CN109181506B - Solvent-free photocuring glass coating and preparation method and application thereof - Google Patents

Solvent-free photocuring glass coating and preparation method and application thereof Download PDF

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Publication number
CN109181506B
CN109181506B CN201810960440.XA CN201810960440A CN109181506B CN 109181506 B CN109181506 B CN 109181506B CN 201810960440 A CN201810960440 A CN 201810960440A CN 109181506 B CN109181506 B CN 109181506B
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solvent
coating
photoinitiator
glass
free
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CN109181506A (en
Inventor
张开宇
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Guangdong Haohui New Material Co ltd
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Guangdong Haohui New Material Co ltd
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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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06Unsaturated polyesters having carbon-to-carbon unsaturation
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/38Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/118Deposition methods from solutions or suspensions by roller-coating
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/32After-treatment
    • 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

Abstract

The invention discloses a solvent-free photocuring glass coating as well as a preparation method and application thereof, wherein the coating comprises the following components in percentage by weight: 40-50% of silane coupling agent grafted trifunctional polyester acrylate, 20-25% of trifunctional polyurethane acrylate, 5-10% of difunctional polyurethane acrylate, 8-15% of hydroxyethyl methacrylate, 8-15% of pentaerythritol triacrylate, 4-6% of a photoinitiator and 0.02-0.05% of a leveling agent 2100. The silane coupling agent grafted on the trifunctional polyester acrylate can form covalent bonds with silanol groups on the surface of glass or molecules on the surface of other inorganic fillers, namely the silane coupling agent can play a role of a bridge for mutually connecting inorganic phases and organic phases, so that the adhesion of the coating on the surface of the glass is effectively improved.

Description

Solvent-free photocuring glass coating and preparation method and application thereof
Technical Field
The invention relates to the field of coatings, in particular to a solvent-free photocureable glass coating and a preparation method and application thereof.
Background
Glass has a structure that is very different from other substrates. Glass is amorphous solid with a random structure, is also liquid in a microscopic view, has a main component of silicon dioxide, is a metastable solid material, and is difficult to generate adhesive force on the surface of a general coating due to the particularity of the metastable solid material.
Although the addition of the coupling agent is helpful to solve the adhesion of the thermosetting coating, the UV-curable coating is very unstable, and the addition of the coupling agent for several minutes or even tens of seconds can cause polymerization reaction, thus the UV-curable coating is difficult to implement in the production process and difficult to control even the stability of the UV-curable coating.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a solvent-free type photocureable glass coating, and a preparation method and application thereof, and aims to solve the problem that the adhesion of the existing UV photocureable coating coated on a glass substrate is poor.
The technical scheme of the invention is as follows:
a solvent-free type photocuring glass coating comprises the following components in percentage by weight: 40-50% of silane coupling agent grafted trifunctional polyester acrylate, 20-25% of trifunctional polyurethane acrylate, 5-10% of difunctional polyurethane acrylate, 8-15% of hydroxyethyl methacrylate, 8-15% of pentaerythritol triacrylate, 4-6% of a photoinitiator and 0.02-0.05% of a leveling agent 2100.
The solvent-free type photocuring glass coating also comprises 0.5-1.5% of phosphate.
The solvent-free type photocuring glass coating is characterized in that the photoinitiator is one or more of photoinitiator 184, photoinitiator BDK and photoinitiator TPO.
A preparation method of a solvent-free type photocuring glass coating comprises the following steps:
adding hydroxyethyl methacrylate into a dispersion cylinder, starting stirring, adding the photoinitiator, stirring until the photoinitiator is completely dissolved, adding silane coupling agent grafted trifunctional polyester acrylate, trifunctional polyurethane acrylate and difunctional polyurethane acrylate, finally adding the leveling agent 2100, stirring uniformly, filtering with a 200-mesh screen, and discharging to obtain the solvent-free photocuring glass coating.
The application of the solvent-free type photocuring glass paint for ironing a pyramid and a pattern on a glass substrate comprises the following steps:
the solvent-free type photocuring glass coating is coated on a glass substrate in a roller way, and is baked and leveled for 2-5min at the temperature of 60-100 ℃, and then is cured for the first time through a UV photocuring machine to form a first paint film;
vacuum electroplating aluminum plating is carried out on the surface of the first paint film, the solvent-free type photocuring glass paint is continuously roll-coated after the paint is well coated, and after the paint is baked and leveled for 2-5min at the temperature of 60-100 ℃, a second paint film is formed by secondary curing through a UV photocuring machine;
and sticking the gold stamping transfer water sticker on the surface of the second paint film, baking at the temperature of 150-200 ℃ for 25-40min, and tearing off the gold stamping transfer water sticker to enable the gold stamping character and the pattern to be left on the second paint film.
The solvent-free photocuring glass coating is applied, wherein the curing energy of the first curing and the second curing is 1200-1500mj/cm2
Has the advantages that: the solvent-free type photocuring glass coating provided by the invention comprises the following components in percentage by weight: 40-50% of silane coupling agent grafted trifunctional polyester acrylate, 20-25% of trifunctional polyurethane acrylate, 5-10% of difunctional polyurethane acrylate, 8-15% of hydroxyethyl methacrylate, 8-15% of pentaerythritol triacrylate, 4-6% of a photoinitiator and 0.02-0.05% of a leveling agent 2100. The silane coupling agent grafted on the trifunctional polyester acrylate can form covalent bonds with silanol groups on the surface of glass or molecules on the surface of other inorganic fillers, namely the silane coupling agent can play a bridge-like role in mutual connection between inorganic phases and organic phases, so that the adhesion of the coating on the surface of the glass is effectively improved.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of the present invention for the application of a solvent-free photocurable glass coating.
Detailed Description
The invention provides a solvent-free type photocuring glass coating and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The traditional solvent-based coating can only be sprayed in a plating and thermal transfer gold stamping way when being used for plating and thermal transfer gold stamping on glass, the coating is sprayed and then baked for 1-3 hours in a high-temperature environment of 80-120 ℃, and then the next step of plating and thermal transfer printing is carried out, wherein the solvent-based coating has the following defects in the production and construction process:
1) the emission of Volatile Organic Compounds (VOC) is too high, the pollution to the atmosphere and the environment is caused, and the national environmental protection requirement is not met; 2) the waste of the energy, because the time overlength of toasting, need long-time heating and thermostatic equipment, active ingredient in the coating is low, and the solvent is through toasting whole volatilizing in the air in the middle of to in order to reduce cost and improve the workability, active ingredient reduces to twenty several to thirty several, causes the waste of a large amount of electric power waste and solvent, and the use of solvent still can bring the injury on the body for the constructor.
Based on the above, the invention provides a solvent-free type photocuring glass coating, which comprises the following components in percentage by weight: 40-50% of silane coupling agent grafted trifunctional polyester acrylate, 20-25% of trifunctional polyurethane acrylate, 5-10% of difunctional polyurethane acrylate, 8-15% of hydroxyethyl methacrylate, 8-15% of pentaerythritol triacrylate, 4-6% of a photoinitiator and 0.02-0.05% of a leveling agent 2100.
The coating of the embodiment is a solvent-free and VOC emission-free environment-friendly coating, the effective components of the coating are one hundred percent, and the coating is not baked at high temperature, so that the energy consumption in the production process of a manufacturer is reduced, and a large amount of production cost is saved; the UV curing time of the coating is 1-5 seconds, the traditional coating needs longer curing time, and the production efficiency is greatly improved while the energy is saved.
Furthermore, because the glass is amorphous solid with a random structure and is also liquid in a microscopic view, the main component of the glass is silicon dioxide, the glass is a metastable solid material, and the traditional light-cured coating is difficult to generate adhesive force on the surface of the glass due to the particularity of the glass. The solvent-free photocurable glass coating in the embodiment can effectively solve the problem of poor adhesion of the photocurable coating on the glass surface by adopting the trifunctional polyester acrylate grafted by the silane coupling agent. Specifically, because the silane coupling agent contains two different chemical functional groups, one end of the silane coupling agent is grafted to the trifunctional polyester acrylate to form a covalent bond, and the other end of the silane coupling agent can react with silanol groups on the surface of glass or molecules on the surface of other inorganic fillers to form another covalent bond; that is, the silane coupling agent can function as a bridge connecting inorganic and organic phases to each other, thereby effectively improving the adhesion of the coating of this embodiment to the glass surface.
In this embodiment, the silane coupling agent grafted trifunctional polyester acrylate has not only very strong adhesion on glass, but also good heat resistance.
In this example, the viscosity of the trifunctional urethane acrylate was very low, the reactivity was high, and the adhesion to glass was also very good.
In a preferred embodiment, the solvent-free photocurable glass coating comprises, by weight: 45% of silane coupling agent grafted trifunctional polyester acrylate, 23% of trifunctional polyurethane acrylate, 8% of difunctional polyurethane acrylate, 10% of hydroxyethyl methacrylate, 10% of pentaerythritol triacrylate, 3.95% of photoinitiator and 0.05% of leveling agent 2100.
In a preferred embodiment, the photoinitiator is one or more of photoinitiator 184, photoinitiator BDK, and photoinitiator TPO, but is not limited thereto.
In a preferred embodiment, the solvent-free photocurable glass coating can be used as both a primer and a topcoat. Preferably, when used as a topcoat, the solventless photocurable glass coating further comprises 0.5-1.5% of a phosphate ester, which can be used to enhance adhesion to an electroplated coating.
Further, the invention also provides a preparation method of the solvent-free type photocuring glass coating, which comprises the following steps: adding hydroxyethyl methacrylate into a dispersion cylinder, starting stirring, adding the photoinitiator, stirring until the photoinitiator is completely dissolved, adding silane coupling agent grafted trifunctional polyester acrylate, trifunctional polyurethane acrylate and difunctional polyurethane acrylate, finally adding the leveling agent 2100, stirring uniformly, filtering with a 200-mesh screen, and discharging to obtain the solvent-free photocuring glass coating.
In a specific embodiment, hydroxyethyl methacrylate (HEMA) is added into a dispersion cylinder to be stirred, then the photoinitiator 184, the photoinitiator BDK and the photoinitiator TPO are sequentially added and dispersed at a high speed until the photoinitiators are completely dissolved, then trifunctional polyester acrylate, trifunctional polyurethane acrylate and difunctional polyurethane acrylate grafted by a silane coupling agent are added and stirred uniformly, finally the leveling agent 2100 is added and stirred for 5 minutes, and the mixture is filtered and discharged by a 200-mesh screen to prepare the solvent-free photocuring glass coating.
Further, the present invention also provides a use of a solvent-free type photo-curable glass coating for ironing a pyramid and a pattern on a glass substrate, as shown in fig. 1, comprising the steps of:
s100, coating the solvent-free photocuring glass coating on a glass substrate in a roller manner, baking and leveling for 2-5min at the temperature of 60-100 ℃, and performing primary curing through a UV photocuring machine to form a first paint film;
s200, performing vacuum electroplating aluminum plating on the surface of the first paint film, continuously roll-coating the solvent-free type photocuring glass paint after the paint is plated, baking and leveling for 2-5min at 60-100 ℃, and performing secondary curing through a UV photocuring machine to form a second paint film;
s300, sticking the gold stamping transfer printing water sticker on the surface of the second paint film, baking at the temperature of 150-200 ℃ for 25-40min, and tearing off the gold stamping transfer printing water sticker to enable the gold stamping character and the pattern to be left on the second paint film.
In a preferred embodiment, the first coating is roll-coated on the glass by a roll coater, the film thickness is 12-18ml, the glass is baked and leveled for 3 minutes at 80 ℃, and the glass is passed through a UV photo-curing machine, the curing machine is a two-branch 3.6 kilowatt lamp tube, the curing energy is 1200-1500mj/cm2And after curing, performing vacuum electroplating aluminum plating, after plating, performing roller coating or heating spraying on a second coating, baking and leveling for 3 minutes at 80 ℃, passing through a UV curing machine, wherein the curing machine is two 3.6 kilowatt lamp tubes, the curing energy is 1200 and 1500mj/cm2, after curing, attaching the gold stamping transfer printing water sticker on the surface, baking for 30 minutes at 180 ℃, tearing off the film, and leaving the gold stamping character and the pattern on the paint film to finish the processing of a finished product.
In this example, the first coating material and the second coating material are substantially the same in formulation composition and each include 45% of silane coupling agent grafted trifunctional polyester acrylate, 23% of trifunctional urethane acrylate, 8% of difunctional urethane acrylate, 10% of hydroxyethyl methacrylate, 10% of pentaerythritol triacrylate, and 4% of a photoinitiator including photoinitiator 184, photoinitiator BDK, photoinitiator TPO, and leveling agent 2100; in the embodiment, the first coating and the second coating are basically consistent in formula, so that the iron can be scalded, and other common vacuum plating finish paint can not be scalded. Except that 0.5-1.5% phosphate ester is added to the second coating, which can be used to enhance adhesion to the electroplated coating.
Further, the paint cured on the glass substrate in this example was subjected to a performance test, and the results were as follows: the adhesive force of the coating on the glass substrate is 5B, the hardness of the coating is 1-2H, the coating does not foam or fall off after being soaked in water for 7 days, and the adhesive force is 5B; the coating does not foam for 1 hour in an environment of 180 ℃, and the adhesion force is 5B after cooling; the adhesion of the coating is still 5B after the coating is boiled in water for 1h at the temperature of 100 ℃;
furthermore, through detection, the hot-pressed pyramid has no phenomena of foaming, cracking, no pinholes in a paint film, dry stir-frying and the like after being baked for 1 hour at 180 ℃, and other performances such as paint film adhesion and the like after being boiled in water for 1 hour at 100 ℃ are not changed, so that the hot-pressed pyramid meets the requirements of customers.
In summary, the solvent-free photocurable glass coating provided by the invention comprises the following components in percentage by weight: 40-50% of silane coupling agent grafted trifunctional polyester acrylate, 20-25% of trifunctional polyurethane acrylate, 5-10% of difunctional polyurethane acrylate, 8-15% of hydroxyethyl methacrylate, 8-15% of pentaerythritol triacrylate, 4-6% of a photoinitiator and 0.02-0.05% of a leveling agent 2100. The silane coupling agent grafted on the trifunctional polyester acrylate can form covalent bonds with silanol groups on the surface of glass or molecules on the surface of other inorganic fillers, namely the silane coupling agent can play a role of a bridge for mutually connecting inorganic phases and organic phases, so that the adhesion of the coating on the surface of the glass is effectively improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (6)

1. The solvent-free photocuring glass coating is characterized by comprising the following components in percentage by weight: 40-50% of silane coupling agent grafted trifunctional polyester acrylate, 20-25% of trifunctional polyurethane acrylate, 5-10% of difunctional polyurethane acrylate, 8-15% of hydroxyethyl methacrylate, 8-15% of pentaerythritol triacrylate, 4-6% of a photoinitiator and 0.02-0.05% of a leveling agent 2100; one end of the silane coupling agent is grafted to the trifunctional polyester acrylate to form a covalent bond.
2. A solvent-free photocurable glass coating according to claim 1 further comprising 0.5-1.5% of a phosphate ester.
3. The solventless photocurable glass coating of claim 1 wherein the photoinitiator is one or more of photoinitiator 184, photoinitiator BDK and photoinitiator TPO.
4. A method for preparing the solvent-free photocurable glass coating according to any one of claims 1-3, comprising the steps of:
adding hydroxyethyl methacrylate into a dispersion cylinder, starting stirring, adding the photoinitiator, stirring until the photoinitiator is completely dissolved, adding silane coupling agent grafted trifunctional polyester acrylate, trifunctional polyurethane acrylate and difunctional polyurethane acrylate, finally adding the leveling agent 2100, stirring uniformly, filtering with a 200-mesh screen, and discharging to obtain the solvent-free photocuring glass coating.
5. Use of the solvent-free photocurable glass coating according to any one of claims 1-3 for stamping pyramids and designs on glass substrates, comprising the steps of:
the solvent-free type photocuring glass coating is coated on a glass substrate in a roller way, and is baked and leveled for 2-5min at the temperature of 60-100 ℃, and then is cured for the first time through a UV photocuring machine to form a first paint film;
vacuum electroplating aluminum plating is carried out on the surface of the first paint film, the solvent-free type photocuring glass paint is continuously roll-coated after plating, and after baking and leveling are carried out for 2-5min at the temperature of 60-100 ℃, a second paint film is formed by secondary curing through a UV photocuring machine;
and sticking the gold stamping transfer water sticker on the surface of the second paint film, baking at the temperature of 150-200 ℃ for 25-40min, and tearing off the gold stamping transfer water sticker to enable the gold stamping character and the pattern to be left on the second paint film.
6. The use of the solvent-free photocurable glass coating according to claim 5, wherein the curing energy of the first curing and the second curing are 1200-1500mj/cm2
CN201810960440.XA 2018-08-22 2018-08-22 Solvent-free photocuring glass coating and preparation method and application thereof Active CN109181506B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102533068A (en) * 2011-12-23 2012-07-04 上海紫江喷铝包装材料有限公司 Ultraviolet curing aluminized transferring coating and preparation method and application thereof
CN107974193A (en) * 2018-01-06 2018-05-01 珠海东诚光固化新材料股份有限公司 A kind of ultraviolet light for glass color mirror cures pigmented finiss and its application
CN108264838A (en) * 2017-12-29 2018-07-10 上海乘鹰新材料有限公司 A kind of flexible, anti-pollution ultraviolet cured paint composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102533068A (en) * 2011-12-23 2012-07-04 上海紫江喷铝包装材料有限公司 Ultraviolet curing aluminized transferring coating and preparation method and application thereof
CN108264838A (en) * 2017-12-29 2018-07-10 上海乘鹰新材料有限公司 A kind of flexible, anti-pollution ultraviolet cured paint composition and preparation method thereof
CN107974193A (en) * 2018-01-06 2018-05-01 珠海东诚光固化新材料股份有限公司 A kind of ultraviolet light for glass color mirror cures pigmented finiss and its application

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