CN1934140A - Environmentally friendly coating compositions and coated articles and coating methods and process and assemblages thereof - Google Patents

Abstract

Disclosed are environmentally friendly, substantially all solids coating compositions, which are curable using ultraviolet and visible radiation. In addition, the disclosed coating compositions are suitable for coating flexible objects and/or objects having angular features, such as, but not limited to, flexible metal objects with angular features. In addition, methods are disclosed for coating surfaces, or at least portions of the surfaces, and curing of the coated surface to obtain partially or fully cured coated surfaces (figure 1). Furthermore, articles of manufacture incorporating fully cured coated surfaces are disclosed, including, for example leaf springs. Also disclosed are methods, processes, production lines, articles of manufacture, and factories which incorporate these environmentally friendly, substantially all solids coating compositions curable using ultraviolet and visible radiation.

Description

Be used for the eco-friendly coating composition of metallizing object, by the object of its coating and the method, technology and the combined system that apply

The cross reference of related application

The application requires the rights and interests of the 60/551st, No. 287 U.S. Provisional Application of submission on March 8th, 2004; The sequence number that the application also requires on March 25th, 2004 to submit to is the rights and interests of 60/556,221 U.S. Provisional Application; The application also requires the rights and interests of the 60/557th, No. 074 U.S. Provisional Application of submission on March 26th, 2004; The application also is that the sequence number of submitting on November 5th, 2004 is 10/983,022, the sequence number of submitting on November 5th, 2004 is 10/982, the sequence number that on December 2nd, 998 and 2004 submitted to is 11/003, the part continuation application of 159 U.S. Patent application, the content of all these applications are incorporated herein by reference thus in full.

Background of invention

Various consumption, science and Industrial products are combined with different metals with various forms and shape.The environmental problem that the evaporation of volatile solvent causes applies this metallic surface with solvent-based coating, owing to may have problems.And this coating may need thermofixation, needing to cause curing oven and relevant energy expenditure to make the curing oven running.

Summary of the invention

The method of composition eco-friendly, actinic radiation curable, total solids basically and metallizing object or plastic object is provided herein.Eco-friendly, actinic radiation curable, the object of the composition of total solids, and the coating flexible basically method as (only as an example) flexible metal or plastic object also is provided herein.Eco-friendly, actinic radiation curable, the composition of total solids basically further is provided herein, and applies and have object that corner characteristics is arranged and have the metal that corner characteristics is arranged or the method for plastic object as (only as an example).Eco-friendly, actinic radiation curable, the composition of total solids basically further is provided herein, and the method that applies object, to produce coating, this coating has the character of improvement when solidifying, the tolerance that coated article body cupping (cupping) is damaged afterwards that for example comprises the tolerance to infringement after the crooked coated article body, the improvement of the tolerance to infringement after the elongation of coated article body, the improvement of tensile strength, the improvement of improvement, or the combination of the character of any above-mentioned improvement.This coating composition generates less volatile matter, produces less waste and needs less energy.And this coating composition can be used for forming the coating of aesthetics, performance and durable character with expectation.Part and full solidified surface are provided in addition, and the goods with full solidified surface.

In one aspect, the composition of the total solids basically of the actinic radiation curable described in the literary composition is made of the mixture of at least a oligopolymer, at least a monomer, at least a light trigger and at least a Nano filling, wherein curing composition showed the 99+% tackiness after under 110 , 100% humidity 10 days, and/or crooked as 180 degree of (only as an example) half inch axle around axle.In another embodiment, curing composition is the coating on metal or the plastic object.In another embodiment, curing composition can provide the coating of flexible, corrosion-resistant, wear-resistant and scrape resistant on metal or plastic object.

In the embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises at least a oligopolymer or the multiple oligopolymer of the about 15-45wt% that is present in the mixture.In another kind of or alternative embodiment aspect above, the composition of the total solids basically of actinic radiation curable comprises at least a monomer or the multiple monomer of the about 25-65wt% that is present in the mixture.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises at least a light trigger or the multiple light trigger of the about 2-10wt% that is present in the mixture.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises at least a Nano filling or the multiple Nano filling of the about 0.1-25wt% that is present in the mixture.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises alternatively up to a kind of filler of about 5wt% or multiple filler.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises alternatively up to a kind of polymerizable pigment dispersion of about 10wt% or multiple polymerizable pigment dispersion.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer of 15～45wt% or a kind of monomer or the multiple monomer of multiple oligopolymer and 25～65wt%.In the another kind of or alternative embodiment aspect this, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or a kind of light trigger of multiple monomer and 2～10wt% or multiple light trigger.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or a kind of Nano filling of multiple light trigger and 0.1～25wt% or multiple Nano filling.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～25wt% or multiple Nano filling and up to a kind of filler or the multiple filler of about 5wt%.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 30～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～5wt% or multiple Nano filling, up to a kind of filler of about 5wt% or multiple filler with up to a kind of polymerizable pigment dispersion or the multiple polymerizable pigment dispersion of about 10wt%; The viscosity at ambient temperature of said composition is up to about 500 centipoises thus.

In another kind of or alternative embodiment, oligopolymer optional from urethane acrylate, aliphatic urethane acrylate, aliphatic polyurethane triacrylate/monomer blend, be mixed with 1, the aliphatic polyurethane triacrylate of 6-hexylene glycol acrylate, six functional polyurethanes acrylate, silication urethane acrylate, aliphatics silication urethane acrylate, polyether acrylate, and combination.In another kind of or alternative embodiment, monomer is selected from Viscoat 295, acrylate derivative, methacrylate derivative, acrylate derivative, tripropylene glycol diacrylate, and combination.

In another or alternative embodiment; light trigger can be selected from phenylbenzene (2; 4; the 6-trimethylbenzoyl) phosphine oxide, benzophenone, ESACURE  KTO, IRGACURE  500, DARACUR  1173, Lucirin  TPO, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-third-1-ketone; 2; 4,6-Three methyl Benzene ketone, 4-methylbenzene ketone, oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone), and combination.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable also comprises the common light trigger (co-photoinitiator) up to about 2%, light trigger is selected from amine acrylate, thioxanthone, dimethyl ketal, benzyl methyl ketal altogether, and combination.

In another or alternative embodiment, filler is selected from the soft silica of polyethylene wax preparation, the synthetic amorphous silica of organic surface-treated, IRGANOX , undressed soft silica, season alkyl wilkinite (alkyl quaternarybentonite), silica gel, the silica gel of acroleic acid esterification, aluminum oxide, zirconium white, zinc oxide, niobium oxides (niobia), titanium dioxide, aluminium nitride, silver suboxide, cerium oxide, and combination.In addition, the median size of filler is less than 10 microns, or less than 5 microns, or even less than 1 micron.

In aspect above-mentioned another or the alternative embodiment, Nano filling can be selected from nano aluminium oxide, nano silicon, nano zircite, nano zirconium dioxide, nanometer silicon carbide, nano-silicon nitride, nanometer plug dragon (sialon), nano aluminum nitride, nano bismuth oxide, nano-cerium oxide, nano cupric oxide, nano-sized iron oxide, nano-calcium carbonate nickel, nano oxidized niobium, oxide nano rare earth, nano phase ag_2 o, nano tin dioxide and nano-titanium oxide, and combination.In addition, the median size of Nano filling is less than 100 nanometers.

In another kind of or alternative embodiment, the polymerizable pigment dispersion is made up of at least a pigment that is connected on the reactive resin; Wherein reactive resin is selected from acrylic resin, methacrylic resin and Vinylite, and pigment is selected from that carbon black, rutile titanium dioxide, organic red, phthalocyanine blue pigment, colcother pigment, isoindoline yellow pigment, phthalocyanine green pigment, quinacridone violet, carbazole violet, mass-tone are black, shallow lemon iron oxide yellow, shallow organic yellow, transparent iron oxide yellow, diaryl orange, quinacridone are red, organic scarlet, shallow organic red and dark organic red.

In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable is suitable for the coating flexible object, for example (only as an example) metal or plastic object.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable is suitable for applying the object that includes corner characteristics.

In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable is suitable as for example uncured coating on (only as an example) metal or the plastic object of flexible article.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable is suitable as the uncured coating on the object that includes corner characteristics.

In another kind of or alternative embodiment, coating can be by spraying, brushing, roller coat, dip coated, blade coating, the showering of curtain formula or its combination, is coated to flexible article for example on the surface of (only as an example) metal or plastic object.In addition, auxiliary/solid injection system or electrostatic spraying system that jet tools includes but not limited to use heavy body low pressure (HVLP) injection system, air.In another kind of or alternative embodiment, coating applies with single or repeatedly manner of application coating.In another kind of or alternative embodiment, the flexible article for example surface of (only as an example) metal or plastic object is partly covered by uncured coating, perhaps in another embodiment or alternative embodiment, the flexible article for example surface of (only as an example) metal or plastic object is all covered by uncured coating.

In another kind of or alternative embodiment, coating can be coated on the body surface that includes corner characteristics by spraying, brushing, roller coat, dip coated, blade coating, the showering of curtain formula or its combination.In addition, auxiliary/solid injection system or electrostatic spraying system that jet tools includes but not limited to use heavy body low pressure (HVLP) injection system, air.In another kind of or alternative embodiment, coating applies with single or repeatedly manner of application coating.In another kind of or alternative embodiment, the body surface that includes corner characteristics is partly covered by uncured coating, perhaps in another embodiment or alternative embodiment, the object surfaces that includes corner characteristics is all covered by uncured coating.

In another kind of or alternative embodiment, the object that includes corner characteristics is flexible, and in another embodiment or alternative embodiment, the object that includes corner characteristics comprises metal, pottery, glass, timber and/or plastics.

In another kind of or alternative embodiment, the flexible article for example quilt of (only as an example) metal or plastic object is coated with the surface by uncured quilt being coated with the surface and being exposed in first actinic radiation of originating and partly solidified.In another kind of or alternative embodiment, the flexible article for example quilt of (only as an example) metal or plastic object is coated with the surface and is exposed in the second-source actinic radiation and completely solidified by partly solidified quilt being coated with the surface.In another kind of or alternative embodiment, the quilt that includes the object of corner characteristics is coated with the surface by uncured quilt being coated with the surface and being exposed in first actinic radiation of originating and partly solidified.In another kind of or alternative embodiment, the quilt that includes the object of corner characteristics is coated with the surface and is exposed in the second-source actinic radiation and completely solidified by partly solidified quilt being coated with the surface.

In another kind of or alternative embodiment, completely crued coating is flexibility, tackiness, hard, level and smooth, corrosion-resistant, erosion resistant, scrape resistant, or its any combination.

In another kind of or alternative embodiment, actinic radiation is selected from visible radiation, near-visible radiation, ultraviolet (UV) radiation, and combination.In addition, uv-radiation is selected from UV-A radiation, uv b radiation, uv b radiation, UV-C radiation, UV-D radiation, or its combination.

In another kind of or alternative embodiment, completely cruedly be coated with the part that the surface is goods.In another kind of or alternative embodiment, goods comprise and completely cruedly are coated with the surface.In another kind of or alternative embodiment, the goods that are coated with can be a kind of like this goods, wherein, improve or improved its at least a function by there being the coating of flexibility, tackiness, hard, level and smooth, corrosion-resistant, erosion resistant, scrape resistant or its any combination.In another kind of or alternative embodiment, goods are laminated spring or automobile chassis.

In aspect another, basically the total solids method for compositions of producing actinic radiation curable comprises: add component, for example, only as an example, at least a oligopolymer, at least a monomer, at least a light trigger, optionally at least a light trigger, at least a Nano filling, optional at least a filler and optional at least a polymerizable pigment dispersion altogether; Take a kind of means that these components are mixed to form homogeneous compositions.In another kind of or alternative embodiment, composition can mix in suitable container or be transferred in the suitable container, such as but not limited to jar.

In one aspect, be (only as an example with the composition coating flexible object of the total solids basically of actinic radiation curable, metal or plastic object), or including the combined system of part surface at least of the object of corner characteristics, this combined system comprises: the composition of the total solids basically of actinic radiation curable is applied to device on this object; Thereby make the surface go up the coating layer portion solidified device that is applied with the coating that first impinge actinic radiation is applied; Thereby and make the completely crued device of upper surface branch cured coating with this object of second impinge actinic radiation; Wherein this curing composition is the coating of flexible, corrosion-resistant, erosion resistant and scrape resistant, and it had the 99+% tackiness after under 110 , 100% humidity 10 days, and/or crooked as 180 degree of (only as an example) half inch axle around axle.

In a kind of embodiment of this combined system, the composition of the total solids basically of actinic radiation curable is made of at least a oligopolymer, at least a monomer, at least a light trigger, the optionally at least a mixture of light trigger, at least a Nano filling, optional at least a filler and optional at least a polymerizable pigment dispersion altogether.In another embodiment, be used for irradiation so that be coated with surface portion solidified device and be positioned at the irradiation station, thereby need not to carry object with being used for shining so that be coated with surperficial completely crued device.In another embodiment, the device that is used for application composition is positioned at and applies the station, wherein object must be moved on to the irradiation station from applying the station.In another embodiment, this class combined system also comprises the device that is used for object is moved on to from the coating station irradiation station.In another embodiment, the device that is used to move comprises travelling belt.

In another kind of or alternative embodiment, the irradiation station comprises and is used to limit actinic radiation to applying the device of the irradiation dose of standing.In another or alternative embodiment, combined system also comprises and is used to make the device of object around at least one rotation.In another or alternative embodiment, combined system further comprises installation station, wherein object to be coated is connected on the moving element.In another embodiment, moving element can make object around at least one rotation.In another kind of or alternative embodiment, moving element can make object move to the irradiation station from applying the station.

In another or alternative embodiment, this class combined system also comprises breakdown station, wherein completely crued coated article body is unloaded from mobile unit.In another embodiment, before unloading, need not completely crued coated article body cooling from mobile unit.

In another kind of or alternative embodiment, be used for coated apparatus and comprise spray equipment, brush-coating device, roller coating device, dip coating apparatus, squeegee apparatus and curtain formula showering device.In another embodiment, be used for coated apparatus and comprise spray equipment.In another embodiment, spray equipment comprises the device that is used for heavy body low pressure (HVLP) spraying.In another kind of or alternative embodiment, be used for coated apparatus and be under the room temperature.In another kind of or alternative embodiment, spray equipment comprises the device that is used for electrostatic spray.In another kind of or alternative embodiment, spray equipment comprise be used for air auxiliary/device of hydraulic spraying.

In another kind of or alternative embodiment, apply the device that the station also comprises the composition of the total solids basically that is used to reclaim the actinic radiation curable that is not adhered to body surface.In another embodiment, the composition with the total solids basically of the actinic radiation curable that reclaimed is applied on the other object subsequently.

At this embodiment that is used for applying the combined system at least a portion surface, the composition of the total solids basically of actinic radiation curable comprises at least a oligopolymer or the multiple oligopolymer of the about 15-45wt% that is present in the mixture.In another kind of or alternative embodiment aspect above, the composition of the total solids basically of actinic radiation curable comprises at least a monomer or the multiple monomer of the about 25-65wt% that is present in the mixture.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises at least a light trigger or the multiple light trigger of the about 2-10wt% that is present in the mixture.In another or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises at least a Nano filling or the multiple Nano filling of the about 0.1-25wt% that is present in the mixture.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises alternatively up to a kind of filler of about 5wt% or multiple filler.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises alternatively up to a kind of polymerizable pigment dispersion of about 10wt% or multiple polymerizable pigment dispersion.In aspect above-mentioned another or the alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer of 15～45wt% or a kind of monomer or the multiple monomer of multiple oligopolymer and 25～65wt%.In the another kind of or alternative embodiment aspect this, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or a kind of light trigger of multiple monomer and 2～10wt% or multiple light trigger.In another or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or a kind of Nano filling of multiple light trigger and 0.1～25wt% or multiple Nano filling.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～25wt% or multiple Nano filling and up to a kind of filler or the multiple filler of about 5wt%.In another or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 30～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～5wt% or multiple Nano filling, up to a kind of filler of about 5wt% or multiple filler with up to a kind of polymerizable pigment dispersion or the multiple polymerizable pigment dispersion of about 10wt%; The viscosity at ambient temperature of said composition is up to about 500 centipoises thus.

In another kind of or alternative embodiment, first actinic radiation that is used to apply the combined system at least a portion surface comprises the actinic radiation that is selected from visible radiation, near-visible radiation, ultraviolet (UV) radiation and combination thereof.In another kind of or alternative embodiment, second actinic radiation that is used to apply the combined system at least a portion surface comprises the actinic radiation that is selected from visible radiation, near-visible radiation, ultraviolet (UV) radiation and combination thereof.In another kind of or alternative embodiment, the irradiation station comprises that minute surface arranges.

In the another kind of or alternative embodiment aspect this, the coated article body is a laminated spring.

In another aspect, be (only as an example with the composition coating flexible object of the total solids basically of actinic radiation curable, metal or plastic object), or include the technology of part surface at least of the object of corner characteristics, this technology comprises: this object is fixed on the transport unit; Composition at the coating station with actinic radiation curable is applied on this body surface; By transport unit the coated article body is moved to the irradiation station; Be coated with the surface and made it partly solidified with first impinge actinic radiation at the irradiation station; And be coated with the surface and made it completely solidified with second impinge actinic radiation at irradiation station; Wherein this curing composition is the coating of flexible, corrosion-resistant, erosion resistant and scrape resistant, and it had the 99+% tackiness after under 110 , 100% humidity 10 days, and/or crooked as 180 degree of (only as an example) half inch axle around axle.

In another embodiment, but this class technology also be included in and object be fixed in the rotating shaft before the coating step.In another kind of or alternative embodiment, but this class technology also be included in be fixed to object in the rotating shaft after, mobile carrier device is so that this object is positioned at applies near the station.In another embodiment, this class technology also comprises when being fixed with the axle rotation of this object, at the composition that applies station coating actinic radiation curable.In another embodiment, transport unit comprises travelling belt.

In another kind of or alternative embodiment, the irradiation station comprises the curing room that comprises first actinic radiation sources and second actinic radiation sources.

In another embodiment, this class technology also comprises by transport unit completely crued coated article body is shifted out curing room, wherein coated article body packing is used for storing or transportation.

At a kind of embodiment of this class technology that is used for applying at least a portion surface, the composition of the total solids basically of actinic radiation curable can comprise at least a oligopolymer or the multiple oligopolymer of the about 15-45wt% that is present in the mixture.In another kind of or alternative embodiment aspect above, the composition of the total solids basically of actinic radiation curable comprises at least a monomer or the multiple monomer of the about 25-65wt% that is present in the mixture.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises at least a light trigger or the multiple light trigger of the about 2-10wt% that is present in the mixture.In another or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises at least a Nano filling or the multiple Nano filling of the about 0.1-25wt% that is present in the mixture.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises alternatively up to a kind of filler of about 5wt% or multiple filler.In another kind of or alternative embodiment aspect above-mentioned, the composition of the total solids basically of actinic radiation curable comprises alternatively up to a kind of polymerizable pigment dispersion of about 10wt% or multiple polymerizable pigment dispersion.In aspect above-mentioned another or the alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer of 15～45wt% or a kind of monomer or the multiple monomer of multiple oligopolymer and 25～65wt%.In the another kind of or alternative embodiment aspect this, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or a kind of light trigger of multiple monomer and 2～10wt% or multiple light trigger.In another or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or a kind of Nano filling of multiple light trigger and 0.1～25wt% or multiple Nano filling.In another kind of or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～25wt% or multiple Nano filling and up to a kind of filler or the multiple filler of about 5wt%.In another or alternative embodiment, the composition of the total solids basically of actinic radiation curable comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 30～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～5wt% or multiple Nano filling, up to a kind of filler of about 5wt% or multiple filler with up to a kind of polymerizable pigment dispersion or the multiple polymerizable pigment dispersion of about 10wt%; The viscosity at ambient temperature of said composition is up to about 500 centipoises thus.

In another kind of or alternative embodiment, apply the station and comprise the device that is used for electrostatic spraying.In another kind of or alternative embodiment, apply station and comprise and be applicable to that air assists/device of hydraulic spraying.In another kind of or alternative embodiment, apply the station and comprise and be applicable to heavy body low pressure (HVLP) coating coated apparatus.In every kind of situation, another kind of or alternative embodiment comprises such technology: wherein coating applies middle coating at single, and perhaps coating is repeatedly applying middle coating.In addition, in every kind of situation, another kind of or alternative embodiment comprises such technology: wherein the surface is partly covered by coating, and perhaps the surface is covered fully by coating.

In another kind of or alternative embodiment, the time between the first actinic radiation step and the second actinic radiation step is less than 5 minutes.In another embodiment, the time between the first actinic radiation step and the second actinic radiation step is less than 1 minute.In another embodiment, the time between the first actinic radiation step and the second actinic radiation step was less than for 15 seconds.

In another kind of or alternative embodiment, the time span of the first actinic radiation step is shorter than the time span of the second actinic radiation step.In another kind of or alternative embodiment, the time span of the first actinic radiation step is longer than the time span of the second actinic radiation step.In another kind of or alternative embodiment, the time span of the first actinic radiation step equals the time span of the second actinic radiation step.

In another kind of or alternative embodiment, the irradiation station comprises at least a light that actinic radiation can be provided, and described actinic radiation is selected from visible radiation, near-visible radiation, ultraviolet (UV) radiation and combination thereof.

In another kind of or alternative embodiment, the irradiation station comprises at least a light source that the actinic radiation that is selected from UV-A radiation, uv b radiation, uv b radiation, UV-C radiation, UV-D radiation or its combination can be provided.

In another kind of or alternative embodiment, the irradiation station comprises that minute surface is arranged so that be coated with surface three dimension curing.In another kind of or alternative embodiment, the irradiation station comprises that light source is arranged so that be coated with surface three dimension curing.In another embodiment, every kind of spectral wavelength scope that light emitted is different.In another embodiment, Different Light has partly overlapping spectral wavelength scope.

In another aspect, be (only as an example with the composition coating flexible object of the total solids basically of actinic radiation curable, metal or plastic object), or include the production line of part surface at least of the object of corner characteristics, this production line comprises a kind of technology, and this technology comprises: this object is fixed on the transport unit; Composition at the coating station with actinic radiation curable is applied on this body surface; By transport unit the coated article body is moved to the irradiation station; Be coated with the surface and made it partly solidified with first impinge actinic radiation at the irradiation station; Be coated with the surface and made it completely solidified with second impinge actinic radiation at the irradiation station; Wherein this curing composition is the coating of flexible, corrosion-resistant, erosion resistant and scrape resistant, and it had the 99+% tackiness after under 110 , 100% humidity 10 days, and/or crooked as 180 degree of (only as an example) half inch axle around axle.

In another aspect, be to be used to produce the facility or the factory of object of composition that scribbles the total solids basically of actinic radiation curable to small part, it comprises the production line of the composition of the total solids basically coating of objects of at least one usefulness actinic radiation curable, this production line comprises a kind of technology, and this technology comprises: this object is fixed on the transport unit; Composition at the coating station with actinic radiation curable is applied on this body surface; By transport unit the coated article body is moved to the irradiation station; Be coated with the surface and made it partly solidified with first impinge actinic radiation at the irradiation station; Be coated with the surface and made it completely solidified with second impinge actinic radiation at the irradiation station; Wherein this curing composition is the coating of flexible, corrosion-resistant, erosion resistant and scrape resistant, and it had the 99+% tackiness after under 110 , 100% humidity 10 days, and/or crooked as 180 degree of (only as an example) half inch axle around axle.

The introducing of reference

All publications, patent and the patent application of mentioning in this specification sheets is incorporated herein by reference thus in full, to the degree that specifically and is individually proposed as each publication, patent or patent application to be incorporated herein by reference.

The accompanying drawing summary

With reference to the detailed description and the accompanying drawing of following illustrated example embodiment, with the better understanding that obtains the inventive method and composition feature and advantage, wherein adopted the principle of present method, composition, equipment and device in the illustrative embodiments, in the accompanying drawing:

Fig. 1 is used for the coating composition coating flexible object described in the literary composition and/or a kind of schema that may technology of angle object is arranged.

Fig. 2 is used for the coating composition coating flexible described in the literary composition and/or a kind of schema that may combined system of angle object is arranged.

Fig. 3 illustrates and obtains the required possible component of coating composition described in the literary composition.

Fig. 4 is the example that applies a kind of method of coating described in the literary composition.

Fig. 5 is the example of coating material solidified a kind of method.

Detailed Description Of The Invention

The coating composition of 100% solid actinic radiation curable described in the literary composition, apply said composition method, be coated with the surface and be coated with goods, by in conjunction with zero volatilization or near zero evaporable organic compound (VOC) from improving environmental quality in essence.In addition, the non-volatile basically thereby quantity discharged of this class component is zero or near zero.This minimizing of quantity discharged significantly reduces atmospheric pollution, particularly compares with the atmospheric pollution that coating composition caused of using solvent flashing.And, adopt method described in the literary composition to make and adopt any water pollution or the soil pollution relevant that technology caused of the coating composition that uses solvent flashing to minimize with waste treatment, further be beneficial to thus and improve environmental quality in fact.In addition, the energy that the coating composition of 100% solid actinic radiation curable described in the literary composition, the method, technology and the combined system that apply said composition, quilt are coated with the surface and are coated with the goods employing is saved energy thus than adopting use solvent flashing or water as the technology much less of the coating composition of solvent.

The glossary of particular term

As used herein, term " erosion resistant " is meant the ability of the anti-infringement of material, and this infringement can cause visible, dark or wide groove.Therefore, scratch is considered to usually than being called the more serious of cut in this area.

As used herein, term " actinic radiation " is meant any source of radiation that can produce polyreaction, for example, only as an example, uv-radiation, near-ultraviolet radiation and visible light.

As used herein, term " has corner characteristics " and is meant the feature with different angles and size, for example, only as an example, the angle of different angles and size.There is corner characteristics also to comprise three-dimensional feature, for example, only as an example, bump, raceway groove, groove, peristoma, limit and projection.

As used herein, term " altogether light trigger " be meant can with the light trigger of another kind of or multiple light trigger coupling.

As used herein, term " inhibiter " is meant and suppresses or partly suppress one or more reagent of corrosive.

As used herein, term " corrosion-resistant " is meant the ability of material opposing oxidative damage.

As used herein, term " curing " is meant the polyreaction of partial coating composition at least.

As used herein, term " curable " be meant to small part can the polymeric coating composition.

As used herein, term " curing catalyst " is meant one or more reagent that promote or strengthen or partly strengthen solidification process in addition.

Term " filler " is meant the material of interpolation with the relative inertness of physics, machinery, heat or the electrical property of change coating.

As used herein, term " flexibility " is clinodactyly, reverse or compress and the ability that do not rupture, and object can randomly be returned to the part of its original-shape or position.

As used herein, term " mineral dye " is meant in use nonvolatile basically particulate composition, and comprises those compositions that are labeled as inert agents, supplement, filler etc. usually in coating or plastics trade.

As used herein, term " irradiation " is meant the surface is exposed in the actinic radiation.

As used herein, term " is milled " and is meant the method for premix, fusing and abrasive flour coating formulation, with the powder that obtains to be suitable for spraying.

As used herein, term " monomer " is meant to comprise and can be connected on the oligopolymer or the material of individual molecule connected to one another.

As used herein, term " motor vehicle " is meant by machinery or the self-driven any vehicle of electric power.Motor vehicle only as an example, comprises automobile, bus, truck, tractor, recreation vehicle and Der Gelaendewagen.

As used herein, term " oligopolymer " is meant the molecule that comprises the single molecule of several multiple.

As used herein, term " light trigger " is meant that the energy that absorbs UV-light and utilize this light promotes the compound of the formation of coating drying layer.

As used herein, term " polymerizable pigment dispersion " is meant and is dispersed in the coating composition attached to the pigment on the polymerizing resin.

As used herein, term " polymerizing resin " or " reactive resin " are meant the resin with reactive functional groups.

As used herein, term " pigment " is meant insoluble or part is solvable, be used to give the compound of color.

As used herein, term " scraping " is meant the physical deformation that is caused by machinery or chemical abrasion.

As used herein, term " vehicle " is meant the liquid portion of solvent-based formulations, and can be in conjunction with solvent and resin.

Coating

Usually, the solvent-based coating preparation is in conjunction with the material of four kinds of base types: pigment, resin (tackiness agent), solvent and additive.Can produce even pigment dispersion by in vehicle, effectively mixing insoluble former granules of pigments, and produce Opaque paint thus.Resin is formed the non-volatile part of vehicle, and help bonding, decision coating cohesion, influence gloss and tolerance to chemical, water and acid/alkali be provided.Usually use three types resin: use resin (acrylic acid or the like, vinyl, urethane, polyester) more; Thermosetting resin (Synolac, Resins, epoxy); And oil.The type of solvent of using in this preparation depends on resin, is organic solvent (as alcohol, ester, ketone, glycol ethers, methylene dichloride, trichloroethane and petroleum distillate) or water.With an organic solvent desalinate/dilute coating composition, and be used for making the coating composition homodisperse from the teeth outwards, then rapid evaporation.Yet because their high volatile volatile, this class organic solvent forms maximum discharge concentration, thereby classifies as volatile organic compounds (VOC) and hazardous air pollutants (HAP).These solvent discharges are related to employer and the employee in the facility that uses VOC and HAP, because over-exposure is in wherein causing injury of the kidney or other to concern healthy obstacle.In addition, when use contained the coating of organic solvent, it was the other problem that will consider that the influence of environment and potential fire are suffered from.And, contain the big curing oven of coating needs of organic solvent, with the curing that causes coating and remove and desolvate.In lease or buy aspect the space be used for big stove, cost of energy that curing process is relevant, possible medical expense, potential environmental purification and the premium of insurance, all these problems need be paid considerable fund from the coating final user.

The curable powder coating of thermosetting powder coating(s) and UV-

Exploitation powder based coating composition and water-base preparation solve the volatile emission problem of following the non-aqueous solvent based coating composition.Powder-base coating can comprise thermoset or UV solidified preparation, can reduce discharging, yet owing to need (for powder thermosetting) heat fusing, floating and curing, this class powder-base coating also needs the considerable time, is used for the space and the energy of big stove.In addition, powder coating also usually presents " tangerine peel " outward appearance of not expecting.Have the reactive part of UV and keep producing the required fusion of high-quality coating and the solid resin of flowing property, can produce the curable powder coating of UV.These powder coating have less energy-consumption, observed quick-setting characteristic effectively and with UV is solidified in the space, are convenient to application of powder coatings, as electrostatic spraying.Use UV to solidify fusing is separated with cure stage with flowing stage, but still need to be used to melt big stove and required expense and the space requirement of this class stove running with flowing stage.

100% solid UV-hardenable coatings

What describe in the literary composition is 100% solids composition that can spray, the method for using the said composition coated surface and the technology of coated surface.100% solid coating composition described in the literary composition comprises actinic radiation curable material (for example monomer and oligopolymer), light trigger, solid pigment dispersion, adhesion promotor, Nano filling and filler, be used for the coating flexible object (only as an example, metal or plastic object) or include the object surfaces of corner characteristics, and this coating composition can spray with ordinary method, include but not limited to HVLP, air auxiliary/no air or single coating electrostatic rotating cup (electrostatic bell), and do not need to apply in addition heat.In addition, 100% solid coating composition described in the literary composition is given the gloss of flexibility, erosion resistance, wear resistance, improvement, the tackiness of improvement, and can be opaque or have transparent coating.

The curable coating composition of 100% solid UV described in the literary composition does not use the solvent of interpolation.This part ground is realized by using the low molecular weight monomers replace organic solvent.But these monomers are volatile unlike organic solvent, therefore easy evaporation unlike volatile organic solvent.And, to compare with volatile organic solvent, this class monomer becomes the overall composition of final coating, and is beneficial to the character and the characteristic of final coating.100% solid coating composition described in the literary composition easily is applied on the surface, and passes through fast setting in UV cruelly, and need not use big curing and drying oven; Reduced the production cost of the purchase required/lease spatial correlation thus with the dried/cured stove, and the cost of energy relevant with the running of dried/cured stove.In addition, more effectively production technique also occurs, because the UV curable coating composition can be applied (being single coating) in single application, this has reduced the coating time and can obtain immediately the ability of " packing and conveying ".And, in this class UV curable coating composition, do not contain volatile organic solvent and limited health, safety and the environmental risk that causes by this kind solvent.

100% solid UV curable coating composition described in the literary composition can be used to the coating flexible object, for example, only as an example, metal or plastic object, or be used for the coating flexible object, or be used for applying the flexible article that comprises metal or plastic composition as the surface of (only as an example) metal or plastic object.In addition, 100% solid UV curable coating composition described in the literary composition can be used to apply the object that includes corner characteristics, for example, only as an example, metal or plastic object, or be used for applying the flexible article that includes corner characteristics, for example, only as an example, metal or plastic object.

The metal types that can use 100% solid UV curable coating composition described in the literary composition to apply includes but not limited to, ferrous metal and alloy (as the steel and the pig iron), brass, bronze, aluminium, cobalt, copper, magnesium, nickel, titanium, tin or zinc, or comprise the alloy of aluminium, iron, cobalt, copper, magnesium, nickel, titanium, tin and/or zinc, add galvanized steel, and the steel of electro-galvanizing.In addition, the composition described in the literary composition can be used to apply the metal of any form known, such as but not limited to the part of cold rolled metal, extrudate, coil, welding or the part of casting.The especially easy oxidized formation oxide on surface in metallic surface is called rust, oxide on surface or metal oxide in the literary composition.Yet other metal such as brass, bronze, aluminium, cobalt, copper, magnesium, nickel, titanium, tin or zinc, or also oxidation and form their corresponding oxide on surface of the alloy that comprises aluminium, iron, cobalt, copper, magnesium, nickel, titanium, tin and/or zinc.In environment with high humidity or salts contg, the formation of rust become in addition more may with take place sooner.Thereby need some protective coatings that the formation of metallic surface upper surface oxide compound is minimized.The gained coating that is obtained by the composition described in the literary composition shows the tackiness of improvement on the metallic surface, and for the erosion resistance and the wear resistance of improvement are provided by matel coated.

When using aqueous composition to come coating metal surfaces, when water evaporated in coating, curing and drying step process, the metallic surface can the oxidation by the process that is known as " dodging rust (flash-rusting) ".Though can form by the sudden strain of a muscle rust that reduce or eliminate water-based paint compositions with hot air blowers drying or use vacuum system, for reducing cost of energy, not have the benefit of increase, and still need big drying oven.On the contrary, 100% solid UV curable coating composition described in the literary composition does not use solvent to comprise water, has therefore avoided forming the possibility of dodging rust.In addition, use this UV curable compositions to reduce the curing process time, this can be avoided forming in higher humidity environment and dodge rust.

100% solid UV curable coating composition described in the literary composition uses former pigment or solid polymerizable pigment dispersion to give composition and gained coating opacity.Solid polymerizable pigment dispersion has limited the needs of former pigment required " milling ".Mill and be meant premix, fusing and former pigment or powder composition ground to form and be suitable for spraying to the manufacturing process that the fines in the composition was gone up or was mixed on the surface.These steps are joined the time and the energy expenditure that cause each to be coated with the goods cost in the technology to be increased.Though former pigment can be incorporated in the composition described in the literary composition, replace former pigment to improve coating processes with the polymerizable pigment dispersion, and eliminated the relevant expense of milling, improve overall manufacturing power thus and reduce professional expenditure.

The color property of pigment such as intensity, transparency/opaqueness, gloss, the depth, rheology and light and chemical stability usually more or less are subjected to containing the granularity of this granules of pigments in the vehicle of granules of pigments and the influence of distribution.Granules of pigments exists with the form of primary particle (50 μ m～500 μ m), aggregation, agglomerate and throw out usually.Primary particle is independent crystal, and aggregation is the set of the primary particle that combines at its crystal face, and agglomerate is the primary particle that connects in its corner and the comparatively loose type of arranging of aggregation.Throw out is made of the primary particle aggregation and the agglomerate of arranging with quite open structure usually, can crack under shearing force.Yet, after after removing shearing force or with dispersion, leaving standstill uninterruptedly, can form throw out again.Pigment particle size and pigment carry the relation that colour system system absorbs between the ability of both visible electromagnetic radiation and are called tinctorial strength or tinting strength.The light-absorbing ability of given pigment (tinting strength) reduces with particle diameter and corresponding surface-area increase improves.Thus, the ability that pigment is remained on minimum pigment particle size will produce maximum tinting strength.The dispersive primary and foremost purpose is that the pigment aggregation is cracked into primary particle with agglomerate, thereby obtains pigment visually and best benefit economically.In the time of in being used in coating composition, this pigment dispersion presents the tinting strength of raising and the enhanced color and luster is provided.Yet what be related to acquisition optimum dispersion body is to form the related technology number of pigment dispersion, for example stirs, shears, mills and grind.If out of true is controlled these technology, may exist so batch with criticize between colour-change and relatively poor colorrendering quality.Selectively, will present minimized aggregation and agglomerant polymerizable pigment dispersion is sneaked in the coating composition simply, thus, by exempt make and/or coating processes in the needs of these steps are improved colorrendering quality.In addition, because the reactive functional group of polymerizable pigment dispersion, pigment becomes gained system component part between polymerization period, because it is connected in this reactive functionality.With respect to the pigment dispersion that only granules of pigments is clamped in the paint matrix, the polymerizable pigment dispersion can be given higher colour stability.Thereby the coating that has added the polymerizable pigment dispersion presents the colorrendering quality of improvement and the colour stability of improvement, higher tinting strength and enhanced opaqueness and glossiness.Only as an example, composition described in the literary composition is heavy painted, and can present acceptable opacity when the thickness that is lower than 50 microns.

Monomer/the resin of various more high-vapor-pressures is incorporated into described in the literary composition in the 100% solid UV curable compositions as vehicle, has eliminated the needs of organic solvent and relevant solvent discharge/evaporation problem effectively.Therefore, this has exempted the needs that atmospheric pollution/emission control technique are incorporated into manufacturing process.As a result, method and composition described in the literary composition can make the time, space and the fund that are used for the air pollution control system maintenance in the operation of having integrated coating step minimize.

Coating is applied, solidifies and the dry required time totally reduces because of using method and composition produces described in the literary composition another advantage to be that this based composition and method cause.Although can adjust conventional coating processes, be to use the UV radiation but not heat comes the initiated polymerization process significantly to shorten the set time that each is coated with goods to adapt to coating composition described in the literary composition and method.But method and composition described in the literary composition can comprise a spot of heat; For example, be used to provide the lamp that is used for solidified UV light and also can produce some heat.In addition, heat can originate by other (room temperature that comprises facility) produce; Yet method and composition described in the literary composition needs minimum (if any) extra heat, to realize suitable curing.In addition, do not contain solvent and exempted with heat coming except that the needs that desolvate in the compositions and methods of the invention, removing the process of desolvating can increase significant time and expense to coating step.Thereby, use the UV line to solidify and remove to desolvate and shorten the time of the total coating processes that is used to finish each coated article body significantly from composition, this make with can handle more part based on the method for solvent in the required identical time, and finish a batch needs less time.

Making and producing the minimized ability in used space (even no matter being that floor area, wall area are top ceiling area (the situation of object when top ceiling hangs)) is crucial for productivity, production cost and startup funds are paid.UV curing composition described herein is exempted solvent and is made it possible to remove big stove from production line.When the coating composition that uses based on solvent, these stoves are used for solidifying and impelling rapid solvent evaporation.The removal of this stove reduces production system volume required (ground, wall and top ceiling space) significantly, and less space is effective to existing production line.In addition, the expense relevant with the running of stove no longer is a problem, and the result is that production cost reduces.For the new production line, from design, remove these stoves and in fact saved the space, thereby available less buildings holds production line, reduce construction cost thus.And because no longer need stove, the expense of new production line is paid less.Since with compare the number that can increase production line based on the technology of solvent, and can be incorporated in the existing production line, the smaller size smaller that the production line of the method and composition described in the literary composition occupies has improved productivity.

As mentioned above, no matter solvent-based coating composition is based on organic solvent and also is based on water, need come the drying coated surface with heat, promotes the evaporation of solvent thus.Realize this process with big stove, the running that can infer these big stoves needs high cost.And, use ventilation system (for example big fan) and air pollution control system all to need energy to operate.Thereby, the hardenable coatings of UV described in the literary composition, composition and method cause significant energy and cost savings by restriction (perhaps exempt) to the needs of big stove, relevant ventilation system and air-purification system, and described big stove, relevant ventilation system and air-purification system are that alternative heat or solvent-based coating composition and method are required.

Glossiness mainly is meant the planeness and the gloss on surface, and when the visual appearance of considering coating and final vision acceptability, these two character are all important.As mentioned above, the polymerizable pigment dispersion is introduced coating composition and can produce higher tinting strength and enhanced glossiness.In addition, filler absorption coating composition and controlled polymerizing condition can be given the planeness of improvement.The control of polymerization process will be described in detail in the back, yet say simply, it comprises the mixture that uses the light trigger with different absorbent properties, thereby the radiation of longer wavelength can be used for exciting a kind of light trigger or multiple light trigger in this mixture, and the radiation of shorter wavelength can be used for exciting other light triggers in this mixture.So, excitating sequence is important.Expectation at first excites the light trigger of longer wavelength, because this can improve adhesion and hold back the filler component in position.Excite the light trigger of shorter wavelength to finish polymerization process afterwards.If do not adopt this excitating sequence (or its distortion, as alternately expose, flash of light or other order), filling compound can be assembled, and forms dim coating.Thereby long wavelength-short wavelength's step can be improved visual appearance and acceptability by improving surface finish, raising surface luster or raising surface finish and surface luster.Yet, if the dim outward appearance of expectation can adopt short wavelength-long wavelength's step.

Only need the coating composition and the technology of single coating step to have sizable benefit.For the amount of used coating composition and the total production time of each coating piece is cost-effective.When with single layer coating, this coating composition must still be given favourable quality, for example erosion resistance or wear resistance.The curable coating composition of UV described in the literary composition uses filler in the mixture of oligopolymer, monomer, polymerizable pigment dispersion and light trigger, come to give the rheological properties of expectation to be applied to lip-deep gained film before being exposed to the UV radiation.These rheological properties comprise viscosity and thixotropic behaviour, make composition can be injected on the surface, make composition can remain on it and arrive this lip-deep position, and the composition drop is flowed together and be full of any slit and do not drip or pour off, on this surface, produce complete, the film of atresia almost thus from this surface.The curable coating composition of UV described in literary composition rheological property this is controlled at the coating of the coverage that obtains having improvement in the single application step, and thus, under the situation of described in the text painted composition, improves the covering power of coating.

100% solid UV curable coating composition described in the literary composition can be applied on the surface by spraying, the showering of curtain formula, dip coated, roller coat or brushing.Yet spraying is one of the most effective coating method, and available heavy body low pressure (HVLP) method or Electrostatic Spray Technology realize.HVLP and Electrostatic Spray Technology are the methods of setting up of improving in coatings industry, thereby it is accidental that these coating compositions that apply means are used in exploitation.The spraying technology of auxiliary/no air type that in addition, the curable compositions of UV described in the literary composition can use air applies.The auxiliary no pneumatic pump of air is normally air-operated, positive displacement, reciprocating piston pump, and it directly is siphoned into coating composition outside the container.Air compressor is with about 1/4 amount operating pumps and rifle of conversion HVLP rifle required air quantity, and with remarkable higher hydrodynamicpressure conveyance fluid.When coating composition escapes into its atomizing of barometric point following time, described then rifle is added to the ending of spraying method with a little air, has eliminated " tail " or heavy edge, makes the eclipsed line or belt minimum thus." air is auxiliary " of method that Here it is " no air ".

Being used for the purging method of clean surface before applying with solvent-based coating composition generally includes this surface is contacted with base clean-out system or acidic cleaner, and this clean-out system is generally the aqueous solution.The example of alkaline cleaner comprises sodium hydroxide and potassium hydroxide.Except clean-out system and water, cleaning solution can randomly comprise tensio-active agent and washing assistant, as SODA ASH LIGHT 99.2, pyrophosphate salt or tri-polyphosphate.Thereby, before applying, need exacting terms to come clean surface with solvent-based compositions.On the contrary, as mentioned above, the method and composition described in the literary composition only needed limited cleaning with simple (if any) before applying object.In one embodiment, before applying with 100% solid UV curable coating composition described in the literary composition, cleaning article only need be with biodegradable organic washing agent and water washing removing loose impurity, surface contaminants, oil and grease, the water flushing, and dry.The water flushing can be used deionization pure water or tap water, and the flow velocity of duration of contact and/or water is time and the flow velocity that is enough to remove from the surface all basically clean-out systems.The purging method that uses than solvent-based coating composition from the waste streams of the purging method of this simplification comprises poisonous and/or objectionable impurities still less.Thereby the purging method that this purging method uses than solvent-based coating composition is environmental friendliness more.

The feature of curable 100% solids composition of the UV described in the literary composition includes but not limited to zero VOC, and zero HAP solidified in the several seconds, solidified (make thus and shorten 99% set time) in 1.5 seconds, the floor space that needs lacks 80%, the little energy 80% that needs, nonflammable, need not dilution, very easily solidify high glossiness, apply with HVLP or electrostatic rotating cup, need not to steam stove, need not thermofixation, no thermal stresses and do not have orange peel effect.In addition, they make the user shorten the production time when producing the better product of high-grade, outward appearance reproducibility.The user can save time, energy and space.In addition, because do not use solvent or vehicle, the user can reduce or exempt discharging.

The invention also discloses the technology and the combined system that are used to apply sprayable uv-curable 100% solids composition described in the literary composition.The feature of this technology includes but not limited to provide the coating of industrial strength, have the recovery of excessively spraying thing, need not to cool off line, immediately " packing and transportation " up to 98%, part reduces in the technology, workholder is less, need not the burning-off workholder, exempts air pollution control system, safer to environment, safer to the employee, reduce production costs, shorten the production time and increase output.

Composition

The mechanical properties of UV coating such as elasticity, flexibility and hardness depend on oligopolymer and the monomeric type that comprises in the coating composition.Only as an example, polyester acrylate has good wear resistance and toughness, and urethane acrylate and polyether acrylate can provide flexibility, elasticity and hardness.Thereby the composition described in the literary composition combines oligopolymer and the monomer of giving various character to coating material solidified, to obtain to have the UV hardenable coatings of good adhesion, high flexibility and wear resistance and scratch resistance.

Composition described in the literary composition is substantially free of solvent, thereby is called solids composition.Thereby the composition of matter that comprises following composition disclosed: UV curable materials (oligopolymer and monomer), light trigger, solid pigment dispersion, adhesion promotor, inhibiter, filler and Nano filling, to obtain the coating of flexibility, wear resistance and scratch resistance, it also shows the tackiness of improvement.Composition described in the literary composition is made up of following material, gross weight based on composition: 15～45% oligopolymer or multiple oligopolymer, 25～65% monomer or multiple monomer, 2～10% light trigger or multiple light trigger, 0～15% solid pigment or multiple solid pigment dispersion, 0.01～2% inhibiter, 0.01～2% filler and 0.1～25% Nano filling mixture; Wherein said composition can be passed through HVLP, and electrostatic rotating cup or air are assisted/no air technology injection, need not add heat, and can solidify by uv irradiating.

Oligopolymer can be selected from mono acrylic ester, diacrylate, triacrylate, polyacrylic ester, urethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate and composition thereof.Spendable suitable compound includes but not limited to Viscoat 295; Oxyalkylated Viscoat 295 is as Viscoat 295 ethoxylation or propenoxylated; 1,6 hexanediol diacrylate; Isobornyl acrylate; Aliphatic urethane acrylate (two-, three-, six-: Ebecryl 230, Ebecryl244, Ebecryl 264, Ebecryl 220); The vinylacrylic acid ester; Epoxy acrylate; The dihydroxyphenyl propane acrylate of ethoxylation; The acrylate of trifunctional, unsaturated ring diketone; Polyester diacrylate; Epoxy diacrylate/monomer blend, aliphatic polyurethane triacrylate/monomer blend, be mixed with 1, the aliphatic polyurethane triacrylate of 6-hexylene glycol acrylate, six functional polyurethanes acrylate, the silication urethane acrylate, aliphatics silication urethane acrylate, CN990 (Sartomer, Exton, PA, U.S.A.), be mixed with the bisphenol epoxies acrylate of Viscoat 295, fatty acid modified dihydroxyphenyl propane acrylate, be mixed with the epoxy polyol of the acroleic acid esterification of Viscoat 295, and composition thereof.

Monomer is selected from ester derivative, the ester derivative of methacrylic ester, Viscoat 295, the vinylformic acid 2-ethyl phenoxy of vinylformic acid 2-ethyl phenoxy, isobornyl acrylate, acrylate; And linking agent, such as but not limited to propoxylation three vinylformic acid glyceryl ester, tripropylene glycol diacrylate, and composition thereof.

In the time of in being exposed to ultraviolet ray, the light trigger component of composition causes the rapid polymerization reaction.Described in the literary composition in the composition used light trigger be classified as radical type; Yet, also can adopt other light trigger type.In addition, can adopt the combination of light trigger, the different spectral qualities in the UV source that is used for initiated polymerization are contained in this combination.In one embodiment, the spectral quality in light trigger and UV source is complementary.Suspect that the composition described in the literary composition can solidify with following equipment: middle medium pressure mercury Jupiter, this lamp produces intensive UV-C (200-280nm) radiation; Or adulterated mercury discharge lamp, depending on doping agent, this discharge lamp produces UV-A (315-400nm) radiation or UV-B (280-315nm) radiation; Perhaps combined lamp depends on used light trigger combination.In addition, the existence of pigment can absorb the radiation of UV district and visible region, reduces the efficient of some type light initiator thus.Yet, phosphine oxide type light trigger, such as but not limited to two acyl group phosphine oxides, in coloured (comprise, only as an example, black) curable coating material of UV effectively.Phosphine oxide also can be used as the light trigger of whitewash.

Light trigger and common light trigger can be selected from: phosphine oxide type light trigger; phenylbenzene (2; 4; the 6-trimethylbenzoyl) phosphine oxide; benzophenone; the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-third-1-ketone is (from Ciba Specialty Chemicals 540 whitePlains Road; Tarrytown; New York; U.S.A. DAROCUR  1173); 2; 4; 6-Three methyl Benzene ketone and 4-methylbenzene ketone; ESACURE  KTO-46 (LambertiS.p.A.; Gallarate (VA); Italy); oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone); acrylic amine; thioxanthone; benzyl methyl ketal, and composition thereof.In addition, light trigger and common light trigger can be selected from: 2-hydroxy-2-methyl-1-phenyl-third-1-ketone is (from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A. DAROCUR  1173), phosphine oxide type light trigger, IRGACURE  500 are (from Ciba Specialty Chemicals 540 White PlainsRoad, Tarrytown, New York, U.S.A.), acrylic amine, thioxanthone, benzyl methyl ketal, and composition thereof.In addition, thioxanthone is used as curing catalyst.Liquid photoinitiators is selected from: benzophenone, 1-hydroxycyclohexylphenylketone, phosphine oxide and composition thereof.Solid photoinitiator is a phosphine oxide.

Other light trigger that is suitable for being used in the present invention's practice includes but not limited to 1-phenyl-2 hydroxy-2-methyls-1-acetone, oligomeric { 2-hydroxy-2-methyl-1-4-(1-methyl ethylene) phenyl-acetone }, 2-hydroxy-2-methyl-1-phenyl-third-1-ketone, two (2; 6-dimethoxy benzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide, 1-hydroxycyclohexylphenylketone and benzophenone, and composition thereof.Other useful initiator for example comprises two (n, 5,2,4-cyclopentadiene-1-yl)-two 2,6-two chloro-3-(1H-pyrroles-1-yl) phenyl titanium and 2-phenmethyl-2-N, N-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone.These compounds be respectively IRGACURE  784 and IRGACURE  369 (all from Ciba Specialty Chemicals 540 White PlainsRoad, Tarrytown, New York, U.S.A.).Simultaneously; other useful light trigger also comprises for example 2-methyl isophthalic acid-4 (methyl sulfo-)-2-morpholinyl third-1-ketone, 4-(2-hydroxyl) phenyl-2-hydroxyl-2-(methyl-propyl) ketone, 1-hydroxycyclohexylphenylketone benzophenone, (cyclopentadiene) (1-methylethyl) benzene-iron phosphofluoric acid ester, 2; 2-dimethoxy-2-phenyl-1-phenyl methyl ketone 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, phenylformic acid, 4-(dimethylamino)-ether, and composition thereof.

Inhibiter is formulated in the coating so that the corrosion of the matrix that it applied minimizes.Suitable inhibiter is optional to be insoluble to the organic compound of water from organic pigment, mineral dye, organo-metallic pigment or other.Also can use corrosion-inhibiting pigment concomitantly, for example comprise phosphoric acid salt or boratory pigment, metallic pigment and metal oxide pigment, such as but not limited to zinc phosphate, zinc borate, silicic acid or silicate, for example Calucium Silicate powder or strontium silicate, and based on the pigment dyestuff inhibiter of aminoanthraquinone.Can use inorganic inhibitor in addition, for example the phenol of the benzotriazole of the salt of nitroisophthalic acid, Weibull, phosphoric acid ester, replacement or replacement.And the keto-earboxylic acid of the titanium of slightly water-soluble carboxylic acid or zirconium composite and resin-bonded especially is suitable as the inhibiter in the coating composition, is used for the protective money metal surface.In addition, a kind of embodiment is the nonmetal corrosion inhibitor of total solids, comprise, only as an example, Cortec Corporation (4119 White BearParkway, St.Paul, MN, M-235 product U.S.A.), and any other upgrading and substitute products.

Pigment is insoluble white, black or coloring matter, be suspended in usually be used for painting or the vehicle of printing ink in, can also comprise for example mica of effect pigment, metallic pigment are aluminium for example, and pearly pigment.Pigment is used for coating decorates and/or defencive function, yet because theirs is insoluble, pigment may be the inducement of variety of issue in liquid coating and/or the dry paint to provide.Think that the example of some film defectives of rising because of pigment comprises: the gloss of not expecting, frosting, the pigment that is caused by gathering fades, the separation of pigment flocculation and/or sedimentation, pigment composition, fragility, wet quick property, easily give birth to fungoid and/or thermolability.

" ideal " dispersion comprises the symmetric suspension of primary particle.Yet mineral dye is usually incompatible with the resin that they are sneaked into, and this causes pigment to be difficult to homodisperse usually.In addition, when dry colour comprises the mixture of primary particle, aggregate and agglomerate, before the production that realizes stable pigment dispersion, this mixture humidification and depolymerization may must be needed the step of milling.Influence the coating character of composition and the optical property of cured film in the concrete degree of scatter that contains in the pigment coating composition.Dispersive improves the improvement that causes glossiness, tinctorial strength, brightness and gloss retention aspect.

Handle surface of pigments for the association reaction functionality and improved dispersing of pigments.The example of surface-modifying agent includes but not limited to polymkeric substance, as polystyrene, polypropylene, polyester, vinylbenzene-methacrylic acid type multipolymer, styrene-propene acid type multipolymer, tetrafluoroethylene, polychlorotrifluoroethylene, polyethylene tetrafluoroethylene type multipolymer, poly aspartic acid, polyglutamic acid and polyglutamic acid-γ-methyl ester; With the properties-correcting agent such as silane coupling agent and alcohol.

These pigment through surface modification have improved the colo(u)rant dispersion in various kinds of resin, these resins for example: alkene, as, only as an example, polyethylene, polypropylene, polyhutadiene etc.; Vinyl is as polyvinyl chloride, polyvinyl ester, polystyrene; Acrylate homopolymer and multipolymer; Resol; Aminoresin; Synolac; Resins, epoxy; Siloxanes; Nylon; Urethane; Phenoxy resin; Polycarbonate; Polysulfone resin; Polyester (chlorination alternatively); Polyethers; Acetal; Polyimide and polyoxyethylene.

Multiple pigment dyestuff can be used in the present composition, includes but not limited to carbon black, azo pigment, phthalocyanine pigment, thioindigo color, anthraquinone pigment, flavanthrene pigment, indanthrene pigment, anthra pyridine pigment, pyranthrone pigments, perylene pigments, perynone pigment and quinacridone pigment.

In the present composition, can use multiple mineral dye, such as but not limited to the oxide compound of titanium dioxide, aluminum oxide, zinc oxide, zirconium white, iron: colcother, iron oxide yellow and iron oxide black, ultramarine, Prussian blue, chromic oxide and chromium hydroxide, barium sulfate, stannic oxide, calcium, titanium dioxide (rutile and anatase octahedrite titanium), vitriol, talcum, mica, silica, rhombspar, zinc sulphide, weisspiessglanz, zirconium dioxide, silicon-dioxide, Cadmium Sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, clay such as kaolin, white mica and sericite.

Be used in solid pigment dispersion in the present composition and can be selected from following pigment with acrylic resin modified bonding: carbon black, rutile titanium dioxide, organic red, phthalocyanine blue pigment, colcother pigment, isoindoline yellow pigment, phthalocyanine green pigment, quinacridone violet, carbazole violet, mass-tone are black, shallow lemon iron oxide yellow, shallow organic yellow, transparent iron oxide yellow, diaryl orange, quinacridone are red, organic scarlet, shallow organic red and dark organic red.These polymerizable pigment dispersions can be distinguished mutually with other pigment dispersion, and it is dispersed in soluble granules of pigments in some type of resin and with granules of pigments and is trapped in the polymeric matrix.Being used in the present composition handles pigment so that they are connected with acrylic resin with the pigment dispersion in the method; Polymerization and intricately were relevant with the character of whole coating when thereby pigment dispersion can be in being exposed to the UV radiation.

The median size of the filler in the present composition comprises that for example, less than about 20 μ m, more for example, median size is the discrete particle of 1～10 μ m; And Nano filling particulate median size comprises, for example, less than about 200nm, more for example, median size is that the discrete particle of 5～50nm is to nano level particle.Add filler and give some rheological property, as viscosity to composition; But, add the mechanical properties generation and micron order filler remarkable different effect of nano-sized filler to coating.Thereby, can be by changing the mechanical properties that the content of micron-scale filler and Nano filling is regulated coating in the coating composition.

Polymer nanocomposites is the blend of nano-sized filler and thermoset or UV curable polymer, and this base polymer nano composite material has the character of improvement with respect to the conventional fillers material.The character of these improvement comprises tensile strength, modulus, heat distortion temperature, impermeability, anti-UV, wear resistance and the scratch resistance and the electric conductivity of improvement.In conjunction with some Nano filling such as nano aluminium oxide and nano-silicon, long-term abrasion resistant coatings can be provided, and not remarkably influenced optical clarity, gloss, color or physical properties.The character of these improvement is because the small size and the high surface area of nano-sized filler cause to a great extent.

Filler and Nano filling can be insoluble inorganic particle or insoluble organic granular.Mineral filler and Nano filling are generally metal oxide, though can use other mineral compound.The example of mineral filler and Nano filling comprises aluminium nitride, aluminum oxide, weisspiessglanz, barium sulfate, bismuth oxide, cadmium selenide, Cadmium Sulfide, calcium sulfate, cerium oxide, chromic oxide, cupric oxide, tin indium oxide, ferric oxide, lead chromate, nickel titanate, niobium oxides, rare earth oxide, silica, silicon-dioxide, silver suboxide, stannic oxide, titanium dioxide, zinc chromate, zinc oxide, zinc sulphide, zirconium dioxide and zirconium white.Alternatively, organic filler and Nano filling are generally the polymeric material that grinds to form the suitable dimension particulate.The example of nano level organic nano filler includes but not limited to, nanometer polytetrafluoroethylcomposite, acrylate nanometer ball colloid, methacrylic ester nanometer ball colloid, and combination, though can use tetrafluoroethylene, acrylate, methacrylic ester and combined micrometer level filler thereof.

Nano aluminium oxide is made up of nano level high-purity alpha-alumina, for example comprises less than 200nm, and is discrete spheroidal particle in about 5～40nm scope.Nano aluminium oxide sneaked into make coating keep good optical clarity, gloss and physical properties in the coating system, thereby can be used for the wear resistance application of the good optical clarity of needs, as glasses based on the composition of nano aluminium oxide; Meticulous polishing is used, and comprises semi-conductor; And nano-complex uses, and comprises the heat management of improvement.In addition, nano aluminium oxide sneaked in the coating composition can obtain adamantine coating, it can replace " hard chrome ", and can be used for applying the object that needs shock resistance.

" hard chrome " obtained by the technology of galvanic deposit thick-layer (0.2mil～30mil or bigger) chromium usually, usually chromium directly is coated on ferrous substrate such as the steel, though it also can be applied on the non-ferrous substrate.Thick chromium almost always deposits from the sexavalent chrome plating bath." hard chrome " can be used for the hard tip of parting tool and form axle or the zone that will stand heavy wear on steel.Usually selecting chromium deposition is to utilize its character that can expect, as hardness, wear resistance, erosion resistance, slipperiness and low-friction coefficient.Can be comprised hydraulic stem and cylinder, aircraft jet engine assembly, cylinder jacket of diesel engine, pneumatic support bar, vibroshock, undercarriage, railway wheel bearing and connecting rod, instrument and the die components of automobile back door and the mould of plastics and rubber industry by the galvanized various elements of hard chrome.

Chromium can exist with two kinds of valence states, trivalent chromium (Cr III) and sexavalent chrome (Cr VI).Chromium III is the essential element in the human body, and is more much lower than the toxicity of chromium (VI).Suck exposure for acute (short-term) and chronic (for a long time), respiratory tract is the toxic main target organ of chromium (VI).Acute exposure in chromium (VI) can take place short of breath, cough and stridulate, and chronic exposure has been found that barrier film perforation and ulcer, bronchitis, decreased lung function, pneumonia and other breathe influence.The human research clearly illustrates that the chromium of suction (VI) is human carcinogen's thing, causes the danger of lung cancer to increase.Clearly, the sexavalent chrome plating bath is relevant with the application that they are used for obtaining hard coat, has significant health risk and environmental toxicity problem.In addition, use the hard chrome electroplating technology can spend several hrs and finish, therefore very time-consuming.Thereby, need exploitation can apply, not have the health risk and the also coating of environmental sound easily and apace.The coating composition of sneaking into nano aluminium oxide is eco-friendly, can be easily and apply, and obtain the coating of hard, highly abrasion-resistant and scrape resistant apace.And, nano aluminium oxide sneaked into also make coating keep good optical clarity, gloss and physical properties in the coating system.

Nano silicon with nano-scale can be sneaked in the coating composition, its nano-scale for example comprises that less than about 200nm, more for example, median size is 5～40nm, its dioxide-containing silica is up to 40～65%, the less increase of composition viscosity and do not lose the coating transparency.In addition, the coating of gained also has toughness, hardness and wear resistance and the scratch resistance of improvement, and coating transparency and not reduction of gloss.When sneaking into nano-silicon in the coating composition, other character and the feature that obtain comprise: it plays opposing gas, the barrier effect of water vapor and solvent, it has the weathering resistance of improvement and the thermal ageing that is suppressed, it shows the cure shrinkage and the reaction heat of reduction, the thermal expansion and the internal stress that reduce, the tear strength that improves, fracture toughness property and modulus, have improvement to many inorganic matrixes (glass for example, aluminium) tackiness, have the didirtresistance of the opposing inorganic impurity (for example coal smoke) of improvement by more hydrophilic surface, and other desirable properties with improvement is as thermostability, didirtresistance, thermal conductivity, dielectricity.

Other can be used as Nano filling and the material that has as the character of wearability, hardness, rigidity, wear resistance, chemical resistant properties and erosion resistance comprises: oxide compound, carbide, nitride, boride, silicate, wustite and titanate.For example, the example of this class Nano filling is but is not limited to: nano zircite, nano zirconium dioxide, nanometer silicon carbide, nano-silicon nitride, nanometer plug dragon (oxynitride of sial), nano aluminum nitride, nano bismuth oxide, nano-cerium oxide, nano cupric oxide, nano-sized iron oxide, nano barium titanate nickel, nano oxidized niobium, oxide nano rare earth, nano phase ag_2 o, nano tin dioxide and nano-titanium oxide.Except these character, these materials at high temperature have high relatively physical strength.

Alternatively, the micron order filler that uses in the present composition is selected from: with the soft silica of polyethylene wax preparation, through the synthetic amorphous silica of organic surface-treated, undressed soft silica, season alkyl wilkinite, silica gel, acroleic acid esterification silica gel, aluminum oxide, zirconium white, zinc oxide, niobium oxides, titanium dioxide, aluminium nitride, silver suboxide, cerium oxide, and combination.Silicon-dioxide is selected from comprising that polyethylene wax or wax carry out surface-treated and synthesizes with natural soft silica with from Ciba Specialty Chemicals 540White Plains Road, Tarrytown, New York, the IRGANOX  of U.S.A..

The flexibility of coating is the critical nature of the coating of bending, distortion or the object that changes shape in other mode, and this object is such as but not limited to the chassis of various springs and motor vehicle.The flexibility of coating makes when object bending, distortion or coating can be crooked or twist and do not rupture when changing shape; And the tackiness of coating makes that coating can remain adhered on the object when object bending, distortion or change shape.Composition of the present invention can be used to obtain flexibility, wear-resisting, scrape resistant and/or corrosion-resistant and have a coating of the adhesive property of improvement.Flexible coating on composition replacement of the present invention thus or replacement object or the goods is wherein owing to exist flexible coating will improve or improve at least a function of object or goods.Can use the example of this object that the present composition applies or goods to include but not limited to the chassis of spring and motor vehicle.Can use the example of this spring of present composition coating to include but not limited to laminated spring, damper spring, wrist-watch spring and bike saddle spring.

The possible method that applies the present composition comprises spraying, brushing, blade coating, the showering of curtain formula, dip-coating and roller coat.On the surface that can spray to expectation, must the prepolymerized viscosity of control.This realizes by using the low molecular weight monomers replace organic solvent.But these monomers also participate in and are beneficial to final coating property and do not evaporate.The viscosity of the present composition is about 2 centipoises～about 1500 centipoises; Wherein under the room temperature about 500 centipoises or littler viscosity make it possible to need not add heat and by HVLP, air auxiliary/no air or electrostatic rotating cup cover coated with single coating.

The purposes of 100% solid UV curable coating composition

The present composition has significant improvement, because they are not contained in any water or the organic solvent that must remove before the realization completely solidified.Thereby the present composition is much smaller and economical to the harm of environment, because less space, less energy and the time of lacking of its needs.In addition, the present composition can be with single layer coating, forms flexible, wear-resisting, scrape resistant and corrosion-resistant and have a coating of the adhesive property of improvement.Thereby, use the compositions and methods of the invention to apply object crooked, that twist or otherwise change shape, shorten the coating time and improved output thus.

Fig. 1 is used for coating flexible object and/or include the process flow sheet of the object of corner characteristics.Cleaning of objects, perhaps directly usefulness coating composition coating of the present invention alternatively before applying at first.Then the coated article body is packed alternatively and transported, be used for any other purposes of human consumer's use, industrial use, science purposes or end user's anticipation.

Fig. 2 is used for the synoptic diagram that UV curable coating composition of the present invention applies the process combination system of object.The fs of combined system is optional installation station, therein object to be coated is fixed on the moving element, only as an example, axle, hook or substrate.Object can be used, and only as an example, nail, screw, screw bolt and nut, band, glue or its any combination fix.In addition, the workman can carry out this pinned task, perhaps alternately, carries out this function with robot.Then, by the device that optionally is used to move the fixed object is moved on to the coating station.The device that optionally is used to move can pass through, and only as an example, travelling belt, rail, track, chain, container, bin, go-cart and combination thereof obtain.In addition, the device that is used to move can be fixed to wall, ground or top ceiling or its arbitrary combination.Applying the station is the place that applies desired object with required coating composition.The device that is used to apply coating composition is positioned at and applies the station.The device that is used to apply coating composition comprises, only as an example, heavy body low pressure spraying (HVLP) device, electrostatic spraying apparatus, air be auxiliary/device or its combination of airless spray unit, brushing, roller coat, dip coated, blade coating, the showering of curtain formula.The multiple device that is used to apply coating composition can make up and be arranged in and apply the station, and end face, bottom surface and the side of guaranteeing to carry out object thus apply.In addition, before coating composition applies and during the object that is fixed is rotated at least one axle, to guarantee even coating.In addition, can comprise mask or template when needing, be attached on the object with will design, logo etc.Apply the station and can comprise polytype coating, comprise different painting colors, as expected.When the coating of coating composition was finished, fixed coated article body can continue rotation, perhaps stops the rotation.Apply the station and can comprise that also optional recovery system reclaims the coating composition of any excessive injection, reclaim at least 98% spray material composition excessively thus.This composition recirculation system make coating composition use and produce in can significantly save because the composition that reclaims can be applied on the objects different in the production line.

Fixed coated article body can be moved on to irradiation station (literary composition is also referred to as curing room) by the device that optionally is used for moving from applying the station now, being solidificated in the irradiation station of coated article body carried out.Along production line with apply the position that the station separate and settle irradiation to stand.In one embodiment, irradiation station has and is used to limit the device that impinge actinic radiation arrives these combined system other parts.Multiple this class device be can suspect, door, curtain, baffle plate included but not limited to and along the band cornue road or the bend of production line.Be used to limit the device of irradiation of the actinic radiation at irradiation station, for example, only as an example, close the door, settle tinted shade or close curtain, be used for protecting the operator cruelly in the UV radiation and shielding apply the station and guarantee that there does not solidify.The three cover UV lamps of arranging in the irradiation station guarantee that end face, bottom surface and side are cruelly in the UV radiation.In addition, every cover UV lamp comprises two kinds of independently lamp types, and only as an example, one is mercury arc lamp, and another is to mix molten iron silver Jupiter, solidifies with the three-dimensional of guaranteeing to suit.Thereby in fact irradiation has six lamps in the station.Alternately, this three-dimensional curing by only using two lamps to realize, only as an example, one is mercury arc lamp in two lamps, and another is to mix molten iron silver Jupiter, guarantees that by the arrangement of mirrors of arranging end face, bottom surface and the side of coated article body also solidified in the UV radiation cruelly.Regardless of used concrete grammar, the position of the interior two kinds of lamp types in irradiation station is indefinite, carries out partly solidifiedly because need not that the coated article body is moved on to different positions, carries out completely solidified then.

In one embodiment, after fixed coated article body is moved into the irradiation station, close the door, fixed coated article body is rotated alternatively.Excite the lamp of longer wavelength to be used for the partly solidified stage, only as an example, mix molten iron silver Jupiter; Excite the lamp of shorter wavelength to be used for the completely solidified stage then, only as an example, mercury arc lamp.Before turning on the lamp of shorter wavelength, need not to close fully the lamp of longer wavelength.After two cure stage, closeall lamp, open the door (, otherwise providing other outlet to object) of irradiation station opposite side, completely crued fixed object is moved to optional breakdown station with optional running gear from the irradiation station if the irradiation station is equipped with door.At optional breakdown station, the completely crued object that is coated with can be unloaded from fixture, and or move to storage facilities with optional running gear, perhaps pack immediately and transport.In addition, the workman can carry out this dismounting task, perhaps alternately, carries out this function with robot.Need not cooling before the dismounting, because apply and no heat requirement of curing step, all steps carry out at ambient temperature.

Fig. 3 describes the explanation of used technology and the component example of UV curable coating composition of the present invention.Usually, in the mixing vessel that uses (only as an example) saw-toothed blade or mixing screw, component is mixed.With the component of enough shearing force blend compositions, level and smooth up to obtaining, uniform coating compound.In addition can be by vibrating, stir, sway or stirring and realize mixing.Prepare expectation composition up to specification, described specification is such as but not limited to tackiness, erosion resistance, wear resistance and the gloss of opaque, color, improvement.In addition, coating comprises oligopolymer and monomeric combination, thereby obtains required specification.Polymerizable pigment dispersion and filler are optionally, as shown in Figure 3, because composition of the present invention comprises transparent coating composition.

Then, as shown in Figure 4, by include but not limited to HVLP, air auxiliary/coating unit of no air or electrostatic rotating cup, said composition be coated on flexible article or include on the object surfaces of corner characteristics.Fig. 4 represents to apply arranging of used shower nozzle, although can adopt other technology, and for example dip-coating, flow coat or the showering of curtain formula.As shown in Figure 4, object is fixed on the rotary fixing device, this is connected to is used for being sent to from the coating coating area transfer system of curing area.Then, as shown in Figure 5, use single UV light source or the combination of light sources of sending and excite the required wavelength eclipsed of used specific light initiator spectral frequency in the composition, the gained coat film is solidified.Fig. 5 represents to be used to finish a kind of exemplary UV lamp bank cloth of three-dimensional solidified.At last, after curing is finished, be coated with the surface and prepare to handle immediately and transport, be need not to wait for that part cooling or solvent discharge are to dissipating.

100% solid UV hardenable coatings by suitable preparation combines with the light of suitable frequency, and the UV irradiation can penetrate Opaque paint to reach base matrix, thus completely solidified coating.Because this solidification process almost is moment, every kind of light needs (for example) average 1.5 seconds, and time and space all obtain saving.Used cure lamp can be high pressure mercury vapour lamp, mix the mercuryvapour lamp of gallium or iron, or combination as required.These lamps can be power by directly applying voltage, microwave or radiowave.

Photoinitiator mixtures with the light frequency that is enough to contain all needs is prepared coating composition.With itself and the lamp or the paired lamp acting in conjunction of arranging for assurance object completely solidified.Polyreaction can be subjected to oligopolymer, light trigger, inhibitor and selection of pigment and UV lamp irradiance and spectrum output influence, particularly in the acrylic double bond conversion with between inductive phase.Compare with the Clear paint preparation, the existence of pigment makes solidifies complexity more, because pigment absorbs the UV radiation.Thereby, when the output of the absorption characteristic that makes light trigger and UV source spectrum is complementary, use variable wavelength UV source that coloured preparation is solidified.

Being used for UV solidified light source comprises: Jupiter, carbon lamp for example, xenon arc lamp, mercury gas lamp, tungsten halogen lamp, laser apparatus, the sun, sun lamp and the luminescent lamp with the ultraviolet fluor of emission.Under the wavelength that obtainable light trigger absorbs by most of commerce, middle medium pressure mercury lamp and high pressure xenon lamp have multiple radioactive rays.In addition, mercury arc lamp can be mixed with iron or gallium.Alternately, laser is single-frequency (single wavelength), can be used in to excite the light trigger that absorbs under the wavelength that maybe can not obtain a little less than crossing when adopting Jupiter.For example, middle medium pressure mercury Jupiter has strong radioactive rays under 254nm, 265nm, 295nm, 301nm, 313nm, 366nm, 405/408nm, 436nm, 546nm and 577/579nm.Thereby, the light trigger that has a strongest absorption at the 350nm place with in the medium pressure mercury Jupiter can not effectively be excited, but use 355nm Nd:YVO ₄(vanadate) solid laser can effectively cause.Merchant with the variation spectrum output in the 250-450nm scope sells the UV/ visible light source and can be directly used in the curing purpose, and can realize the wavelength selection with optical band pass or long logical colour filter.Thereby as described herein, the user can utilize best light trigger absorption characteristic.

Regardless of light source, the emmission spectrum of lamp must with the absorption spectrum crossover of light trigger.Need to consider two aspects of light trigger absorption spectrum: wavelength that is absorbed and absorption intensity (molar extinction coefficient).Only as an example; DAROCUR  4265 is (from Ciba SpecialtyChemicals 540 White Plains Road; Tarrytown; New York; U.S.A.) light trigger HMPP in (2-hydroxy-2-methyl-1-phenyl-third-1-ketone) and TPO (phenylbenzene (2; 4; the 6-trimethylbenzoyl) phosphine oxide) absorption peak is arranged at 270-290nm and 360-380nm place; and DAROCUR  1173 is (from Ciba Specialty Chemicals 540White Plains Road; Tarrytown; New York; U.S.A.) at 245nm; there is absorption peak at 280nm and 331nm place; and ESACURE  KTO-46 is (from Lamberti; S.p.A.; Gallarate (VA); Italy) between 245nm and 378nm, absorption peak is arranged; and IRGACURE  907 is (from Ciba Specialty Chemicals 540 White PlainsRoad; Tarrytown; New York; U.S.A.) MMMP in absorbs at the 350nm place; IRGACURE  500 (is that IRGACURE  184 is (from Ciba Specialty Chemicals540 White Plains Road; Tarrytown; New York, U.S.A.) and the blend of benzophenone) between 300nm and 450nm, absorb.

In preparation, add pigment and improved the opaqueness of gained coating, and can influence the ability that any entire body is solidified (through curing).In addition, the pigment that is added can absorb the incident curing radiation, influences the performance of light trigger thus.Thereby the curing properties of opaque colored coating depends on the pigment of existence, each assembly side, illuminate condition and substrate reflection.Thereby to pigment and light trigger separately the consideration of the UV/ visible light absorption UV that can be used for optimizing colored pigment solidify.Usually, be used for the curing transparent preparation those compare, the light trigger that is used to solidify coloured preparation (has higher molar extinction coefficient between the 300nm～450nm) at long wavelength.Although the existence of pigment can absorb the radiation of UV and visible region, reduce the absorption that is suitable for radiation curing, phosphine oxide type light trigger thus; such as but not limited to two acyl group phosphine oxides; in the UV hardenable coatings material of coloured (comprise, only as an example, black) effectively.Phosphine oxide also can be used as the light trigger of whitewash, and can carry out effective entire body curing to the present composition.

The mercury gas discharge lamp is the solidified UV source that is widely used in most, because it is the lamp very efficiently with strong UV-C (200-280nm) radiation, but it also has the spectral radiation line in UV-A (315-400nm) and UV-B (280-513nm) zone.The spectrum efficiency of this lamp of the strong influence of mercury pressure in UV-A, UV-B and UV-C zone.In addition,, can change hg spectrum strongly,, in UV-B and UV-C district, also change mainly in the UV-A district by in silver, adding (doping) small amount of silver, gallium, indium, lead, antimony, bismuth, manganese, iron, cobalt and/or nickel with metal iodide or bromide form.Adulterated gallium 403 and 417nm launch strong ray; And doping iron makes the spectral radiant power in the UV-A district of 358-388nm increase by 2 times, and simultaneously because the existence of iodide, UV-B and UV-C radiation reduce 3-7 doubly.As mentioned above, the existence of pigment in coating formulation can absorb incident radiation, thereby influences exciting of light trigger.Thereby expectation selects to be used for the UV source of used pigment dispersion and light trigger, photoinitiator mixtures or light trigger/coinitiator mixture adaptively.For example, only as an example, the mercury arc lamp (358-388nm emission) of mixing iron and light trigger ESACURE  KTO-46 (from Lamberti, S.p.A., Gallarate (VA) Italy) (absorbs between 245-378nm) that to use together be ideal.

Have different spectral response curves or some spectrum crossovers and enough different a plurality of lamps can be used for the mixture of exciting light initiator or the mixture of light trigger and its initiator.For example, only as an example, mix molten iron silver Jupiter (358-388nm emission) and be used in combination with pure water silver Jupiter (200-280nm emission).The order that applies excitaton source can be indefinite, is used to obtain the enhanced coating characteristic, for example, only as an example, slickness, gloss, tackiness, wear resistance and erosion resistance.It is favourable earlier being coated with the surface with the irradiation of longer wavelength light source, because it is held back filler particles in position and causes the polyreaction of near surface, provides coating smooth and that adhere thus.Subsequently, be exposed in the radiation of higher-energy, shorter wavelength and make the film fast setting that retains that has been fixed on the appropriate location by the initial polymerization stage.

The irradiation time that can regulate every type of lamp is to improve the curing of the present composition.A kind of method that is used to solidify the present composition of the body surface that is used for the coating flexible object or includes corner characteristics is, to be coated with in the adulterated mercury arc lamp that the surface is exposed to longer wavelength, its exposure duration is than being exposed to shorter in the shorter wavelength mercury arc lamp.But this exposure scheme can cause coating material solidified fold/wrinkling.Therefore, other exposure scheme adopts the exposure duration that equates for the adulterated mercury arc lamp of short wavelength's mercury arc lamp and longer wavelength, perhaps alternatively, the exposure duration of the adulterated mercury arc lamp of longer wavelength comparable short wavelength's mercury arc lamp exposure duration longer.

Test is coated with the surface

100% solid UV hardenable coatings of the present invention has good weather resistance, and is particularly useful for suffering physical abrasion or is exposed to surface under the various weather conditions.The mechanical properties of solid coating and their various testing method are at " Mechanical Properties of SolidCoatings " Encyclopedia of Analytical Chemistry, John Wiley ﹠amp; Sons describes in 2000, and its content is incorporated herein by reference thus in full.Coating of the present invention, composition and method satisfy and exceed at least a described test, and more than one these are tested in some cases, the requirement of all these tests in other cases.The explanation of following test only is provided as an example.

For example, the compositions and methods of the invention provide the solidified coating of improvement, show improvement during it is tested below at least a: rub resistance, shock resistance, erosion resistance, anti-sudden strain of a muscle rust property, higher gloss, exterior durability such as gloss conservation degree, anti-breaking property, to the tackiness and the slipperiness of matrix.

The rub resistance test is to be used to measure coating to caused the accelerator of abrasive tolerance by friction.Though wear-resisting wiping property testing mainly is intended at coated inside, they use at exterior coating sometimes, as the other measurement of film properties.In common friction testing, coating is coated on the scraping test panel with specified film thickness, solidify, make it then through benefiting from the friction of straight line friction testing machine.Wear-resisting wiping is that coating is removed to the required friction cycle index of specified endpoint.Perhaps, after specified friction cycle index, measure the measurement of weight loss as rub resistance, and the loss of the equivalent of calculating film thicknesses.

Shock resistance is to be used to estimate coating for shock strength that falls object or flexible traditional method.This test can be used single body (projectile) shape at single height of drop, changes projectile weight simultaneously.Expection shock strength according to specimen is selected projectile size and height of drop.Many specimen are impacted to measure for the suitable starting point of projectile weight.Specimen is clamped in securely in the air ring of whereabouts tower bottom.Fixed support is adjusted to suitable height of drop, and projectile is inserted in the support.Discharge projectile and make it fall the center of specimen.Carry out 20～25 times series and impact,, height of drop is increased a unit if specimen is passed through.If the specimen breakage reduces by a unit with height of drop.Alternatively, use the height of drop test panel that increases gradually, with the minimum height of drop of determining to produce any fracture or peel off from matrix.These ballistic results be used for calculating impact failure weight-50% specimen under this impact with that point of breakage.Usually projectile is a circular object, and diameter is 38mm (1.5 inches)～51mm (2 inches), and falls from the height of about 0.66m (26 inches)～1.5m (60 inches).

For the gratifying coating of performance, they must be adhered on their coated matrix.Can use several different methods to determine that coating is adhered to lip-deep degree.Normally used evaluation technique uses pocket knife or pulls method (pull-off) adhesion test machine and carries out.The pocket knife test is to need the tool using cutter to dig the simple test of cutter on coating.It determines that whether coating is adhered on the matrix or is adhered to (in the multiple coating system) on another coating with enough levels usually.Performance is based on the degree of difficulty and the size that is removed coating of removing coating from matrix.Alternatively, use pocket knife and cutting liner,, coating is cut " X " down to the surface by forming two otch that intersect to form the 30～miter angle of " X " shape.Attempt coating is provoked from matrix or from following coating with point of a knife at the place, summit.

The more formal form of pocket knife test is tape test, and it can carry out under the condition of humidity humidity being arranged or do not have.How humidity shows under meeting generation corrosive condition if being attached to the band adhesive property that detects coating of adhering/peel off in the test.Apply and remove Pressure Sensitive Tape on the otch that in coating, forms.This test has two kinds of versions; Tape test of X-otch and stroke lattice tape test.The otch down to two 30～miter angles of matrix is used sharp razor blade, scalper, pocket knife or other cutting facility to form to switch in the coating in the tape test of X-otch, and it intersects to form " X ".Use ruler to guarantee to form straight otch.Band is placed on the center in otch point of crossing, removes fast then.Observe the X-incision tract then, observe coating from matrix or removing and rating with Front-coating mirror.Alternatively, draw the lattice tape test and be mainly used in test less than the thick coating of 5mil (125 microns).It uses lattice rather than X pattern.Lattice obtains by using the special grid cutting unit that cuts liner or have a plurality of default blades, has proper spacing and parallel to guarantee otch.Apply and pull off band then; Observe incision tract and rating then.In one embodiment, that composition of the present invention produces is flexible, corrosion-resistant, the coating of erosion resistant and scrape resistant, it had the 99+% tackiness after under 110 , 100% humidity 10 days, and/or crooked as 180 degree of (only as an example) half inch axle around axle.

More quantitative tackiness test is to pull test (pull off test), wherein will load fixture by tackiness agent, is commonly referred to support or stake, is fixed on the coating.By using the portable tackiness tstr that pulls, load is applied to the surface is gradually upward pulled off up to support.Pull off the power that required power or support bear according to support, produce tensile strength, in pound/square inch (psi) or MPa (MPa).In the system that comprises support, tackiness agent, coating system and matrix, along the most weak plane breakage will take place, and come out by fracture surface.This testing method with compare as the shear-stress that scraping or pocket knife adhesion apply with other method, make the tensile stress maximization, and the result is incomparable.The scraping test is limited to usually on slick flat surface to be tested.Adhesive measuring method is to push away to be coated with the surface below round pin or ring, and this pin or ring apply load with the amount that increases gradually, up to removing coating from stromal surface.

But tackiness also is the measuring result of some hardness tests, and this test is undertaken by pencil hardness, gravel meter (Gravelometer), impact (falling objects etc.) or bent spindle, as it is indicated to cut coating.At last, in some chemical resistance test processs when coating foaming, bubbling or even can be designated as the tackiness forfeiture when coming off.

Wear resistance can be by being called abrasive material (ablative) the air blast silicon-carbide particle measure being coated with on the test panel flow velocity with about 45g/min.Continue to grind up to coating and gall, and measure the amount of the abrasive material that is used for reaching worn-off.Wear resistance is represented with the gram number of per 25.4 μ m film thickness abrasive materials.A kind of similar test comprises that using run by gravity that silicon-dioxide or silicon carbide abrasive are fallen from specified altitude assignment by pipe is coated with on the plane surface.Silicon-dioxide (sand) is the abrasive material than silicon carbide milder, and its slower erosion rate can be used to distinguish different coating.Run by gravity rather than compulsory airflow are used in the knockout test, and obtain slower grinding rate.Wear resistance for the knockout test is represented with the volume (liter) of the sand of every mil (25.4 μ m) film thickness.In one embodiment, the present composition produces the coating that has greater than the knockout wear resistance of 100 liters/mil.

The scratch resistance test is that multiple abrasion property is carried out quantitative integrated approach.This technology is included on the specimen and produces the scratch of control with the diamond point.Make this diamond point or sharp metal tip, under constant or progressive load, streak and be coated with the surface.Coating will begin damaged under certain critical load.Critical load can very accurately be measured by acoustic sensor, frictional force and the opticmicroscope that is connected to the indentor anchor clamps.Once known critical load is used for the adhesive property of quantitative different film/substrate combination, and these parameters constitute the unique tag of tested vanish system.

The pencil hardness test method is to push away by the pencil lead with known hardness to be coated with test panel, comes to measure fast, cheaply the step of the film hardness of organic coating on the matrix.Classification obtains hard and soft classification to pencil, and hardness changes to 9B from 9H." H " represents hardness, " B " expression expression blackness, and HB represents hard and black pencil.The hardest pencil is 9H, then is 8H, 7H, 6H, 5H, 4H, 3H, 2H and H.The centre of hardness level is F; Be HB, B, 2B, 3B, 4B, 5B, 6B, 7B, 8B and 9B then, 9B is the softest.The hardness of some coatings makes the 9H pencil can not scratch them; Yet these coatings still obtain the 9H classification represents their hardness.In the pencil hardness test method, will be coated with test panel and be placed on the firm horizontal surface, will push away with 1/4 inch (6.5mm) stroke from the operator with the pencil of miter angle clamping.This method begins with the hardest pencil, continues to reduce any of hardness level to two terminal point; One, film (pencil hardness) can not cut or excavate to pencil, and perhaps two, pencil can not scratch film (scraping scratch hardness).

Effectively coating must satisfy multiple erosion resistance requirement.The erosion resistance test evaluation comprises: salt fog, (scab) and cyclic corrosion evaluation and relevant creep retraction (creepback) scab.The testing method that is used for estimating salt air corrosion comprises test piece is fixed on temperature controlled compartment, sprays the aqueous solution of salt or salt mixture then to test piece with thin aerosol form.Although can be according to the temperature of chamber and the composition change method of salts solution, solution be 5% salt (sodium-chlor) solution usually.Test piece is inserted in this chamber, under the constant temperature salts solution is mapped on the sample with very trickle liquid spray painting.Because spraying is constant, sample is wetting all the time and corroded all the time thus.Can often rotate sample contacts with the saline solution mist equably guaranteeing.The time length of test can be 24-480 hour or longer.Test piece exposed 400 hours at least and do not form the sign of any tangible underfilm corrosion, other appearance change of bubbling or may cause for example by the pin hole in the coating, then provable have an enhanced corrosion resistance.Usually, maximum allow the creep withdrawal to be 2-4mm, be less than 10% surface simultaneously at least and in the sharp edge scope of 2-4mm, be corroded.Stricter test comprises the sign that is exposed to few 900 hours and does not form any tangible underfilm corrosion, for example bubble or other appearance change, maximum allow the creep withdrawal to be 2-4mm, be less than 10% surface simultaneously at least and in the sharp edge scope of 2-4mm, be corroded.

The corrosion test that scabs comprises employing salt spray step, but scratches test piece to form cut in coating.Produce the corrosion of scar shape along the cut in the coating afterwards, and self show as the air bubble-shaped outward appearance of dispersing out from cut.If test piece does not show and bubbles or surface corrosion after 1 week, or other appearance change, maximum creep withdrawal is up to 2mm and is less than 10% surface at least and is corroded in the sharp edge scope of 3mm, and then provable have a scab erosion resistance of corrosion test of enhanced.Stricter test comprises and exposing up to 2 weeks scraping the test piece that streaks, and do not show scar shape corrosive sign.

Employing comprises that step (as taking place in the SaltSprayTest) evaluation that continues to be exposed in wet part is coated with the surface and perhaps can not imitates the real conditions that is coated with the surface experience, can the wet and dried environment of experience in the reality period.Thereby adopt wet/do circulation, wet cycle period spray or do not spray saline solution that to estimate coating be to estimate more really for coating used in everyday.Continously wetting during the SaltSprayTest makes can not form this passive state zone of oxidation.

" curing " test is used for the adhesion strength and the solvent resistance on integrity, coating and the surface of evaluate cure.Used step applies it with specimen for getting test piece, adopt then selected curing for example actinic radiation solidify accordingly.Making coating and solidified test piece stand to rub then makes the surface expose required friction number of times with evaluation.Breakage is generally determined by penetrating substrate surface.Usually, also that friction surface is used cloth immerses in organic solvent such as the methylethylketone (MEK), as the means of accelerated test condition and to the test of the stability of solvent contact.Once friction is once circulation back and forth, and highly anti-solvent coating reaches the rank that surpasses 100 pairs of frictions.And, galled spots takes place by which point is determined at, can also obtain to solidify the rereading of test.

Be to estimate the thermotolerance of coating, will be coated with test piece put into stove and estimate loss of adhesion after the different thermo-contact time, break, rupture, fade, hazing or haze.The used type of furnace includes but not limited to convection furnace.The curable corrosion resistant coating of UV described in the literary composition descends maintenance after at least 1 hour at least 210 ℃, and after keeping at least 10 hours under at least 210 ℃, no loss of adhesion, crack-free, rupture, fade, hazing or haze, can satisfy or exceed stable on heating requirement.

In the time of corrosion test, coating also experiences many other judgement criterias, anti-broken the evaluation and thermal shock test.Anti-broken test is mainly used in simulation and flies upward the influence of the impact of fragment to top coat.Normally the gravel meter is designed for evaluation table finishing coat (paint, varnish, metal plating etc.) for flying upward the tolerance that thing impacts the fragmentation that causes by gravel or other.Usually, test sample is fixed on the back side of gravel meter, adopts air pressure to sample model throw out about 300 blocks of gravels, hexagonal metal block or other band angle object.Take off test sample then, softly brush lightly with clean cloth and wipe away, then adhesive tape is layed onto on the whole test surfaces.Remove any loose part that adhesive tape will pull off coating.Outward appearance and standard substance with specimen contrasts to determine broken rank then, perhaps also can adopt range estimation.Broken rank is made of the numeral of the viewed number of chips of indication.

Thermal shock test is the most violent temperature test, is designed for demonstration product when under extreme conditions stretching and how shows.Thermal shock test is set up a kind of environment, will show in a short time that coating experiences the secular variation meeting and how to show under mal-condition.The various modification of test comprise resilience for the temperature coating of rapid change, for example winter when being experienced when for example house, garage or warehouse move into the ice-cold environment in the external world from warm environment, or reverse situation.This class thermal shock test has hot fast pulling speed (30 ℃ of per minutes), and can be gas-gas or liquid-liquid Impact Test.Thermal shock test is harsh more a kind of in the temperature test, is used to test coating, packing material, aircraft parts, military hardware or the electronics that will experience mal-condition.Most test block experience gas-gas thermal shock tests move into test article the another kind of temperature from a kind of extreme temperature with mechanical means in this test.Can use totally-enclosed thermal shock test chamber to avoid being exposed to undesirably in the envrionment temperature, thermal shocking is minimized.In the thermal shock test, the cold-zone of chamber can remain on-54 ℃ (65 ), and the hot-zone can be made as 160 ℃ (320 ).The sample model was kept at least one hour in each section, move around intersegmental then, repeatedly circulation.The number of times of heat shock cycling can be from 10 or 20 times to up to 1500 times.Observe the curable corrosion resistant coating of UV described in the literary composition for do not have loss of adhesion up to 20 times circulation, break, rupture, fade, hazing or haze, can satisfy and exceed the requirement of thermal shock test.

Other mechanical properties of testable coating comprises tensile strength, flexibility, cupping and the elongation when damaged.

Use the evaluation of flexible test method when being coated with matrix when crooked, the tolerance of coating to rupturing and/or breaking away from from flexible matrix.Flexibility is measured by bent spindle test or T-crooked test usually.The bent spindle test is included on the cone mandrel or crooked matrix, normally tinsel or the rubber type of material of being coated with on the cylindrical mandrel of various diameters.The length of the conical smooth steel core axle of standard is 203mm (8 inches), and an end diameter is 3mm (0.125 inch), and the other end diameter is 38mm (1.5 inches).The coated side that is coated with matrix upwards, with leverage with it around bent spindle, if there is fracture, measure the degree of fracture.To fissured distance, this distance can be used to determine elongation per-cent to illustrate from the small end of axle in range estimation.(still, do not indicate in this testing method, the elongation of being determined by stretching can produce and rupture-value that breaking point is relevant.) the axle diameter at crack arrests place is write down as resistance to fracture or flexibility.The cylindrical mandrel test is qualified/defective test, and it comprises that quilt is coated with matrix to be placed on the axle, and coated side upwards, and is manually at the appointed time interior that sample is crooked around about 180 degree of axle with even velocity.Usually use the axle of 6 diameters as 25mm (1.0 inches)～3.2mm (0.125 inch).Model is crooked on the axle of maximum diameter, check the crack then immediately.If there is not the crack to produce, use next less axle, go down like this up to producing damaged or having passed through the axle test of minimum diameter.Record can not produce fissured minimum diameter.This test can be used to calculate the coated elongate rate.

The T-crooked test comprises having being placed on by the matel coated model in the smooth mouth surface bench vice and clamping of 50mm (2 inches) minimum width.The necessary sufficiently long of model, making to need the bending of number of times, promptly about 150mm (6in).Then with crooked 90 degree of model, and coating takes off in the outside of bool, then manually further crookedly can be inserted in the vice up to bent ends; Grip vice is crooked to finish 180 degree.The tip of bool is Horizon as far as possible.This is called as 0T (zero-T) bool.Use the crack of 5～10 times lens examination bool then, the covering Pressure Sensitive Tape is also removed to determine whether coating can be pulled off.Repeat this process then, bent ends is placed in the vice around crooked 180 degree of 0T bool, formation 1T bool.Continue this process and form bools such as 2T, 3T.Do not see that the minimum T bending that crack and coating do not pull off is a report value.Notice that the radius-of-curvature of bool increases along with each continuous bend, and the required coated elongate rate of formation bool reduces along with each continuous bend.In one embodiment, the present composition produces flexible coating up to about 2T.

Erichsen test carries out being coated on the coating of flexible matrix.Cupping may be than the stricter test of bent spindle test.In Erichsen test, the distortion of model can proceed to the degree of metal fracture, and this fracture can not take place in the axle test usually.This method comprise with by the matel coated panel clamp between semisphere punch die and identation cup device.Exert pressure in model, forming domed shape to indentor, and coating is in a side of projection.Pressure boost breaks away to designated depth or up to coating failure and/or from matrix.

Tensile strength is material to the resistibility of the power of tending to it is torn, and is measured as that material can bear and the maximum tension that do not split.Tensile strength is measured on isolating coating usually, is estimated but can be coated with on the matrix at quilt.The tensile test device is usually in conjunction with super-sensitive electronics load Weighing system, and the use tonometer is surveyed the load cell that is applied to the load on the specimen.Specimen is sandwiched between two handles, and one of them handle is connected to the load cell in the mobile pinblock, and another handle is fixed on the pedestal of tstr.Pinblock is connected on two vertically disposed screw rods, uses the syncmotor transmission case assembly to make this screw rod rotation.Being applied to the distance that load on the specimen and pinblock move all is presented on the chart recorder.

Elongation is by the distortion that applies the drawing force generation, and is calculated as length variations divided by original length.Elongation is to be used for determining that a slice film can stretch how long measure before fracture., perhaps must not rupture around bottle, pipe or one section crooked 360 degree of rope with around the elongation of the angle of a timber that forms V font object, a metal for a kind of coating of exploitation, this information is useful.This testing method is included in assigned temperature and humidity condition is regulated isolating test membrane down, then specimen is cut into known size.Then with specimen holder between two handles, and stretch and to break up to it.Elongation can be between per minute 5～100%.

Embodiment

Embodiment 1: the preparation that is used for clear coating composition.

Prepare the embodiment that is used for clear coating composition by mixing following component with mixing screw, has excellent wear with generation, scratch resistance, erosion resistance and adhesive flexible coating: 25.683% aliphatic polyurethane triacrylate (EBECRYL  264, from UCBSurface Specialties, Brussels, Belgium), 18.032% vinylformic acid 2-ethyl phenoxy, 26.229% isobornyl acrylate, ester derivative adhesion promotor (the EBECRYL  168 of 8.743% methacrylic ester, from UCB Surface Specialties, Brussels, Belgium), 14.210% propoxylation, three vinylformic acid glyceryl ester-nano silicons (Nanocryl  C-155, be called Nanocryl  XP 21 0953 in the past, from hansechemie AG, Geesthacht, Germany), 5.464%DARACUR  1173 is (from CibaSpecialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.) and ESACURE  KTO-46 (from Lamberti, S.p.A., Gallarate (VA), Italy).With mixing screw with these component thorough mixing, up to obtaining homogeneous compositions.This composition can apply and use ultraviolet light polymerization by HVLP.

Embodiment 2: the preparation that is used for black combination.

Be prepared as follows the embodiment of colored composition, have excellent wear, scratch resistance, erosion resistance and adhesive flexible coating with generation: the clear coating composition that mixes 94.43% embodiment 1 with mixing screw, with 3.60% with carbon black (the solid pigment dispersion of modified acroleic acid bonding, PC 9317, from Elementis, Staines, UK) and 2.06% through the synthetic amorphous silica of organic surface-treated (SYLOID  RAD 221 is from Grace Davison divisionof WR Grace ﹠amp; Co., Columbia, MD U.S.A.) is mixed in above-mentioned 94.43% the clear coating composition.With mixing screw these additives are dispersed in the whole Clear paint, up to forming even black coating composition, this coating can apply and use ultraviolet light polymerization by HVLP.

Embodiment 3: the step that is used for forming wear resistance, scratch resistance, erosion resistance and adhesive transparent flexible coating with improvement.

Another kind of embodiment is the step that is used to prepare clear coating composition.The component of coating composition mixes under air, because the existence of oxygen prevents premature polymerization.Expectation remains on minimum with irradiation light, particularly should avoid using sodium vapour lamp.Yet, can select to use the set lights of dark place.Be used in coating composition make in, the element that contacts with coating compound with monomer, for example mixing vessel and hybrid blade should be made by stainless steel or plastics preferably polyethylene or polypropylene.Should avoid using polystyrene and PVC, because monomer and coating compound can dissolve them.In addition, should avoid contacting of monomer and coating compound and soft steel, copper alloy, acid, alkali and oxygenant.In addition, must avoid brass fittings, because they can cause premature polymerization or gelling.For the preparation of Clear paint, basic is to obtain thorough mixing, and shearing control subsequently is also nonessential.Mix the thorough mixing that to realize clear coating composition after 1-3 hour with 1/3 horsepower of (hp) mixing tank and 50 gallons of tubulars.Less amount, 5 gallons at the most, available laboratory stirrer (1/15-1/10hp) mixed after 3 hours realizes thorough mixing.Circle wall container is desirable, because this can be avoided gathering and any and incomplete mixing relevant contingency question of solid oligomer in the corner.Another factor be blender blade should be arranged on mixing vessel bottom at a distance of half distance of mixing tank diameter.Earlier oligopolymer is added in the mixing vessel, the oligopolymer mild heat can be beneficial to if desired handle.Oligopolymer should not be heated to more than 120 , thereby heating if desired recommends to use temperature control process furnace or heating jacket.Should avoid using band heater.Then add monomer and colloidal suspension, add ester/monomer adhesion promoter subsequently with any order.Add light trigger at last and be exposed to the time minimization in the light to guarantee whole compositions.After having added all components, the mixing vessel lucifuge is mixed.After the mixing, have bubble to exist, coating looks like cloud form.These bubbles dissipate rapidly, form transparent coating composition.As final step, before shifting out coating composition, scrape the bottom of mixing vessel and watch whether there is any not molten oligopolymer from mixing vessel.This implements as preventive measures, to guarantee to have carried out thorough mixing.If the composition thorough mixing filters the strainer of coating composition by 1 micron with deep bed filter so.Composition is standby afterwards.

Embodiment 4: the step that is used for forming wear resistance, scratch resistance, erosion resistance and adhesive coloured flexible paint with improvement.

Another kind of embodiment is the preparation process of Color paint.At this, the mixing tank that will have sufficient power and structure is used to produce laminar flow and efficiently realizes dispersing of pigments with the blade of mixing tank.For the little laboratory amount that is lower than 400mL, laboratory blender or agitator are just enough, yet, for amount, can use the laboratory blender of 1/15-1/10hp, but mixing can be carried out several days up to pottle.For commercial quantities, can use to have 250 gallons of round wall sloping bottom tanks, mixing screw or the sawtooth mixing tank of 30hp at least.For the preparation colored composition, earlier clear coating composition is mixed, referring to embodiment 4.Before in adding clear coating composition to the pre-mixing of pigment dispersion mixture, because this can guarantee to obtain desirable color.By in closed container, vibrating the pre-mixing that pigment dispersion is easily realized pigment dispersion, dress dust respirator simultaneously.Then filler, premixed pigment/pigment dispersion and solid photoinitiator are added in this clear coating composition, mixed 11/2～2 hour.By carrying out the bottom sampling and detecting not molten pigment and determine the blended completeness.This by extract from mixing tank bottom a small amount of coloured mixture and from the teeth outwards coating film realize.Then this thin layer is detected the existence of any not molten pigment.Make this mixture filter 100 order strainers then.Well-mixed colored paint composition shows seldom or not molten pigment not.

Embodiment 5: with the technology of wear resistance, scratch resistance, erosion resistance and adhesive transparent flexible coating coated board spring outside surface with improvement.

Another kind of embodiment is the technology with the composition coated board spring outside surface of the total solids basically of the actinic radiation curable described in the embodiment 1.But this technology is connected in the rotating shaft with laminated spring and begins, and then this molectron is connected on the transfer system.Laminated spring can use biodegradable organic washing agent in independently cleaning station pre-washing, but perhaps laminated spring can pre-washing before being connected in the rotating shaft.But the coating fully on laminated spring surface is guaranteed in the rotation of rotating shaft/laminated spring assembly during the attention coating step.By transfer system but rotating shaft/laminated spring assembly is moved into the coating coated segment then, but rotating shaft/laminated spring assembly is placed near the electrostatic coating system.This electrostatic coating system has three shower nozzles, and coated article body end face, bottom surface and lateral coating are guaranteed in arranging of these three shower nozzles.But in rotating shaft before three shower nozzle spray paint compositions/laminated spring assembly rotation.When but rotating shaft/laminated spring assembly continues rotation, apply coating composition simultaneously then from three static nozzles.But the rotating shaft that will be coated with/laminated spring assembly is transported into by travelling belt and is positioned at the more curing room of lower end of production line then.This curing room has Liang Taomen, and these doors are during curing closed with the protection operator and avoided the irradiation of UV radiating.Being placed with three cover UV lamps in the curing room all is exposed in the UV radiation to guarantee end face, bottom surface and side.In addition, every cover UV lamp comprise two independently the lamp type to guarantee suitable curing: one is mercury arc lamp, and another is to mix molten iron silver Jupiter.Thereby in fact six lamps arranged in the curing room.Notice that this three-dimensional curing can realize that one is mercury arc lamp by only using two lamps, another is to mix molten iron silver Jupiter, guarantees end face, bottom surface and lateral irradiation with the mirror group.In case be positioned at curing room, just door closed and make once more the rotation of axle/laminated spring assembly.Open then and mix molten iron silver Jupiter and be used for the partly solidified stage, open mercury arc lamp afterwards and be used for completely solidified.Attention need not to close fully before opening mercury arc lamp mixes molten iron silver Jupiter, and the time that is exposed in the doping mercury arc lamp is shorter than the time that is exposed in the pure water silver Jupiter.Close two lamps and stop the rotation of axle/laminated spring assembly.Open the door of curing room opposite side, the completely crued laminated spring that will have transparent, flexible, tackiness, wear resistance, scrape resistant and a corrosion-resistant finishes with travelling belt moves to the bagging area away from curing room then.Then but laminated spring is unloaded, packs and transport from rotating shaft.

Embodiment 6: with the technology of wear resistance, scratch resistance, erosion resistance and adhesive coloured flexible paint coated board spring outside surface with improvement.

Another kind of embodiment is the technology with the composition coated board spring outside surface of the total solids basically of the actinic radiation curable described in the embodiment 2.But this technology is connected in the rotating shaft with laminated spring and begins, and then this molectron is connected on the transfer system.Laminated spring can use biodegradable organic washing agent in independently cleaning station pre-washing, but perhaps laminated spring can pre-washing before being connected in the rotating shaft.But the coating fully on laminated spring surface is guaranteed in the rotation of rotating shaft/laminated spring assembly during the attention coating step.By transfer system but rotating shaft/laminated spring assembly is moved into the coating coated segment then, but rotating shaft/laminated spring assembly is placed near the electrostatic coating system.This electrostatic coating system has three shower nozzles, and coated article body end face, bottom surface and lateral coating are guaranteed in arranging of these three shower nozzles.But in rotating shaft before three shower nozzle spray paint compositions/laminated spring assembly rotation.When but rotating shaft/laminated spring assembly continues rotation, apply coating composition simultaneously then from three static nozzles.But the rotating shaft that will be coated with/laminated spring assembly is transported into by travelling belt and is positioned at the more curing room of lower end of production line then.This curing room has Liang Taomen, and these doors are during curing closed with the protection operator and avoided the irradiation of UV radiating.Being placed with three cover UV lamps in the curing room all is exposed in the UV radiation to guarantee end face, bottom surface and side.In addition, every cover UV lamp comprise two independently the lamp type to guarantee suitable curing: one is mercury arc lamp, and another is to mix molten iron silver Jupiter.Thereby in fact six lamps arranged in the curing room.Notice that this three-dimensional curing can realize that one is mercury arc lamp by only using two lamps, another is to mix molten iron silver Jupiter, guarantees end face, bottom surface and lateral irradiation with the mirror group.In case be positioned at curing room, just door closed and make once more the rotation of axle/laminated spring assembly.Open then and mix molten iron silver Jupiter and be used for the partly solidified stage, open mercury arc lamp afterwards and be used for completely solidified.Attention need not to close fully before opening mercury arc lamp mixes molten iron silver Jupiter, and the time that is exposed in the doping mercury arc lamp is shorter than the time that is exposed in the pure water silver Jupiter.Close two lamps and stop the rotation of axle/laminated spring assembly.Open the door of curing room opposite side, the completely crued laminated spring that will have black, flexibility, tackiness, wear resistance, scrape resistant and a corrosion-resistant finishes with travelling belt moves to the bagging area away from curing room then.Then but laminated spring is unloaded, packs and transport from rotating shaft.

Embodiment 7: the tackiness test with wear resistance, scratch resistance, erosion resistance and adhesive coloured flexible paint of improvement.

Another kind of embodiment is the adhesion stability of testing solidified coating on the laminated spring that applies as described in example 6 above, and this solidified coating is obtained by the UV curable coating composition described in the embodiment 2.To be coated with laminated spring and under 110 , 100% humidity, be kept 10 days postevaluation tackinesss.Use cross-hatching to test and carry out the tackiness test, wherein draw the lattice tape test and use lattice, this pattern is obtained by the special grid cutting unit with a plurality of default blades, has proper spacing and parallel to guarantee otch.Pass coating and form otch downwards up to substrate surface.Apply and remove Pressure Sensitive Tape on the otch that in coating, forms, pull this band from cutting area then, and observe any coating that is removed.After under 110 , 100% humidity 10 days, express the tackiness of 99+% by the coating of the acquisition of the composition described in the embodiment 2.

All per-cent is all based on weight.EBECRYL  can be from USB Surface Specialties, Brussels, and Belgium obtains.SYLOID  can be from Grace Davison division of WRGrace ﹠amp; Co., Columbia, MD, U.S.A. obtains.The solid pigment dispersion that is adopted can be from Elementis, Staines, and UK obtains.DAROCUR  light trigger can be from CibaSpecialty Chemicals 540 White Plains Road, Tarrytown, and New York, U.S.A. obtains.ESACURE  can be from Lamberti, S.p.A., and Gallarate (VA), Italy obtains.Nanocryl  can be from hanse chemie AG, Geesthacht, and Germany obtains.

Although described the present invention in conjunction with some embodiment, but do not really want scope of the present invention is confined to the specific form of being set forth, on the contrary, contain and to be included in the spirit and scope of the invention, as defined by the appended claims this class replacement scheme, flexible program and equivalent.

Claims (26)

1. the composition of the total solids basically of actinic radiation curable, it comprises the mixture of at least a oligopolymer, at least a monomer, at least a light trigger and at least a Nano filling, wherein cured compositions showed the tackiness of 99+% after under 110 , 100% humidity 10 days, and/or crooked around axle 180 degree.

2. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a oligopolymer is a kind of oligopolymer or the multiple oligopolymer that is present in the about 15-45wt% in the mixture.

3. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a monomer is a kind of monomer or the multiple monomer that is present in the about 25-65wt% in the mixture.

4. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a light trigger is a kind of light trigger or the multiple light trigger that is present in the about 2-10wt% in the mixture.

5. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a Nano filling is a kind of Nano filling or the multiple Nano filling that is present in the about 0.1-25wt% in the mixture.

6. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said mixture also comprises up to a kind of filler of about 5wt% or multiple filler.

7. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said mixture also comprises up to a kind of polymerizable pigment dispersion of about 10wt% or multiple polymerizable pigment dispersion.

8. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said mixture comprises a kind of oligopolymer or the multiple oligopolymer of 15～45wt%, a kind of monomer of 25～65wt% or multiple monomer, a kind of light trigger of 2～10wt% or multiple light trigger, 0.1 a kind of Nano filling of～25wt% or multiple Nano filling, up to a kind of filler of about 5wt% or multiple filler with up to a kind of polymerizable pigment dispersion or the multiple polymerizable pigment dispersion of about 10wt%; The viscosity at ambient temperature of said composition is up to about 500 centipoises thus.

9. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a oligopolymer is selected from urethane acrylate, aliphatic urethane acrylate, aliphatic polyurethane triacrylate/monomer blend, is mixed with 1, the aliphatic polyurethane triacrylate of 6-hexylene glycol acrylate, six functional polyurethanes acrylate, silication urethane acrylate, aliphatics silication urethane acrylate, polyether acrylate, and combination.

10. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a monomer is selected from ester derivative, the tripropylene glycol diacrylate of ester derivative, the methacrylic ester of Viscoat 295, vinylformic acid 2-ethyl phenoxy, isobornyl acrylate, propoxylation three vinylformic acid glyceryl ester, acrylate, the ester derivative of acrylate, and combination.

11. the composition of the total solids basically of the actinic radiation curable of claim 1; wherein said at least a light trigger is selected from phenylbenzene (2; 4; the 6-trimethylbenzoyl) phosphine oxide, benzophenone, ESACURE  KTO, IRGACURE  500, DARACUR  1173, Lucirin  TPO, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-third-1-ketone; 2; 4; 6-Three methyl Benzene ketone, 4-methylbenzene ketone, oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone), and combination.

12. the composition of the total solids basically of the actinic radiation curable of claim 1, it also comprises the common light trigger up to about 2%, and this common light trigger is selected from amine acrylate, thioxanthone, dimethyl ketal, benzyl methyl ketal, and combination.

13. the composition of the total solids basically of the actinic radiation curable of claim 6, wherein said at least a filler comprises particle, and being selected from, and combination with the soft silica of polyethylene wax preparation, the synthetic amorphous silica of organic surface-treated, IRGANOX .

14. the composition of the total solids basically of the actinic radiation curable of claim 13, the median size of wherein said filler particles is less than 10 microns.

15. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said at least a Nano filling comprises particle, and be selected from nano aluminium oxide, nano silicon, nano zircite, nano zirconium dioxide, nanometer silicon carbide, nano-silicon nitride, nanometer plug dragon, nano aluminum nitride, nano bismuth oxide, nano-cerium oxide, nano cupric oxide, nano-sized iron oxide, nano barium titanate nickel, nano oxidized niobium, oxide nano rare earth, nano phase ag_2 o, nano tin dioxide and nano-titanium oxide, and make up.

16. the composition of the total solids basically of the actinic radiation curable of claim 7, wherein said polymerizable pigment dispersion is made up of at least a pigment that is connected on the reactive resin.

17. the composition of the total solids basically of the actinic radiation curable of claim 16, wherein said reactive resin is selected from acrylic resin, methacrylic resin and Vinylite.

18. the composition of the total solids basically of the actinic radiation curable of claim 17, wherein pigment is selected from that carbon black, rutile titanium dioxide, organic red, phthalocyanine blue pigment, colcother pigment, isoindoline yellow pigment, phthalocyanine green pigment, quinacridone violet, carbazole violet, mass-tone are black, shallow lemon iron oxide yellow, shallow organic yellow, transparent iron oxide yellow, diaryl orange, quinacridone be red, organic scarlet, shallow organic red and dark organic red.

19. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said composition is suitable for the coating flexible metal object.

20. the composition of the total solids basically of the actinic radiation curable of claim 1, at least a portion of said composition coating flexible metal object surface wherein, and coating is uncured.

21. the composition of the total solids basically of the actinic radiation curable of claim 20, wherein uncured coating is applied on the described surface by electrostatic spraying apparatus.

22. the composition of the total solids basically of the actinic radiation curable of claim 21 wherein applies uncured coating with single application.

23. being coated with the surface by the uncured quilt with claim 21 is exposed to prepare in the actinic radiation completely crued and is coated with the surface.

24. the composition of the total solids basically of the actinic radiation curable of claim 1, wherein said composition can be used ultraviolet (UV) radiation curing, described uv-radiation is selected from UV-A radiation, uv b radiation, uv b radiation, UV-C radiation, UV-D radiation, or its combination.

25. completely crued goods that are coated with the surface that comprise claim 23.

26. the goods of claim 25, wherein these goods are laminated springs.

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