CN115160908B - Solvent-free UV matte coating and preparation method thereof - Google Patents

Solvent-free UV matte coating and preparation method thereof Download PDF

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CN115160908B
CN115160908B CN202210799292.4A CN202210799292A CN115160908B CN 115160908 B CN115160908 B CN 115160908B CN 202210799292 A CN202210799292 A CN 202210799292A CN 115160908 B CN115160908 B CN 115160908B
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prepolymer
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CN115160908A (en
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张�杰
季锦卫
朱文祥
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Zhejiang Hailide New Material Co ltd
Hailide New Material Research Shanghai Co ltd
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Zhejiang Hailide New Material Co ltd
Hailide New Material Research Shanghai 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
    • 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/42Gloss-reducing agents
    • 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium

Abstract

The invention discloses a solvent-free UV matte coating and a preparation method thereof, wherein the solvent-free UV matte coating comprises the following components: UV prepolymer resin containing carbon-carbon double bonds; a reactive diluent containing a carbon-carbon double bond; functional diluents or prepolymers containing both monoisocyanate groups and carbon-carbon double bonds; an organic matting agent containing hydroxyl groups or amine groups or a surface-treated inorganic matting agent containing reactive functional groups capable of chemically reacting with functional diluents or isocyanate functional groups in the prepolymer to chemically bond the matting agent to the UV prepolymer resin. The solvent-free UV matte coating and the preparation method thereof can improve the stability and durability of gloss and the environmental tolerance of the gloss retention effect. The invention can realize the comprehensive requirements of low odor, abrasion resistance, scratch resistance, gloss retention, adhesion, chemical resistance, stain resistance and the like of coating products through the combination reaction of the functional diluent or prepolymer and the active extinction powder, the active wax powder or the wax dispersion.

Description

Solvent-free UV matte coating and preparation method thereof
Technical Field
The invention belongs to the technical field of floor coatings, and relates to a matte coating, in particular to a solvent-free UV matte coating and a preparation method thereof.
Background
The UV paint is a novel surface coating treatment technology which is developed at the end of the sixty of the twentieth century, and under the irradiation of ultraviolet rays, the UV paint instantaneously generates photochemical free radical polymerization reaction by exciting an internal photoinitiator to generate free radical chain polymerization reaction of active substances such as monomers, prepolymers and the like. Because the reactive diluent monomer is adopted to replace the solvent, a high-solid-content even solvent-free coating system can be prepared, the product is green and environment-friendly, and film forming substances with different hardness and elasticity can be obtained by selecting proper types and proportion of the reactive prepolymer and the reactive diluent monomer. The cured products have high curing speed, high production efficiency, good chemical resistance and excellent heat resistance, are widely used in a plurality of fields at present, and gradually expand at a higher growth rate every year.
PVC floor is used as a synthetic floor decoration material, has been widely applied to house decoration and public place floor decoration at present, and is popular with consumers and clients because of vivid decoration effect, good environmental adaptability, durability, simple and easy operation of laying process, low cost and convenient renovation. The UV coating is used as an important coating material for protecting the surface layer of the PVC floor, and has the important functions of gloss, hardness, chemical resistance, wear resistance, scratch resistance and the like on the use experience and lasting stability of the PVC floor.
The coating effect of the paint is divided into two main types: one is transparent effect, does not influence the demonstration of the texture, pattern, flower color, etc. of the base material; the other is a solid color effect, namely, the substrate is completely shielded, and the coating effect is a paint color effect. The color film layer is adopted to show the color, texture and effect of the floor when the hierarchical structure of the PVC floor is designed, so that most of PVC floors are transparent coated when the coating effect is selected. For clear coating, it is further classified into matte and glossy. Because the PVC floor market is more favored by a matte system, the paint is mostly required to be added with the matting powder when the paint is prepared according to a formula, the matting powder is utilized to form an uneven surface on the surface of the paint, and light rays are diffusely reflected on the surface of the paint to achieve the aim of matting. The matting powder used in the existing paint is basically dispersed on the surface or inside of the paint in a physical mixing mode, has weak binding force with paint resin, is easily damaged on the uneven surface after external force or friction, causes the problems of rising and brightening of gloss and the like, and has poor gloss stability and gloss retention durability; on the other hand, as most of the surfaces of the inorganic extinction powder have porous structures, and the extinction powder and the resin system have weak binding force and are easy to be impacted, destroyed and stripped by external force, the surface defects are increased, so that the chemical resistance and the pollution resistance of the coating are obviously reduced, and the use feeling and the lasting stability of the product are influenced.
In view of this, there is an urgent need to design a new UV coating to overcome at least some of the above-mentioned drawbacks of existing UV coatings.
Disclosure of Invention
The solvent-free UV matte coating and the preparation method thereof provided by the invention can improve the stability and durability of gloss and the environmental tolerance of the gloss retention effect.
In order to solve the technical problems, according to one aspect of the present invention, the following technical scheme is adopted:
a solvent-free UV-matt coating, comprising:
UV prepolymer resin containing carbon-carbon double bonds;
a reactive diluent containing a carbon-carbon double bond;
functional diluents or prepolymers containing both monoisocyanate groups and carbon-carbon double bonds; and
an organic matting agent containing hydroxyl groups or amine groups or a surface-treated inorganic matting agent containing reactive functional groups capable of chemically reacting with functional diluents or isocyanate functional groups in the prepolymer to chemically bond the matting agent to the UV prepolymer resin.
As an embodiment of the present invention, the solvent-free UV-matte coating includes:
1-80 parts by mass of a UV prepolymer resin containing carbon-carbon double bonds;
1-60 parts by mass of a reactive diluent containing carbon-carbon double bonds;
0.1 to 50 parts by mass of a functional diluent or prepolymer containing both a monoisocyanate group and a carbon-carbon double bond;
0.1 to 30 parts by mass of organic extinction powder containing hydroxyl or amino or inorganic extinction powder with treated surface, namely active extinction powder;
0.1-15 parts by mass of a photoinitiator;
0.01-8 parts by mass of wetting dispersant;
0.01-5 parts by mass of an antifoaming agent;
0.01-5 parts by mass of leveling agent;
0.01-5 parts by mass of an anti-settling agent;
0.01-8 parts by mass of active wax powder or wax slurry;
the isocyanate group of the functional diluent or prepolymer can participate in the reaction of substances with active hydrogen, and the carbon-carbon double bond can be initiated by the free radical of the photoinitiator to participate in the free radical polymerization of the UV resin or monomer, so that the target molecular structure realizes bridging bonding.
As an embodiment of the present invention, the solvent-free UV-matte coating further comprises at least one of the following components:
0-15 parts by mass of inert extinction powder;
0-20 parts by mass of silicon micropowder;
0-20 parts by mass of talcum powder;
0-20 parts by mass of alumina powder.
As one embodiment of the present invention, the UV prepolymer resin is free of active hydrogen species that can react with isocyanate functional groups; the UV prepolymer resin comprises at least one of bisphenol A epoxy modified acrylate prepolymer, modified epoxy acrylate prepolymer, polyester modified acrylate prepolymer, polyurethane modified acrylate prepolymer and pure acrylate prepolymer.
As an embodiment of the present invention, the UV prepolymer resin is a resin product having a viscosity of 50000 mPa-s or less at a temperature of 25 ℃; the UV prepolymer resin is an easily extinction and self-extinction UV prepolymer resin.
As an embodiment of the present invention, the reactive diluent includes at least one of 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, 2-phenoxyethyl acrylate, tetrahydrofuran methacrylate, pentaerythritol tetraacrylate, isobornyl acrylate, lauryl acrylate.
The reactive diluents and UV prepolymer resins are required to not contain active hydrogen groups (e.g., hydroxyl, amine groups) that react with isocyanate functionality that would otherwise react with the functional diluent or prepolymer itself.
As an embodiment of the present invention, the functional diluent or prepolymer includes at least one of isocyanate ethyl acrylate, isocyanatoethyl methacrylate, allyl isocyanate, and urethane-modified acrylate containing a mono-isocyanate functional group.
As one implementation mode of the invention, the extinction powder is chemically bonded with the UV resin, so that the scratch resistance of the extinction powder is improved, and the stability and durability of the surface gloss of the coating are maintained; meanwhile, the extinction powder (matte powder) and the UV resin are chemically bridged, so that the compactness of the coating is improved, and the influence of external chemical substances, external force and stains can be better resisted;
the inert extinction powder does not contain active hydrogen groups such as hydroxyl, amino and the like, and does not participate in the reaction with functional diluent or isocyanate functional groups in the prepolymer;
the active wax powder or the wax slurry is provided with at least one of hydroxyl, amino and carbon-carbon double bond characteristic functional groups, and the contained active functional groups can react with the UV monomer prepolymer, the functional diluent or isocyanate functional groups in the prepolymer to chemically bond the wax with the UV resin, so that the binding force of the wax on the surface of the coating is improved, the compactness of the coating is improved, the scratch resistance and wear resistance are improved, and the surface glossiness of the coating is further stabilized and the influence of the external environment is resisted.
As one embodiment of the present invention, the photoinitiator, wetting dispersant, defoamer, leveling agent, anti-settling agent do not contain active hydrogen substances capable of reacting with isocyanate;
the photoinitiator, the wetting dispersant, the defoamer, the flatting agent and the anti-settling agent are the combination of one or more products with the effect of the function;
the silica powder, talcum powder and alumina powder are the combination of one or more products, and in the aspect of filler particle size, the average particle size is preferably 3-10 mu m, and the scraper fineness is less than 50 mu m.
According to another aspect of the invention, the following technical scheme is adopted: the preparation method of the solvent-free UV matte coating comprises the following steps:
adding UV prepolymer resin, reactive diluent, functional diluent or prepolymer and photoinitiator with set mass into a stirring container for stirring;
adding a wetting dispersant, a defoaming agent and a leveling agent with set quality, and dispersing at a high speed for a set time;
sequentially adding extinction powder, active wax powder or wax slurry and filler with set quality into a dispersing container for dispersing;
after dispersion is stable, adding the anti-settling agent with set quality, and continuously stirring and mixing for set time to obtain the solvent-free matte UV coating.
The invention has the beneficial effects that: the solvent-free UV matte coating and the preparation method thereof can improve the stability and durability of gloss and the environmental tolerance of the gloss retention effect.
The invention comprehensively realizes the comprehensive requirements of low odor, abrasion resistance, scratch resistance, gloss retention, adhesion, chemical resistance, stain resistance and the like of coating products by combining and reacting the functional diluent or prepolymer with the active organic matting powder, the active wax powder or the wax dispersion and selecting the prepolymer resin, the diluent monomer, the photoinitiator, the wear-resistant filler and the auxiliary agent in a matching way.
According to the invention, the wax powder or wax dispersion with the reactive group reacts with the functional diluent or prepolymer to reduce the friction coefficient of the layer at the rear of the cured UV coating, improve the scratch resistance and wear resistance of the UV coating, and enhance the matte retention effect of the coating after external force (such as friction) is applied.
Drawings
FIG. 1 is a flow chart of a method for preparing a solvent-free UV matte coating according to an embodiment of the invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The description of this section is intended to be illustrative of only a few exemplary embodiments and the invention is not to be limited in scope by the description of the embodiments. It is also within the scope of the description and claims of the invention to interchange some of the technical features of the embodiments with other technical features of the same or similar prior art.
In the specification, "plural", "several" means "two or more"; "plurality", "several" means "two or more".
The invention discloses a solvent-free UV matte coating, which comprises the following components: UV prepolymer resin containing carbon-carbon double bonds; a reactive diluent containing a carbon-carbon double bond; functional diluents or prepolymers containing both monoisocyanate groups and carbon-carbon double bonds; an organic matting agent containing hydroxyl groups or amine groups or an inorganic matting agent with a treated surface, which contains reactive functional groups that can chemically react with functional diluents or isocyanate functional groups in the prepolymer, chemically bonding the matting agent to the UV prepolymer resin.
In one embodiment of the present invention, the solvent-free UV-matte coating comprises: 1-80 parts by mass of a UV prepolymer resin containing carbon-carbon double bonds; 1-60 parts by mass of a reactive diluent containing carbon-carbon double bonds; 0.1 to 50 parts by mass of a functional diluent or prepolymer containing both a monoisocyanate group and a carbon-carbon double bond; 0.1 to 30 parts by mass of organic extinction powder containing hydroxyl or amino or inorganic extinction powder with treated surface, namely active extinction powder; 0.1-15 parts by mass of a photoinitiator; 0.01-8 parts by mass of wetting dispersant; 0.01-5 parts by mass of an antifoaming agent; 0.01-5 parts by mass of leveling agent; 0.01-5 parts by mass of an anti-settling agent; 0.01-8 parts by mass of active wax powder or wax slurry. The isocyanate group of the functional diluent or prepolymer can participate in the reaction of substances with active hydrogen, and the carbon-carbon double bond can be initiated by the free radical of the photoinitiator to participate in the free radical polymerization of the UV resin or monomer, so that the target molecular structure realizes bridging bonding.
In one embodiment, the solvent-free UV-matt coating further comprises at least one of the following components: 0-15 parts by mass of inert extinction powder; 0-20 parts by mass of silicon micropowder; 0-20 parts by mass of talcum powder; 0-20 parts by mass of alumina powder.
The UV prepolymer resin used in the invention comprises one or a combination of a plurality of prepolymers of epoxy modified acrylate prepolymer, polyurethane modified acrylate prepolymer, polyester modified acrylate prepolymer, pure acrylate prepolymer and the like containing carbon-carbon double bonds, and when yellowing resistance is required, the selection of a resin system with weather resistance and poor ultraviolet resistance, such as bisphenol A type epoxy resin modified acrylate, aromatic polyurethane modified acrylate and the like, is avoided. A resin product having a viscosity of 50000 mPas (25 ℃) or less is preferable in terms of the viscosity of the resin; in terms of resin dilutability, UV prepolymer resin with high dilution and viscosity reduction efficiency can be selected from reactive diluents such as 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and dipropylene glycol diacrylate; in terms of glossiness after resin curing, UV prepolymer resin easy to extinction and self-extinction is preferred, so that extinction efficiency is higher when the resin is matched with the matte powder, the addition amount of the matte powder is reduced, and the influence of the matte powder on system viscosity, thixotropy, storage stability and the like is reduced.
Reactive diluents used in the present invention are reactive acrylic diluent monomers containing a carbon-carbon double bond, such as 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, 2-phenoxyethyl acrylate, tetrahydrofuran methacrylate, pentaerythritol tetraacrylate, and the like.
The reactive diluents and UV prepolymer resins cannot contain active hydrogen groups (e.g., hydroxyl, amine groups) that react with isocyanate functionality or react with the functional diluent or prepolymer itself.
The functional diluent or prepolymer used in the invention is different from the reactive diluent, is an acrylate monomer or prepolymer containing both a monoisocyanate group and a carbon-carbon double bond, and has a dual curing function. The isocyanate group can participate in the reaction with substances with active hydrogen such as hydroxyl, amino, carboxyl and the like, and the carbon-carbon double bond can be initiated by the free radical of the photoinitiator to participate in the free radical polymerization of other active substances such as UV resin or monomers and the like, so that the target molecular structure realizes bridging bonding. Such functional diluents or prepolymers, such as isocyanate ethyl acrylate, isocyanatoethyl methacrylate, allyl isocyanate, and the like.
The active matting powder used in the invention is organic matting powder containing hydroxyl or amino or inorganic matting powder with treated surface, and the active functional group can react with functional diluent or isocyanate functional group in prepolymer, so that the matting powder is chemically bonded with UV resin, the scratch resistance of the matting powder is improved, and the stability and durability of the surface gloss of the coating are maintained; on the other hand, the coating density is improved by chemically bridging the dummy powder and the UV resin, so that the influence of external chemical substances, external force, stains and the like can be better resisted.
The active wax powder or the wax slurry used in the invention has at least one of characteristic functional groups such as hydroxyl, amino, carbon-carbon double bond and the like, and the contained active functional groups can react with the isocyanate functional groups in the UV monomer prepolymer, the functional diluent or the prepolymer to chemically bond the wax and the UV resin, so that the bonding force of the wax on the surface of the coating is improved, the compactness of the coating is improved, the friction coefficient of the coating material is reduced, the scratch resistance and wear resistance of the coating are improved, and the surface glossiness of the coating is further stabilized and the influence of external environment is resisted;
the inert extinction powder used in the invention does not contain active hydrogen groups such as hydroxyl, amino and the like, does not participate in the reaction with isocyanate functional groups in the functional diluent or prepolymer, and has the particle size, the particle size distribution, the oil absorption value, whether the surface treatment and the treatment mode, the density, the porosity, the specific surface area and the like are required to be selected and adjusted correspondingly by combining the extinction efficiency, the viscosity thixotropic property, the transparency, the anti-settling property, the stability and the like in the paint formula;
the photoinitiator used in the invention comprises one or a combination of a plurality of cleavage type photoinitiators (such as 4-dimethylaminoethyl benzoate, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, benzoin dimethyl ether and the like), hydrogen abstraction type photoinitiators (such as 4-dimethylaminoethyl benzoate, isooctyl p-dimethylaminobenzoate, isopropyl thioxanthone, benzophenone and the like), macromolecule type photoinitiators (such as JRCure-A151, JRCure-1508 and the like) and the like, and the preferred photoinitiator has low odor or odor removing effect;
the wetting dispersant, the defoamer, the flatting agent and the anti-settling agent used in the invention do not contain active hydrogen substances which can react with isocyanate groups; the wetting dispersant, the defoamer, the flatting agent and the anti-settling agent are the combination of one or more products with the functional effect, and the preferred wetting dispersant has good matte powder and filler dispersion performance and good viscosity reduction effect; the optional defoaming agent has high defoaming efficiency and does not influence the recoating property of the coating; in one embodiment, the leveling agent combines leveling and does not affect recoatability.
The silicon micropowder, talcum powder and alumina powder used in the invention are the combination of one or more products, and the filler particle size is preferably 3-10 mu m in average particle size, and the scraper fineness is less than 50 mu m.
The invention further discloses a preparation method of the solvent-free matte UV coating for the PVC floor, and FIG. 1 is a flow chart of a preparation method of the solvent-free matte UV coating in an embodiment of the invention; referring to fig. 1, the preparation method may include the following steps: adding UV prepolymer resin, reactive diluent, functional diluent or prepolymer and photoinitiator with set mass into a stirring cylinder according to a metering fraction; starting a stirrer to stir; after being uniformly mixed, the mixture is added with a wetting dispersant, a defoaming agent and a leveling agent for high-speed dispersion for 30min (other time can be also adopted); and sequentially adding inert extinction powder, active wax powder or wax slurry and filler (silicon micropowder, talcum powder and alumina powder or no filler is added) into a dispersion cylinder for high-speed dispersion, and adding an anti-settling agent for continuous stirring and mixing for 30min (or other time) after the dispersion is stable, so that the solvent-free matte UV coating is obtained.
In one use scenario of the present invention, all steps and processes of the method of the present invention are performed in a water-free state, taking care to control the ambient humidity to within 50%.
In the partial examples and the partial comparative examples of the present invention, the raw materials of each component of the UV-matt coating are shown in table 1, and the unit of each data corresponds to parts by mass.
Figure BDA0003733394960000071
Figure BDA0003733394960000081
Table 1 formula implementation material compounding ratio specification table
In some examples of the present invention and some comparative examples, the application properties of the resulting solvent-free UV-matt coating are shown in table 2.
Figure BDA0003733394960000082
Figure BDA0003733394960000091
Table 2 comparison of results of Performance tests on formulations
Note that: description of the test methods
a, heat storage test is 50 ℃/week;
adhesive force test reference GBT 9286-2021;
c, scratch resistance test is referred to ISO1518;
scratch resistance test reference EN16094;
gloss test reference GBT 9754-2007;
and h, the stain resistance is blue-black ink/1 h.
After the UV coating is affected by the outside (such as friction), the change of gloss is small, the matte effect is durable, the gloss retention is aimed at the matte and low-gloss coating, but the gloss retention is not the gloss or high-gloss coating, and the gloss or gloss coating generally does not need to be added with matting powder. The key to realizing the matte gloss retention is that the functional diluent or prepolymer reacts with the matting powder with a reactive group, the matting powder can be organic or inorganic, the matting powder is chemically connected into the functional diluent or prepolymer molecular chain, the residual carbon-carbon double bonds of the functional diluent or prepolymer can be cured and dried together with other conventional UV prepolymer resins and reactive diluents through the later ultraviolet light curing to form a UV coating, the matting powder is further fixedly combined on the resin of the UV coating, the matting powder cannot be peeled off and fall off from the UV resin when external force (such as friction) is applied, the rough surface formed by the matting powder initially has a light scattering effect, the low gloss matte effect is brought, and the rough surface of the paint film surface cannot be damaged and the gloss cannot be increased when external force (such as friction) is applied due to the fact that the matting powder is chemically combined with the resin. The reason for the increase in gloss is that the uneven surface formed by the ordinary matting powder on the paint film is flattened and vanished after external force is applied, and the light scattering property is reduced, resulting in the increase in gloss.
In conclusion, the solvent-free UV matte coating and the preparation method thereof provided by the invention can improve the stability and durability of gloss and improve the environmental tolerance of the gloss retention effect.
The invention comprehensively realizes the comprehensive requirements of low odor, abrasion resistance, scratch resistance, gloss retention, adhesion, chemical resistance, stain resistance and the like of coating products by combining and reacting the functional diluent or prepolymer with the active organic matting powder, the active wax powder or the wax dispersion and selecting the prepolymer resin, the diluent monomer, the photoinitiator, the wear-resistant filler and the auxiliary agent in a matching way.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The description and applications of the present invention herein are illustrative and are not intended to limit the scope of the invention to the embodiments described above. Effects or advantages referred to in the embodiments may not be embodied in the embodiments due to interference of various factors, and description of the effects or advantages is not intended to limit the embodiments. Variations and modifications of the embodiments disclosed herein are possible, and alternatives and equivalents of the various components of the embodiments are known to those of ordinary skill in the art. It will be clear to those skilled in the art that the present invention may be embodied in other forms, structures, arrangements, proportions, and with other assemblies, materials, and components, without departing from the spirit or essential characteristics thereof. Other variations and modifications of the embodiments disclosed herein may be made without departing from the scope and spirit of the invention.

Claims (7)

1. A solvent-free UV-matt coating, characterized in that the solvent-free UV-matt coating comprises:
1-80 parts by mass of a UV prepolymer resin containing carbon-carbon double bonds;
1-60 parts by mass of a reactive diluent containing carbon-carbon double bonds;
0.1 to 50 parts by mass of a functional diluent or prepolymer containing both a monoisocyanate group and a carbon-carbon double bond;
0.1 to 30 parts by mass of organic extinction powder containing hydroxyl or amino or inorganic extinction powder with treated surface, namely active extinction powder; the light extinction powder contains active functional groups which can react with functional diluents or isocyanate functional groups in the prepolymer, and the extinction powder is chemically bonded with the UV prepolymer resin;
0.1-15 parts by mass of a photoinitiator;
0.01-8 parts by mass of wetting dispersant;
0.01-5 parts by mass of an antifoaming agent;
0.01-5 parts by mass of leveling agent;
0.01-5 parts by mass of an anti-settling agent;
0.01-8 parts by mass of active wax powder or wax slurry;
the isocyanate group of the functional diluent or the prepolymer can participate in the reaction of a substance with active hydrogen, and the carbon-carbon double bond can be initiated by the free radical of the photoinitiator to participate in the free radical polymerization of the UV prepolymer resin or the reactive diluent, so that the target molecular structure realizes bridging bonding;
the solvent-free UV-matt coating further comprises at least one of the following components:
0-15 parts by mass of inert extinction powder;
0-20 parts by mass of silicon micropowder;
0-20 parts by mass of talcum powder;
0-20 parts by mass of alumina powder;
the functional diluent or prepolymer comprises at least one of isocyanate ethyl acrylate, isocyanatoethyl methacrylate, allyl isocyanate and polyurethane modified acrylate containing a mono-isocyanate functional group;
the active wax powder or the wax slurry is provided with at least one structure of hydroxyl, amino and carbon-carbon double bond characteristic functional groups, and the contained active functional groups can react with the UV prepolymer resin, the functional diluent or isocyanate functional groups in the prepolymer to chemically bond the wax and the UV prepolymer resin, so that the binding force of the wax on the surface of the coating is improved, the compactness of the coating is improved, the scratch resistance and the wear resistance are improved, and the surface glossiness of the coating is further stabilized and the influence of the external environment is resisted.
2. The solvent-free UV-matt coating according to claim 1, characterized in that:
the UV prepolymer resin is free of active hydrogen species that can react with isocyanate functional groups; the UV prepolymer resin comprises at least one of bisphenol A epoxy modified acrylate prepolymer, modified epoxy acrylate prepolymer, polyester modified acrylate prepolymer, polyurethane modified acrylate prepolymer and pure acrylate prepolymer.
3. The solvent-free UV-matt coating according to claim 2, characterized in that:
the UV prepolymer resin is a resin product with a viscosity of 50000 mPas or less at 25 ℃; the UV prepolymer resin is an easily extinction and self-extinction UV prepolymer resin.
4. The solvent-free UV-matt coating according to claim 1, characterized in that:
the reactive diluent comprises at least one of 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate, 2-phenoxyethyl acrylate, tetrahydrofuran methacrylate, pentaerythritol tetraacrylate, isobornyl acrylate, and lauryl acrylate.
5. The solvent-free UV-matt coating according to claim 1, characterized in that:
the active extinction powder and the UV prepolymer resin are in chemical bridging, so that the coating density is improved, and the influence of external chemical substances, external force and stains can be better resisted;
the inert extinction powder does not contain hydroxyl and amino active hydrogen groups and does not participate in the reaction with functional diluent or isocyanate functional groups in the prepolymer.
6. The solvent-free UV-matt coating according to claim 1, characterized in that:
the photoinitiator, the wetting dispersant, the defoamer, the flatting agent and the anti-settling agent do not contain active hydrogen substances which can react with isocyanate;
the photoinitiator, the wetting dispersant, the defoamer, the flatting agent and the anti-settling agent are the combination of one or more products with the effect of the function;
the silica powder, talcum powder and alumina powder are the combination of one or more products, the average particle diameter of the filler is 3-10 mu m, and the scraper fineness is less than 50 mu m.
7. A process for preparing the solvent-free UV-matt coating according to any of claims 1 to 6, characterized in that it comprises:
adding UV prepolymer resin, reactive diluent, functional diluent or prepolymer and photoinitiator with set mass into a stirring container for stirring;
adding a wetting dispersant, a defoaming agent and a leveling agent with set quality, and dispersing at a high speed for a set time;
sequentially adding extinction powder, active wax powder or wax slurry and filler with set quality into a dispersing container for dispersing;
after dispersion is stable, adding the anti-settling agent with set quality, and continuously stirring and mixing for set time to obtain the solvent-free matte UV coating.
CN202210799292.4A 2022-07-06 2022-07-06 Solvent-free UV matte coating and preparation method thereof Active CN115160908B (en)

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EP2459627B1 (en) * 2009-07-29 2016-06-29 Covestro Deutschland AG Multi-layer products comprising acrylate containing coatings
JP6039085B2 (en) * 2012-09-28 2016-12-07 ハンワ ケミカル コーポレイション Heat dissipation coating composition and heat dissipation structure
CN102895126B (en) * 2012-11-02 2014-07-02 东华大学 Method for preparing organic/inorganic hybrid filler for dental repair resin
US20200190245A1 (en) * 2016-11-14 2020-06-18 Covestro Deutschland Ag Composite materials based on dual-curing isocyanurate polymers
CN109354830B (en) * 2018-11-05 2021-02-26 镇江市鑫泰绝缘材料有限公司 Preparation and repair method of self-repairing epoxy resin for electrical insulation
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