CN116179073A - Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof - Google Patents

Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof Download PDF

Info

Publication number
CN116179073A
CN116179073A CN202310039018.1A CN202310039018A CN116179073A CN 116179073 A CN116179073 A CN 116179073A CN 202310039018 A CN202310039018 A CN 202310039018A CN 116179073 A CN116179073 A CN 116179073A
Authority
CN
China
Prior art keywords
silane
vinyl
parts
nanoparticle
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310039018.1A
Other languages
Chinese (zh)
Inventor
朱忠敏
叶小明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD
Original Assignee
DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD filed Critical DONGLAI COATING TECHNOLOGY (SHANGHAI) CO LTD
Priority to CN202310039018.1A priority Critical patent/CN116179073A/en
Publication of CN116179073A publication Critical patent/CN116179073A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to a nanoparticle modified UV curing coating and a preparation method and application thereof, wherein the raw materials of the coating comprise (0.1-5) vinyl-terminated silane coupling agent parts and nanoparticle dispersion liquid in a mass ratio of (0.1-5), an acid catalyst, a photo-curing resin, a reactive diluent, a photoinitiator, a leveling agent, an ultraviolet absorber and an organic solvent. Compared with the prior art, the inorganic nano particles introduced by the invention not only enhance the hardness, wear resistance, scratch resistance, weather resistance and chemical resistance of the paint film, but also can effectively absorb ultraviolet rays, thereby greatly improving the weather resistance and ageing resistance of the paint film; in addition, the inorganic nano particles are treated by the silane coupling agent and participate in UV curing reaction, and the organosilicon component is introduced into a paint film component, so that the coating has better weather resistance and corrosion resistance than the common polyurethane acrylate coating due to high Si-O bond energy.

Description

Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of coatings, in particular to a nanoparticle modified UV (ultraviolet) curing coating and a preparation method and application thereof.
Background
Light weight and intelligence are the main trend of future automobiles, and more plastic parts are applied to inner and outer decoration parts of automobiles. Polycarbonate (PC) is one of the most widely used materials, has the advantages of light weight, transparency, good impact resistance and flexible structural design, and is widely applied to the fields of automobile parts such as labels, intelligent B columns and the like. But PC materials are not enough in hardness, easy to scratch, easy to degrade under illumination and easy to be corroded by chemicals, so that when the PC materials are used for automobile body exterior trim parts such as labels, B columns, grids and the like, a layer of Hard Coating (HC) is required to be coated for protection so as to improve the performances of abrasion resistance, scratch resistance, weather resistance, chemical corrosion resistance and the like.
In the prior art, a PC piece is coated by using a UV curing hard coating, and the UV coating mainly uses polyacrylate and polyurethane as main components, and can meet certain requirements on hardness, wear resistance and weather resistance, but the comprehensive performance of the UV coating still has defects such as hardness, weather resistance, wear resistance and chemical resistance, and can not meet the experimental performance requirements of different host factories, so that a large improvement space is still provided in actual use.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nanoparticle modified UV curing coating, a preparation method and application thereof. The inorganic nano particles introduced by the paint not only enhance the hardness, wear resistance, scratch resistance, weather resistance and chemical resistance of the paint film, but also can effectively absorb ultraviolet rays, thereby greatly improving the weather resistance and ageing resistance of the paint film.
According to the invention, the inorganic nano particles are treated by using the vinyl-terminated silane coupling agent, so that a large number of double bonds on the nano particles can participate in ultraviolet curing reaction, and the inorganic nano particle modified UV coating is obtained after curing.
The aim of the invention can be achieved by the following technical scheme:
the invention aims at providing a nanoparticle modified UV curing coating, which comprises the raw materials of (0.1-5) vinyl-terminated silane coupling agent and nanoparticle dispersion liquid in a mass ratio of (0.1-5), and acid catalyst, photo-curing resin, reactive diluent, photoinitiator, leveling agent, ultraviolet absorber and organic solvent.
Further, the raw materials of the coating comprise, by weight, 0.1 to 5 parts of vinyl-terminated silane coupling agent, 0.1 to 5 parts of nanoparticle dispersion liquid, 0.05 to 2 parts of acid catalyst, 10 to 50 parts of photo-curing resin, 2 to 30 parts of reactive diluent, 0.1 to 5 parts of photoinitiator, 0.05 to 2 parts of flatting agent, 0.05 to 2 parts of ultraviolet absorber and 20 to 65 parts of organic solvent.
Further, the vinyl-terminated silane coupling agent comprises one or more of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyl triisopropoxysilane, methyl vinyl dimethoxysilane, vinyl triacetoxysilane, 3- (methacryloyloxy) propyl trimethoxysilane, 3- (methacryloyloxy) propyl triethoxysilane, 3- (methacryloyloxy) propyl triisopropoxysilane, 3- (methacryloyloxy) propyl methyldimethoxysilane, 3- (methacryloyloxy) propyl methyldiethoxysilane, or 3-methacryloxypropyl tris (trimethylsiloxane) silane; the light-cured resin is one or more of polyfunctional aliphatic polyurethane acrylate oligomers with the functionality of 4-15; the reactive diluent comprises one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 4-butanediol dimethacrylate, isobornyl acrylate, isobornyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or dipropylene glycol diacrylate or tripropylene glycol diacrylate; the organic solvent comprises one or more of methanol, ethanol, isopropanol, n-butanol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate.
Further, the vinyl-terminated silane coupling agent comprises one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triisopropoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane, 3- (methacryloyloxy) propyl triethoxy silane or 3- (methacryloyloxy) propyl triisopropoxy silane; the photocurable resin is one or more of a polyfunctional aliphatic urethane acrylate oligomer having a functionality of 6 or 9, which is commercially available, for example, those commercially available under the trade names Ebecryl (zhan new company), neoRad (DSM company), sartomer (alcamer company), ethercure (chang chemical company), desmolux (kosi company), etc., and in some embodiments of the present invention, those having the product types CN9010NS, CN8885NS, neoRad U-41, ebecryl 8415, or Etercure 61992 are used; the reactive diluent comprises one or more of 1, 6-hexanediol diacrylate, isobornyl acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate; the organic solvent comprises one or more of ethanol, isopropanol, ethylene glycol butyl ether, propylene glycol methyl ether, butyl acetate or propylene glycol methyl ether acetate.
Further, the dispersion medium in the nanoparticle dispersion liquid comprises ethanol, isopropanol or glycol; the dispersed phase in the nanoparticle dispersion liquid comprises nano SiO 2 Nano TiO 2 Nano CeO 2 Nano Al 2 O 3 Or nano ZrO 2 ；
Further, the solid content in the nanoparticle dispersion liquid is 5-50%; the particle size of the disperse phase is 5-100nm.
Further, the acid catalyst comprises one or more of hydrochloric acid, sulfuric acid, acetic acid, p-toluenesulfonic acid, lactic acid or citric acid; the photoinitiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone (PI-184), 2-hydroxy-2-methyl-1-phenyl acetone (DAROCURE 1173) or TPO; the leveling agent comprises a modified acrylate leveling agent or an organosilicon leveling agent, and in certain embodiments of the invention, BYK333, BYK310, BYK353 or Tego450 are used; the ultraviolet absorber is a hindered amine ultraviolet absorber, and in certain embodiments of the present invention Tinuvin123, tinuvin292, tinuvin152 (Basf) or Sanduvor3058 (Clariant) are used.
Further, the mass fraction of the solute in the acid catalyst is 0.1% -20%.
The second object of the invention is a method for preparing the nanoparticle modified UV curable coating, which comprises the following steps:
step one, placing an organic solvent and nanoparticle dispersion liquid in a container, and stirring until the organic solvent and nanoparticle dispersion liquid are uniform;
step two, adding a vinyl-terminated silane coupling agent into the container in the step one, adding an acid catalyst, and stirring until the reaction is complete;
thirdly, adding the photo-curing resin and the reactive diluent into the container in the second step, and stirring until the mixture is uniform;
and step four, adding a photoinitiator, a leveling agent and an ultraviolet absorber into the container in the step three, and stirring until the mixture is uniform to obtain the nanoparticle modified UV curing coating.
More specifically:
step one, weighing an organic solvent and a nanoparticle dispersion liquid according to a formula, mixing and stirring at room temperature for 10 min-1 h;
and step two, weighing one or more vinyl-terminated silane coupling agents according to the formula, and if the formula contains multiple vinyl-terminated silane coupling agents, uniformly stirring after mixing at room temperature. And then slowly dripping the mixture into the mixed solution in the step one, dripping an acid catalyst according to the formula, and continuing stirring at room temperature for reaction for 6-48 h.
And thirdly, adding the photo-curing resin and the reactive diluent according to the formula, and continuously stirring for 0.5-3 h at room temperature.
And step four, continuously adding the photoinitiator, the flatting agent and the ultraviolet absorbent according to the formula, and continuously stirring at room temperature for 10 min-2 h to obtain the nanoparticle modified UV curing coating.
The third object of the invention is to apply the nanoparticle modified UV curing coating to the surface coating of the automobile exterior plastic part, so as to improve the wear resistance, weather resistance and chemical resistance of the automobile exterior plastic part. The automobile exterior plastic part comprises automobile marks, decorative strips, grids and other parts
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the inorganic nano particles are treated by the silane coupling agent with double bonds, the silicon hydroxyl is obtained through silane hydrolysis, and then the silane coupling agent is condensed with the hydroxyl on the surfaces of the inorganic nano particles, so that the double bonds capable of participating in curing reaction are carried on the surfaces of the nano particles, and the inorganic nano particle modified inorganic-organic hybrid coating is successfully prepared after UV curing.
(2) According to the invention, the inorganic nano particles are treated by the silane coupling agent and participate in UV curing reaction, and the organosilicon component is introduced into a paint film component, so that the coating has better weather resistance and corrosion resistance than the common polyurethane acrylate coating due to high Si-O bond energy.
(3) The inorganic nano particles introduced by the invention can effectively absorb ultraviolet rays, so that the weather resistance and the ageing resistance of a paint film are greatly improved, and the paint film is very suitable for application in coating of automotive exterior trim parts.
(4) The nanoparticle modified UV curing coating designed by the invention can effectively solve the problem of insufficient comprehensive performance of the traditional polyurethane or polyacrylate coating, and the construction method is simple and convenient, has low energy consumption and is suitable for large-scale industrial application.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
The nanoparticle modified UV curing coating comprises the following components in parts by weight:
Figure BDA0004050451200000051
the preparation method is as follows:
step one, weighing propylene glycol methyl ether, butyl acetate and nano SiO according to a formula 2 Stirring the dispersion liquid at room temperature for 20min;
step two, weighing vinyl triethoxysilane according to a formula, slowly dripping the vinyl triethoxysilane into the mixed solution in the step one, dripping acetic acid aqueous solution with a formula amount, and stirring at room temperature for reaction for 12 hours;
step three, adding CN9010NS, trimethylolpropane triacrylate and isobornyl acrylate according to the formula, and continuously stirring at room temperature for 2 hours;
and step four, metering PI-184, BYK333 and Tinuvin292 according to the formula, and continuously stirring for 30min at room temperature.
The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 8-10 mu m, firstly, the PC substrate is flash-dried at 60-70 ℃, and then is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 After spray curing, relevant performance test experiments were carried out, and the experimental results are shown in table 1.
Example 2
The nanoparticle modified UV curing coating comprises the following components in parts by weight:
Figure BDA0004050451200000061
step one, weighing ethylene glycol butyl ether, propylene glycol methyl ether acetate and nano TiO according to a formula 2 Stirring the dispersion liquid at room temperature for 40min;
step two, weighing 3- (methacryloyloxy) propyl trimethoxysilane according to a formula, slowly dripping the 3- (methacryloyloxy) propyl trimethoxysilane into the mixed solution in the step one, dripping hydrochloric acid aqueous solution with a formula amount, and stirring at room temperature for reaction for 6 hours;
step three, adding CN8885NS, pentaerythritol tetraacrylate and 1, 6-hexanediol diacrylate according to the formula, and continuously stirring for 3 hours at room temperature;
and step four, metering PI-184, BYK310 and Tinuvin152 according to the formula, and continuously stirring for 30min at room temperature.
The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 9-12 mu m, firstly, the coating is flash-dried at 60-70 ℃, then, the coating is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 After spray curing, relevant performance test experiments were carried out, and the experimental results are shown in table 1.
Example 3
The nanoparticle modified UV curing coating comprises the following components in parts by weight:
Figure BDA0004050451200000071
the preparation method comprises the following steps:
step one, weighing isopropanol, propylene glycol methyl ether and nano CeO according to a formula 2 Stirring the dispersion liquid at room temperature for 30min;
step two, weighing vinyl trimethoxy silane and 3- (methacryloyloxy) propyl triisopropoxy silane according to a formula, mixing and stirring uniformly, then slowly dripping the mixture into the mixed solution in the step one, dripping lactic acid aqueous solution with a formula amount, and stirring at room temperature for reacting for 48 hours;
step three, metering NeoRad U-41, dipentaerythritol hexaacrylate and 1, 6-hexanediol diacrylate according to a formula, and continuously stirring for 1h at room temperature;
and step four, metering DAROCURE1173, tego450 and Sanduvor3058 according to the formula, and stirring for 40min at room temperature.
The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 9-15 mu m, firstly, the coating is flash-dried at 60-70 ℃, then, the coating is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 Spraying and curing the mixture to obtain a phaseThe performance test experiments are shown in Table 1.
Example 4
The nanoparticle modified UV curing coating comprises the following components in parts by weight:
Figure BDA0004050451200000081
the preparation method comprises the following steps:
step one, weighing ethylene glycol butyl ether, propylene glycol methyl ether and nano SiO according to a formula 2 Dispersion, nano ZrO 2 Stirring the dispersion liquid at room temperature for 40min;
step two, weighing 3- (methacryloyloxy) propyl triethoxysilane according to a formula, slowly dripping the 3- (methacryloyloxy) propyl triethoxysilane into the mixed solution in the step one, dripping a citric acid aqueous solution with a formula amount, and stirring at room temperature for reaction for 36 hours;
step three, EBECRYL 8415 and trimethylolpropane triacrylate are metered in according to the formula, and stirring is continued for 2 hours at room temperature;
and step four, metering PI-184, TPO, BYK353 and Tinuvin123 according to the formula, and continuously stirring at room temperature for 40min.
The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 10-15 mu m, firstly, the coating is flash-dried at 60-70 ℃, then the coating is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 After spray curing, relevant performance test experiments were carried out, and the experimental results are shown in table 1.
Example 5
The nanoparticle modified UV curing coating comprises the following components in parts by weight:
Figure BDA0004050451200000091
the preparation method comprises the following steps:
step one, weighing propylene glycol methyl ether, butyl acetate and nano TiO according to a formula 2 Stirring the dispersion liquid at room temperature for 30min;
step two, weighing vinyl trimethoxy silane and 3- (methacryloyloxy) propyl trimethoxy silane according to a formula, uniformly stirring after mixing, slowly dripping the mixture into the mixed solution in the step one, dripping acetic acid aqueous solution with a formula amount, and stirring at room temperature for reaction for 24 hours;
step three, metering ETERCURE 61992, dipentaerythritol hexaacrylate and isobornyl acrylate according to the formula, and continuously stirring for 1h at room temperature;
and step four, metering PI-184, tego450 and Tinuvin292 according to the formula, and continuously stirring for 30min at room temperature.
The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 10-16 mu m, firstly, the coating is flash-dried at 60-70 ℃, then, the coating is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 After spray curing, relevant performance test experiments were carried out, and the experimental results are shown in table 1.
Comparative example 1
2.0 parts of vinyl triethoxysilane, nano SiO in the formula of example 1 2 3.2 parts of dispersion liquid, 40.5 parts of propylene glycol methyl ether, 0 part of vinyl triethoxysilane instead of nano SiO 2 0 part of dispersion, 45.7 parts of propylene glycol methyl ether ", and the other parts are the same as in example 1. The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 10-15 mu m, firstly, the coating is flash-dried at 60-70 ℃, then the coating is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 After spray curing, relevant performance test experiments were carried out, and the experimental results are shown in table 1.
Comparative example 2
2.4 parts of 3- (methacryloyloxy) propyltrimethoxysilane in the formulation of example 2 and nano TiO 2 3.6 parts of dispersion liquid, 39.2 parts of ethylene glycol butyl ether, 2.4 parts of 3- (methacryloyloxy) propyl trimethoxysilane and nano TiO 2 0 part of dispersion, 42.8 parts of ethylene glycol butyl ether, and the same as in example 2. The nano particle modified UV curing coating is obtained, the coating is sprayed on the surface of a PC substrate, the film thickness is 10-15 mu m, firstly, the coating is flash-dried at 60-70 ℃, then the coating is cured by a UV curing furnace, and the curing energy is 1500-3000 mJ/cm 2 After spraying and curingRelevant performance test experiments were performed, and the experimental results are shown in table 1.
TABLE 1 nanoparticle modified UV curable coating Properties
Figure BDA0004050451200000101
Note that: abrasion resistance tests were according to ASTM D1044, xenon lamp aging was according to SAE J2527.
It can be seen from table 1 that the addition of inorganic nanoparticles can significantly increase the hardness of the paint film, thereby improving the wear resistance thereof. The inorganic nano particle modification can also obviously improve the weather resistance of a paint film, thereby meeting the use requirement of outdoor conditions. The inorganic nano particles are treated by the silane coupling agent with double bonds, the silicon hydroxyl is obtained through silane hydrolysis, and then the silane coupling agent is condensed with the hydroxyl on the surfaces of the inorganic nano particles, so that double bonds capable of participating in curing reaction are carried on the surfaces of the nano particles, and the inorganic-organic hybrid coating modified by the inorganic nano particles is successfully prepared after UV curing.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. The nanoparticle modified UV curing coating is characterized in that the raw materials of the coating comprise (0.1-5) a vinyl-terminated silane coupling agent part and nanoparticle dispersion liquid in a mass ratio of (0.1-5), an acid catalyst, a photo-curing resin, a reactive diluent, a photoinitiator, a leveling agent, an ultraviolet absorber and an organic solvent.
2. The nanoparticle modified UV-curable coating according to claim 1, wherein the raw materials of the coating comprise, by weight, 0.1 to 5 parts of a vinyl-terminated silane coupling agent, 0.1 to 5 parts of a nanoparticle dispersion, 0.05 to 2 parts of an acid catalyst, 10 to 50 parts of a photocurable resin, 2 to 30 parts of a reactive diluent, 0.1 to 5 parts of a photoinitiator, 0.05 to 2 parts of a leveling agent, 0.05 to 2 parts of an ultraviolet absorber, and 20 to 65 parts of an organic solvent.
3. A nanoparticle modified UV-curable coating according to claim 2, wherein,
the vinyl-terminated silane coupling agent comprises one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (2-methoxyethoxy) silane, vinyl triisopropoxy silane, methyl vinyl dimethoxy silane, vinyl triacetoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3- (methacryloxy) propyl triethoxy silane, 3- (methacryloxy) propyl triisopropoxy silane, 3- (methacryloxy) propyl methyl dimethoxy silane, 3- (methacryloxy) propyl methyl diethoxy silane or 3-methacryloxy propyl tri (trimethylsiloxane) silane;
the light-cured resin is one or more of polyfunctional aliphatic polyurethane acrylate oligomers with the functionality of 4-15;
the reactive diluent comprises one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 4-butanediol dimethacrylate, isobornyl acrylate, isobornyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or dipropylene glycol diacrylate or tripropylene glycol diacrylate;
the organic solvent comprises one or more of methanol, ethanol, isopropanol, n-butanol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate.
4. A nanoparticle modified UV-curable coating according to claim 3,
the vinyl-terminated silane coupling agent comprises one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triisopropoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane, 3- (methacryloyloxy) propyl triethoxy silane or 3- (methacryloyloxy) propyl triisopropoxy silane;
the light-cured resin is one or more of polyfunctional aliphatic polyurethane acrylate oligomer with functionality of 6 or 9;
the reactive diluent comprises one or more of 1, 6-hexanediol diacrylate, isobornyl acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate;
the organic solvent comprises one or more of ethanol, isopropanol, ethylene glycol butyl ether, propylene glycol methyl ether, butyl acetate or propylene glycol methyl ether acetate.
5. The nanoparticle modified UV-curable coating of claim 2, wherein the dispersion medium in the nanoparticle dispersion comprises ethanol, isopropanol or ethylene glycol; the dispersed phase in the nanoparticle dispersion liquid comprises nano SiO 2 Nano TiO 2 Nano CeO 2 Nano Al 2 O 3 Or nano ZrO 2 。
6. The nanoparticle modified UV-curable coating of claim 5, wherein the nanoparticle dispersion has a solids content of 5 to 50wt%; the particle size of the disperse phase is 5-100nm.
7. A nanoparticle modified UV-curable coating according to claim 2, wherein,
the acid catalyst comprises one or more of hydrochloric acid, sulfuric acid, acetic acid, p-toluenesulfonic acid, lactic acid or citric acid aqueous solution;
the photoinitiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone or TPO;
the leveling agent comprises a modified acrylic ester leveling agent or an organosilicon leveling agent,
the ultraviolet absorber is hindered amine ultraviolet absorber.
8. The nanoparticle modified UV-curable coating according to claim 7, wherein the mass fraction of solute in the acid catalyst is 0.1% to 20%.
9. A method of preparing a nanoparticle modified UV-curable coating according to any one of claims 1 to 8, comprising the steps of:
step one, placing an organic solvent and nanoparticle dispersion liquid in a container, and stirring until the organic solvent and nanoparticle dispersion liquid are uniform;
step two, adding a vinyl-terminated silane coupling agent into the container in the step one, adding an acid catalyst, and stirring until the reaction is complete;
thirdly, adding the photo-curing resin and the reactive diluent into the container in the second step, and stirring until the mixture is uniform;
and step four, adding a photoinitiator, a leveling agent and an ultraviolet absorber into the container in the step three, and stirring until the mixture is uniform to obtain the nanoparticle modified UV curing coating.
10. Use of a nanoparticle modified UV-curable coating according to any one of claims 1 to 8, wherein the coating is applied to the surface coating of automotive exterior plastic parts to improve the wear resistance, weather resistance and chemical resistance of automotive exterior plastic parts.
CN202310039018.1A 2023-01-12 2023-01-12 Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof Pending CN116179073A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310039018.1A CN116179073A (en) 2023-01-12 2023-01-12 Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310039018.1A CN116179073A (en) 2023-01-12 2023-01-12 Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116179073A true CN116179073A (en) 2023-05-30

Family

ID=86443657

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310039018.1A Pending CN116179073A (en) 2023-01-12 2023-01-12 Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116179073A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117247499A (en) * 2023-10-12 2023-12-19 杭州爱科自动化技术有限公司 Nanoparticle reinforced resin, preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117247499A (en) * 2023-10-12 2023-12-19 杭州爱科自动化技术有限公司 Nanoparticle reinforced resin, preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN104419234B (en) Cured composition, cured product thereof, hard primer and hard coating
TWI523922B (en) A method for producing an organic-inorganic composite, a hardened composition, a hardened product of a hardened composition, a hard coat material, a hard coat film and a silane coupling agent
EP2594612B1 (en) Anti-glare coating composition and anti-glare coating film having superior abrasion resistance and contamination resistance
CN102295881A (en) Preparation method for high-hardness organic-inorganic hybrid ultraviolet light curing coating, and application thereof
CN1206288C (en) UV curable paint compositions and method of making and applying same
CN105153924B (en) High hydrophilic high abrasion organic/inorganic hybrid photocuring coating composition
KR101664735B1 (en) Anti-fingerprint hardcoating composition and anti-fingerprint hardcoating film using the same
CN102020913B (en) Ultraviolet cured wood paint and preparation method thereof
CN103031034A (en) White finish coat photocurable UV (ultraviolet) paint and preparation method thereof
CN104194613A (en) Recoatable UV-curing colored one-step-coating aluminum powder paint and preparation method thereof
KR101725026B1 (en) Composition for hard coating film having high hardness and Film for protecting display panel having high hardness
TW200932848A (en) Coating composition and coating film having enhanced abrasion resistance and fingerprint traces removability
JP2002067238A (en) Film having cured coat of radiation-cured type resin composition
WO2022160983A1 (en) Water-based uv coating, and preparation method therefor and application thereof
KR101949204B1 (en) Hard coating composition
TW201333055A (en) Thin-film laminate
JP2009084398A (en) Resin composition and process for production thereof
CN110684460A (en) Low-cost high-wear-resistance UV (ultraviolet) curing coating and preparation method and application thereof
CN116179073A (en) Nanoparticle modified UV (ultraviolet) curing coating and preparation method and application thereof
JP2010260905A (en) Photocurable composition
CN104418958B (en) The manufacture method of organic mineral complex, solidification compound and solidfied material thereof, firmly it is coated with material, hard coat film and silane coupler
KR102100028B1 (en) Uv-curable matt paint composition and coating film using the same
JP2012017404A (en) Photocurable resin composition and photocurable coating agent using the same
JP2011201930A (en) Composition for hardcoat and base material coated therewith
JP2001164117A (en) High-refractive-index composition and antireflection laminate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination