CN112280440A - UV adhesive coating, preparation method thereof and preparation method of coated workpiece - Google Patents
UV adhesive coating, preparation method thereof and preparation method of coated workpiece Download PDFInfo
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- CN112280440A CN112280440A CN201910679029.XA CN201910679029A CN112280440A CN 112280440 A CN112280440 A CN 112280440A CN 201910679029 A CN201910679029 A CN 201910679029A CN 112280440 A CN112280440 A CN 112280440A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
- 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
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
- B05D2502/005—Acrylic polymers modified
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2504/00—Epoxy polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2602/00—Organic fillers
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Abstract
The invention discloses a UV adhesive coating, a preparation method thereof and a preparation method of a coated workpiece, and belongs to the field of high polymer materials. The coating comprises the following components in percentage by weight: 35-75 wt% of modified epoxy acrylate resin, 10-55 wt% of modified pure acrylate resin, 5-25 wt% of reaction monomer, 0.1-5 wt% of photoinitiator and 0.1-5 wt% of auxiliary agent. The coating provided by the invention has excellent adhesive force, chemical resistance, high temperature resistance and water resistance, and avoids the phenomena of cracking, bubbling or falling off of a bonded interface and the like in the use process of the coating.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a UV adhesive coating and a preparation method thereof, and a preparation method of a coated workpiece.
Background
The Ultraviolet light curing glue (also known as shadowless glue, Ultraviolet glue for short) coating has the advantages of environmental protection, high efficiency and excellent performance, and has permeated into various fields of industry, agriculture, traffic, national defense and daily life. With the development of science and technology, the demand of UV adhesive coating is also increasing. In the conventional art, a UV glue coating is commonly used as an adhesive, for example, for fixing the lamp trim parts of a Light Emitting Diode (LED).
The related art provides a UV glue coating including: urethane acrylate, acrylate reactive diluent, curing agent, photoinitiator and auxiliary agent.
The inventors found that the related art has at least the following problems:
the UV adhesive coating has poor water resistance, chemical resistance and high temperature resistance, and particularly when the UV adhesive coating is used in a high-temperature environment, for example, when an LED lamp interior part is fixed, the form of the UV adhesive coating can be converted in the high-temperature environment, and the paint film of a bonded interface cracks, bubbles or falls off due to different shrinkage rates of the metal interior part and the UV adhesive coating.
Disclosure of Invention
The embodiment of the invention provides a UV adhesive coating, a preparation method thereof and a preparation method of a coated workpiece, which can solve the technical problems. The technical scheme is as follows:
in one aspect, the UV glue coating is provided, and comprises the following components in percentage by weight:
35-75 wt% of modified epoxy acrylate resin, 10-55 wt% of modified pure acrylate resin, 5-25 wt% of reaction monomer, 0.1-5 wt% of photoinitiator and 0.1-5 wt% of auxiliary agent.
In one possible implementation, the modified neat acrylate resin is selected from one or more of a carboxyl-functional modified neat acrylate resin, a double bond-functional modified neat acrylate resin, or an epoxy-functional modified neat acrylate resin.
In one possible implementation, the modified epoxy acrylate resin includes: one or more of novolac epoxy acrylate resin, bisphenol A epoxy acrylate resin and bisphenol F epoxy acrylate resin.
In one possible implementation, the photoinitiator is a free radical polymerization photoinitiator.
In one possible implementation, the radical polymerization photoinitiator includes: 2,4,6 trimethyl benzoyl diphenyl phosphine oxide, 2-hydroxy-methyl phenyl propane-1-ketone and isopropyl thioxanthone.
In one possible implementation, the reactive monomer comprises: one or more of pentaerythritol triacrylate, 2-hydroxyethyl methacrylate, and propoxylated glycerol triacrylate.
In one possible implementation, the auxiliary agent includes: one or more of adhesion promoter, defoaming agent, wetting agent and flatting agent.
In one possible implementation manner, the adhesion promoter includes phosphate ester acrylate, the defoamer is one or more of polyoxyethylene, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane, and the leveling agent is an acrylate leveling agent.
In another aspect, there is provided a method for preparing a UV glue coating, the method being used for preparing any one of the above coatings, the method comprising:
according to the weight percentage of each component, adding modified epoxy acrylate resin, modified pure acrylate resin, reaction monomer and photoinitiator in sequence, and stirring to enable the particle size of reactants in a reaction system to reach a reference value;
adding a reaction auxiliary agent, and uniformly stirring to obtain the UV adhesive coating.
In still another aspect, there is provided a method for producing a coated workpiece including any one of the above-described coatings, the method including:
obtaining a workpiece to be coated, and coating the coating on the workpiece to be coated to obtain a first coated workpiece;
and carrying out ultraviolet light curing on the first coated workpiece to obtain the coated workpiece containing the coating.
In one possible implementation manner, the thickness of the coating on the workpiece to be coated is 50-100 microns, the energy of ultraviolet curing is 500-700mJ/cm, and the viscosity of the coating is 1000 ± 300 mpa-sec/25 ℃.
The beneficial effects brought by the UV adhesive coating at least comprise:
the UV adhesive coating disclosed by the invention is based on the epoxy group in the modified epoxy acrylate resin, so that the coating has good waterproofness, and the bonding force and the flexibility of the coating are enhanced by the modified pure acrylate resin; the coating provided by the embodiment of the invention has excellent adhesive force, chemical resistance, high temperature resistance and water resistance by adding the auxiliary agent and compounding with the components in a synergistic manner, and avoids the phenomena of cracking, bubbling or falling off of a bonded interface in the use process of the coating.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a UV adhesive coating according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a coated workpiece according to an embodiment of the present invention.
Detailed Description
Unless defined otherwise, all technical terms used in the examples of the present invention have the same meaning as commonly understood by one of ordinary skill in the art.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The Ultraviolet light curing glue (also known as shadowless glue, Ultraviolet glue for short) coating has the advantages of environmental protection, high efficiency and excellent performance, and has permeated into various fields of industry, agriculture, traffic, national defense and daily life. With the development of science and technology, the demand of UV adhesive coating is also increasing. In the conventional art, a UV glue coating is commonly used as an adhesive, for example, for fixing the lamp trim parts of a Light Emitting Diode (LED). However, because the UV glue coating has poor water resistance, chemical resistance and high temperature resistance, especially when used in high temperature environments, such as fixing LED lamp interior parts, the form of the UV glue coating is transformed in the high temperature environment, and the paint film on the adhered interface cracks, bubbles or falls off due to the different shrinkage rates of the metal lamp interior and the UV glue coating. When the UV adhesive film falls off, the preparation raw materials can generate cracking reaction, and further generate irritant gases such as aldehydes or sulfur and the like, so that the health of a human body is influenced or the environment is polluted. In view of this, the embodiment of the present invention provides a UV glue coating.
The UV adhesive coating comprises the following components in percentage by weight:
35-75 wt% of modified epoxy acrylate resin, 10-55 wt% of modified pure acrylate resin, 5-25 wt% of reaction monomer, 0.1-5 wt% of photoinitiator and 0.1-5 wt% of auxiliary agent.
The modified pure acrylate resin comprises: carboxyl functional modified pure acrylate resin or double bond functional modified pure acrylate resin or epoxy modified pure acrylate resin.
The coating provided by the embodiment of the invention at least has the following technical effects:
the coating provided by the embodiment of the invention is based on the epoxy group in the modified epoxy acrylate resin, so that the coating has good waterproofness, and the bonding force and the flexibility of the coating are enhanced by modifying the pure acrylate resin; the coating provided by the embodiment of the invention has excellent adhesive force, chemical resistance, high temperature resistance and water resistance by adding the auxiliary agent and compounding with the components in a synergistic manner, and avoids the phenomena of cracking, bubbling or falling off of a bonded interface in the use process of the coating.
Meanwhile, the UV adhesive coating is an ultraviolet curing coating, has good dripping effect, smooth surface, no color, transparency, low energy consumption, high environmental protection and high adhesion, and particularly has excellent high temperature resistance, can be subjected to high-temperature baking regardless of the different shrinkage rates of metal and plastic, does not fall off an adherend, and still has good adhesion even after being subjected to high-temperature baking; moreover, the coating has good water resistance; the coating meets the requirements of heavy metal, phthalate and polycyclic aromatic hydrocarbon on safety and environmental protection, has small pollution to the environment and low toxicity to constructors, and protects the safety of manual production. The coating of the present invention is free of volatile solvents. Less harmful volatiles are absorbed by workers when operating. Meanwhile, the pollution to the atmosphere is reduced, and the method has excellent environmental friendliness.
As an example, the weight percentage of the modified epoxy acrylate resin provided by the embodiment of the present invention may be 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, or the like.
The weight percentage of the modified pure acrylate resin may be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, or the like.
The weight percent of reactive monomer may be 5 wt%, 15 wt%, 20 wt%, or 25 wt%, etc.
The weight percentage of photoinitiator may be 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 9, 9.5, or 10 weight percent.
The weight percentage of the adjuvant may be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 9 wt%, 9.5 wt%, or 10 wt%.
The modified pure acrylate resin provided by the embodiment of the invention can be selected from one or more of the following components according to the commodity code or name: one or more of Guangdong Haohui new material company HA502, Sartomerin company SARTOMERCN146, Changxing chemical material Zhuhai company DR-A870, Guangzhou five-element materials science and technology company F707H, and Dissman Chinese company Agisyn9790 dpm.
In some embodiments of the invention, the carboxy-functionally modified pure acrylate resin is selected from Hakken chemical materials, Dow corporation DR-A870.
In one possible implementation, the modified neat acrylate resin is selected from one or more of a carboxyl-functional modified neat acrylate resin, a double bond-functional modified neat acrylate resin, or an epoxy-modified neat acrylate resin.
The carboxyl functional group, the double bond functional group or the epoxy functional group in the pure acrylate resin is modified through modifying the carboxyl functional group or the double bond functional group in the pure acrylate resin and the epoxy functional group in the pure acrylate resin.
The modified pure acrylate resin can be single carboxyl functional modified pure acrylate resin or double bond functional modified pure acrylate resin or epoxy modified pure acrylate resin, or the combination of carboxyl functional modified pure acrylate resin and double bond functional modified pure acrylate resin, or the combination of carboxyl functional modified pure acrylate resin and epoxy modified pure acrylate resin, or the combination of epoxy modified pure acrylate resin and double bond functional modified pure acrylate resin.
When the modified neat acrylate resin is a combination of a carboxyl-functional modified neat acrylate resin and a double bond-functional modified neat acrylate resin, the molar ratio of the two may be 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, and the like.
When the modified neat acrylate resin is a combination of a carboxyl-functional modified neat acrylate resin and an epoxy-modified neat acrylate resin, the molar ratio of the two may be 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, and the like.
When the modified neat acrylate resin is a combination of an epoxy-modified neat acrylate resin and a double bond functional modified neat acrylate resin, the molar ratio of the two may be 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, and the like. The embodiment of the present invention does not limit the ratio of the above-mentioned components when they are combined.
In one possible implementation, the coating comprises the following components in percentage by weight:
35-75 wt% of modified epoxy acrylate resin, 10-55 wt% of modified pure acrylate resin, 5-25 wt% of reaction monomer, 0.1-10 wt% of photoinitiator and 0.1-10 wt% of auxiliary agent.
In one possible implementation, the coating comprises the following components in percentage by weight:
40-70 wt% of modified epoxy acrylate resin, 10-50 wt% of modified pure acrylate resin, 5-20 wt% of reaction monomer, 0.1-5 wt% of photoinitiator and 0.1-5 wt% of auxiliary agent.
In one possible implementation, the coating comprises the following components in percentage by weight:
35-65 wt% of modified epoxy acrylate resin, 15-40 wt% of modified pure acrylate resin, 10-20 wt% of reaction monomer, 0.3-5 wt% of photoinitiator and 0.3-5 wt% of auxiliary agent.
In one possible implementation, the coating comprises the following components in percentage by weight:
40-65 wt% of modified epoxy acrylate resin, 15-35 wt% of modified pure acrylate resin, 12-20 wt% of reaction monomer, 0.5-5 wt% of photoinitiator and 0.5-5 wt% of auxiliary agent.
In one possible implementation, the coating comprises the following components in percentage by weight:
40-60 wt% of modified epoxy acrylate resin, 10-35 wt% of modified pure acrylate resin, 14-20 wt% of reaction monomer, 0.5-3 wt% of photoinitiator and 1-5 wt% of auxiliary agent.
In one possible implementation, the coating comprises the following components in percentage by weight:
45-65 wt% of modified epoxy acrylate resin, 10-45 wt% of modified pure acrylate resin, 15-20 wt% of reaction monomer, 0.2-3 wt% of photoinitiator and 2-5 wt% of auxiliary agent.
In one possible implementation, the modified epoxy acrylate resin includes: one or more of novolac epoxy acrylate resin, bisphenol A epoxy acrylate resin and bisphenol F epoxy acrylate resin.
The novolac epoxy acrylate resin provided by the embodiment of the invention can be selected from the following components under the trade names or code numbers: one or more of Guangdong Boxing new material science and technology Limited B-191A, Dismann China Limited Agisyn9750, Shadoma Guangzhou Limited CN2003, Meiyuan Shenzhen chemical Limited SC6300, Shanghai Santong material science and technology Limited SE 1636.
In some embodiments of the present invention, the novolac epoxy acrylate resin is selected from shanghai santong materials science and technology limited SE 1636.
The modified epoxy acrylate resin provided by the embodiment of the invention comprises a phenolic epoxy group, a bisphenol AH epoxy group and a bisphenol F epoxy group, so that the coating containing the modified epoxy acrylate resin has good water resistance.
As an example, the modified epoxy acrylate resin may be a novolac epoxy acrylate resin alone, a bisphenol a epoxy acrylate resin, or a bisphenol F type epoxy acrylate resin; the epoxy resin may be a combination of a novolac epoxy acrylate resin and a bisphenol a epoxy acrylate resin, a combination of a novolac epoxy acrylate resin and a bisphenol F epoxy acrylate resin, a combination of a bisphenol a epoxy acrylate resin and a bisphenol F epoxy acrylate resin, or a combination of a novolac epoxy acrylate resin, a bisphenol a epoxy acrylate resin, and a bisphenol F epoxy acrylate resin. Type of combination embodiments of the present invention are not limited.
As an example, when the modified epoxy acrylate resin is a combination of both a novolac epoxy acrylate resin and a bisphenol a epoxy acrylate resin, the molar ratio of the two may be: 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. The embodiment of the invention does not limit the proportion of the combination of the novolac epoxy acrylate resin and the bisphenol A epoxy acrylate resin.
When the modified epoxy acrylate resin is a combination of a novolac epoxy acrylate resin and a bisphenol F type epoxy acrylate resin, the molar ratio of the two may be: 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. The embodiment of the invention does not limit the proportion of the combination of the novolac epoxy acrylate resin and the bisphenol F epoxy acrylate resin.
When the modified epoxy acrylate resin is a combination of both a bisphenol a epoxy acrylate resin and a bisphenol F type epoxy acrylate resin, the molar ratio of the two may be: 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. The embodiment of the present invention does not limit the ratio of the combination of the bisphenol a epoxy acrylate resin and the bisphenol F epoxy acrylate resin.
When the modified epoxy acrylate resin is a combination of novolac epoxy acrylate resin, bisphenol a epoxy acrylate resin and bisphenol F epoxy acrylate resin, the molar ratio of the three may be: 1:0.1:0.6, 1:0.2:0.6, 1:0.3:0.6, 1:0.4:0.6, 1:0.5:0.6, 1:0.6:0.6, 1:0.7:0.6, 1:0.8:0.6, etc. The embodiment of the invention does not limit the combination proportion of the novolac epoxy acrylate resin, the bisphenol A epoxy acrylate resin and the bisphenol F epoxy acrylate resin.
In one possible implementation, the photoinitiator is a free radical polymerization photoinitiator.
Photoinitiators are classified into two categories, radical polymerization photoinitiators and cationic polymerization photoinitiators, according to a photolysis mechanism. The embodiment of the invention selects the free radical polymerization photoinitiator, the free radical polymerization photoinitiator has certain light absorption capacity in an ultraviolet region (250-400 nm) or a visible light region (400-800 nm), after absorbing light energy, the molecules of the free radical polymerization photoinitiator are transited from a ground state to an excited singlet state, and are transited to an excited triplet state through intersystem crossing, and after the excited singlet state or the excited triplet state is subjected to monomolecular or bimolecular chemical action, active fragments capable of initiating the polymerization of reaction monomers are generated, so that the reaction monomers are subjected to polymerization reaction.
In one possible implementation, the free radical polymerization photoinitiator is an acylphosphine oxide based photoinitiator.
In one possible implementation, the acylphosphine oxide-based photoinitiator includes: 2,4,6 trimethyl benzoyl diphenyl phosphine oxide, 2-hydroxy-methyl phenyl propane-1-ketone and isopropyl thioxanthone.
The acylphosphine oxide photoinitiator may be any one of 2,4,6 trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-methylphenylpropane-1-one, and isopropylthioxanthone, or may be a combination of 2,4,6 trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-methylphenylpropane-1-one; it may also be a combination of both 2,4,6 trimethylbenzoyl-diphenylphosphine oxide and isopropylthioxanthone; or a combination of both 2-hydroxy-methylphenylpropane-1-one and isopropyl thioxanthone; the compound may also be a combination of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-methylphenylpropane-1-one, and isopropylthioxanthone.
When the acylphosphine oxide photoinitiator is a combination of 2,4,6 trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-methylphenylpropane-1-one, the molar ratio of the two may be: 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. The proportion of the combination of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 2-hydroxy-methylphenylpropane-1-one in the examples of the present invention is not limited.
When the acylphosphine oxide photoinitiator is a combination of 2,4,6 trimethylbenzoyl-diphenylphosphine oxide and isopropylthioxanthone, the molar ratio of the two may be: 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. The embodiment of the present invention does not limit the ratio of the combination of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and isopropylthioxanthone.
When the acylphosphine oxide photoinitiator is a combination of 2-hydroxy-methylphenylpropane-1-one and isopropyl thioxanthone, the molar ratio of the two may be: 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.4, 0.5:1.5, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. The embodiment of the invention does not limit the ratio of the combination of the 2-hydroxy-methyl phenyl propane-1-ketone and the isopropyl thioxanthone.
When the acylphosphine oxide photoinitiator is a combination of 2,4,6 trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-methylphenylpropane-1-one, and isopropylthioxanthone, the molar ratio of these three components may be 1:0.1:0.6, 1:0.2:0.6, 1:0.3:0.6, 1:0.4:0.6, 1:0.5:0.6, 1:0.6:0.6, 1:0.7:0.6, 1:0.8:0.6, etc. The embodiment of the invention does not limit the combination ratio of the 2,4,6 trimethyl benzoyl diphenyl phosphine oxide, the 2-hydroxy-methyl phenyl propane-1-ketone and the isopropyl thioxanthone.
In one possible implementation, the reactive monomers include: one or more of pentaerythritol triacrylate, 2-hydroxyethyl methacrylate, and propoxylated glycerol triacrylate.
The reaction monomer is subjected to polymerization reaction under the action of a photoinitiator, and the viscosity of the coating system is adjusted. Because the reaction monomer provided by the embodiment of the invention contains side hydroxyl, the prepared coating has the advantages of difficult volatilization, strong diluting capability and quick curing under the irradiation of ultraviolet light.
As an example, the reactive monomer may be any one of pentaerythritol triacrylate, 2-hydroxyethyl methacrylate, propoxylated glycerol triacrylate; may be a combination of pentaerythritol triacrylate and 2-hydroxyethyl methacrylate; may be a combination of both pentaerythritol triacrylate and propoxylated glycerol triacrylate; can be the combination of 2-hydroxyethyl methacrylate and propoxylated glycerol triacrylate; the compound can also be a combination of pentaerythritol triacrylate, 2-hydroxyethyl methacrylate and propoxylated glycerol triacrylate.
When the reactive monomer is a combination of pentaerythritol triacrylate and 2-hydroxyethyl methacrylate, the molar ratio of the two may be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, etc. When the reactive monomer is a combination of pentaerythritol triacrylate and propoxylated glycerol triacrylate, the molar ratio of the two may be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, etc. When the reactive monomer is a combination of 2-hydroxyethyl methacrylate and propoxylated glycerol triacrylate, the molar ratio of the two may be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, etc. When the reaction monomer is a combination of pentaerythritol triacrylate, 2-hydroxyethyl methacrylate, and propoxylated glycerol triacrylate, the molar ratio of the three may be 1:1:0.5, 1:1.1:0.6, 1:1.2:0.7, 1:1.3:0.8, 1:1.4:0.9, 1:1.5:0.5, 1:1.6:0.6, 1:2:1.5, 1:2.1:1.2, 1:2.2:1.7, 1:2.5:1.8, 1:2.5:1.9, 1:2.6:1.8, 1:3:2.5, etc. The embodiment of the present invention does not limit the ratio of the above-mentioned components when they are combined.
In one possible implementation, the auxiliary agent comprises: one or more of adhesion promoter, defoaming agent, wetting agent and flatting agent.
The adhesion promoter can improve the binding force between the resin and various base materials, and in the embodiment of the invention, the adhesion and the toughness of the coating system can be improved. For example, when a workpiece is coated with a coating, the adhesion between the coating and the workpiece to be coated and the toughness of the coating are increased.
The defoaming agent can eliminate foams in the coating and improve the surface tension of the coating in the using process.
Wetting agents make the coating more water wettable. The coating is wetted by reducing the surface tension or interfacial tension of the coating, allowing water to spread on or penetrate the surface of the coating.
The leveling agent can promote the coating to form a flat, smooth and uniform coating film in the drying film-forming process. Can effectively reduce the surface tension of the coating and improve the leveling property and uniformity of the coating.
The auxiliary agent provided by the embodiment of the invention can be any one of an adhesion promoter, a defoaming agent, a wetting agent and a leveling agent, or a combination of the promoter and the defoaming agent, or a combination of the promoter and the wetting agent, or a combination of the defoaming agent and the wetting agent, or a combination of the wetting agent and the leveling agent, or a combination of the promoter, the defoaming agent and the wetting agent, or a combination of the promoter, the defoaming agent and the leveling agent, or the like. The embodiment of the invention does not limit the combination mode, and does not limit the proportion of the components after combination.
In one possible implementation, the adhesion promoter is a phosphate acrylate. For example, trifunctional acid ester (product code: SARTOMER CD9051), 2-hydroxyethyl methacrylate phosphate or phosphate acrylate, and the like.
In some embodiments of the invention, the adhesion promoter is a trifunctional acid ester (product code SARTOMER CD9051)
In one possible implementation, the defoaming agent is one or more of polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene polyoxyethylene glycerol ether, and polydimethylsiloxane. For example, an anti-foaming agent having a product designation of digao TEGO Airex 986 may be selected.
In one possible implementation, the leveling agent is an acrylate leveling agent. In some embodiments of the present invention, the acrylate leveling agent is a BYK 361N product. The acrylate leveling agent can promote the flowing and leveling of the coating film, does not influence the interlayer adhesion of the coating film, and has the defoaming effect. The compatibility of the acrylate leveling agent is an important index of the capability of controlling the surface state of a coating film. The compatibility is too good, and the paint is dissolved in a coating film, so that a new interface cannot be formed on the surface of the coating film, and the leveling effect cannot be provided; the compatibility is too poor, and the coating film cannot be uniformly distributed on the surface of the coating film, and the coating film can be mutually gathered, so that the defect of shrinkage cavity is easily generated. The gloss of the coating film is lowered, and undesirable side effects such as fogging are generated. Only with ideal controlled compatibility, a new interface layer can be formed on the surface of the coating film to play a role in leveling.
The molecular weight of the acrylate leveling agent provided by the embodiment of the invention is 6000-20000, the glass transition temperature is less than-20 ℃, and the surface tension is less than 25-26 mN/m. Therefore, the good leveling effect of the acrylic leveling agent can be ensured.
In one aspect, an embodiment of the present invention provides a method for preparing a UV glue coating, where the method is applied to any one of the above coatings, and the method includes:
and step 102, adding a reaction auxiliary agent, and uniformly stirring to obtain the UV adhesive coating.
It is to be noted that after the modified epoxy acrylate resin, the modified pure acrylate resin, the reaction monomer and the photoinitiator are added, the reaction system is stirred to ensure that the particle size of reactants in the reaction system is less than 10 microns, so as to achieve the purpose of uniform dispersion.
In another aspect, an embodiment of the present invention provides a method for preparing a coated workpiece, where the coated workpiece includes any one of the coatings described above, and the method includes:
obtaining a workpiece to be coated, and coating a coating on the workpiece to be coated to obtain a first coated workpiece;
and carrying out ultraviolet curing on the first coated workpiece to obtain a coated workpiece containing the coating.
In one possible implementation, the obtaining of the workpiece to be coated comprises: and (4) carrying out oil removal, dust removal and drying treatment on the coated workpiece to obtain the workpiece to be coated. The workpiece to be coated is subjected to oil removal and dust removal treatment to ensure that the surface of the workpiece to be coated is clean, so that the coating is easily adhered to the surface of the workpiece.
In one possible implementation, the thickness of the coating on the workpiece to be coated may be between 50 microns and 100 microns. For example, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, or the like. The thickness of such a coating is set to ensure adhesion between the coating and the workpiece to be coated.
In one possible implementation, the energy of the UV curing may be 500-700mj/cm2(unit: mJ/cm). For example, 500mj/cm2、550mj/cm2、600mj/cm2、650mj/cm2Or 700mj/cm2And the like.
In one possible implementation, the coating is applied to a workpiece to be coated, resulting in a first coated workpiece, comprising:
and coating the coating on the workpiece to be coated in a dripping coating mode to obtain a first coated workpiece.
In one possible implementation, the viscosity of the coating is 1000. + -. 400 mPas/25 ℃ in mpa.s/25 ℃.
The viscosity of the coating provided by the embodiment of the invention can be 600mpa.s/25 ℃, 700mpa.s/25 ℃, 800mpa.s/25 ℃, 900mpa.s/25 ℃, 1000mpa.s/25 ℃ and the like.
Based on the viscosity provided by the embodiment of the invention, the prepared UV adhesive coating has high adhesiveness.
As an example, as shown in fig. 1, an embodiment of the present invention provides a schematic structural diagram of a paint fixing material provided by this embodiment, before painting, after the paint is placed in a dedicated dispenser device, the substrate is degreased, dedusted and dried, the substrate surface is painted by a dispenser device, a material to be fixed is loaded on the paint, and the paint on the substrate is adhered to the substrate and the material to be fixed and cured by irradiation of a mercury lamp, so as to obtain a workpiece with a shadowless paint.
The preparation method of the UV glue coating provided by the embodiment of the invention is further described by the optional embodiment.
In the following alternative examples, those whose operations are not conditional are performed according to conventional conditions or conditions recommended by the manufacturer. The raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Example 1
Adding 45.1 wt% of novolac epoxy acrylate resin, 35 wt% of carboxyl functional modified pure acrylate resin, 15.4 wt% of pentaerythritol triacrylate and 1.1 wt% of 2,4,6 trimethyl benzoyl-diphenyl phosphine oxide in sequence, stirring to ensure that the particle size of reactants in the reaction system is less than 10 mm, adding 0.3 wt% of acrylate leveling agent, 0.1 wt% of polyoxypropylene pentaerythritol ether and 3 wt% of trifunctional acid ester, and uniformly stirring to obtain the UV adhesive coating.
Example 2
Adding 50.1 wt% of novolac epoxy acrylate resin, 30 wt% of carboxyl functional modified pure acrylate resin, 15 wt% of pentaerythritol triacrylate and 1.5 wt% of 2,4,6 trimethyl benzoyl-diphenyl phosphine oxide in sequence, stirring to ensure that the particle size of reactants in the reaction system is less than 10 mm, adding 0.3 wt% of acrylate leveling agent, 0.1 wt% of polyoxypropylene pentaerythritol ether and 3 wt% of trifunctional acid ester, and uniformly stirring to obtain the UV adhesive coating.
Example 3
Adding 55.1 wt% of novolac epoxy acrylate resin, 25 wt% of carboxyl functional modified pure acrylate resin, 14.7 wt% of pentaerythritol triacrylate and 1.8 wt% of 2,4,6 trimethyl benzoyl-diphenyl phosphine oxide in sequence, stirring to ensure that the particle size of reactants in the reaction system is less than 10 mm, adding 0.3 wt% of acrylate leveling agent, 0.1 wt% of polyoxypropylene pentaerythritol ether and 3 wt% of trifunctional acid ester, and uniformly stirring to obtain the UV adhesive coating.
Example 4
Adding 60 wt% of novolac epoxy acrylate resin, 20 wt% of carboxyl functional modified pure acrylate resin, 14.5 wt% of pentaerythritol triacrylate and 2.1 wt% of 2,4,6 trimethyl benzoyl-diphenyl phosphine oxide in sequence, stirring to ensure that the particle size of reactants in the reaction system is less than 10 mm, adding 0.3 wt% of acrylate leveling agent, 0.1 wt% of polyoxypropylene pentaerythritol ether and 3 wt% of trifunctional acid ester, and uniformly stirring to obtain the UV adhesive coating.
Comparative example
Adding 80 wt% of novolac epoxy acrylate resin, 5 wt% of carboxyl functional modified pure acrylate resin, 5 wt% of pentaerythritol triacrylate and 2.1 wt% of 2,4,6 trimethyl benzoyl-diphenyl phosphine oxide in sequence, stirring to ensure that the particle size of reactants in the reaction system is less than 10 mm, and adding 0.3 wt% of acrylate leveling agent; 0.1 wt% of polyoxypropylene pentaerythritol ether and 3 wt% of trifunctional acid ester, and uniformly stirring to obtain the UV adhesive coating.
The above embodiments are further described generally in tabular form below.
Table 1 UV glue coating examples
TABLE 2 Performance test indexes
TABLE 3 test results
Examples 1-4 are coatings provided using examples of the present invention having component amounts within the component ranges provided in the examples of the present invention, and comparative examples are coatings having various performance parameters experimentally obtained using coatings not within the component amounts provided in the examples of the present invention.
The above examples and test results show that the UV glue coating provided by the invention has the characteristics of fast curing time, good flexibility, good water resistance, good performance, good temperature resistance and good chemical resistance, and in addition, after the UV glue coating in examples 1 to 4 of the invention and the UV glue coating in the comparative example pass through a UV curing machine with the same energy and the same linear speed, the UV glue coating in the comparative example has strong off-line odor and is not yet formed into a film when the UV glue coating is off-line.
All the above-mentioned alternative solutions can be combined with any other to form the alternative embodiments of the present disclosure, and the above-mentioned embodiments are only illustrative embodiments of the present disclosure, and are not intended to limit the scope of the present disclosure, and any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. The UV adhesive coating is characterized by comprising the following components in percentage by weight:
35-75 wt% of modified epoxy acrylate resin, 10-55 wt% of modified pure acrylate resin, 5-25 wt% of reaction monomer, 0.1-5 wt% of photoinitiator and 0.1-5 wt% of auxiliary agent.
2. The coating according to claim 1, wherein the modified neat acrylate resin is selected from one or more of a carboxyl-functional modified neat acrylate resin, a double bond-functional modified neat acrylate resin, or an epoxy-functional modified neat acrylate resin.
3. The coating of claim 1, wherein the modified epoxy acrylate resin comprises: one or more of novolac epoxy acrylate resin, bisphenol A epoxy acrylate resin and bisphenol F epoxy acrylate resin.
4. The coating of claim 1, wherein the photoinitiator is a free radical polymerization photoinitiator.
5. The coating of claim 4, wherein the free radical polymerization photoinitiator comprises: 2,4,6 trimethyl benzoyl diphenyl phosphine oxide, 2-hydroxy-methyl phenyl propane-1-ketone and isopropyl thioxanthone.
6. The coating of claim 1, wherein the reactive monomer comprises: one or more of pentaerythritol triacrylate, 2-hydroxyethyl methacrylate, and propoxylated glycerol triacrylate.
7. The coating according to any one of claims 1 to 6, wherein the auxiliary agent comprises: one or more of adhesion promoter, defoaming agent, wetting agent and flatting agent.
8. The coating of claim 7, wherein the adhesion promoter comprises phosphate acrylate, the defoamer is one or more of polyoxyethylene, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane, and the leveling agent is acrylate leveling agent.
9. A method of preparing a UV glue coating, the method being for preparing a coating according to any one of claims 1-8, the method comprising:
according to the weight percentage of each component, adding modified epoxy acrylate resin, modified pure acrylate resin, reaction monomer and photoinitiator in sequence, and stirring to enable the particle size of reactants in a reaction system to reach a reference value;
adding a reaction auxiliary agent, and uniformly stirring to obtain the UV adhesive coating.
10. A method for producing a coated workpiece, characterized in that the coated workpiece comprises the coating material according to any one of claims 1 to 8, the method comprising:
obtaining a workpiece to be coated, and coating the coating on the workpiece to be coated to obtain a first coated workpiece;
and carrying out ultraviolet light curing on the first coated workpiece to obtain the coated workpiece containing the coating.
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