WO2016127452A1 - 电子束固化涂料、电子束固化涂层的制备方法以及应用 - Google Patents

电子束固化涂料、电子束固化涂层的制备方法以及应用 Download PDF

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WO2016127452A1
WO2016127452A1 PCT/CN2015/073560 CN2015073560W WO2016127452A1 WO 2016127452 A1 WO2016127452 A1 WO 2016127452A1 CN 2015073560 W CN2015073560 W CN 2015073560W WO 2016127452 A1 WO2016127452 A1 WO 2016127452A1
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electron beam
acrylate
dispersion
coating
inorganic nano
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PCT/CN2015/073560
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English (en)
French (fr)
Inventor
邓鹏飏
吴启超
丰俊湘
柳美华
董德文
宋岱瀛
陈慧雪
杨卫东
王东勇
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广东天安新材料股份有限公司
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Priority to US15/545,825 priority Critical patent/US20180002549A1/en
Priority to JP2017555823A priority patent/JP6552639B2/ja
Priority to EP15881614.0A priority patent/EP3257901B1/en
Publication of WO2016127452A1 publication Critical patent/WO2016127452A1/zh

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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/34—Silicon-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
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    • 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
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
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    • C08K3/20—Oxides; Hydroxides
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to the technical field of surface coatings, in particular to an electron beam curing coating, a preparation method of an electron beam curing coating and an application thereof.
  • Plastics are used more and more in daily life, from household appliances, indoor and outdoor decoration, to automotive parts.
  • plastics have at least two fatal weaknesses: one is that the weather resistance is not good, it is easy to decompose under the action of light and heat, reducing its service life, and some even decompose to produce toxic products and gases; the second is that plastic is relatively soft. The surface is easily scratched.
  • some properties can be improved by adding a photothermal stabilizer and an anti-wear agent, other properties are inevitably damaged, and the amount of raw materials required for bulk modification is large, which increases the cost.
  • the surface coating technology not only changes the appearance of the plastic, but also improves the physicochemical properties of the surface. By adding functional additives, the chemical resistance, weather resistance, scratch resistance and antibacterial properties of the plastic can be significantly improved. At the same time, since the surface coating is thin, the amount of functional materials is small, and the cost of the product is less increased.
  • the coated coating can be obtained by thermal curing or radiation.
  • Solvent-based and water-based coatings are generally heat-cured, but the solvent-based system has a low solid content, and a large amount of solvent is released into the air, causing environmental pollution; although the aqueous system can increase the solid content, the specific heat of water is large. The volatilization rate is slow, and a large amount of heat energy needs to be provided.
  • the curing channel is generally long and the curing speed is slow.
  • Radiation methods include ultraviolet light and electron beam irradiation.
  • the coating method used in the radiation method can be 100% solid content, does not contain organic solvents, has no VOC, and has a fast curing speed, and is an emerging coating curing method.
  • UV curing technology Due to the fast curing speed, UV curing technology has been applied on a large scale, but compared with UV curing, electron beam curing has the following advantages: high utilization of electric energy; faster curing speed; energy of electron beam Large enough to directly open the acrylate, generate free radicals, initiate polymerization, thus eliminating the need for an initiator, improving the storage stability of the coating, and reducing the color and odor caused by the by-products of photoinitiator decomposition; The penetration ability is as high as a few centimeters, and the ultraviolet light can only pass through a thickness of several tens of micrometers.
  • nanofillers have been widely used. Since the nano-filler has a particle size of less than 100 nm, the nano-filler is used as a component of the coating, and the transparency of the coating is not affected by the nano-filler, while the mechanical properties of the coating such as abrasion resistance, weather resistance and chemical properties such as light resistance and chemicals Sex has been significantly improved.
  • nanomaterials such as silica, titania, zinc oxide, and aluminum oxide have a large amount of hydroxyl groups on the surface, which are highly polar, and have poor compatibility with organic monomers and prepolymers, although physical methods such as sanding are used.
  • Ball milling can disperse nano-fillers in organic monomers and solvents, but the stability is not good. This is because nanoparticles are easy to aggregate together to form secondary particles, which are much larger in size than primary nanoparticles and have an effect. The transparency and gloss of the coating.
  • the technical problem to be solved by the present invention is to provide an electron beam curing coating and an electron beam curing coating.
  • the electron beam curing coating of the present application is used for a coating material to provide a coating having good hardness and weather resistance.
  • an electron beam curing coating comprising:
  • the dispersion of the inorganic nanomaterial is prepared according to the following steps:
  • the dispersion of the inorganic ultraviolet absorber is prepared according to the following steps:
  • the inorganic nano material is one or two of silicon dioxide and aluminum oxide
  • the inorganic nano-UV absorber is titanium dioxide or zinc oxide.
  • the silane coupling agent is an acrylate-based silane and a halogenated alkylsilane coupling agent.
  • the silica has a particle diameter of 5 to 100 nm, and the alumina has a particle diameter of 12 to 100 nm.
  • the content of the dispersion of the inorganic nanomaterial is 10 to 30 parts by weight.
  • the acrylate prepolymer is selected from the group consisting of aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, melamine acrylate, polyester acrylate, polyether acrylate, silicone acrylate, polybutylene One or more of a diene acrylate, a polyacrylate acrylate, and an acrylate oligomer; the polyfunctional monomer is a polyfunctional acrylate.
  • the electron beam curing paint further comprises a leveling lubricant, an antifoaming agent, a pigment or a nano antibacterial agent; and the pigment is contained in an amount of 0.1 to 10 parts by weight.
  • the application also provides a method for preparing an electron beam cured coating, comprising the following steps:
  • the preparation method of the dispersion of the inorganic nano material comprises the following steps:
  • the preparation method of the dispersion of the inorganic ultraviolet absorber comprises the following steps:
  • the inorganic nano material is one or two of silicon dioxide and aluminum oxide
  • the inorganic nano-UV absorber is titanium dioxide or zinc oxide.
  • the electron beam curing device is a low energy electron beam device, the electron beam curing dose is 5 to 100 kGy, and the electron beam curing speed is 100 to 1000 m/min.
  • the electron beam cured coating has a thickness of 10 to 100 ⁇ m.
  • the present application also provides an electron beam-cured coating according to the above aspect or the use of the electron beam-cured coating prepared by the above scheme on an automotive interior or decorative panel.
  • the present application provides an electron beam curing coating comprising a dispersion of an inorganic nano material, a dispersion of an inorganic nano UV absorber, a polyfunctional monomer and an acrylate prepolymer, wherein the dispersion of the inorganic nano material is selected from the group consisting of One or two of a dispersion of silicon oxide and a dispersion of alumina, the dispersion of the inorganic nano-ultraviolet absorber is selected from a dispersion of titanium dioxide or a dispersion of zinc oxide; and the present application passes on silica, oxidation
  • the surface modification of aluminum, titanium dioxide and zinc oxide enables uniform dispersion in the acrylate without agglomeration, which is beneficial to improve the performance of the electron beam curing coating.
  • the present application is to add an inorganic nano material dispersion and an inorganic nano ultraviolet absorber.
  • the dispersion makes the electron beam curing coating as a coating with good hardness and weather resistance.
  • the embodiment of the invention discloses an electron beam curing coating, comprising:
  • the preparation method of the dispersion of the inorganic nano material comprises the following steps:
  • the preparation method of the dispersion of the inorganic ultraviolet absorber comprises the following steps:
  • the inorganic nano material is one or two of silicon dioxide and aluminum oxide
  • the inorganic nano-UV absorber is titanium dioxide or zinc oxide.
  • the present application provides an electron beam curing coating comprising a dispersion of an inorganic nano material, a dispersion of an inorganic ultraviolet absorber, a polyfunctional monomer and an acrylate prepolymer; and the inorganic nanoparticle
  • the material and the inorganic ultraviolet absorber are uniformly dispersed in the acrylate monomer respectively, and no agglomeration occurs, thereby avoiding the influence on the coating performance, and the coating has good wear resistance and weather resistance.
  • the dispersion of the inorganic nano material is one or both of a dispersion of silica and a dispersion of alumina.
  • the electron beam curing coating described in the present application adds a dispersion of silica, so that the electron beam curing coating as a material of the electron beam curing coating gives the coating a good hardness; and the dispersion of the added alumina also makes the coating It has high hardness; the dispersion of silica and alumina dispersed in the electron beam curing coating will make the protective coating have better hardness and better wear resistance.
  • the surface of silica and alumina has a large amount of hydroxyl groups, has a large polarity, and has poor compatibility with organic monomers and prepolymers. Therefore, it is necessary to disperse silica and alumina in organic monomers and solvents, respectively.
  • the nanoparticles of silica and alumina are easily aggregated to form secondary particles, which affect the properties of the coating.
  • the present application provides an inorganic nanomaterial preparation.
  • the inorganic nanomaterial is one or both of silica and alumina.
  • the preparation method of the inorganic nano material comprises the following steps:
  • the present application treats the surface of silica and alumina to be uniformly dispersed in the organic monomer to form a stable transparent or translucent dispersion; thus, silica or The dispersion of alumina serves as a component of the electron beam-curing coating to give it better performance.
  • the inorganic nanomaterials described in the present application are silica and alumina, and the solution of the inorganic nanomaterial is first mixed with an organic solvent to obtain a mixed solution.
  • the solution of the inorganic nanomaterial is preferably a hydrosol in which inorganic nanomaterials are dispersed in water, such as silica gel and aluminum sol. Nano-silica particles are easily dispersed in water to form a stable dispersion due to electrostatic repulsion.
  • silica hydrosol, or silica gel has been used as a very economical green raw material.
  • the size of the silica gel is mainly 5 nm, 7 nm, 12 nm, 20 nm and 50 nm, and the pH is preferably 2 to 12.
  • silica gels are as follows: Ludox (DuPont), NexSil (NYACOL Technologies, Inc.), CAB-O-SPERSE (CABOT Corporation), Bindzil and Levasil (AkzoNobel), AERODISP (EVONIK Industries), HTSi-11L (Nanjing) Haitai Nano Co., Ltd., VK-S series (Hangzhou Wanjing New Materials Co., Ltd.), but not limited to these.
  • the aluminum sol may be a dispersion of alumina or an alumina modified silica gel, such as aluminum sol (Shandong Shanda Colloid Materials Co., Ltd.), XZ-1128 (Hefei Xiangzheng Chemical Technology Co., Ltd.), A-10 (Dalian Snow Chemical New Materials Science and Technology Co., Ltd.), VK-L30W (Hangzhou Wanjing New Materials Co., Ltd.), NanoPhase's Al-2255 and so on.
  • Nano-silica has small particle size and large surface area, so there are a large number of hydroxyl groups on the surface, and its hydroxyl density is about 4.6/nm 2 .
  • the silanol can lose hydrogen ions at pH 2 or higher, producing silicon-oxygen anion, which is easy to A stable dispersion is obtained in the water.
  • the silica particles are easily agglomerated to form large aggregates, which precipitate and fail to form a stable dispersion. Therefore, the present application uses a silane coupling agent to treat the surface of the silica, reduce the concentration of the hydroxyl group, and reduce the polarity to increase the affinity with the organic solvent and the monomer.
  • the organic solvent includes one or more of a low boiling point alcohol, an ether and a ketone, wherein the alcohol is one or more of methanol, ethanol, isopropanol and butanol; Tetrahydrofuran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl
  • One or more of ether and propylene glycol monobutyl ether; one or two of ketones such as acetone and methyl ethyl ketone, and other solvents include acetonitrile and dimethylformamide.
  • the amount of the above organic solvent to be added is preferably from 50% to 500% by weight based on the weight of the silica gel, and more preferably from 50% to 300% by weight.
  • the reaction of silane is greatly affected by pH and temperature. Under acidic conditions, it is easy to hydrolyze to produce silanol groups, and under alkaline conditions, condensation reaction is easy to occur. Under neutral conditions, hydrolysis and condensation reactions are slow; It facilitates the progress of hydrolysis and condensation reactions. Therefore, the present application adjusts the pH of the above mixed solution, and the pH value may be one or more of an acid such as formic acid, acetic acid, hydrochloric acid and nitric acid or a base such as ammonia, sodium hydroxide and potassium hydroxide. To adjust, the pH is preferably from 2 to 6.
  • the application then reacts the pH adjusted solution with an acrylate monomer and a silane coupling agent, and the hydrolyzed silane coupling agent reacts with the surface of the inorganic nanoparticle silica to increase the oil solubility of the silica, and then It is dissolved in an acrylate monomer to obtain a dispersion of an inorganic nanomaterial.
  • the reaction temperature is preferably from 30 ° C to 100 ° C, more preferably from 50 ° C to 80 ° C; and the reaction time is preferably from 1 h to 24 h, more preferably from 2 h to 12 h, and most preferably from 2 h to 6 h.
  • the silane coupling agent described in the present application preferably contains a group capable of generating a radical by electron beam irradiation or a group which causes radical crosslinking, and the above group includes (meth) acrylate, (meth) acrylamide, ethylene.
  • the silane coupling agent of the present application is preferably a silane coupling agent containing a halogenated alkyl group, a base group, an amino group, an epoxy group, a mercapto group or a halogenated alkyl group.
  • the mass ratio of the silane coupling agent to silica is preferably from 1:100 to 10:1, more preferably from 5:100 to 5:1, and most preferably from 1:10 to 1:1.
  • the amount of the silane coupling agent is related to the particle size or specific surface area of the silica. The smaller the particles, the larger the amount of the silane coupling agent required, and vice versa.
  • the acrylate monomer is used in an amount of from 0.5 to 10 times, preferably from 1 to 8 times, more preferably from 2 to 5 times the weight of the silica.
  • the silane coupling agent which can participate in the crosslinking reaction contains a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an amino group, and an epoxy group.
  • the (meth) acrylate group-containing silane is preferably ⁇ -(meth)acryloyloxypropyltrimethoxysilane or ⁇ -(meth)acryloyloxypropyltriethoxysilane.
  • ⁇ -(meth)acryloyloxypropyltriisopropoxysilane ⁇ -(meth)acryloyloxypropylmethyldimethoxysilane, ⁇ -(meth)acryloyloxypropane Of methyldiethoxysilane, ⁇ -(meth)acryloxypropyldimethylmethoxysilane and ⁇ -(meth)acryloxypropyldimethylethoxysilane One or more.
  • Such silanes are preferably (meth)acrylamidopropyltrimethoxysilane, (meth)acrylamidopropyltriethoxysilane, (meth)acrylamidopropyltriisopropoxysilane, (methyl) Acrylamide propylmethyldimethoxysilane, (meth)acrylamidopropylmethyldiethoxysilane, (meth)acrylamidopropyldimethylmethoxysilane, (meth)propylene Amidopropyldimethylethoxysilane, (meth)acrylamide (2-methyl)propyltrimethoxysilane, (meth)acrylamide (2-methyl)ethyltrimethoxysilane, ( Methyl)acrylamide (2-methyl)propyltriethoxysilane, (meth)acrylamide (2-methyl)ethyltriethoxysilane, N-[2-(meth)acrylamide Ethyl]aminopropy
  • the vinyl group-containing silane is preferably vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triisopropoxysilane, vinyl triptoxysilane, vinyl tris ( ⁇ -methoxy B) Oxy)silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyltriacetoxy One or more of a silane, a divinyltetramethyldisiloxane, and a tetravinyltetramethylcyclotetrasiloxanekind.
  • the epoxy group-containing silane is preferably 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, 3- (2,3-epoxypropoxy)propyltriisopropoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 3-(2,3-epoxy Propoxy)propylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propyldimethylmethoxysilane, 3-(2,3-epoxypropoxy)propyl One of methyl monooxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane or A variety.
  • Silane ⁇ -aminopropyldimethylmethoxysilane, ⁇ -aminopropyldimethylethoxysilane, N-methyl- ⁇ -aminopropyltrimethoxysilane, N-methyl- ⁇ -Aminopropyltriethoxysilane, N-anilinopropyltrimethoxysilane, N-anilinopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane , N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane and N- ⁇ -( One or more of aminoethyl)- ⁇ -aminopropylmethyldiethoxysilane.
  • a silane which easily generates a radical under the action of an electron beam can be represented by the structural formula XR 9 SiR 11 p (OR 12 ) 3-p wherein p is 0 to 2 and R 9 is an alkyl group having 1 to 5 carbon chains, R 11 and R 12 are alkane having 1 to 3 carbon chains, which may be the same or different, and X is Cl, Br, I or SH or the like.
  • Such silanes are preferably 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxylate Silane, 3-mercaptodimethyl methoxysilane, 3-mercaptopropyldimethylethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropyldimethylethoxysilane , 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-bromopropylmethyldimethoxy
  • the present application preferably employs a halogen-containing silane coupling agent-modified silica which is capable of generating free radicals at a lower electron beam radiant energy to rapidly cure the coating.
  • the acrylate monomer described in the present application may be a monofunctional monomer, may be a bifunctional monomer, or may be a polyfunctional monomer, and is not particularly limited herein.
  • the monofunctional monomer is preferably hydroxyethyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, dodecyl acrylate, tetradecyl acrylate, octadecyl acrylate, isobornyl acrylate, acrylic acid Caprolactone, 2-methoxyethyl acrylate, 2-butoxyethyl acrylate, 2-dimethylaminoethyl acrylate, 2-diisopropylaminoethyl acrylate, methacrylic acid Ester phosphate, ethoxyethoxyethyl acrylate, tetrahydrofuran methanol acrylate, phenoxyethyl acrylate, hexanediol me
  • the difunctional acrylate monomer is preferably 1,3-propanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, diethyl Diol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate (different molecular weight), dipropylene glycol diacrylate, triglycerol diacrylate, neopentyl glycol diacrylate Ester, ethoxy neopentyl glycol diacrylate, propoxy neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, ethoxylated bisphenol A diacrylate, zinc diacrylate and o-benzene One or more of diethanol diacetate diacrylate.
  • the polyfunctional acrylate monomer is preferably trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, glycerol triacrylate, Ethoxylated glycerol triacrylate, propoxylated glycerin triacrylate, trimethylolpropane tetraacrylate, ethoxylated pentaerythritol tripropenyl ester, propoxylated pentaerythritol tripropenyl ester, three One of 2-hydroxyethyl isocyanurate triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetrapropanol ester, propoxylated pentaerythritol tetrapropanol ester and dipentaerythritol monohydroxypentaacrylatekind or more.
  • the methacrylate compound of the above monomer is also suitable.
  • the invention also provides a preparation method of the dispersion of the alumina, the preparation process and the raw materials used are the same as the silica, and no further description is given here.
  • the present application also provides a method for preparing a dispersion of a UV absorber, that is, a dispersion of titanium dioxide and a dispersion of zinc oxide.
  • the present application disperses nano titanium dioxide or zinc oxide separately In the monomer, a stable transparent or translucent dispersion is formed.
  • Nano-TiO2 and zinc oxide are good visible-light transparent inorganic UV absorbers, but they have photocatalytic properties and are easy to decompose organic matter.
  • the application of the silane coupling agent to treat titanium dioxide and zinc oxide on the one hand increases their compatibility with the monomer, and on the other hand, the surface of the nano titanium dioxide and zinc oxide particles is coated with an inorganic silicon dioxide layer. Reduce its photocatalytic performance.
  • the inorganic ultraviolet absorber titanium dioxide and zinc oxide dispersion the raw material is a solution of titanium dioxide and zinc oxide, which may be a solution of titanium dioxide and zinc oxide in an organic solvent such as an alcohol, or may be aqueous,
  • the application is preferably an aqueous solution of titanium dioxide and an aqueous solution of zinc oxide.
  • the preparation process of the dispersion of the titanium dioxide dispersion and the zinc oxide described in the present application is the same as the preparation method of the dispersion of the inorganic nano material, and will not be described herein.
  • the dispersion of the inorganic nanomaterial dispersion and the inorganic ultraviolet absorbent is prepared, it is used as a component of an electron beam curing coating.
  • the electron beam curing coating provided by the present application includes a dispersion of an inorganic nano material, a dispersion of an inorganic ultraviolet absorber, a polyfunctional monomer and an acrylate prepolymer; and the inorganic nano material and the inorganic ultraviolet absorber in the above components
  • the miscibility of the functional group monomer and the acrylate prepolymer is not good, so it is necessary to first modify the silane coupling agent to increase the affinity between them.
  • Inorganic nanomaterials and inorganic ultraviolet absorbers have poor film forming properties or are not completely formed into films. Therefore, it is necessary to use a polyfunctional monomer and an acrylate prepolymer as a matrix material for film formation, and thus the electron beam curing coating described in the present application
  • the components are complementary and synergistic.
  • the inorganic nanomaterial silica can increase the hardness of the coating as an electron beam curing coating, but the amount required is large. If a small amount of alumina is added, the hardness of the coating can be improved, and the wear resistance of the coating can be remarkably improved. However, silica and alumina do not improve the weatherability of the coating.
  • the addition of a small amount of titanium dioxide or zinc oxide can selectively absorb and filter out the ultraviolet light harmful to the coating in sunlight, and increase the weather resistance of the coating. .
  • the use of titanium dioxide and zinc oxide alone does not improve the hardness and wear resistance of the coating.
  • the inorganic nano material of the present application is selected from one or two of silica and alumina, and the inorganic ultraviolet absorber is selected from titanium dioxide or zinc oxide to form a coating formed by the electron beam curing coating.
  • Good hardness and weather resistance Preferably, the present application preferably selects three inorganic materials among the silica, alumina, titania and zinc oxide as components of the electron beam-curing coating.
  • the best performance of the electron beam curing coating is:
  • the electron beam curing coating includes a dispersion of silica, a dispersion of alumina, and a dispersion of a dispersion of titanium dioxide and zinc oxide, so that the coating has good hardness, wear resistance and weather resistance at the same time. .
  • the role of the acrylate prepolymer in the overall coating is important, and the selection of a suitable prepolymer can improve the toughness, abrasion resistance and weatherability of the coating.
  • the acrylate prepolymer contains a plurality of (meth) acrylate functional groups, mainly including fat and aromatic urethane acrylate, epoxy acrylate, melamine acrylate, polyester acrylate, polyether acrylate, silicone acrylic acid One or more of ester, polybutadiene acrylate, polyacrylate acrylate, and acrylate oligomer; aliphatic urethane acrylate, polyether acrylate, and polyacrylate acrylate are preferred because of Contains no aromatic groups and has good weatherability.
  • the acrylate prepolymer preferably contains three or more functional groups to increase the crosslinking density after curing.
  • aliphatic urethane acrylates include ETECCRYL of Cytec, such as 264, 4866, 8210, 8301, 8402, 8411; Sartomer's CN9006NS, CN9010NS, CN9013NS, CN9110NS, CN970A60NS, CN971A80NS, CN975NS, CN989NS, etc.; Dymax Oligomers & Coatings BR -144,BR-302,BR-582E8,BR-582H15,BRC-443,BRC-841,BRC-843,BRC-970BT,BRC-990, etc., Changqing Company's 6103,6130B-80,6134B-80, 6145-100,6150-100,6158B-80,6170,6195-100,6196-100,6197,5105A,DR-U011,DR
  • the molecular weight of the acrylate prepolymer is preferably from 1,000 to 10,000, more preferably from 1,000 to 5,000, most preferably from 1,000 to 3,000.
  • the content of the acrylate prepolymer is preferably from 10 parts by weight to 80 parts by weight, more preferably from 10 parts by weight to 60 parts by weight, most preferably from 20 parts by weight to 50 parts by weight.
  • the polyfunctional monomer described in the present application is preferably one or more of the above polyfunctional acrylates, and the polyfunctional monomer is contained in an amount of 2 to 30 parts by weight, preferably 5 to 20 parts by weight.
  • the electron beam-curable coatings described in the present application also include other additives such as leveling agents, antifoaming agents and pigments, which can be added to the formulation to improve problems during the coating process, such as increasing the wetting property to the surface and reducing the bubbles. Produce, increase decorativeity, etc.
  • Leveling wetting agents include BYK-UV 3500, BYK-UV 3535, BYK-377, EVONIK INDUSTRIES from BYK RAD2010, RAD 2011, RAD 2100, RAD 2250, RAD 2300, RAD 2500, RAD 2600, RAD 2700, Wet 270, Dow Corning 28, 57, 67, 730, 930, 8211, XIAMETER OFX series by Dow Corning.
  • the antifoaming agent includes BYK-067A, BYK-088, BYK-1790, BYK-1791, BYK-A 535, EVONIK INDUSTRIES of BYK Company Airex 900, Airex 920, Airex950, Airex 962, Airex 990, Silok 4010, 4012, 4020, 4050, 4070, 4500, 4920, etc. of Guangzhou Snooker Chemical Co., Ltd., 54, 710, 810, 910, 1500, etc. of Dow Corning.
  • a pigment may be added to the electron beam-curable coating to change the color of the coating to increase its decorative properties without affecting its curing performance.
  • the pigment is preferably from 0.1 part by weight to 10 parts by weight, more preferably from 0.2 part by weight to 5 parts by weight. Most preferably, it is 1 part by weight to 3 parts by weight.
  • the pigments include carbon black, cobalt blue, iron oxide red, iron oxide yellow, nickel titanium yellow, and organic pigments.
  • the present application provides an electron beam curing coating comprising a dispersion of an inorganic nano material, a dispersion of an inorganic nano UV absorber, a polyfunctional monomer and an acrylate prepolymer, wherein the dispersion of the inorganic nano material is selected from the group consisting of One or two of a dispersion of silicon oxide and a dispersion of alumina, the dispersion of the inorganic nano-ultraviolet absorber is selected from a dispersion of titanium dioxide or a dispersion of zinc oxide; and the present application passes on silica, oxidation
  • the surface modification of aluminum, titanium dioxide and zinc oxide enables uniform dispersion in the acrylate without agglomeration, which is beneficial to improve the performance of the electron beam curing coating.
  • the inorganic nano-material dispersion and the inorganic nano-ultraviolet absorber dispersion are added to make the electron beam-curable coating as a coating having good hardness and weather resistance.
  • the application also provides a method for preparing a protective coating, comprising the following steps:
  • the preparation method of the dispersion of the inorganic nano material comprises the following steps:
  • the preparation method of the dispersion of the inorganic ultraviolet absorber comprises the following steps:
  • the inorganic nano material is silica or alumina
  • the inorganic nano-UV absorber is titanium dioxide or zinc oxide.
  • the present application also provides a preparation method of the protective coating.
  • the present application firstly disperses the inorganic nano material, the dispersion of the inorganic nano ultraviolet absorber, the polyfunctional monomer and the acrylate.
  • the prepolymer is mixed to obtain a coating, and the coating is applied to a base layer, followed by electron beam curing to obtain an electron beam cured coating.
  • the preparation process of the dispersion liquid of the inorganic nano material and the dispersion of the inorganic ultraviolet absorber is as described above, and will not be described herein.
  • the above coating methods are well known to those skilled in the art, such as brushing, rolling, spraying, and curtain coating, and the present application is not particularly limited.
  • the coating is irradiated with an electron beam to obtain a cured film.
  • the electron beam curing device is selected to be capable of emitting a high energy, medium energy or low energy electron beam, preferably a low energy electron beam, and the acceleration voltage is preferably 50 to 250 kV.
  • the irradiation chamber is protected with a degassing gas such as nitrogen or argon to make the concentration of oxygen less than 500 mg/L, preferably less than 300 mg/L.
  • the curing dose is preferably from 5 to 100 kGy, more preferably from 10 to 80 kGy, most preferably from 10 to 50 kGy; the curing rate is preferably from 100 to 1000 m/min, most preferably from 300 to 1000 m/min, most preferably from 500 to 1000. m/min.
  • the thickness of the obtained electron beam cured film is preferably from 1 ⁇ m to 2 mm, preferably from 10 ⁇ m to 1 mm, and most preferably from 10 ⁇ m to 100 ⁇ m.
  • the invention also provides for the use of the electron beam cured coating on automotive interior or decorative panels.
  • the decorative board may be a plastic material
  • the plastic material may be a pure polymer material or may be blended with an inorganic filler, and may be a film or a sheet material.
  • plastic materials include polyolefin, polystyrene, expanded polystyrene, impact polystyrene, polypropylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyamide (nylon 6, nylon) 66, etc.), polyvinyl chloride, polyurethane, polycarbonate, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyoxymethylene, polyetheretherketone, polyether, polyimide, polyether amide Imine, phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, cellulose acetate, starch, chitin, gelatin, polylactic acid, polyhydroxyalkanoate, polycaprolactone, poly(
  • the present invention is preferably a commonly used plastic such as polyvinyl chloride, polypropylene, polyethylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, and polylactic acid, polyhydroxyalkanoate, polycaprolactone, poly( Biodegradable plastics such as DL-lactide-co-glycolide, polypropylene carbonate, and cyclohexene carbonate.
  • a commonly used plastic such as polyvinyl chloride, polypropylene, polyethylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, and polylactic acid, polyhydroxyalkanoate, polycaprolactone, poly( Biodegradable plastics such as DL-lactide-co-glycolide, polypropylene carbonate, and cyclohexene carbonate.
  • the present application detects the performance of an electron beam cured coating, and the hardness, abrasion resistance and weather resistance of the cured coating can be detected by standard methods.
  • the hardness of the paint film can be measured by referring to the standard ASTM D3363-74.
  • the coated panel is placed on a fixed horizontal surface.
  • the pencil is at 45° to the layer and pushed forward by 10 mm at a speed of 5-10 cm/sec.
  • the surface of the sample was visually observed to be scratched.
  • the pencil hardness test pen can be from 1H to 9H. The larger the value, the higher the hardness.
  • the affinity of the paint film and the bottom plate can be referred to the national standard GB/T 9286-1998 paint film cross-cut test rating method.
  • Cut and cut 6 parallel cutting lines vertically and horizontally on the prepared test plate with the cutting tool (the spacing is determined by the coating thickness and the hardness of the substrate, ranging from 1 to 3 mm), and the coating is cut with a transparent tape. Evenly peel off the tape, check the cutting surface with a 4x magnifying glass, 0 is the best adhesion, the cutting edge is completely smooth, no one is off; 1 level has a little coating off at the intersection of the incision, but the cross-cut area is affected Can not be greater than 5%; more than 2, can not meet the requirements.
  • the abrasion resistance was measured by a Taber abrasion machine in accordance with the ASTM 4060 standard.
  • the test sample has a diameter of 10 cm, the grinding wheel model is Calibrase cs-10, the load weight is 1 kg, and the wear cycle is 2000.
  • the weight of the test sample before and after the abrasion was recorded, and the weight loss was expressed in milligrams.
  • Weatherability is carried out using an accelerated aging test chamber QUV.
  • the QUV tester's UVA-340 lamp provides the best solar light spectrum with a critical short wavelength range from 365 nanometers to 295 nanometers at the sun cutoff wavelength.
  • the maximum irradiance at 340 nm was 0.68 W/cm 2 and the test temperature was 50 degrees, provided that it was 8 hours light and then condensed for 4 hours.
  • the full set of tests lasted 1920 hours (80 days).
  • the change of the surface color of the sample after the test is expressed by CIE L*a*b* color space, the L* value indicates the brightness of the color, the a* value indicates the green red value of the color, the b* value indicates the blue-yellow value of the color, and the color difference is expressed by the formula.
  • Nexsil 12 is a dispersion of silica in water at a concentration of 30%, particles of 12 nm, and a pH of 9.3, which is produced by Nyacol Nano Technologies, Inc.
  • Al-2255 is a 20 nm dispersion of alumina in water at a concentration of 30% produced by Nanophase Technologies.
  • VK-T32 is a dispersion of anatase titanium dioxide produced by Hangzhou Wanjing New Material Co., Ltd. in water at a concentration of 20% and a particle size of 10 nm.
  • NanoBYK-3840 is a dispersion of zinc oxide in water produced by Altana with a zinc oxide content of 40% and a particle size of 20 nm.
  • organosilanes ⁇ -(meth)acryloyloxypropyltriethoxysilane, vinyltriethoxysilane and 3-chloropropyltriethoxysilane were obtained from Gelest.
  • the polyfunctional monomer pentaerythritol triacrylate (PETA) and 1,6-hexanediol diacrylate (HDDA) were obtained from Sartomer.
  • Polyvinyl chloride and polypropylene sheets are produced by Foshan Tianan Plastic Co., Ltd.
  • VK-T32 (containing anatase titanium dioxide 20%, 10 nm) was added to 600g of ethanol, the pH was adjusted to 3-4 with hydrochloric acid, then 120g of pentaerythritol triacrylate (PETA) was added, and finally 15g of ⁇ -(meth) propylene was added.
  • PETA pentaerythritol triacrylate
  • ⁇ -(meth) propylene 15g
  • Acyloxypropyltriethoxysilane and 15g 3-chloropropyltriethoxysilane the mixed solution was heated to 60 ° C and stirred for 6 h, the solvent ethanol and water were removed by vacuum using a rotary evaporator, the temperature was not Above 60 ° C, a viscous translucent dispersion of titanium dioxide in PETA is obtained.
  • NanoBYK-3840 (containing 40% zinc oxide, 20 nm) was added with 150 g of water and 600 g of ethanol, the pH was adjusted to 3-4 with hydrochloric acid, then 120 g of pentaerythritol triacrylate (PETA) was added, and finally 15 g of ⁇ -(methyl) was added.
  • PETA pentaerythritol triacrylate
  • Acryloyloxypropyltriethoxysilane and 15 g of 3-chloropropyltriethoxysilane the mixed solution was heated to 60 ° C and kept under stirring for 6 h, and the solvent ethanol and water were removed by vacuum using a rotary evaporator. Not more than 60 ° C, a viscous translucent dispersion of zinc oxide in PETA is obtained.
  • VK-T32 containing anatase titanium dioxide 20%, 10 nanometers
  • NanoBYK-3840 (containing 40% zinc oxide, 20 nm) was added to 150 g of water and 600 g of ethanol, the pH was adjusted to 3-4 with hydrochloric acid, then 120 g of pentaerythritol triacrylate (PETA) was added, and finally 30 g of 3-chloropropyl group was added.
  • PETA pentaerythritol triacrylate
  • Triethoxysilane the mixed solution is heated to 60 ° C and stirred for 6 h, the solvent ethanol and water are removed under vacuum by a rotary evaporator at a temperature not exceeding 60 ° C to obtain a viscous translucent dispersion of zinc oxide in PETA. .
  • the urethane acrylate prepolymer is dissolved in 1,6-hexanediol diacrylate, then an appropriate amount of silica monomer dispersion is added, and finally, an appropriate amount of leveling agent is added.
  • RAD 2500 and defoamer The total amount of Airex 900, leveling agent and antifoaming agent was 1%, and the resulting coating was applied by roll coating on untreated polyvinyl chloride or corona treated polypropylene sheets to form a coating of about 10 microns.
  • the coating was cured in an electron beam irradiation chamber under nitrogen protection with an irradiation voltage of 150 kV and an irradiation dose of 40 KGy.
  • the adhesion of the coating to the board is 0 to 1 grade.
  • the addition of silica does not affect the transparency of the coating, but it can significantly increase the hardness of the coating.
  • the urethane acrylate prepolymer 6195-100 is dissolved in 1,6-hexanediol diacrylate, and then an appropriate amount of a monomer dispersion of silica is added, and finally, an appropriate amount is added.
  • Leveling agent RAD 2500 and defoamer The total amount of Airex 900, leveling agent and antifoaming agent was 1%, and the resulting coating was applied by roll coating on untreated polyvinyl chloride or corona treated polypropylene sheets to form a coating of about 10 microns.
  • the coating is cured in an electron beam irradiation chamber under nitrogen protection, the irradiation voltage is 150KV, the irradiation dose is the minimum dose required when the coating reaches 5H, and the adhesion of the coating to the sheet is 0 to 1.
  • the urethane acrylate prepolymer 6195-100 was dissolved in 1,6-hexanediol diacrylate, and then the monomer dispersion of the silica of Example 3 was added and examples. 4 alumina, and finally add the right amount of leveling agent RAD 2500 and defoamer
  • the total amount of Airex 900, leveling agent and antifoaming agent was 1%, and the resulting coating was applied by roll coating on untreated polyvinyl chloride or corona treated polypropylene sheets to form a coating of about 10 microns.
  • the coating is cured in an electron beam irradiation chamber under nitrogen protection, the irradiation voltage is 150KV, the irradiation dose is 25KGy, and the adhesion of the coating to the sheet is 0 to 1.
  • the urethane acrylate prepolymer 6195-100 was dissolved in 1,6-hexanediol diacrylate according to the formulation of Table 4, and then the monomer dispersion of the silica synthesized in Example 8 was added. , the dispersion of the alumina synthesized in Example 9 and the titanium dioxide or zinc oxide of Example 10 or 11, and finally adding an appropriate amount of leveling agent RAD 2500 and defoamer The total amount of Airex 900, leveling agent and antifoaming agent was 1%, and the resulting coating was applied by roll coating on untreated polyvinyl chloride or corona treated polypropylene sheets to form a coating of about 10 microns. ,
  • the coating is cured in an electron beam irradiation chamber under nitrogen protection.
  • the irradiation voltage is 150KV
  • the irradiation dose is 25KGy
  • the adhesion between the coating and the sheet is 0 to 1.
  • the addition of titanium dioxide or zinc oxide does not affect the radiation. Take the dose.
  • the urethane acrylate prepolymer 6195-100 was dissolved in 1,6-hexanediol diacrylate, and then the monomer dispersion of the silica synthesized in Example 8 was added or Example 9 A monomer dispersion of the synthesized alumina, a titanium oxide synthesized in Example 10 or a dispersion of zinc oxide of Example 11, and finally an appropriate amount of a leveling agent is added.
  • RAD 2500 and defoamer The total amount of Airex 900, leveling agent and antifoaming agent was 1%, and the resulting coating was applied by roll coating on untreated polyvinyl chloride or corona treated polypropylene sheets to form a coating of about 20 microns.
  • the coating is cured in an electron beam irradiation chamber under nitrogen protection.
  • the irradiation voltage is 150KV
  • the irradiation dose is 25KGy
  • the adhesion between the coating and the sheet is 0 to 1.
  • the addition of titanium dioxide or zinc oxide does not affect. Irradiation dose.

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Abstract

一种电子束固化涂料，其包括：无机纳米材料的分散液、无机纳米紫外吸收剂的分散液、多官能团单体与丙烯酸酯预聚体；其中所述无机纳米材料的分散液选自二氧化硅的分散液与氧化铝的分散液中的一种或两种，所述无机紫外吸收剂的分散液为二氧化钛的分散液或氧化锌的分散液。通过对二氧化硅、氧化铝、二氧化钛与氧化锌分别进行表面改性，使其分别溶于丙烯酸酯单体中，形成了无机材料的分散液，而未发生团聚，且与多官能团单体、丙烯酸酯预聚体亲和性较好，使得到的电子束固化涂料可用于涂层材料，使涂层具有较好的硬度与耐候性。

Description

电子束固化涂料、电子束固化涂层的制备方法以及应用
本申请要求于2015年02月15日提交中国专利局、申请号为201510085333.3、发明名称为“电子束固化涂料、电子束固化涂层的制备方法以及应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及表面涂层技术领域，尤其涉及电子束固化涂料、电子束固化涂层的制备方法以及应用。
背景技术
塑料在日常生活中的应用越来越广泛，从家用电器、室内外装饰，到汽车部件，都需要用到塑料。但塑料至少有两个致命的弱点：其一是耐候性不好，在光热的作用下容易分解，降低其使用寿命，有的甚至分解产生有毒的产物和气体；其二是塑料比较软，表面容易划伤。在塑料挤出成型时，虽然可以通过加入光热稳定剂及耐磨剂等来提高某些性能，但另外一些性能必然受到损害，而且本体改性需要的原材料用量大，增加了成本。
表面涂层技术不但可以改变塑料的外观，而且使表面的物理化学性能得到改善。通过加入功能性添加剂，可以显著提高塑料的耐化学品、耐候性、耐划伤与抗菌等性能；同时由于表面涂层很薄，功能材料的用量少，对产品成本增加较少。
涂层的涂料可以通过热固化或辐射的方法获得。溶剂型和水性涂料，一般是热固化的，但溶剂型体系的固含量较低，大量的溶剂释放到空气中，引起环境污染；水性体系虽然可以提高固含量，但水的比热较大，挥发速度慢，需要提供大量的热能，固化通道一般较长，固化速度慢。辐射方法包括紫外光和电子束照射，辐射方法采用的涂料可以是100％固含量，不含有机溶剂，没有VOC，固化速度快，是新兴的涂料固化方法。由于固化速度快，紫外光固化技术已经得到大规模应用，但与紫外光固化相比，电子束固化具有如下优点：电能的利用率高；固化速度更快；电子束的能 量大，足以直接打开丙烯酸酯，产生自由基，引发聚合反应，因此不需要引发剂，提高了涂料的储存稳定性，并降低光引发剂分解产生的副产物带来的颜色和气味；电子束的穿透能力强，能高达几厘米，而紫外光只能透过几十微米的厚度。
随着纳米技术的发展，纳米填料得到了广泛应用。由于纳米填料粒径小于100纳米，将纳米填料作为涂料的组分，涂料的透明性不受纳米填料的影响，而涂料的机械性能如耐磨性、耐候性以及化学性能如耐光热和化学品性都得到明显的提高。但是一般纳米材料如二氧化硅、二氧化钛、氧化锌和氧化铝等的表面有大量的羟基，极性大，与有机单体和预聚体的相容性不好，虽然用物理方法如砂磨，球磨等能将纳米填料分散在有机单体和溶剂中，但稳定性都不太好，这是由于纳米颗粒很容易聚集在一起，形成二次颗粒，尺寸比初级纳米粒子大很多，且影响涂层的透明性和光泽。
发明内容
本发明解决的技术问题在于提供一种电子束固化涂料与电子束固化涂层，本申请的电子束固化涂料用于涂层材料，使涂层具有较好的硬度与耐候性。
有鉴于此，本申请提供了一种电子束固化涂料，包括：
Figure PCTCN2015073560-appb-000001
所述无机纳米材料的分散液按照以下步骤制备：
A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
所述无机紫外吸收剂的分散液按照以下步骤制备：
A)将无机纳米紫外吸收剂的溶液与有机溶剂混合，得到混合溶液， 调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米紫外吸收剂的分散液；
所述无机纳米材料为二氧化硅与氧化铝中的一种或两种；
所述无机纳米紫外吸收剂为二氧化钛或氧化锌。
优选的，所述硅烷偶联剂为丙烯酸酯基硅烷和卤代烷基硅烷偶联剂。
优选的，所述二氧化硅粒径为5～100nm，所述氧化铝的粒径为12～100nm。
优选的，所述无机纳米材料的分散液的含量为10～30重量份。
优选的，所述丙烯酸酯预聚体选自脂肪族聚氨酯丙烯酸酯、芳香族聚氨酯丙烯酸酯、环氧丙烯酸酯、三聚氰胺丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、有机硅丙烯酸酯、聚丁二烯丙烯酸酯、聚丙烯酸酯丙烯酸酯和丙烯酸酯齐聚物中的一种或多种；所述多官能团单体为多官能团丙烯酸酯。
优选的，所述电子束固化涂料中还包括流平润滑剂、消泡剂、颜料或纳米抗菌剂；所述颜料的含量为0.1～10重量份。
本申请还提供了一种电子束固化涂层的制备方法，包括以下步骤：
将5～50重量份的无机纳米材料的分散液、1～10重量份的无机纳米紫外吸收剂的分散液、2～30重量份的多官能团单体、10～80重量份的丙烯酸酯预聚体混合，得到涂料；
将所述涂料涂布于基材上，然后进行电子束固化，得到电子束固化涂层；
所述无机纳米材料的分散液的制备方法，包括以下步骤：
A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
所述无机紫外吸收剂的分散液的制备方法，包括以下步骤：
A)将无机纳米紫外吸收剂的溶液与有机溶剂混合，得到混合溶液， 调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米紫外吸收剂的分散液；
所述无机纳米材料为二氧化硅与氧化铝中的一种或两种；
所述无机纳米紫外吸收剂为二氧化钛或氧化锌。
优选的，所述电子束固化的设备为低能电子束设备，所述电子束固化的剂量为5～100kGy，所述电子束固化的速度为100～1000m/min。
优选的，所述电子束固化涂层的厚度为10～100μm。
本申请还提供了一种上述方案所述的电子束固化涂料或上述方案所所制备的电子束固化涂层在汽车内饰或装饰板材上的应用。
本申请提供了一种电子束固化涂料，其包括无机纳米材料的分散液、无机纳米紫外吸收剂的分散液、多官能团单体与丙烯酸酯预聚体，其中无机纳米材料的分散液选自二氧化硅的分散液与氧化铝的分散液中的一种或两种，无机纳米紫外吸收剂的分散液选自二氧化钛的分散液或氧化锌的分散液；并且本申请通过对二氧化硅、氧化铝、二氧化钛与氧化锌进行表面改性，使其能够均匀分散于丙烯酸酯中而不发生团聚，有利于提高电子束固化涂料的性能，本申请通过添加无机纳米材料分散液与无机纳米紫外吸收剂分散液，使电子束固化涂料作为涂层具有较好的硬度与耐候性。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明实施例公开了一种电子束固化涂料，包括：
Figure PCTCN2015073560-appb-000002
所述无机纳米材料的分散液的制备方法，包括以下步骤：
A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
所述无机紫外吸收剂的分散液的制备方法，包括以下步骤：
A)将无机纳米紫外吸收剂的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米紫外吸收剂的分散液；
所述无机纳米材料为二氧化硅与氧化铝中的一种或两种；
所述无机纳米紫外吸收剂为二氧化钛或氧化锌。
本申请提供了一种电子束固化涂料，所述电子束固化涂料包括无机纳米材料的分散液、无机紫外吸收剂的分散液、多官能团单体与丙烯酸酯预聚体；并使所述无机纳米材料与无机紫外吸收剂分别均匀分散于丙烯酸酯单体中，未发生团聚现象，从而避免了对涂层性能的影响，且使涂层具有较好的耐磨性与耐候性。
在所述电子束固化涂料中，所述无机纳米材料的分散液为二氧化硅的分散液与氧化铝的分散液中的一种或两种。本申请所述电子束固化涂料中添加二氧化硅的分散液，使电子束固化涂料作为电子束固化涂层的材料使涂层具有较好的硬度；而添加氧化铝的分散液也使涂层具有较高的硬度；在电子束固化涂料中同时添加二氧化硅的分散液与氧化铝的分散液会使保护涂层具有更好的硬度，且具有较好的耐磨性。二氧化硅与氧化铝的表面有大量的羟基，极性大，与有机单体、预聚体的相容性不好，因此需要将二氧化硅与氧化铝分别分散在有机单体和溶剂中，但是二氧化硅与氧化铝的纳米颗粒很容易聚集在一起，形成二次颗粒，而影响涂层的性质，为了提高电子束固化涂层的性质，本申请提供了一种无机纳米材料的制备方法，所述无机纳米材料为二氧化硅与氧化铝中的一种或两种。所述无机纳米材料的制备方法包括以下步骤：
A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所 述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
在制备无机纳米材料的过程中，本申请将二氧化硅、氧化铝的表面进行处理，使之能够均匀分散在有机单体中，形成稳定的透明或半透明分散液；因此将二氧化硅或氧化铝的分散液作为电子束固化涂料的组分，使其具有较好的性能。
本申请所述无机纳米材料为二氧化硅与氧化铝，首先将所述无机纳米材料的溶液与有机溶剂混合，得到混合液。所述无机纳米材料的溶液优选为无机纳米原料分散在水中的水溶胶，如硅胶与铝溶胶。纳米二氧化硅粒子由于静电排斥作用很容易分散在水中形成稳定的分散液，目前二氧化硅的水溶胶即硅胶已经作为一种很经济的绿色原料。所述硅胶的尺寸主要有5nm、7nm、12nm、20nm与50nm，pH值优选为2～12。一些商品化的硅胶如下：Ludox(杜邦公司)，NexSil(NYACOL Technologies,Inc.)，CAB-O-SPERSE(CABOT Corporation)，Bindzil和Levasil(AkzoNobel)，AERODISP(EVONIK Industries)，HTSi-11L(南京海泰纳米有限公司)，VK-S系列(杭州万景新材料有限公司)，但也不限这些。
所述铝溶胶可以是氧化铝的分散液，也可以是氧化铝改性的硅胶，如铝溶胶(山东山大胶体材料有限责任公司)，XZ-1128(合肥翔正化学科技公司)，A-10(大连斯诺化学新材料科学技术有限公司)，VK-L30W(杭州万景新材料有限公司)，NanoPhase公司的Al-2255等等。
纳米二氧化硅的颗粒小，表面积很大，故表面有大量的羟基，其羟基密度约为4.6/nm2，硅羟基在pH值2以上就能失去氢离子，产生硅氧负离子，很容易在水中得到稳定的分散液。但在有机溶剂或单体中，由于羟基之间很强的氢键作用，二氧化硅粒子很容易团聚在一起形成大的聚集体，沉淀下来，不能形成稳定的分散液。因此本申请采用硅烷偶联剂来处理二氧化硅表面，减少羟基浓度，降低极性，以增加与有机溶剂和单体的亲和性。
但是硅烷偶联剂除了极少数能溶于水外，绝大部分在水中的溶解度很 低，故需要加入水溶性溶剂来增加硅烷在硅溶胶水溶液中的溶解度。所述有机溶剂包括低沸点醇类、醚类与酮类中的一种或多种，其中所述醇类如甲醇、乙醇、异丙醇与丁醇中的一种或多种；醚类如四氢呋喃、1,4-二氧六环、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丙醚与丙二醇单丁醚中的一种或多种；酮类如丙酮与丁酮中的一种或两种，其它溶剂还包括乙腈与二甲基甲酰胺等。上述有机溶剂的加入量优选为硅胶重量的50％～500％，更优选为50％～300％。
硅烷的反应受pH和温度的影响较大，在酸性条件下，容易水解产生硅羟基，而在碱性条件下容易产生缩合反应，在中性条件下，水解和缩合反应都很慢；提高温度有助于水解和缩合反应的进行。因此本申请调节上述混合溶液的pH值，pH值可以用酸如甲酸、乙酸、盐酸与硝酸中的一种或多种或碱如氨水、氢氧化钠与氢氧化钾中的一种或多种来调节，pH值优选为2～6。
本申请然后将调节pH后的溶液与丙烯酸酯单体、硅烷偶联剂反应，水解后的硅烷偶联剂与无机纳米颗粒二氧化硅的表面反应，增加了二氧化硅的油溶性，再将其溶于丙烯酸酯单体中，而得到无机纳米材料的分散液。所述反应温度优选为30℃～100℃，更优选为50℃～80℃；反应时间优选为1h～24h，更优选为2h～12h，最优选为2h～6h。
本申请所述硅烷偶联剂优选为含有电子束照射可以产生自由基的基团或导致自由基交联的基团，上述基团包括(甲基)丙烯酸酯、(甲基)丙烯酰胺、乙烯基、氨基、环氧、巯基或卤代烷基，本申请所述硅烷偶联剂优选为含有卤代烷基的硅烷偶联剂。所述硅烷偶联剂与二氧化硅的质量比优选为1:100～10:1，更优选为5:100～5:1，最优选为1:10～1:1。所述硅烷偶联剂的用量与二氧化硅的颗粒大小或比表面积有关，颗粒越小，需要的硅烷偶联剂的量越大，反之亦然。所述丙烯酸酯单体的用量是二氧化硅重量的0.5～10倍，优选为1～8倍，更优选为2～5倍。
可参与交联反应的硅烷偶联剂含有(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基基团、氨基基团与环氧基团。
含(甲基)丙烯酸酯基团的硅烷可以用结构式CH2＝CR1-CO-O-R2SiR3 m(OR4)3-m表示，其中m为0～2，R1为H或CH3，R2为含有1～5个碳链的烷基，R3和R4为含有1～3个碳链的烷烃，R3和R4可以相同也可以不同。所述含有(甲基)丙烯酸酯基团的硅烷优选为γ-(甲基)丙烯酰氧基丙基三甲氧基硅烷、γ-(甲基)丙烯酰氧基丙基三乙氧基硅烷、γ-(甲基)丙烯酰氧基丙基三异丙氧基硅烷、γ-(甲基)丙烯酰氧基丙基甲基二甲氧基硅烷、γ-(甲基)丙烯酰氧基丙基甲基二乙氧基硅烷、γ-(甲基)丙烯酰氧基丙基二甲基甲氧基硅烷与γ-(甲基)丙烯酰氧基丙基二甲基乙氧基硅烷中的一种或多种。
含丙烯酰胺基团的硅烷可以用结构式CH2＝CR5-CO-NH-R6SiR7 n(OR8)3-n表示，其中n为0～2，R5为H或CH3，R6为含有1～5个碳链的烷基，R7和R8为含有1～3个碳链的烷烃，R7和R8可以相同也可以不同。这类硅烷优选为(甲基)丙烯酰胺丙基三甲氧基硅烷、(甲基)丙烯酰胺丙基三乙氧基硅烷、(甲基)丙烯酰胺丙基三异丙氧基硅烷、(甲基)丙烯酰胺丙基甲基二甲氧基硅烷、(甲基)丙烯酰胺丙基甲基二乙氧基硅烷、(甲基)丙烯酰胺丙基二甲基甲氧基硅烷、(甲基)丙烯酰胺丙基二甲基乙氧基硅烷、(甲基)丙烯酰胺(2-甲基)丙基三甲氧基硅烷、(甲基)丙烯酰胺(2-甲基)乙基三甲氧基硅烷、(甲基)丙烯酰胺(2-甲基)丙基三乙氧基硅烷、(甲基)丙烯酰胺(2-甲基)乙基三乙氧基硅烷、N-[2-(甲基)丙烯酰胺乙基]胺丙基三甲氧基硅烷、N-[2-(甲基)丙烯酰胺乙基]胺丙基三乙氧基硅烷、3-(甲基)丙烯酰胺丙基三乙酰氧基硅烷、(甲基)丙烯酰胺乙基三甲氧基硅烷、(甲基)丙烯酰胺乙基三乙氧基硅烷、(甲基)丙烯酰胺甲基三甲氧基硅烷与(甲基)丙烯酰胺甲基三乙氧基硅烷中的一种或多种。
含乙烯基的硅烷优选为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷、乙烯基三特丁氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、乙烯基甲基二甲氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基二甲基甲氧基硅烷、乙烯基二甲基乙氧基硅烷、乙烯基三乙酰氧基硅烷、二乙烯基四甲基二硅氧烷与四乙烯基四甲基环四聚硅氧烷中的一种或多 种。
含环氧基团的硅烷优选为3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基三异丙氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二乙氧基硅烷、3-(2,3-环氧丙氧)丙基二甲基甲氧基硅烷、3-(2,3-环氧丙氧)丙基二甲基一氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷与2-(3,4-环氧环己基)乙基三乙氧基硅烷中的一种或多种。
含氨基的硅烷优选为γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-氨丙基甲基二甲氧基硅烷、γ-氨丙基甲基二乙氧基硅烷、γ-氨丙基二甲基甲氧基硅烷、γ-氨丙基二甲基乙氧基硅烷、N-甲基-γ-氨丙基三甲氧基硅烷、N-甲基-γ-氨丙基三乙氧基硅烷、N-苯胺丙基三甲氧基硅烷、N-苯胺丙基三乙氧基硅烷、N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷与N-β-(氨乙基)-γ-氨丙基甲基二乙氧基硅烷中的一种或多种。
在电子束作用下容易产生自由基的硅烷可以用结构式XR9SiR11 p(OR12)3-p表示，其中p为0～2，R9为含有1～5个碳链的烷基，R11和R12为含有1～3个碳链的烷烃，它们可以相同也可以不同，X为Cl、Br、I或SH等。这类硅烷优选为3-巯丙基三甲氧基硅烷、3-巯丙基三乙氧基硅烷、3-巯丙基甲基二甲氧基硅烷、3-巯丙基甲基二乙氧基硅烷、3-巯丙基二甲基甲氧基硅烷、3-巯丙基二甲基乙氧基硅烷、3-氯丙基三甲氧基硅烷、3-氯丙基三乙氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基甲基二乙氧基硅烷、3-氯丙基二甲基甲氧基硅烷、3-氯丙基二甲基乙氧基硅烷、3-溴丙基三甲氧基硅烷、3-溴丙基三乙氧基硅烷、3-溴丙基甲基二甲氧基硅烷、3-溴丙基甲基二乙氧基硅烷、3-溴丙基二甲基甲氧基硅烷、3-溴丙基二甲基乙氧基硅烷、3-碘丙基三甲氧基硅烷、3-碘丙基三乙氧基硅烷、3-碘丙基甲基二甲氧基硅烷、3-碘丙基甲基二乙氧基硅烷、3-碘丙基二甲基甲氧基硅烷与3-碘丙基二甲基乙氧基硅烷中的一种或多种。
本申请优选采用含有卤素的硅烷偶联剂改性二氧化硅，其能在较低电子束辐射能量下产生自由基使涂层迅速固化。
本申请所述丙烯酸酯单体可以为单官能团单体、可以为双官能团单体，也可以为多官能团单体，本申请不作特别的限制。所述单官能团单体优选为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸异辛酯、丙烯酸十二烷基酯、丙烯酸十四烷基酯、丙烯酸十八烷基酯、丙烯酸异冰片酯、丙烯酸己内酯、丙烯酸-2-甲氧基乙基酯、丙烯酸-2-丁氧基乙酯、2-二甲基氨基乙基丙烯酸酯、2-二异丙氨基乙基丙烯酸酯、甲基丙烯酸酯磷酸酯、乙氧基乙氧乙基丙烯酸酯、四氢呋喃甲醇丙烯酸酯、苯氧乙基丙烯酸酯、己二醇甲氧基单丙烯酸酯、乙氧基化新戊二醇甲氧基单丙烯酸酯、聚乙二醇甲氧基单丙烯酸酯(各种不同的分子量)、2,3-环氧丙基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯与1,1,1,3,3,3-六氟异丙基甲基丙烯酸酯中的一种或多种。
所述双官能团丙烯酸酯单体优选为1,3-丙二醇二丙烯酸酯、1、4-丁二醇二丙烯酸酯、1、6-己二醇二丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、聚乙二醇二丙烯酸醇酯(各种不同的分子量)、二丙二醇二丙烯酸酯、三丙三醇二丙烯酸酯、新戊二醇二丙烯酸酯、乙氧基新戊二醇二丙烯酸酯、丙氧基新戊二醇二丙烯酸酯、环己烷二甲醇二丙烯酸酯、乙氧基化双酚A二丙烯酸酯、二丙烯酸锌与邻苯二甲酸二乙醇二丙烯酸酯中的一种或多种。
所述多官能团丙烯酸酯单体优选为三羟甲基丙烷三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯、甘油三丙烯酸酯、乙氧基化甘油三丙烯酸酯、丙氧基化甘油三丙烯酸酯、二缩三羟甲基丙烷四丙烯酸酯、乙氧基化季戊四醇三丙烯醇酯、丙氧基化季戊四醇三丙烯醇酯、三-2-羟乙基异氰脲酸酯三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧基化季戊四醇四丙烯醇酯、丙氧基化季戊四醇四丙烯醇酯与双季戊四醇单羟基五丙烯酸酯中的一种或多种。
上述单体的甲基丙烯酸酯化合物同样适用。
本发明同样提供了所述氧化铝的分散液的制备方法，其制备过程以及采用的原料与二氧化硅相同，此处不再进行赘述。
本申请同时还提供了紫外吸收剂的分散液，即二氧化钛的分散液与氧化锌的分散液的制备方法。本申请将纳米二氧化钛或氧化锌分别分散在有 机单体中，形成稳定的透明或半透明分散液。纳米二氧化钛与氧化锌是很好的可见光透明的无机紫外吸收剂，但是它们具有光催化性能，容易分解有机物。本申请采用硅烷偶联剂将二氧化钛与氧化锌处理后，一方面增加了它们与单体的相容性，另一方面可以在纳米二氧化钛和氧化锌的颗粒表面涂一层无机二氧化硅层，降低其光催化性能。
按照本发明，所述无机紫外吸收剂二氧化钛与氧化锌的分散液，原料是二氧化钛与氧化锌的溶液，可以是二氧化钛与氧化锌在有机溶剂如醇类中的溶液，也可以是水性的，本申请优选为二氧化钛的水溶液与氧化锌的水溶液。本申请所述二氧化钛的分散液与氧化锌的分散液的制备过程与无机纳米材料的分散液的制备方法相同，此处不再进行赘述。
本申请在所述无机纳米材料的分散液与所述无机紫外吸收剂的分散液制备完成后，将其作为了电子束固化涂料的组分。
本申请提供的电子束固化涂料中包括无机纳米材料的分散液、无机紫外吸收剂的分散液、多官能团单体与丙烯酸酯预聚体；上述组分中无机纳米材料与无机紫外吸收剂与多官能团单体、丙烯酸酯预聚体的混溶性不好，因此需要先通过硅烷偶联剂改性来增加它们之间的亲和性。无机纳米材料与无机紫外吸收剂本身成膜性不好或不能完全成膜，因此需要采用多官能团单体与丙烯酸酯预聚体作为成膜的基体材料，因此本申请所述电子束固化涂料中的组分是相辅相成，协同作用的。
无机纳米材料二氧化硅作为电子束固化涂料可以增加涂层的硬度，但需要的量很大，若添加少量的氧化铝，则在提高硬度的同时，能显著提高涂层的耐磨性。但二氧化硅和氧化铝并不能提高涂层的耐候性，少量二氧化钛或氧化锌的加入，能选择性地吸收和过滤掉太阳光中的对涂层有害的紫外光，增加涂层的耐候性。但二氧化钛和氧化锌单独使用并不能提高涂层的硬度和耐磨性。因此本申请所述无机纳米材料选自二氧化硅与氧化铝中的一种或两种，所述无机紫外吸收剂选自二氧化钛或氧化锌中，以使电子束固化涂料形成的涂层具有较好的硬度与耐候性。作为优选方案，本申请优选在二氧化硅、氧化铝、二氧化钛与氧化锌中选择三种无机材料作为电子束固化涂料的组分。在实施例中，电子束固化涂料性能最好的情况是： 电子束固化涂料中包括二氧化硅的分散液、氧化铝的分散液以及二氧化钛的分散液与氧化锌的分散液中的一种，使涂层同时具有较好的硬度、耐磨性与耐候性。
丙烯酸酯预聚体在整个涂层中作用很重要，选择适当的预聚体可以提高涂层的韧性，耐磨性和耐候性。所述丙烯酸酯预聚体含有多个(甲基)丙烯酸酯官能团，主要包括脂肪和芳香族聚氨酯丙烯酸酯、环氧丙烯酸酯、三聚氰胺丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、有机硅丙烯酸酯、聚丁二烯丙烯酸酯、聚丙烯酸酯丙烯酸酯和丙烯酸酯齐聚物中的一种或多种；脂肪族聚氨酯丙烯酸酯、聚醚丙烯酸酯和聚丙烯酸酯丙烯酸酯是优选的，因为其不含芳香基团，有比较好的耐候性。所述丙烯酸酯预聚体最好含有三个以上的官能团，以增加固化后的交联密度。其中脂肪族聚氨酯丙烯酸酯包括Cytec公司的EBECRYL如264,4866，8210，8301，8402，8411等；Sartomer公司的CN9006NS，CN9010NS，CN9013NS，CN9110NS，CN970A60NS，CN971A80NS，CN975NS，CN989NS等；Dymax Oligomers&Coatings公司的BR-144，BR-302，BR-582E8，BR-582H15，BRC-443，BRC-841，BRC-843，BRC-970BT，BRC-990等，长青公司的6103，6130B-80，6134B-80，6145-100，6150-100，6158B-80，6170，6195-100，6196-100，6197，5105A，DR-U011，DR-U012，DR-U024，DR-U052，DR-U053，DR-U095，DR-U110，DR-U129，DR-U591等等。
丙烯酸酯预聚体有不同的分子量和粘度，在组成配方时不能使整体粘度太大以影响涂布。所述丙烯酸酯预聚体的分子量优选为1000～10000，更优选为1000～5000，最优选为1000～3000。所述丙烯酸酯预聚体的含量优选为10重量份～80重量份，更优选为10重量份～60重量份，最优选为20重量份～50重量份。
本申请所述多官能团单体优选为上述多官能团丙烯酸酯中的一种或多种，所述多官能团单体的含量为2～30重量份，优选为5～20重量份。本申请所述电子束固化涂料中还包括其它助剂如流平剂、消泡剂和颜料等可加入配方中以改善在涂布过程中产生的问题如增加对表面的润湿性能，降低气泡的产生，增加装饰性等。流平润湿剂包括BYK公司的BYK-UV 3500，BYK-UV 3535，BYK-377，EVONIK INDUSTRIES的
Figure PCTCN2015073560-appb-000003
RAD2010，
Figure PCTCN2015073560-appb-000004
RAD 2011，
Figure PCTCN2015073560-appb-000005
RAD 2100，
Figure PCTCN2015073560-appb-000006
RAD 2250，
Figure PCTCN2015073560-appb-000007
RAD 2300，
Figure PCTCN2015073560-appb-000008
RAD 2500，
Figure PCTCN2015073560-appb-000009
RAD 2600，
Figure PCTCN2015073560-appb-000010
RAD 2700，
Figure PCTCN2015073560-appb-000011
Wet 270，Dow Corning公司的Dow Corning 28，57，67，730，930，8211，XIAMETER OFX系列。所述消泡剂包括BYK公司的BYK-067A，BYK-088，BYK-1790，BYK-1791，BYK-A 535，EVONIK INDUSTRIES的
Figure PCTCN2015073560-appb-000012
Airex 900，
Figure PCTCN2015073560-appb-000013
Airex 920，
Figure PCTCN2015073560-appb-000014
Airex950，
Figure PCTCN2015073560-appb-000015
Airex 962，
Figure PCTCN2015073560-appb-000016
Airex 990，广州斯诺柯化学有限公司的Silok 4010，4012，4020，4050，4070，4500，4920等，Dow Corning公司的54，710，810，910，1500等等。
电子束固化涂料中可以添加颜料来改变涂层颜色，从而增加其装饰性能，而不影响其固化性能，所述颜料优选为0.1重量份～10重量份，更优选为0.2重量份～5重量份，最优选为1重量份～3重量份。所述颜料包括炭黑、钴蓝、氧化铁红、氧化铁黄、镍钛黄以及有机颜料等。
本申请提供了一种电子束固化涂料，其包括无机纳米材料的分散液、无机纳米紫外吸收剂的分散液、多官能团单体与丙烯酸酯预聚体，其中无机纳米材料的分散液选自二氧化硅的分散液与氧化铝的分散液中的一种或两种，无机纳米紫外吸收剂的分散液选自二氧化钛的分散液或氧化锌的分散液；并且本申请通过对二氧化硅、氧化铝、二氧化钛与氧化锌进行表面改性，使其能够均匀分散于丙烯酸酯中而不发生团聚，而有利于提高电子束固化涂料的性能。本申请通过添加无机纳米材料分散液与无机纳米紫外吸收剂分散液，使电子束固化涂料作为涂层具有较好的硬度与耐候性。
本申请还提供了一种保护涂层的制备方法，包括以下步骤：
将5～50重量份的无机纳米材料的分散液、1～10重量份的无机纳米紫外吸收剂的分散液、5～20重量份的多官能团单体、10～80重量份的丙烯酸酯预聚体混合，得到涂料；
将所述涂料涂布于基材上，然后进行电子束固化，得到电子束固化涂层；
所述无机纳米材料的分散液的制备方法，包括以下步骤：
A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
所述无机紫外吸收剂的分散液的制备方法，包括以下步骤：
A)将无机纳米紫外吸收剂的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米紫外吸收剂的分散液；
所述无机纳米材料为二氧化硅或氧化铝；
所述无机纳米紫外吸收剂为二氧化钛或氧化锌。
本申请还提供了所述保护涂层的制备方法，在制备保护涂层的过程中，本申请先将无机纳米材料的分散液、无机纳米紫外吸收剂的分散液、多官能团单体与丙烯酸酯预聚体进行混合，得到涂料，再将所述涂料涂布于基层上，然后进行电子束固化，得到电子束固化涂层。
在上述制备涂层的过程中，所述无机纳米材料的分散液与无机紫外吸收剂的分散液的制备过程如上所述，此处不再进行赘述。
上述涂布的方法为本领域技术人员熟知的，如刷涂、滚涂、喷涂和帘涂等，本申请不作特别的限制。所述涂料经电子束照射而得固化膜。电子束固化所选用的设备为能够发出高能、中能或低能电子束，优选为低能电子束，加速电压优选为50～250KV。照射室用脱性气体如氮气或氩气保护，使氧气的浓度小于500mg/L，最好是低于300mg/L。固化的剂量优选为5～100kGy，更优选为10～80kGy，最优选为10～50kGy；固化速度优选为100～1000米/分钟，最优选为300～1000米/分钟，最优选为500～1000米/分钟。
所得电子束固化膜的厚度优选为1μm～2mm，最好从10μm～1mm，最佳从10μm～100μm。
本发明还提供了所述电子束固化涂层在汽车内饰或装饰板材上的应用。
所述装饰板材可以为塑料，所述塑料可以是纯的高分子材料，也可以是与无机填料共混的，可以是薄膜，也可以是板材。这些塑料材料包括聚烯烃、聚苯乙烯、发泡聚苯乙烯、耐冲击性聚苯乙烯、聚丙烯晴、丙烯晴-丁二烯-苯乙烯共聚物、聚酯、聚酰胺(尼龙6、尼龙66等)、聚氯乙烯、聚氨酯、聚碳酸酯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚甲醛、聚醚醚酮、聚乙醚、聚酰亚胺、聚醚酰亚胺、酚醛树脂、脲醛树脂、三聚氰胺甲醛树脂、醋酸纤维素、淀粉、甲壳素、明胶、聚乳酸、聚羟基脂肪酸酯、聚己内酯、聚(DL-丙交酯-共-乙醇酸交酯)、聚碳酸亚丙酯、聚碳酸环己烯酯等。本发明优选为聚氯乙烯、聚丙烯、聚乙烯、聚苯乙烯、丙烯晴-丁二烯-苯乙烯共聚物等常用的塑料以及聚乳酸、聚羟基脂肪酸酯、聚己内酯、聚(DL-丙交酯-共-乙醇酸交酯)、聚碳酸亚丙酯、聚碳酸环己烯酯等可生物降解的塑料。
本申请检测电子束固化涂层的性能，固化后涂层的硬度、耐磨性和耐候性等可用标准方法检测。漆膜的硬度测量可参照标准ASTM D3363-74，将带有涂层的面板置于固定的水平面上，铅笔与图层成45°，以5～10厘米/秒的速度向前推10毫米，以肉眼观察样品表面是否被刮伤。依铅笔硬度的顺序，由硬到软逐步测试，直到笔尖完全不会刮伤涂布面为止。铅笔硬度专用测试笔可从1H到9H，数值越大表示硬度越高。
漆膜与底板的亲和性可参照国标GB/T 9286-1998漆膜划格试验评级方法。用切割刀具在准备好的规定试板上纵横垂直交叉切割6条平行切割线(间距由涂层厚度和底材硬度确定，从1到3毫米不等)，用透明胶带黏贴涂层切断处，均匀撕出胶带，用4倍放大镜检查切割表面，0级表示附着力最佳，切割边缘完全平滑，无一格脱落；1级在切口交叉处有少许涂层脱落，但交叉切割面积受影响不能大于5％；超过2级，达不到要求。
耐磨性根据ASTM4060标准用泰伯磨损机测定。测试样品直径为10厘米，砂轮型号为Calibrase cs-10，载荷重量为1公斤，磨损周期为2000。记录磨损前后测试样品的重量，失重以毫克表示。
耐候性是用加速老化试验箱QUV来进行的。QUV测试仪的UVA-340灯管可提供最佳太阳光模拟光谱，临界短波长范围从365纳米到太阳光截 止波长的295纳米。在340nm的最大辐照强度为0.68W/cm2，测试温度为50度，条件是8小时光照，然后4小时冷凝。全套测试持续1920小时(80天)。测试后样品表面颜色的改变用CIE L*a*b*色空间表示，L*值表示颜色的明度、a*值表示颜色的绿红值、b*值表示颜色的蓝黄值，色差用公式
Figure PCTCN2015073560-appb-000017
来表示。
为了进一步理解本发明，下面结合实施例对本发明提供的电子束固化涂料与涂层的制备方法进行详细说明，本发明的保护范围不受以下实施例的限制。
Nexsil 12是一种含二氧化硅在水中的分散液，浓度为30％，颗粒为12纳米，pH值为9.3，其由Nyacol Nano Technologies,Inc.生产。
Figure PCTCN2015073560-appb-000018
Al-2255是20纳米的氧化铝在水中的分散液，浓度为30％，由Nanophase Technologies生产。
VK-T32是杭州万景新材料有限公司生产的锐钛型二氧化钛在水中的分散液，浓度为20％，颗粒为10纳米。
NanoBYK-3840是Altana公司生产的氧化锌在水中的分散液，氧化锌含量为40％，颗粒大小为20纳米。
有机硅烷γ-(甲基)丙烯酰氧基丙基三乙氧基硅烷、乙烯基三乙氧基硅烷与3-氯丙基三乙氧基硅烷都是从Gelest获得的。
多官能团单体季戊四醇三丙烯酸酯(PETA)与1,6-己二醇二丙烯酸酯(HDDA)是从Sartomer获得的。
丙烯酸酯预聚体DR-U011,6150-100和6195-100脂肪族聚氨酯丙烯酸酯是从台湾长兴材料工业股份有限公司购买的。
聚氯乙烯和聚丙烯板材由佛山市天安塑料有限公司生产。
实施例1
100g Nexsil 12(含二氧化硅30％，12纳米)加入100g乙醇，pH值用盐酸调到3～4，然后加入60g季戊四醇三丙烯酸酯(PETA)，最后加入15gγ-(甲基)丙烯酰氧基丙基三乙氧基硅烷；混合溶液加热到60℃并保 温搅拌6h；溶剂乙醇和水采用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化硅在PETA的粘稠的透明分散液。
实施例2
200g Nexsil 12(含二氧化硅30％，12纳米)加入200g乙醇，pH值用盐酸调到3～4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入15gγ-(甲基)丙烯酰氧基丙基三乙氧基硅烷和15g乙烯基三乙氧基硅烷；混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化硅在PETA的粘稠的透明分散液。
实施例3
200g Nexsil 12(含二氧化硅30％，12纳米)加入200g乙醇，pH值用盐酸调到3-4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入15gγ-(甲基)丙烯酰氧基丙基三乙氧基硅烷和15g 3-氯丙基三乙氧基硅烷，混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化硅在PETA的粘稠的透明分散液。
实施例4
200克Al-2255(含氧化铝30％，20纳米)加入400克乙醇，然后加入120克季戊四醇三丙烯酸酯(PETA)，最后加入15克γ-(甲基)丙烯酰氧基丙基三乙氧基硅烷和15克3-氯丙基三乙氧基硅烷。混合溶液加热到60度并保温搅拌6小时。溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60度。得到氧化铝在PETA的粘稠的透明分散液。
实施例5
300g VK-T32(含锐钛型二氧化钛20％，10纳米)加入600g乙醇，pH值用盐酸调到3-4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入15gγ-(甲基)丙烯酰氧基丙基三乙氧基硅烷和15g 3-氯丙基三乙氧基硅烷，混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化钛在PETA的粘稠的半透明分散液。
实施例6
150g NanoBYK-3840(含氧化锌40％，20纳米)加入150g水和600g乙醇，pH值用盐酸调到3-4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入15gγ-(甲基)丙烯酰氧基丙基三乙氧基硅烷和15g 3-氯丙基三乙氧基硅烷，混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到氧化锌在PETA的粘稠的半透明分散液。
实施例7
200g Nexsil 12(含二氧化硅30％，12纳米)加入200g乙醇，pH值用盐酸调到3～4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入7.5gγ-(甲基)丙烯酰氧基丙基三乙氧基硅烷和22.5g 3-氯丙基三乙氧基硅烷；混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化硅在PETA的粘稠的透明分散液。
实施例8
200g Nexsil 12(含二氧化硅30％，12纳米)加入200g乙醇，pH值用盐酸调到3～4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入30g 3-氯丙基三乙氧基硅烷；混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化硅在PETA的粘稠的透明分散液。
实施例9
200克Al-2255(含氧化铝30％，20纳米)加入400克乙醇，然后加入120克季戊四醇三丙烯酸酯(PETA)，最后加入30克3-氯丙基三乙氧基硅烷。混合溶液加热到60度并保温搅拌6小时。溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60度。得到氧化铝在PETA的粘稠的透明分散液。
实施例10
300g VK-T32(含锐钛型二氧化钛20％，10纳米)加入600g乙醇，pH值用盐酸调到3-4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入30g 3-氯丙基三乙氧基硅烷，混合溶液加热到60℃并保温搅拌6h， 溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到二氧化钛在PETA的粘稠的半透明分散液。
实施例11
150g NanoBYK-3840(含氧化锌40％，20纳米)加入150g水和600g乙醇，pH值用盐酸调到3-4，然后加入120g季戊四醇三丙烯酸酯(PETA)，最后加入30g 3-氯丙基三乙氧基硅烷，混合溶液加热到60℃并保温搅拌6h，溶剂乙醇和水用旋转蒸发仪在真空下脱去，温度不超过60℃，得到氧化锌在PETA的粘稠的半透明分散液。
实施例12
本实施例按表一的配方，将聚氨酯丙烯酸酯预聚体溶解在1,6-己二醇二丙烯酸酯中，然后加入适量的二氧化硅的单体分散液，最后加入适量的流平剂
Figure PCTCN2015073560-appb-000019
RAD 2500和消泡剂
Figure PCTCN2015073560-appb-000020
Airex 900，流平剂和消泡剂的总量为1％，所得的涂料用滚涂方法涂布在未处理的聚氯乙烯或经电晕处理的聚丙烯板材上形成约10微米的涂层，涂层在氮气保护下的电子束辐照室中固化，辐照电压为150KV，辐照剂量为40KGy。涂层与板材的附着力为0到1级。二氧化硅的加入不影响涂层的透明性，但能显著提高涂层的硬度。
表1二氧化硅分散液对硬度影响的数据表
Figure PCTCN2015073560-appb-000021
Figure PCTCN2015073560-appb-000022
实施例13
本实施例按表二的配方，将聚氨酯丙烯酸酯预聚体6195-100溶解在1,6-己二醇二丙烯酸酯中，然后加入适量的二氧化硅的单体分散液，最后加入适量的流平剂
Figure PCTCN2015073560-appb-000023
RAD 2500和消泡剂
Figure PCTCN2015073560-appb-000024
Airex 900，流平剂和消泡剂的总量为1％，所得的涂料用滚涂方法涂布在未处理的聚氯乙烯或经电晕处理的聚丙烯板材上形成约10微米的涂层，涂层在氮气保护下的电子束辐照室中固化，辐照电压为150KV，辐照剂量为涂层达到5H时需要的最小剂量，涂层与板材的附着力为0到1级。
表2二氧化硅表面处理用硅烷对电子束剂量的影响
Figure PCTCN2015073560-appb-000025
实施例14
本实施例按表3的配方，将聚氨酯丙烯酸酯预聚体6195-100溶解在1,6-己二醇二丙烯酸酯中，然后加入实施例3的二氧化硅的单体分散液和实施例4的氧化铝，最后加入适量的流平剂
Figure PCTCN2015073560-appb-000026
RAD 2500和消泡剂
Figure PCTCN2015073560-appb-000027
Airex 900，流平剂和消泡剂的总量为1％，所得的涂料用滚涂方法涂布在未处理的聚氯乙烯或经电晕处理的聚丙烯板材上形成约10微米的涂层，涂层在氮气保护下的电子束辐照室中固化，辐照电压为150KV， 辐照剂量为25KGy，涂层与板材的附着力为0到1级。
表3氧化铝对涂层硬度影响的数据表
Figure PCTCN2015073560-appb-000028
实施例15
本实施例系列按表4的配方，将聚氨酯丙烯酸酯预聚体6195-100溶解在1,6-己二醇二丙烯酸酯中，然后加入实施例8合成的的二氧化硅的单体分散液，实施例9合成的氧化铝和实施例10或11的二氧化钛或氧化锌的分散液，最后加入适量的流平剂
Figure PCTCN2015073560-appb-000029
RAD 2500和消泡剂
Figure PCTCN2015073560-appb-000030
Airex 900，流平剂和消泡剂的总量为1％，所得的涂料用滚涂方法涂布在未处理的聚氯乙烯或经电晕处理的聚丙烯板材上形成约10微米的涂层，
涂层在氮气保护下的电子束辐照室中固化，辐照电压为150KV，辐照剂量为25KGy，涂层与板材的附着力为0到1级，二氧化钛或氧化锌的加入并不影响辐照剂量。
表4透明耐磨电子束固化涂层及其耐候性数据表
Figure PCTCN2015073560-appb-000031
实施例16
按表5的配方，将聚氨酯丙烯酸酯预聚体6195-100溶解在1,6-己二醇二丙烯酸酯中，然后加入实施例8合成的的二氧化硅的单体分散液或实施例9合成的氧化铝的单体分散液，实施例10合成的二氧化钛或实施例 11的氧化锌的分散液，最后加入适量的流平剂
Figure PCTCN2015073560-appb-000032
RAD 2500和消泡剂
Figure PCTCN2015073560-appb-000033
Airex 900，流平剂和消泡剂的总量为1％，所得的涂料用滚涂方法涂布在未处理的聚氯乙烯或经电晕处理的聚丙烯板材上形成约20微米的涂层，涂层在氮气保护下的电子束辐照室中固化，辐照电压为150KV，辐照剂量为25KGy，涂层与板材的附着力为0到1级，二氧化钛或氧化锌的加入并不影响辐照剂量。
表5透明耐磨电子束固化涂层及其耐候性数据表
Figure PCTCN2015073560-appb-000034
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种电子束固化涂料，包括：
    Figure PCTCN2015073560-appb-100001
    所述无机纳米材料的分散液按照以下步骤制备：
    A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
    B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
    所述无机紫外吸收剂的分散液按照以下步骤制备：
    A)将无机纳米紫外吸收剂的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
    B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米紫外吸收剂的分散液；
    所述无机纳米材料为二氧化硅与氧化铝中的一种或两种；
    所述无机纳米紫外吸收剂为二氧化钛或氧化锌。
  2. 如权利要求1所述的电子束固化涂料，其特征在于，所述硅烷偶联剂为丙烯酸酯基硅烷和卤代烷基硅烷偶联剂。
  3. 如权利要求1所述的电子束固化涂料，其特征在于，所述二氧化硅粒径为5～100nm，所述氧化铝的粒径为12～100nm。
  4. 如权利要求1所述的电子束固化涂料，其特征在于，所述无机纳米材料的分散液的含量为10～30重量份。
  5. 如权利要求1所述的电子束固化涂料，其特征在于，所述丙烯酸酯预聚体选自脂肪族聚氨酯丙烯酸酯、芳香族聚氨酯丙烯酸酯、环氧丙烯酸酯、三聚氰胺丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、有机硅丙烯酸酯、聚丁二烯丙烯酸酯、聚丙烯酸酯丙烯酸酯和丙烯酸酯齐聚物中的一种 或多种；所述多官能团单体为多官能团丙烯酸酯。
  6. 如权利要求1所述的电子束固化涂料，其特征在于，所述电子束固化涂料中还包括流平润滑剂、消泡剂、颜料或纳米抗菌剂；所述颜料的含量为0.1～10重量份。
  7. 一种电子束固化涂层的制备方法，包括以下步骤：
    将5～50重量份的无机纳米材料的分散液、1～10重量份的无机纳米紫外吸收剂的分散液、2～30重量份的多官能团单体、10～80重量份的丙烯酸酯预聚体混合，得到涂料；
    将所述涂料涂布于基材上，然后进行电子束固化，得到电子束固化涂层；
    所述无机纳米材料的分散液的制备方法，包括以下步骤：
    A)将无机纳米材料的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
    B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米材料的分散液；
    所述无机紫外吸收剂的分散液的制备方法，包括以下步骤：
    A)将无机纳米紫外吸收剂的溶液与有机溶剂混合，得到混合溶液，调节所述混合溶液的pH值；
    B)将步骤A)得到的溶液、丙烯酸酯单体与硅烷偶联剂反应，得到无机纳米紫外吸收剂的分散液；
    所述无机纳米材料为二氧化硅与氧化铝中的一种或两种；
    所述无机纳米紫外吸收剂为二氧化钛或氧化锌。
  8. 如权利要求7所述的制备方法，其特征在于，所述电子束固化的设备为低能电子束设备，所述电子束固化的剂量为5～100kGy，所述电子束固化的速度为100～1000m/min。
  9. 如权利要求7所述的制备方法，其特征在于，所述电子束固化涂层的厚度为10～100μm。
  10. 权利要求1～6任一项所述的电子束固化涂料或权利要求7～9任一项所制备的电子束固化涂层在汽车内饰或装饰板材上的应用。
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