CN116376384B - UV-LED cured high-performance environment-friendly coating - Google Patents

UV-LED cured high-performance environment-friendly coating Download PDF

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CN116376384B
CN116376384B CN202310434722.7A CN202310434722A CN116376384B CN 116376384 B CN116376384 B CN 116376384B CN 202310434722 A CN202310434722 A CN 202310434722A CN 116376384 B CN116376384 B CN 116376384B
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coating
acrylic resin
cured high
aminophenyl
led
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CN116376384A (en
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刘刚
徐欢
王凯华
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Jiangsu Youngeree New Material Corp
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a UV-LED cured high-performance environment-friendly coating, which belongs to the technical field of coatings and comprises the following components: acrylic resin, photosensitive resin, ethyl acetate, butyl acetate, cellulose acetate butyrate, a mixed photoinitiator, an auxiliary agent and an alcohol solvent. Through mutual coordination of the components, the coating has the characteristics of good light transmittance, high hardness and strong adhesive force, can be rapidly cured into a film, has excellent corrosion resistance, UV yellowing resistance and storage stability, reduces the maintenance cost of electronic products, and prolongs the service life of the products.

Description

UV-LED cured high-performance environment-friendly coating
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-performance environment-friendly UV-LED cured coating.
Background
The paint is a viscous liquid which is coated on the surface of the protected or decorated object and can form a film firmly attached to the coated object, and is usually prepared by taking resin, oil or emulsion as the main material, adding pigment, filler, corresponding auxiliary agent and the like, and using organic solvent or water. The paint has the functions of protecting, decorating, masking the defects of products and the like, and is widely applied in a plurality of fields.
With the development of electronic technology, electronic products have become an indispensable part of our lives. However, in the process of using and storing the electronic product, the electronic product is usually subjected to chemical, vibration, high dust, salt mist, humidity and high temperature environments, and the surface can be scratched, corroded, softened, deformed, mildewed and the like, so that the usability and the service life are affected, and a layer of coating is required to be coated on the surface to play a role in protection.
With the widespread use of electronic products, the use of special coatings for electronic products is increased successively, people are not only required to meet the performances of wear resistance, water resistance, moisture resistance and the like, more coatings are required to have the performances of high temperature resistance, radiation resistance, ultraviolet resistance, static resistance and the like, the appearance effect of the coatings is also improved to some extent, the pursuit of consumers on attractive appearance is met, and meanwhile, the technical innovation is also an important topic in the coating industry.
Chinese patent CN101358048 discloses an ultraviolet curing coating for surface coating of electronic products, which is prepared from the following components in percentage by weight: 10-30wt% of difunctional polyurethane acrylate, 5-40wt% of high-functional acrylate monomer hybridized into a core, 5-30wt% of high-functional acrylate monomer subjected to ethoxylation or propoxylation, 0-15wt% of monofunctional monomer, 1-6wt% of photoinitiator, 0-5wt% of modified nano material, 0.1-2wt% of flatting agent and 10-50wt% of solvent.
Chinese patent CN101831208A discloses a photo-curable coating for digital electronic products, which comprises the following components in percentage by weight: 30-60wt% of polyurethane propylene ester oligomer, 1-10wt% of auxiliary resin, 10-25wt% of reactive diluent, 15-35wt% of diluent, 0.1-1wt% of auxiliary agent and 1-10wt% of photoinitiator.
However, the existing coating still cannot have excellent adhesion, wear resistance, water resistance, ultraviolet (UV) resistance and the like, and as the severity of environmental pollution is increased, the development of environment-friendly coatings is becoming more and more important. The development of the environment-friendly coating not only can meet the requirement of environmental protection, but also has higher performance, can effectively improve the performance and service life of electronic products, and brings double benefits to the electronic industry. Therefore, the development of the high-performance environment-friendly electronic paint has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-performance environment-friendly coating cured by the UV-LED, which has high hardness, strong adhesive force, excellent corrosion resistance, UV yellowing resistance and storage stability, reduces the maintenance cost of electronic products and prolongs the service life of the products.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a UV-LED cured high-performance environment-friendly coating comprises acrylic resin, photosensitive resin, acetate, cellulose acetate butyrate, a mixed photoinitiator, an auxiliary agent and an alcohol solvent; wherein,
the acrylic resin comprises a polyester acrylate resin and an N- (4-aminophenyl) acrylamide modified acrylic resin.
The UV-LED cured high-performance environment-friendly coating containing the components has the advantages that the coating is optimized by the modified acrylic resin, and the components are matched with each other, so that the prepared coating is good in light transmittance, high in hardness and strong in adhesive force, can be rapidly cured into a film, has excellent corrosion resistance, UV yellowing resistance and storage stability, reduces the maintenance cost of electronic products, prolongs the service life of the products, and meets the environment-friendly requirement.
Preferably, in the acrylic resin, the weight ratio of the polyester acrylate resin to the N- (4-aminophenyl) acrylamide modified acrylic resin is 1:0.3-0.5, and more preferably 1:0.34-0.5.
Preferably, the polyester acrylate resin is at least one of aliphatic polyester acrylate, and more preferably at least one of polymethyl methacrylate resin, polyethyl methacrylate resin, and polybutyl methacrylate resin.
As a preferable scheme, the N- (4-aminophenyl) acrylamide modified acrylic resin is polymerized by taking acrylic acid monomer and N- (4-aminophenyl) acrylamide as raw materials.
As a further preferable embodiment, the preparation method of the N- (4-aminophenyl) acrylamide modified acrylic resin comprises the steps of:
1) Adding N- (4-aminophenyl) acrylamide and an acrylic acid monomer into a solvent, and adding an initiator and a catalyst to react to obtain an intermediate;
2) And (2) adding an acrylic acid monomer and an initiator into the intermediate obtained in the step (1) for reaction, adding a chain transfer agent, continuing the reaction for 20-50min, cooling and filtering to obtain the UV-LED cured high-performance environment-friendly coating.
In the step 1) of preparing the N- (4-aminophenyl) acrylamide modified acrylic resin,
the mass ratio of the acrylic acid monomer to the N- (4-aminophenyl) acrylamide is 1:0.5-1; and/or
The acrylic acid monomer is a mixture of acrylic acid and acrylic ester, and the mixing mass ratio is 1:0.5-2, and is more preferably 1:1-1.5; and/or
The acrylic ester is any one of ethyl acrylate, butyl acrylate, isobutyl acrylate, ethyl methacrylate, n-butyl methacrylate and isobutyl methacrylate, and more preferably ethyl methacrylate and n-butyl methacrylate; and/or
The initiator is one or more of redox initiators, and the addition amount of the initiator is 0.5-5% of the weight of the acrylic acid monomer, and is more preferably 2-4%; and/or
The catalyst is one or more of imidazole catalysts, and the addition amount of the catalyst is 0.5-3% of the weight of the acrylic acid monomer, and is more preferably 2-3%; and/or
The solvent is toluene or methylene dichloride, and the addition amount of the solvent is 100-400% of the weight of the acrylic acid monomer, and more preferably 300-400%; and/or
The reaction temperature is 90-120 ℃ and the reaction time is 0.5-2h.
In the step 2) of preparing the N- (4-aminophenyl) acrylamide modified acrylic resin,
the acrylic acid monomer is the same as the step 1), and the addition amount is 150-250% of the mass of the acrylic acid monomer in the step 1); and/or
The types of the initiator are the same as those of the step 1), and the addition amount is 100-150% of the mass of the initiator in the step 1); and/or
The chain transfer agent is one or more of aliphatic thiols, and the addition amount of the chain transfer agent is 5-8% of the total mass of the acrylic acid monomer, and is more preferably 5-6%; and/or
The reaction temperature is the same as that of the step 1), and the reaction time is 3-8h.
According to the method, the acrylic acid monomer and the N- (4-aminophenyl) acrylamide are used as raw materials to prepare the modified acrylic resin, the dosage of the N- (4-aminophenyl) acrylamide is limited, the molecular chain of the resin simultaneously contains an acrylic acid soft chain segment and a benzene ring rigid chain segment, the resin is endowed with good toughness and hardness, and the amino group in the N- (4-aminophenyl) acrylamide reacts with the carboxyl group in the acrylic acid to generate a certain amount of crosslinking structure, so that the coating can be quickly solidified into a paint film with the crosslinking structure on the surface of an object, the adhesiveness of the coating is improved, the coating is not easy to fall off in the use process, and the acid and alkali corrosion resistance of the coating is also improved; the coating is compounded with acrylate resin, so that the hardness of the coating is further increased, the storage stability of the coating is improved, the maintenance cost of electronic products is reduced, and the service life of the products is prolonged.
Preferably, the photosensitive resin is any one of phosphoric acid acrylate, urethane acrylate and aliphatic urethane acrylate, and more preferably urethane acrylate.
Preferably, the cellulose acetate butyrate is a mixture of two cellulose acetate butyrates with different butyryl contents, and the mass ratio of the two cellulose acetate butyrates is 0.5-2:1, and more preferably 1-1.5:1; the cellulose acetate butyrate has an acetyl content of 2% and a butyryl content of 46-52%, and is more preferably CAB-551-0.2 and CAB-553-0.4. The addition of two kinds of cellulose acetate butyrate with different butyryl contents can fully exert the anti-UV yellowing performance of the cellulose acetate butyrate, and when the two kinds of cellulose acetate butyrate with different butyryl contents are added in a specific proportion, the anti-UV yellowing performance is further increased, the storage stability of the paint can be increased, and the service life of the paint is prolonged.
Preferably, the mixed photoinitiator is one or more of a cleavage type photoinitiator and a cationic photoinitiator; the cleavage type photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexyl phenylketone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone, alpha-diethoxyacetophenone, alpha-dimethoxy-a-phenylacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinphenyl) -1-butanone, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide; the cationic photoinitiator is one or more of didodecyl benzene iodonium salt, long-chain alkoxy diphenyl iodonium salt, phenylthio phenyl diphenyl sulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenyl sulfonium hexafluorophosphate.
Preferably, the auxiliary agent comprises a diluent, a leveling agent and matting powder.
As a further preferable embodiment, the diluent is any one or more of triethylene glycol diacrylate, tripropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane diacrylate, dipentaerythritol pentaacrylate, and more preferably a mixture of trimethylolpropane triacrylate (TMPTA) and propylene glycol diacrylate (TPGDA), and the mixing mass ratio is 1:0.5-2, and more preferably 1:1-1.3.
As a further preferable scheme, the leveling agent is one or more of fluorocarbon leveling agent, acrylic leveling agent, polydimethylsiloxane, polymethylalkylsiloxane and organic modified polysiloxane. The leveling agent can improve the leveling property and uniformity of the coating.
As a further preferred embodiment, the matting agent is preferably one or more of a pure polyester matting resin, ultrafine silica, talc, aluminum stearate, calcium duralumin, a polymethylurea resin, a white carbon black matting agent and a silica matting agent. The matting agent is capable of reducing the surface gloss of the coating.
Preferably, the alcohol solvent is one or more of ethanol, isopropanol, ethylene glycol, propylene glycol methyl ether and propylene glycol ethyl ether; isopropyl alcohol is more preferred.
As a preferred scheme, the UV-LED cured high-performance environment-friendly coating comprises the following components in percentage by weight:
15-30% of acrylic resin, 8-15% of photosensitive resin, 12-16% of ethyl acetate, 10-20% of butyl acetate, 1-5% of cellulose acetate butyrate, 4-8% of mixed photoinitiator, 15-20% of auxiliary agent and the balance of alcohol solvent.
As a further preferred scheme, the UV-LED cured high performance environmental protection coating comprises, in weight percent:
15-30% of acrylic resin, 8-15% of photosensitive resin, 12-16% of ethyl acetate, 10-20% of butyl acetate, 1-5% of cellulose acetate butyrate, 4-8% of mixed photoinitiator, 8-12% of diluent, 0.2-1% of flatting agent, 5-10% of matting powder and the balance of alcohol solvent.
As a still further preferred scheme, the UV-LED cured high performance environmental protection coating comprises, in weight percent:
20% of acrylic resin, 10% of photosensitive resin, 15% of ethyl acetate, 15% of butyl acetate, 2% of cellulose acetate butyrate, 5% of mixed photoinitiator, 10% of diluent, 0.5% of flatting agent, 8% of matting powder and the balance of alcohol solvent.
The invention also provides a preparation method of the UV-LED cured high-performance environment-friendly coating, which comprises the following steps:
uniformly mixing acrylic resin, photosensitive resin, ethyl acetate, butyl acetate, cellulose acetate butyrate and alcohol solvents according to a proportion; and then adding the mixed photoinitiator and the auxiliary agent, and uniformly mixing to obtain the UV-LED cured high-performance environment-friendly coating.
The invention also provides a use method of the UV-LED cured high-performance environment-friendly coating, which comprises the following steps: and coating the UV-LED cured high-performance environment-friendly coating on the surface of an object in a brushing or spraying mode, and finishing the instant irradiation of light by using a UV-LED lamp.
The invention also provides application of the N- (4-aminophenyl) acrylamide modified acrylic resin in preparing the UV-LED cured high-performance environment-friendly coating.
The beneficial effects are that:
the beneficial effects of the invention are as follows: the invention provides a UV-LED cured high-performance environment-friendly coating which comprises acrylic resin, photosensitive resin, ethyl acetate, butyl acetate, cellulose acetate butyrate, a mixed photoinitiator, an auxiliary agent and an alcohol solvent, wherein the components in the coating have good compatibility, the coating has good light transmittance and strong adhesive force under the combined action of the components, can be rapidly cured into a film, has excellent corrosion resistance and storage stability, reduces the maintenance cost of electronic products, prolongs the service life of the products and meets the environment-friendly requirement; the N- (4-aminophenyl) acrylamide modified acrylic resin is added into the paint to optimize the paint, so that the hardness, adhesive force and acid and alkali corrosion resistance of the final product paint can be effectively improved; the paint is also added with two kinds of cellulose acetate butyrate with different butyryl contents, so that the UV yellowing resistance of the cellulose acetate butyrate can be fully exerted, when the two kinds of cellulose acetate butyrate with different butyryl contents are added in a specific proportion, the UV yellowing resistance is further increased, the storage stability of the paint can be increased, the paint can still keep higher performance after long-time storage, and the service life is prolonged.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely exemplary of the scope of the claimed invention and one skilled in the art can make various changes and modifications to the invention of the present application in light of the disclosure, which should also fall within the scope of the claimed invention.
As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably without the use of quantitative terms. Thus, for example, a component comprising "an" additive may be interpreted to mean that the component comprises "one or more" additives.
Where a composition is described as comprising or including a particular component, it is contemplated that optional components not referred to by the present invention are not excluded from the composition, and that the composition may consist or consist of the recited components, or where a method is described as comprising or including a particular process step, it is contemplated that optional process steps not referred to by the present invention are not excluded from the method, and that the method may consist or consist of the recited process steps.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
The terms "comprising" and "including" and variations thereof, when appearing in the specification and claims, are not intended to be limiting. The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits in certain circumstances. However, other embodiments may be preferred under the same or other circumstances. In addition, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
The invention provides a UV-LED cured high-performance environment-friendly coating, which comprises the following components in percentage by weight: 15-30% of acrylic resin, 8-15% of photosensitive resin, 12-16% of ethyl acetate, 10-20% of butyl acetate, 1-5% of cellulose acetate butyrate, 4-8% of mixed photoinitiator, 8-12% of diluent, 0.2-1% of flatting agent, 5-10% of matting powder and the balance of alcohol solvent.
The UV-LED cured high-performance environment-friendly coating is prepared by the following method: mixing acrylic resin, photosensitive resin, ethyl acetate, butyl acetate, cellulose acetate butyrate and alcohol solvent according to a proportion, and uniformly stirring; and then adding the mixed photoinitiator and the auxiliary agent for mixing, and stirring uniformly at a high speed to obtain the high-performance environment-friendly coating cured by the UV-LED.
The application method of the UV-LED cured high-performance environment-friendly coating comprises the following steps: the UV-LED cured high-performance environment-friendly coating is coated on the surface of an object in a brushing or spraying mode, the object is polished in advance and dedusted completely before being coated, and the UV-LED lamp is used for irradiating light for curing immediately after the brushing is completed.
The UV-LED curing equipment used was:
model: a009;
power: 16W/cm 2 ；
Dominant wavelength: 395nm;
irradiation height: 10cm;
illumination intensity: 100%.
The invention is further illustrated by means of the following specific examples. The various chemical reagents used in the examples of the present invention were obtained by conventional commercial means unless otherwise specified.
Example 1
A UV-LED cured high-performance environment-friendly coating comprises the following components in percentage by weight:
20% of acrylic resin, 10% of polyurethane acrylic ester, 15% of ethyl acetate, 15% of butyl acetate, 2% of cellulose acetate butyrate, 2% of 2-hydroxy-2-methyl-1-phenylpropione, 3% of 1-hydroxycyclohexyl benzophenone, 5% of TMPTA, 5% of TPGDA, 0.5% of polyether modified polydimethylsiloxane, 8% of calcium duraluminate and 14.5% of isopropanol.
The acrylic resin is a mixture of the first resin and the second resin, and the mixing weight ratio is 1:0.42; the first resin is a polyethylmethacrylate resin.
The cellulose acetate butyrate is CAB-551-0.2 and CAB-553-0.4 of 1.2:1.
The second resin is N- (4-aminophenyl) acrylamide modified acrylic resin and is prepared by the following method:
1.9kg of N- (4-aminophenyl) acrylamide, 0.9kg of acrylic acid and 1.7kg of ethyl methacrylate are added into 10kg of toluene, 0.04kg of benzoyl peroxide and 0.04kg of N, N-diethylaniline are added, 0.07kg of 1-methylimidazole are added, and the temperature is raised to 100 ℃ for reaction for 1.5 hours to obtain an intermediate; adding 1.8kg of acrylic acid, 3.4kg of ethyl methacrylate, 0.05kg of benzoyl peroxide and 0.05kg of N, N-diethylaniline, continuously reacting for 5 hours, adding 0.48kg of dodecyl mercaptan, continuously reacting for 40 minutes, cooling and filtering to obtain the catalyst.
The UV-LED cured high-performance environment-friendly coating is prepared by the following method: mixing acrylic resin, polyurethane acrylic ester, ethyl acetate, butyl acetate, cellulose acetate butyrate and isopropanol according to a proportion, and uniformly stirring; and then adding 2-hydroxy-2-methyl-1-phenylpropion, 1-hydroxycyclohexyl benzophenone, TMPTA, TPGDA, polyether modified polydimethylsiloxane and calcium duraluminate, mixing, and stirring uniformly to obtain the UV-LED cured high-performance environment-friendly coating.
Example 2
The UV-LED cured high-performance environment-friendly coating has the same component content as that of the example 1, except that the addition amount of N- (4-aminophenyl) acrylamide in the preparation process of N- (4-aminophenyl) acrylamide modified acrylic resin is 1.3kg, and the rest is the same as that of the example 1.
Example 3
The UV-LED cured high-performance environment-friendly coating has the same component content as in example 1, except that in the preparation process of N- (4-aminophenyl) acrylamide modified acrylic resin, the addition amount of N- (4-aminophenyl) acrylamide is 2.7kg, and the rest is the same as in example 1.
Example 4
The UV-LED cured high-performance environment-friendly coating has the components with the content basically same as that of the example 1, except that the acrylic resin is N- (4-aminophenyl) acrylamide modified acrylic resin and butyl acrylate resin with the mixing weight ratio of 0.34:1, and the rest is the same as that of the example 1.
Example 5
The UV-LED cured high-performance environment-friendly coating has the components with the content basically same as that of the example 1, except that the acrylic resin is N- (4-aminophenyl) acrylamide modified acrylic resin and butyl acrylate resin with the mixing weight ratio of 0.5:1, and the rest is the same as that of the example 1.
Example 6
The UV-LED cured high-performance environment-friendly coating has the components with the content basically same as that of the example 1, except that cellulose acetate butyrate is CAB-551-0.2 and CAB-553-0.4 in the mass ratio of 0.8:1, and the rest is the same as that of the example 1.
Example 7
The UV-LED cured high-performance environment-friendly coating has the components with the content substantially the same as that of the example 1, except that cellulose acetate butyrate is CAB-551-0.2 and CAB-553-0.4 in the mass ratio of 1:1, and the rest is the same as that of the example 1.
Example 8
The UV-LED cured high-performance environment-friendly coating has the components with the content basically same as that of the example 1, except that cellulose acetate butyrate is CAB-551-0.2 and CAB-553-0.4 in the mass ratio of 1.5:1, and the rest is the same as that of the example 1.
Example 9
The UV-LED cured high-performance environment-friendly coating has the components with the content basically same as that of the example 1, except that cellulose acetate butyrate is CAB-551-0.2 and CAB-553-0.4 in the mass ratio of 2:1, and the rest is the same as that of the example 1.
Comparative example 1
The UV-LED cured high-performance environment-friendly coating has the same component content as that of the example 1, except that N- (4-aminophenyl) acrylamide modified acrylic resin is replaced by acrylic resin, and the acrylic resin is prepared by the following method:
1.9kg of styrene, 0.91kg of acrylic acid and 1.7kg of ethyl methacrylate are added into 10kg of toluene, 0.04kg of benzoyl peroxide and 0.04kg of N, N-diethylaniline are added, 0.07kg of 1-methylimidazole are added, and the temperature is raised to 100 ℃ for reaction for 1.5 hours to obtain an intermediate; adding 1.8kg of acrylic acid, 3.4kg of ethyl methacrylate, 0.05kg of benzoyl peroxide and 0.05kg of N, N-diethylaniline, continuously reacting for 5 hours, adding 0.48kg of dodecyl mercaptan, continuously reacting for 40 minutes, cooling and filtering to obtain the catalyst.
The remainder was the same as in example 1.
Comparative example 2
The UV-LED cured high-performance environment-friendly coating has the components with the content basically same as that of the embodiment 1, except that the acrylic resin is butyl acrylate resin, namely N- (4-aminophenyl) acrylamide modified acrylic resin is not contained, and the rest is the same as that of the embodiment 1.
Comparative example 3
A UV-LED cured high-performance environment-friendly coating has the same component content as that of the embodiment 1, except that cellulose acetate butyrate is CAB-551-0.2, and the rest is the same as that of the embodiment 1.
Comparative example 4
A UV-LED cured high-performance environment-friendly coating has the same component content as in example 1, except that cellulose acetate butyrate is CAB-553-0.4, and the rest is the same as in example 1.
Example 14
The UV-LED cured high-performance environment-friendly coating of the examples 1-9 and the comparative examples 1-4 is prepared by mixing the materials according to the proportion, and then the high-performance environment-friendly coating cured by the UV-LED is prepared by a spraying method according to the proportion of 50g/m 2 The coating amount of (2) is sprayed on the surface of a switch panel which is polished in advance and dedusted, and the coating is immediately cured into a film by using an LED-UV lamp to irradiate light after finishing the coating, so that the coating has a matte effect and does not appearNo orange peel, particles and shrinkage cavity phenomenon, and then the following detection is carried out.
Detection of
The UV-LED cured high-performance environment-friendly paint prepared in each example and comparative example is sprayed on a switch panel, and then the following performance test is carried out;
detecting one step,
Hardness: according to GB/T6739-2006 standard, pencil hardness is adopted for detection, and the detection result is shown in Table 1;
adhesion force: detecting according to GB/T9286-2021 standard;
the results are shown in Table 1.
TABLE 1 coating hardness, adhesion
Group of Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Hardness of 4H 4H 4H 2H 2H
Adhesion force 5B 5B 5B 4B 3B
Table 1 shows the effect of N- (4-aminophenyl) acrylamide-modified acrylic resin on the hardness of the coating, as shown in Table 1, the coating hardness of examples 1-3 was 4H, whereas the N- (4-aminophenyl) acrylamide-modified acrylic resin of comparative example 1 did not contain X segments, and the resulting coating had a hardness significantly lower than that of examples 1-3, and the comparative example 2 did not contain a modified epoxy acrylate tree, and the resulting coating had a hardness similarly lower than that of examples 1-3, and it was found that the presence of N- (4-aminophenyl) acrylamide in the N- (4-aminophenyl) acrylamide-modified acrylic resin was optimized for the coating, and the hardness was improved. Likewise, the adhesion of the coatings obtained in comparative examples 1 and 2 was also lower than in examples 1-3, indicating that the presence of N- (4-aminophenyl) acrylamide in the modified acrylic resin helps to promote adhesion of the coating.
And (2) detection of second and corrosion resistance: according to GB/T1763-1989, the acid and alkali corrosion resistance of the paint was judged by measuring the time when the paint was peeled off, foamed and changed in color in 5% HCl solution and 5% NaOH solution, and the test results are shown in Table 2.
Surface and corrosion resistance
Table 2 shows the time when the paint is respectively soaked in HCl solution and NaOH solution to fall off, foam and change color, and observing Table 2, the paint obtained in the preferred embodiment 1 is foamed after being soaked in 5% NaOH solution for 188 hours, the foaming phenomenon occurs after being soaked in 5% HCl solution for 142 hours, and the time when the paint obtained in the embodiments 1-5 fall off, foam and change color is above 150 hours and 135 hours, which indicates that the paint provided by the invention has excellent acid and alkali corrosion resistance; comparative example 1 and comparative example 1 show that the presence of N- (4-aminophenyl) acrylamide in the N- (4-aminophenyl) acrylamide modified acrylic resin has the advantage of improving the acid and alkali corrosion resistance of the coating; in comparative examples 1 and 2, the N- (4-aminophenyl) acrylamide-modified acrylic resin was not added in comparative example 2, and it was found that the use of a certain amount of the N- (4-aminophenyl) acrylamide-modified acrylic resin and the acrylic resin in combination had a significant effect on the corrosion resistance of the paint.
Detection of three, UV yellowing resistance detection: according to GB/T1865-2009, performing artificial weathering and artificial radiation exposure experiments, and detecting a yellowing value (total color difference) delta E of the paint after 168 hours under UVA illumination; the test results are shown in Table 3.
TABLE 3 UV yellowing resistance
Group of Example 1 Example 6 Example 7 Example 8 Example 9 Comparative example 3 Comparative example 4
ΔE 0.2 0.7 0.3 0.2 0.5 1.3 1.2
Table 3 shows the effect of the composition of cellulose acetate butyrate on the UV yellowing resistance of the coating, and from the data in Table 2, it is clear that the coating prepared with two cellulose acetate butyrates has a more excellent UV yellowing resistance than the coating prepared with a single cellulose acetate butyrates, and that the two cellulose acetate butyrates, when added in a specific ratio (1:1-1.5), give the coating a more excellent yellowing resistance.
And (3) detection of storage stability: referring to GB/T6753.3-1986 standard, the adhesive force of the paint after being stored for 60 days at 50+/-2 ℃ is tested, and whether caking, agglomeration, mildew and the like occur or not is observed; the test results are shown in Table 4.
TABLE 4 storage stability
Group of Appearance of Adhesion force
Example 1 No caking, agglomeration and mildew 5B
Example 4 No caking, agglomeration and mildew 5B
Example 5 No caking, agglomeration and mildew 5B
Comparative example 1 Caking occurred 2B
Comparative example 2 Agglomeration occurs 2B
Comparative example Caking occurred 3B
Comparative example Caking occurred 2B
Observing Table 4, the coatings obtained in examples 1, 4 and 5 show no caking, agglomeration and mildew after being stored for 30 days at 50+/-2 ℃, and the adhesive force is still 5B, so that the high-performance environment-friendly coating cured by the UV-LED prepared by the invention has excellent storage stability and can be stored for a long time. The paint of comparative example 1 was agglomerated after 30 days of storage at 50.+ -. 2 ℃ and the comparative example 2 was agglomerated, which revealed that the use of N- (4-aminophenyl) acrylamide-modified acrylic resin in combination with acrylic resin had a remarkable gain in the storage stability of the paint. It can also be seen that caking occurred in both of the comparisons 3, 4 and the adhesion was reduced from original 5B to 3B, 2B, thus it was found that when two cellulose acetate butyrates were added in a specific ratio (1:1-1.5), a more excellent storage stability was obtained for the coating.
In summary, the invention provides a UV-LED cured high-performance environment-friendly coating, which has the advantages of strong adhesive force, excellent corrosion resistance, UV yellowing resistance and storage stability, reduced maintenance cost of electronic products and prolonged service life of the products through the optimization effect of N- (4-aminophenyl) acrylamide modified acrylic resin and bi-component cellulose acetate butyrate.
It should be understood that the details of the preparation method are not described in detail in the above description, and are common parameters that can be easily conceived by those skilled in the art, so that the detailed description thereof may be omitted.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (9)

1. The UV-LED cured high-performance environment-friendly coating is characterized by comprising the following components in percentage by weight: 15-30% of acrylic resin, 8-15% of photosensitive resin, 12-16% of ethyl acetate, 10-20% of butyl acetate, 1-5% of cellulose acetate butyrate, 4-8% of mixed photoinitiator, 15-20% of auxiliary agent and the balance of alcohol solvent;
wherein the acrylic resin comprises polyester acrylic resin and N- (4-aminophenyl) acrylamide modified acrylic resin, and the mass ratio of the polyester acrylic resin to the N- (4-aminophenyl) acrylamide modified acrylic resin is 1:0.3-0.5;
the preparation method of the N- (4-aminophenyl) acrylamide modified acrylic resin comprises the following steps:
1) Adding N- (4-aminophenyl) acrylamide and an acrylic acid monomer into a solvent, and adding an initiator and a catalyst to react to obtain an intermediate;
2) Adding an acrylic acid monomer and an initiator into the intermediate obtained in the step 1) for reaction, adding a chain transfer agent, continuing the reaction, cooling and filtering to obtain the UV-LED cured high-performance environment-friendly coating;
in the step 1), the mass ratio of the acrylic acid monomer to the N- (4-aminophenyl) acrylamide is 1:0.5-1;
in the step 2), the addition amount of the acrylic acid monomer is 150-250% of the mass of the acrylic acid monomer in the step 1);
in the steps 1) and 2), the acrylic acid monomer is a mixture of acrylic acid and acrylic ester, and the mixing mass ratio is 1:0.5-2.
2. The UV-LED cured high performance environmental protection coating according to claim 1, wherein the mass ratio of polyester acrylate resin to N- (4-aminophenyl) acrylamide modified acrylic resin in the acrylic resin is 1:0.34-0.5.
3. The UV-LED cured high performance environmental protection coating of claim 1, wherein the polyester acrylate resin is at least one of aliphatic polyester acrylates.
4. The UV-LED cured high-performance environment-friendly coating is characterized in that the N- (4-aminophenyl) acrylamide modified acrylic resin is polymerized by taking acrylic acid monomer and N- (4-aminophenyl) acrylamide as raw materials.
5. The UV-LED cured high performance environmental protection coating according to claim 1, wherein the acrylate is any one of ethyl acrylate, butyl acrylate, isobutyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate.
6. The UV-LED cured high performance environmental protection coating according to claim 1, wherein the cellulose acetate butyrate is a mixture of two cellulose acetate butyrates with different butyryl contents, the mass ratio of the two cellulose acetate butyrates with different butyryl contents is 0.5-2:1; the acetyl content in cellulose acetate butyrate is 2%, and the butyryl content is 46-52%.
7. The UV-LED cured high performance environmental coating of claim 1, comprising, in weight percent:
15-30% of acrylic resin, 8-15% of photosensitive resin, 12-16% of ethyl acetate, 10-20% of butyl acetate, 1-5% of cellulose acetate butyrate, 4-8% of mixed photoinitiator, 8-12% of diluent, 0.2-1% of flatting agent, 5-10% of matting powder and the balance of alcohol solvent.
8. A method for preparing the UV-LED cured high performance environmental protection coating according to any one of claims 1-7, comprising the steps of:
mixing acrylic resin, photosensitive resin, ethyl acetate, butyl acetate and cellulose acetate butyrate according to a proportion, and uniformly mixing with an alcohol solvent; and then adding the mixed photoinitiator and the auxiliary agent, and uniformly mixing to obtain the UV-LED cured high-performance environment-friendly coating.
9. A method of using the UV-LED cured high performance environmental coating of any one of claims 1-7, comprising:
and coating the UV-LED cured high-performance environment-friendly coating on the surface of an object in a brushing or spraying mode, and immediately irradiating the UV-LED lamp for photo-curing.
CN202310434722.7A 2023-04-21 2023-04-21 UV-LED cured high-performance environment-friendly coating Active CN116376384B (en)

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