinyl siloxane solution of platinum-vinyl siloxane complex with the weight of 5000ppm and 0.05g of AIBN are added, after uniform mixing, a planetary power mixer is thrown in for vacuum removal of the cyclohexane and air bubbles, and the viscous-state polysiloxane type noctilucent coating (the content of the noctilucent powder is 3.33 wt%) with uniform dispersion of the noctilucent powder is obtained.
Example 2
100g of methyl vinyl silicone oil (the viscosity is 15000 MPa.S) with the vinyl content of 1.44 wt%, 20g of methyl hydrogen-containing silicone oil (the viscosity is 250 MPa.S) with the hydrogen content of 0.36 wt% and 0.06g of ethynl cyclohexanol are dissolved in 40g of cyclohexane and evenly mixed, then 60g of methyl MQ resin, 10g of vinyl MQ resin with the vinyl content of 1.0wt% and 15g of noctilucent powder GL-4A are added, 0.1g of vinyl siloxane solution of platinum-vinyl siloxane complex and 0.1g of AIBN are added, and after even mixing, a planetary power mixer is thrown to remove solvent cyclohexane and air bubbles in vacuum, thus obtaining the viscous-state polysiloxane type noctilucent coating (the content of 7.32 wt%) with evenly dispersed noctilucent powder.
Example 3
100g of methyl vinyl silicone oil (the viscosity is 3000 MPa.S) with the vinyl content of 2.0wt%, 15g of methyl hydrogen-containing silicone oil (the viscosity is 50 MPa.S) with the hydrogen content of 1.0wt%, 0.04g of ethynl cyclohexanol are dissolved in 35g of petroleum ether, after uniform mixing, 50g of methyl MQ resin, 7g of vinyl MQ resin with the vinyl content of 2.0wt%, 10g of noctilucent powder GL-8C, 0.08g of vinyl siloxane solution of platinum-vinyl siloxane complex and 0.08g of AIBN are added, after uniform mixing, a planetary power mixer is thrown in for vacuum removal of solvent cyclohexane and air bubbles, and the viscous-state polysiloxane type noctilucent coating with uniformly dispersed noctilucent powder (the content of 5.49 wt%) is obtained.
Comparative example 1
Taking an acrylic ester solution which is used as a substrate of the commonly sold luminous paint on the market, and adding a proper amount of luminous powder BL-2A to prepare the luminous paint with luminous powder content of 3.33 wt%.
Comparative example 2
A polyurethane solution which is used as a substrate of the commonly sold noctilucent paint is taken and added with a proper amount of noctilucent powder GL-4A to prepare the noctilucent paint with 7.32 wt% of noctilucent powder.
Comparative example 3
Epoxy resin solution which is used as a substrate of the commonly sold noctilucent paint is taken and added with proper noctilucent powder GL-8C to prepare the noctilucent paint with noctilucent powder content of 5.49 wt%.
The luminous paints prepared in examples 1 to 3 and comparative examples 1 to 3 were respectively coated on tetrafluoroethylene grooves having a side length of 2cm and a depth of 0.5cm, air-dried for 48 hours to prepare a plurality of luminous paint films, 5 pieces of each of the luminous paint films prepared in examples 1 to 3 and comparative examples 1 to 3 were left outdoors for 30 days, and then afterglow luminance tests were carried out to find average values, as shown in table 1 below.
TABLE 1
Figure BDA0003128834240000051
As shown in Table 1, the afterglow luminance of the noctilucent paint films prepared in the embodiments 1, 2 and 3 is significantly higher than that of the comparative examples 1, 2 and 3 in 1min, 5min, 10min and 30min, which shows that the noctilucent paint film prepared by the invention has better weather resistance in long-term outdoor environment.
5 pieces of the noctilucent paint films of the examples 1-3 and the comparative examples 1-3 are respectively measured for Shore hardness at 100 ℃ to obtain an average value, which is specifically shown in the following table 2.
TABLE 2
Mean value of samples Shore Hardness (HD)
Example 1 70
Example 2 71
Example 3 73
Comparative example 1 42
Comparative example 2 45
Comparative example 3 38
As shown in Table 2, the Shore hardness of the noctilucent paint films prepared in the examples 1, 2 and 3 is significantly higher than that of the noctilucent paint films prepared in the comparative examples 1, 2 and 3 at a high temperature of 100 ℃, which shows that the noctilucent paint films prepared by the invention have higher dimensional stability at a higher temperature.
The noctilucent paint prepared by the invention can effectively prevent noctilucent powder from settling, so that the noctilucent powder is uniformly distributed in a coating layer, and the luminous intensity of the formed noctilucent paint film is consistent; the noctilucent paint does not need to use a solvent in the using and constructing process, is nontoxic and harmless, and is environment-friendly; the formed noctilucent paint film can be used for a long time in outdoor environment, the aging degree of the paint film is reduced, the brightness is kept, and the formed noctilucent paint film can be used in high-temperature environment of not higher than 250 ℃.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (5)

1. The high-weather-resistance polysiloxane type luminous paint is characterized by comprising the following components in parts by mass: 100 parts of methyl vinyl silicone oil, 10-20 parts of methyl hydrogen-containing silicone oil, 30-60 parts of methyl MQ resin, 5-10 parts of vinyl MQ resin, 5-15 parts of noctilucent powder, 0.01-0.06 part of inhibitor and 0.1-0.2 part of curing agent; the content of vinyl in the methyl vinyl silicone oil is 1.2 to 2.0 weight percent, and the viscosity is 3000-30000 MPa.S; the methyl hydrogen-containing silicone oil contains 0.3 to 1.0 weight percent of hydrogen and has the viscosity of 50 to 500 MPa.S; the molecular weight of the methyl MQ resin is 6000-; the molecular weight of the vinyl MQ resin is 6000-8000, and the vinyl content is 1.0-3.0 wt%; the curing agent is a mixture of a platinum catalyst and azobisisobutyronitrile, the platinum catalyst is 5000ppm of vinyl siloxane solution of a platinum-vinyl siloxane complex, and the mass ratio of the platinum catalyst to the azobisisobutyronitrile is 1: 1.
2. The highly weatherable polysiloxane type luminous paint as claimed in claim 1, wherein the luminous powder is a rare earth aluminate oxide, and the luminous powder is one selected from GL-4A, GL-8C, BL-2A, HL-730 and HL-825.
3. The highly weatherable polysiloxane-based luminous paint according to claim 1, wherein the inhibitor is ethynylcyclohexanol or methylbutynol.
4. The method for preparing the high weather resistance polysiloxane type luminous paint as claimed in claim 1, which is characterized by comprising the following steps: uniformly mixing 100 parts by mass of methyl vinyl silicone oil, 10-20 parts by mass of methyl hydrogen-containing silicone oil, 30-60 parts by mass of methyl MQ resin, 5-10 parts by mass of vinyl MQ resin, 5-15 parts by mass of noctilucent powder, 0.01-0.06 part by mass of inhibitor and 0.1-0.2 part by mass of curing agent in 30-40 parts by mass of solvent, and removing the solvent by vacuum defoaming to obtain the high-weatherability polysiloxane type noctilucent coating.
5. The method for preparing the high weather-resistant polysiloxane type luminous paint as claimed in claim 4, wherein the solvent is cyclohexane or petroleum ether.
CN202110696882.XA 2021-06-23 2021-06-23 High-weather-resistance polysiloxane type luminous paint and preparation method thereof Active CN113402975B (en)

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