TW200530146A - Method and compositions for improving durability of coated or decorated ceramic substrates - Google Patents

Abstract

Methods for coating a ceramic substrate with a colored composition, including at least one curable organic binder and at least one colorant, and a substantially clear coating composition are disclosed. The first applied coating further comprises a plurality of spacer particles.

Description

200530146 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a particularly suitable method. [Prior art] Coating compositions used to coat ceramic substrates are used by the food and beverage industry to break glass and other pottery containers. They are usually coated with information and / or decorated with information, such as the contents or functionality of the container. Or other marks to identify the product and / or its source. In many countries, beverages such as beer and soda are sold in recyclable glass bottles. After the beverage is consumed, the glass bottle is recycled for refilling. They are then cleaned ", poisoned, refilled, relabeled, and then locked for sale. There are many disadvantages to printed patterns and paper labels. For example, both paper tags and printed patterns are expensive, cumbersome, and easy It disappears after being exposed to water or other substances. In addition, 'Xu μ's adhesive on the pattern becomes very sticky during the bottle cleaning process, which can cause damage or loss to the machine. To avoid the pattern on the pattern With paper labels, more permanent decorations have been used to recycle the glass surface of containers. These more permanent decorations are used in the form of pastes, which contain glass-like materials (or glass raw material mixtures), and The carrier is typically finely milled particles of volatile organic solvents or waxes (" voc ,,). After the paste is applied to the glass surface by hot-melt silk printing or other applied techniques, the glass is exposed to high temperatures. Under fire (as in Example 65.0), all carriers are driven off by volatilization and / or thermal decomposition, and the glassy mixture is melted to bond the glassy mixture to the glass surface. When printing, glassy mixtures or other materials to be printed are used on the desired pattern of 96457.doc 200530146 to heat the barrier. After the glassy mixture is melted or softened, it is transferred to the barrier through an extruder and transferred to The substrate burns. Pigments have no sense of this high temperature and are contained in pastes to provide the color of the composition. These pigments contain heavy metals in blood type, such as red money, white faults, and yellow chromium. About this The V0C and heavy metals of the ㈣-like method are harmful to the environment. The high-temperature combustion step requires considerable energy consumption and a risk of harm to workers. Strive to avoid the use of organic solvents and heavy metals in coatings and / or decorative ceramic containers. 'And reducing energy consumption involves the use of a hardenable organic binder system. Traditional organic pigments need to be in a hardenable binder system, which is a method of blocking pw printing.' It is applied to the ceramic under the conditions of method and temperature On the surface 'and no hardener is active under this condition. Heat-cured organic binders' decorated containers are heated in an oven -Temperature activates the hardener to harden the adhesive, but does not degrade the pigment, which causes the adhesive and pigment to attach to the container. However, 'if a second layer is required, the subsequent barrier application will usually make the previous coating The color layer is peeled off from the container, or the color layer may be damaged, resulting in a defective product. If the first layer is hardened or partially hardened before the second layer is applied, the peeling or other injury is caused when the next layer is applied It can be avoided 'but the processing speed, efficiency and / or energy use are obviously lost. / UV light hardening adhesive can be used to prefabricate multi-layer oil black meter, which can avoid each layer of ink before applying a layer Hardening (or partial hardening day: damage to the lower layer. However, this requires the UV curing device to be installed after each ink coating configuration, increasing equipment cost and complexity. 96457.doc 200530146 This coating composition for bottles Usually in harsh physical and chemical environments. In particular, recovery bottles are typically repeated cleaning cycles in an aggressive cleaning solution. The underlying ceramic substrate is susceptible to decomposition by such corrosive cleaning solutions, and the softened underlying substrate may cause the coating composition thereon to be detached from the substrate. This problem is exacerbated for coating compositions used as fine decorative objects, such as writing on small sizes. Fine lines are sometimes damaged or removed by repeated corrosive cleaning, although they have no significant effect on a large area. In the manufacture of glass containers, a "heat-seal coating" is usually applied to newly formed containers, which results in a thin film of tin oxide on the outer layer of the container. The presence of tin oxide coatings has been found to have a positive effect on the ability of organic decorations to withstand repeated corrosive cleaning. However, tin oxide films do not produce the required durability. In order to provide superior decorative effects to the composition and method for coating ceramic containers, its cost is competitive. There is a need for minimizing energy consumption and / or resistance to rough environments. SUMMARY OF THE INVENTION The present invention is directed to a method for coating a ceramic substrate, which comprises using at least one colored coating composition on at least a portion of the substrate, and the composition contains at least one hardenable organic binder. And at least one coloring agent " use a substantially transparent coating composition on at least a part of the substrate, the composition contains a hardenable organic binder, and essentially simultaneously will be in a colored coating composition The transparent coating group on the solid f: the adhesive in the material is hardened; whether it is a colored coating or a substantially transparent coating sentence can be used for first-person coating ', and the coating used for the first time contains 96964. doc 200530146 Multiparticle. Substrates coated according to these methods are also included in the field of the present invention. [Embodiments] The present invention is generally directed to methods for coating ceramic substrates. Ceramic research, referring to a wide range of substrates, which are generally brittle, heat-resistant and / or formed of one or more non-metallic minerals, including but not limited to pottery, clay, clay, white pottery, refractory brick and clay , Porcelain, glass ceramics and glass. The ceramic substrate can be varnished or unvarnished, and can be of any shape, size or structure. The colored coating composition of the present invention includes at least one hardenable organic binder and at least A coloring agent. As used herein, "coloring agent" and similar words refer to any substance that imparts color and / or other opacity and / or other visual effects to the composition, such as dyes, pigments, hair dyes, and the like Analogs. The excipient may include finely divided solid powders as in the examples, which are insoluble but wet-adjustable under the conditions of use. The color-imparting pigments are known to those skilled in the art, and a roster of specific examples can be found in Off Patent No. 6,214,414. Either a single vehicle or a mixture of two or more vehicles can be used. Local temperature-resistant pigments, such as glass-like mixture paints and coatings, which usually contain Γ, can be used, but because high temperatures are not required in the present invention, high temperature-resistant pigments can also be used. Therefore, according to the present invention, general pigments can be avoided without sacrificing appearance. In the present invention, a non-limiting == particularly excludes heavy metals-, _. Curry / ° or 5 to 35 weights of the composition of the present invention. / η, tongue denier. / 9 count. Any pigment or dye that is typically used in coatings based on the total weight of the composition can be used, such as 200530146 such as titanium dioxide, carbon black, DPPBO red, phthalocyanine or blue, iron oxide, bismuth vanadate, Naphthol AS, anthraquinone, fluorene, aluminum, and quinacridone. Other materials that can be used as coloring agents in the present invention that affect the appearance of the composition include special effect pigments and / or special effect compositions that produce a variety of effects such as reflectance, pearl luster, metallic luster, phosphorescence, Fluorescence, light color, thermal color, and angular color. Such special utility pigments / compositions generally impart color to the composition, while certain special utility pigments " and the character does not impart a color that the composition can perceive, but it provides the group of the invention: other perceivable Properties, such as visual properties. The substantially transparent coatings' colored coatings also contain at least one hardenable organic binder, which may be the same as or different from the hardenable organic binder applied in the colored coating composition. "Substantially transparent paint" and similar words refer to paints that impart a dot or no color to the underlying substrate or paint. As shown above, the present invention is directed to a method for coating a ceramic substrate, which includes using two coating compositions on a substrate, a colored coating composition, and a substantially transparent coating composition. The paint can be reused in two sequential colors, or transparent and colored. Fen material used for the first time, depending on the condition, this coating is sometimes used for the second time, it also contains a lot of ^ particles. The particles may be organic, inorganic, or a combination thereof, spherical, aspheric, or a combination thereof. Organic particles can be polymeric, non-polymeric, or a combination thereof. Such particles may be solid, hollow, or a combination thereof. Appropriate inorganic particles are available as a dull filler and may include, for example, glass, including glass silicate glass, and ceramics. Organic particles: Xi is very wide. Organic particles suitable for use in the present invention may include a variety of poly ^ 96457.doc -10- 200530146. This compound, these particles can not articulate the required rigidity and A combination of thermal softening properties. In certain embodiments, certain organic particles are particularly advantageous in achieving the desired gloss, because Np is mobilized to obtain a smooth and shiny surface. Appropriate polymer materials: dextran, polysiloxane, polyacrylate, polyacrylamide, styrene, polyurethane, and polyester. Non-limiting examples of suitable polyamides include polyamide 12, polyamide 11, and polyamide 6/12. The coatings used in accordance with the present invention may include softened organic particles and / or organic particles that may not undergo cis-human processing, and / or inorganic particles. At this time, the element may be rigid at the first temperature or lower, and soften at the second, lower, or lower second temperature, at which time the adhesive hardens, and at the first temperature The adhesive is not hardened. Therefore, the particles are rigid at all relevant temperatures, g Huang Li, P /, at the temperature of hardening or lower than 3 == not softened, and during the coating described herein, the substrate will be exposed Yuqi :: 丨 'without any appreciable softening. This " non-softening " particles are useful when transported to, for example, surface structures, friction systems, abrasion resistance, and / or special reflectivity. This particle may be present in the coating composition in an amount sufficient to show the desired effect, and its specificity and similarity mean that the particle will not immediately dissolve the agent at a temperature at which it is detained. Unhardened sticky. All of them have higher structural integrity. More specifically, an eight-component mixture used in the composition is unhardened, and the particles in the transparent coating group mouth of the colored composition selected in the "adhesives" are the compound J at the first temperature. w A 士士 U—The temperature is typically the temperature at which the mouthpiece is applied to the substrate and / or · ,,,, or the subsequent coating may be applied at the temperature of 96457.doc 200530146 on the substrate. This temperature May be room temperature, or it may be at some elevated temperature. In some embodiments, the adhesive hardens and the particles soften at a second temperature. 'Hardening' and similar words refer to chemical reactions, which The various components of the organic binder are linked together to form a thermosetting polymer. "Softening" and similar words refer to the loss of sufficient structural rigidity in the particles to cause deformation and / or other shape changes on the particles. For example, the particles protrude from the surface of the composition of the present invention, change the shape at the second temperature or below, "melt" or smooth the coating film surface; because of this smoothing, when the particles, the coating film surface is minimized. When disappearing, the gloss decreases usually :: to. In other specific embodiments, one or more of the compositions used contain particles that have first and third integrity. The first one maintains rigidity and / or structure under the conditions of temperature. In addition to the temperature parameters, the particles can be dissolved in the remaining material. "Ten ... 5 agents and / or compositions ^ Human ^ It is difficult to choose to cut wet. Excessive dissolution = ΓΓΓ can decompose, swell, or soften outside of it: outside the surface: intercalated, or may otherwise get unwanted: may not be fully wetted by the adhesive, but in some applications Important surface structures may be produced. Particles can be used for maximum or non-Wei choice to maximize the compartment function, and the maximum size and particle size distribution are selected. The particle size is based on demand and the effect of cutting / outsourcing. The particle size is less than 丨 micron. K 3 has an average meter, and it is found that in certain non-limiting examples, the average particle size in certain embodiments that meets at least 3 micrometers and 疋 meets the average particle diameter to 96457.doc 200530146 and less than 5 micrometers. In some specific implementations For example, the particle size can typically be about the same size as when the coating layer is precipitated. If the particles are too small relative to the coating layer, they have no compartment effect, and if they are too large, they may protrude, or they may be too large. Protrudes from the surface and reduces the final gloss of the paint or decoration, even after softening. Of course this highlighting may be required in some cases, where the particle size and / or softening properties can be selected appropriately. The particle size can also be selected Measured by the mesh size used for hot-melt silk-screen printing. The shield may become clogged with particles, which is too large to pass, resulting in poor print quality. The adhesive used according to the present invention may be selected from any technique Suitable organic coating compositions are known. These include compositions that contain organic resin components, such as being able to be applied to a ceramic substrate in a substantially liquid state, and then hardened to Long-term hardening state. Hardening can be accomplished by thorium methods, such as heating, ultraviolet radiation, electron beams, or some other form of energy that hardens the adhesive. In some embodiments, the adhesive includes one or more organic Component, it will undergo a hardening reaction when the hardening energy is used. In certain non-limiting specific embodiments, the composition may include an epoxy resin and an amine hardener (such as an example of dicyandiamide) such as US Patent No. “μ · As disclosed in No. 1, and other non-limiting specific embodiments of the present invention, the adhesive may further include a blocked isocyanuron hardener, such as disclosed in US Patent No. 6,214,414, which is hereby incorporated by reference. Other suitable resins include, for example, two dilute acid polymers containing a radical or acid, a polymer containing a hydroxyl group or an acid, an isocyanate or a polymer containing a polyurethane, Polyurea granules of amine or isocyanate, or any other polymer that is functional, acidic, amine, amine, urethane, isocyanate, or epoxy-functional Thing. Suitable hardeners can be determined by those skilled in the art, and may include one or more amine-based plastics, phenol plastics, polyepoxides, polyacids, isocyanates, polyol 'polyamines, anhydrides, and carbodiimides. Either a combination of binder and 7 or hardener can be used. In a non-limiting example, "Polyepoxy-functional reactive organic resins can be used." "Polyepoxy-functional" means that the number average molecular weight is calculated. "This resin contains more than one per mole on average. Epoxy groups, or about two or more warp groups per mole on average. In other non-limiting embodiments, ultraviolet radiation or electron beam (EB) radiation can be used to initiate adhesive hardening, which is suitably modulated to contain Reactive functional groups that are designed to be thermoset by exposure to radiation. These include a variety of free radical-curing hydrazones, such as acrylic acid vinegar, vinyl functional materials, acrylic polymers and polymers, and vinyl Mystery and Unsaturated Poly 8. It can also be a cationic starting material, such as cycloaliphatic epoxy or vinyl ether. Appropriate free radical or cationic photoinitiator-generally use UV curing and optionally EB Hardening. A combination of free radical and cationic hardening is also possible, such as the combination of material beam hardening plus king and the heat hardening composition as described above. In a non-limiting specific embodiment, it is used in the present invention. sticky The mixture has or changes to have a viscosity 'suitable for printing under ah to ⑽; other temperature and °, used in, non-limiting specific embodiments. For thermosetting systems, the curing mechanism of the adhesive is chosen to let it It has a little or no before two temperatures and the shirt adhesive hardens. To avoid excessive hardening, 96457.doc -14- 200530146 the difference between the first and second temperatures can be at least scratched, and more blood type is more than 5 (TC, although other temperature differences can also be used in the present invention. For hardenable organic adhesives in one or more colored coating compositions = hardenable organic adhesives for substantially transparent coating compositions ^ 可Are the same or different. Similarly 'if there are particles used in two colored and substantially transparent coating compositions, they can also be the same or different. In some applications, the coating adheres to the ceramic to some extent On the material, it is necessary to close or reach a permanent coating film on the substrate. This kind of high-durability coating is usually required for containers that need to be repeatedly cleaned (such as in a poplar solution). Generally The bottling industry cleans and recycles the bottles before refilling. Bottles may be treated with an adhesion promoter before use of the composition of the present invention, or the adhesive may contain adhesion promoters such as organic functional siloxanes, silicones, or Titanate. In other applications, t 'can be removed from the container after a limited number of recyclings to the beverage bottle industry. For example, seasonal or holiday decorations can be placed on the bottle during the promotion period and ended at the end Removal after the promotion period. The ceramic substrate can be treated with a composition that increases peeling before applying the coating composition.-A non-limiting example is a composition used to treat a ceramic substrate, to enhance the decay resistance The peeling of the coating composition of the present invention during cleaning is a polyethylene, and σ, such as a polyethylene emulsion. The composition for increasing peeling can be used for cold coating processing as an example. As mentioned above, and a certain aspect of the present invention The particles in the compositions of the non-limiting specific embodiments are rigid at a first temperature or below. This particle has substantial structural rigidity at this temperature. At this time, the composition is coated on the surface 96457.doc -15- 200530146. 'In the case of a hot-melt composition, it can be > J to increase significantly; In some concrete examples of bismuth, the particles used to harden the adhesive ^ ^ ^ ^ ^ ^ ^ ^ particles will lose their structural properties. The initial rigidity need not exclude all elasticity or plasticity, but is sufficient to provide the integrity of the coating when the coating composition is not hardened. This structural integrity eliminates the need for subsequent hardening of each layer on the substrate. In this method, the function of the particles is "compartment", which maintains the paint at the substantially required position until it hardens. Because of the integrity of the previously applied layer or layers, the application of two or more layers of the present invention Films, such as coatings of different colors or coatings of one or more colors, and one or more coatings that are substantially transparent, can be used without the need for a hardening step between the different coatings. After all the required layers are applied You can use the hardening energy to harden all the layers simultaneously and substantially. "The report only hardens" and similar words mean that the adhesive is not only partially hardened. "Miscellaneous u η Shi Lingbei same-day hardening" and similar words refer to hardening all coatings in a single hardening step. . Typical market bottle decoration processing uses hot stamping, with a temperature range from C to 12 ° C, and a hardening temperature range from 15th generation to fine. C. Polyvinylamine 12 particles have been found to be particularly suitable. Other polymer systems May be suitable for different temperature ranges. ≫ ^ 地 地 ^. The agent contains 20 to 95% by weight, the weight% is based on the total weight of the composition. For example, the colored coating adhesive may be 35 to 65% by weight, The substantially transparent coating adhesive may be from 95% to 95% by weight, for example, from 65 to 95% by weight or from 75 to 95% Cao 0 / Gan, Li / 0 ° In certain non-limiting specific embodiments, in the present invention Relatively small size and amount of particles used in coatings do not produce visible reflectivity. When particles are used, the particle content of the composition is typically 5 to 50 96457.doc -16- 200530146 wt%, or 10 to 35 wt% , Or 15 to 30% by weight, weight% is calculated based on the total weight of the composition. Density, particle size, and particle size distribution will determine the appropriate amount of quantity to achieve the function of the compartment and the desired film appearance. Examples can be issued S more weight% of militako may Relatively dense particles are required: to achieve the effect of using particles of similar density. Reactive waxes may optionally be included in certain non-limiting specific embodiments of the invention. These are long-chain aliphatic materials, which Contains at least one reactive group with active hydrogen, usually selected from the group consisting of hydroxyl, amino, ureido, aminoformamidine, and aminoformamyloxy, which have physical properties and are generally associated with wax. Stearyl alcohol is often used Examples of reactive waxes, but many other compounds are also known in the art. Reactive waxes can optionally constitute compositions up to " S% by weight, such as from 0.5 to 15% by weight of the composition. Certain non-limiting embodiments of the present invention may contain substantially transparent and / or colorless fillers, and are particularly suitable for use in substantially transparent, and these fillers are generally finely divided Solid particles, which impart the final coating (for a point that is "substantially colorless or not: color, and / or absorb a little or no colored light (for" substantially transparent ^). It can be used to add In the compartment particles of the invention, the filler usually has a maximum length of less than 500 nanometers, such as less than 100 nanometers, less than 50 nanometers, less than 20 nanometers, or in the range of 5 to 2G nanometers. In certain non-limiting embodiments, the filler is hydrophobic. Examples of suitable hydrophobic fillers include AEROSIL smoked stone evening soil, which is designed as R972, R974, like η, R812S, R805 (New Jersey Rldgefleld is nicknamed the company). When needed-a substantially transparent and / or colorless filler or two or more mixtures 96457.doc 200530146 quality transparent and / or colorless filler Both can be used. When present in certain embodiments of colored μ-compounds, the 'substantially transparent and di-filling agents typically comprise from 0.01 to 20% by weight of the composition, such as from 1 to 2: 2 Up to 5% 'while similar amounts can also be added to substantially transparent coatings, for higher gloss applications # it may be necessary to minimize inorganic additions. Strictly other added substances may also be used in the composition of the present invention as appropriate.

This is an antioxidant, a degassing aid and a flow regulator. These are just examples and others can be used if needed. Other additives may include improved rheology, opacity, durability, lubricity, color brightness, and many other functions known to those skilled in the art. When present, additional materials may be used in customary amounts for their customary purposes. Typically these additional selected materials *, when present, can constitute up to U Q / o of the coating composition of the present invention. According to the present invention, when two or more different coating layers are used on a substrate, at least one layer is colored and at least one layer is substantially transparent. A " coating, coating, or clothing layer is generally a single coating composition. Colored: The coating layer can give the label color or other opacity or give the substrate 5, and put fruit on it. The transparent coating layer on Λ shell can give the transparent part of the label or can be used on virtually all substrates. Under or above the coating # the substrate itself & for protection and / or durability. When the second coating is t # connected and / or spaced from the first coating, the particles in the first coating maintain the integrity of the unhardened first layer by the function of the compartment. Therefore, coatings that are next to, adjacent to, and / or spaced from previous coatings do not interfere with previous coatings of 96457.doc -18-200530146. The final coating can also contain particles, but because it does not face the next rigorous printing job, it need not include particles. In certain embodiments, at least one of the colored paint sets described above. It is used for ceramic tile substrates. The colored coating composition can be used on at least a portion of the substrate or on at least a portion of the coating previously applied to the substrate. Colored coatings can be used on substrates with unlinked characters or designs. Substantially transparent coatings can be used as a transparent surface protective paint to cover at least a portion of the colored layer. In certain non-limiting embodiments, one or more substantially transparent coatings can be used as the initial coating film on the substrate. When used as a first coat, a ' substantially clear coating can also contain many compartment particles. One or more colored coatings can be recoated on all or part of the clear coating film. This :: row also reduces or reduces the decomposition of the colored coating composition, because the underlying transparent composition can act as a barrier between the ceramic base material and the colored coating film composition. A second substantially transparent coating can be applied to all or part of one or more colored coating films. The second substantially transparent coating may be the same or different from the first substantially transparent compound. 'In a specific embodiment, the particles of the' compartment are not in the surface protective coating or the top-layer composition ', they are colored or transparent in order to make them shiny and transparent. Beitoyue's coating composition is particularly suitable for improving the durability of colored coating compositions' and can be used on at least a portion of a colored coating composition or under at least a portion of a colored coating composition, or both. As an example, the colored coating composition of the lower layer contains compartment particles and can be used for ceramic substrates. 96457.doc -19- 200530146 The transparent coating composition on the male is used thereon. The range of the lower layer coating composition covered by the substantially transparent coating composition may be changed in a specific implementation. In fact, the transparent coating composition covers substantially all objects to which the coating is applied, such as the entire glass. bottle. However, since the decomposition of the lower coating composition basically occurs at the edges of the lower coating composition (that is, the interface between the ceramic substrate and the lower coating composition), which is substantially transparent, the coating composition can cover the edges of the lower coating composition. As a result, Hao Jintao is also part of the substrate. The colored coating composition of the lower layer can be covered with the coating composition of the lower layer relatively easily with a substantially transparent coating composition with delicate details such as printing or thin lines. The coating compositions that are substantially transparent in these specific embodiments are made with a portion of the object that is 'below 5_㈣ the surface area of the substrate, or lower than the surface area of the substrate' and, in other examples, even lower than the surface area of the ceramic substrate. 〇% may be covered by a substantially transparent coating composition. The substantially transparent coating composition can be applied to the underlying coating composition using the same or different techniques. Before any colored layer is coated on the substrate ' the substantially transparent coating provides durability to any colored layer on top. In these specific embodiments, the substantially transparent layer provides protection at the interface between the colored layer and the substrate from rogue attacks. The order in which the coatings (colored and substantially transparent) are used depends on the characteristics of the desired end product, including any design or other indicators used thereon, and the external environmental requirements of the substantially transparent coating composition Process of protection 96457.doc -20- 200530146

According to the present invention, a multi-colored organic decoration can be applied to a ceramic substrate in a rapid and continuous manner in the printing process. Each coating may be the same as or different from the other coatings. After all the coatings have been applied, the coated substrate is heated to a temperature of liters to harden all the coatings substantially simultaneously. Hardening of one or more coated coating compositions in a composition comprising a blocked isocyanate is performed at a temperature sufficient to deblock the polyisocyanate: a system based on amine-hardened epoxy groups, hardened The temperature is typically at least 150 ° C. 〇, and may reach 2⑻. ◦ The degree of modification of the door should not be so high as to cause unnecessary staining or other coatings ... Different resin systems or other methods will use different curing temperatures & in certain non-limiting embodiments, two or more such as

The composition described herein is a part of a substrate of 5 W I, and the composition hardens substantially at exactly the same temperature as 325 ° C or below.

As shown above, according to the method of the present invention, the coating composition can be used on the ceramic substrate of the costume and / or on the soil layer that has been once or more previously. In the latter case, you will notice that the next coating 1 can be directly applied to the substrate, at least partially on one or more other coatings, two == combinations thereof; "used to at least-part of the substrate; " Similar to $ ::: some substitutions', because all the decorative layers are eventually applied to the base 4 of 1 = 14. These layers are coated at elevated temperatures, making the cooler magic ... " Wen Guo basically will The coating will be cured quickly. This curing effect 4 == the clarity of the strip is helpful in allowing multilayer coating without; ΓΠ! Coating clarity 'and / or allowing multilayer coating without separation The layer is hardened. In certain non-limiting specific embodiments, it is necessary that the application temperature of the coating layer is lower than the temperature at which the previously applied coating will liquefy or excessively soften. This enhances the maintenance of fine lines: resolution and resolution of previously applied concrete layers. This method is particularly suitable for applying the mark of a trademark to a glass bottle, or for any other application, in # clarity: Need to write, for example. The composition used in accordance with the present invention generally cures quickly after application to contact, such as those that can be advantageously used for decorative lines, which operate at high speeds, where bottles or other ceramic materials are subsequently coated. "This invention basically describes the application of using hot-melt silk screen printing.

What is the use of coatings such as spray coating, curtain coating, rolling? Coating, printing or brushing. κ R The substrate coated according to the present invention may be a heat-sealed coating, forming a tin oxide film underneath the coating. However, the perceptible durability is achieved using samples, even when the amount of tin oxide film is lower than what is generally considered to be the smallest: The substances produced according to the invention can also be cold-coated, with organic lubricant coatings such as polyethylene To enhance resistance to mechanical abrasion. As used herein, unless expressly stated otherwise, all numbers such as those representing values, ranges, or or / may be read as if they were literal, beginning with `` about, '' even if the word is not monthly I wo n’t. Any numerical enumerations enumerated here are intended to include all sub-ranges of the θ, π daggers enclosed here. The plural surrounds the singular and vice versa. Moreover, the term "composite used for in-person and lonely picking up daggers" refers to prepolymerization or multiple. "Do not both 'Yutou" poly "refers to two examples. 96457.doc 22 200530146 The present invention further takes the following examples Description, which is an illustration and not a limitation, and all parts thereof are weight ratios and all percentages are weight% unless otherwise indicated. The following materials are used in the examples: EPON 8 80 Bipan A diglycidyl ether, Houston, Texas Resolution Performance Product 〇EPON 1001 Bipan A diglycidyl ether, Houston, Texas Resolution Performance Product 〇VESTAGON B1400, Blocked polyisocyanate, a copolymer of isophorone dicyandiamide and trimethoxypropane, and ε-caprolactam in a molar ratio of 3: 1: 3, Germany] \ ^ 1'1 〇6811583 80, coatings and colorants. TI-PURE R-706 Titanium Dioxide Pigment, EI du Pont de Nemours & Co. ΝΕΟ GEN DGH, Wilmington, Dallas. Dry Branch Kolin Co. SPHERICEL 110P8, Hollow Borosilicate, Dry Branch, Georgia Glass microspheres, average diameter 11.7 microns, Potters Industries, Valley Forge, Pennsylvania, Inc. MODAFLOW powder III flow modifier, ethyl acrylate-isooctyl acrylate copolymer containing sulphur dioxide, St. Louis, Missouri Solutia Inc. UVITEX〇B whitening agent, 2,2 '-(2,5-fluorenyldiyl) bis [5-l, l-dimethylethyl]]-benzoxazole, Basil, Switzerland Bart's chemical BYK-405 rheology control agent, polyhydroxycarboxylic acid ammonium amine solution, BYK Chemical of Wesel, Germany 96457.doc -23- 200530146 DYHARD 100M dicyandiamide, 98% miniaturization < 40 microns, Germany Trostberg SKW Trostberg Akiengesellschaft

AEROSIL R974 Hydrophobic fuming stone earth, Degussa AG ORGASOL 1002 D NAT 1 Polyamine 6 powder, Frankfort am Main, Germany, average particle size 20 microns, Atofina Chemicals ORGASOL 2001 UD NAT 1 Polyamine 12 Powder, average particle size 5 microns, Atofina Chemicals, Philadelphia, PA

VESTOSINT 2070 Polyamide 12 powder, with an average particle size of 5 microns, Degussa AG DOVERPHOS S-680, a dihardenyl isopentaerythritol diphosphite antioxidant from Marl, Germany, from FLUORAD, Dow Chemical Company, Dover, Ohio Fluorosurfactant FC 4430 is a non-ionic polymeric surfactant from 3M Specialty Materials INTERPROME 4049 in St. Paul, Minnesota. The azo-based naphthol red colorant, Sino INTERPROME 4047 pigment from China, and Sino from China. Example 1 According to a specific embodiment of the present invention, a white decorative composition was prepared using organic particles (VESTOSINT 2070 Polyamidamine 12 powder). Mix the material from feed 1 at 80 ° C to 110 ° C until homogeneous. The material of feed 2 was added to the mixture of feed 1 and mixed at 80 ° C to 110 ° C to obtain a white uniform polymer. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. 96457.doc -24- 200530146 Ingredient weight, g% by weight Feed 1 EPON 880 50.00 25.08 EPON 1001F 60.00 30.10 Stearyl alcohol 10.00 5.02 Feed 2 Ti02 32.00 16.05 Blue dye 0.1355 0.07 Purple dye 0.9184 0.46 DOVERPHOS S-680 1.01 0.51 VESTOSINT 2070 32.53 16.32 M0DAFL0W powder III (65%) 4.00 2.01 UVITEX 0B 1.00 0.50 DYHARD 100M 7.73 3.88 Example 2 According to a specific embodiment of the present invention, an organic particle (VESTOSINT 2070 polyamide 12 powder) and inorganic particles (SPHERICEL 110P8) are used. Glass beads) mixture to prepare a white decorative composition. Mix the material from feed 1 at 80 ° C to 110 ° C until homogeneous. The material of feed 2 was added to the mixture of feed 1 and mixed at 80 ° C to 110 ° C to obtain a white uniform slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, g% by weight Feed 1 EPON 880 45.00 21.72 EPON 1001F 65.00 31.37 96457.doc -25- 200530146 Stearyl alcohol 20.00 9.65 Feed 2 Ti02 32.00 15.45 Blue dye 0.1350 0.07 Purple dye 0.9180 0.44 SPHERICEL 110P8 10.00 4.83 DOVERPHOS S -680 1.04 0.50 VESTOSINT 2070 丨 20.71 10.00 MODAFLOW powder III (65%) 4.00 1.93 UVITEX OB 1.00 0.48 DYHARD 100M 7.37 3.56 Example 3 According to a specific embodiment of the present invention, organic particles (ORGASOL 2001 UD NAT 1 Polyamine 12 powder) ) Preparation of a white decorative composition. The materials of feed 1 are mixed at 80 ° C to 110 ° C until homogeneous. The material of feed 2 was added to the mixture of feed 1 and mixed at 80 ° C to 110 ° C to obtain a white uniform slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, g% by weight Feed 1 EPON 880 50.00 25.66 EPON 1001F 55.00 30.79 Stearyl alcohol 10.00 5.13 Feed 2 Ti02 32.00 16.42 Blue dye 0.14 0.07 96457.doc -26- 200530146 Purple dye 0.92 0.47 DOVERPHOS S-680 0.98 0.50 ORGASOL 2001 UD NAT 1 28.12 14.43 MODAFLOW Powder III 4.00 2.05 (65%) UVITEX OB 1.00 0.51 DYHARD 100M 7.73 3.96 Example 4 A white decorative composition was prepared by mixing only inorganic particles (SPHERICEL 110P8 hollow glass beads). Mix the materials of feed 1 at 80 ° C to 110 ° C until homogeneous. The material of feed 2 was added to the mixture of feed 1 and mixed for one hour at 80 ° C to 110 ° C to obtain a white uniform slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, g% by weight Feed 1 EPON 880 50.00 25.08 EPON 1001F 60.00 30.10 Stearyl alcohol 10.00 5.02 Feed 2 Ti02 32.00 16.05 SPHERICEL 110P8 32.53 16.32 MODAFLOW powder 4.00 2.01 III UVITEX OB 1.00 0.50 DYHARD 100M 7.73 3.88 DOVERPHOS S-680 1.0 0.51 96457.doc -27- 200530146 Blue dye 0.1355 0.07 Purple dye 0.9184 0.46 Example 5 A red decorative composition was prepared which was used for surface printing on the decorative objects of Examples 1 to 4. This decorative composition does not include particles as it acts as a subsequent decorative layer. Mix the materials from Feed 1 at 80 ° C to 110 ° C until homogeneous. The mixture was further mixed at 80 ° C to 110 ° C for one hour to produce a red uniform slurry. The resulting red decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, g% by weight Feed 1 EPON 880 55.00 36.89 EPON 1001F 45.00 30.19 Stearyl alcohol 10.00 6.71 VESTAGON B1400 10.00 6.71 Feed 2 INTERPROME 4049 4.00 2.69 INTERPROME 4047 8.00 5.36 Ti〇2 3.00 2.01 Fluorosurfactant FC 4430 0.50 0.34 MODAFLOW Powder III 3.00 2.01 DOVERPHOS S 680 0.74 0.50 B—YK 405 0.56 0.38 DYHARD 100M 7.88 5.29 AEROSIL R974 1.40 0.94 96457.doc -28- 200530146 This red ink was successfully printed on each previous white ink instance. A decoration machine is used as a typical multi-ink coating method; / blade is prepared to bake for 45 minutes at 3 ° C when the hardening step is performed, and the resulting bottle decoration provides properties of acceptable appearance and thin film performance. Example 6 Gloss measurement The white compositions prepared in Examples 1 to 4 were printed on glass bottles using Stnuz GP-4 in a semi-automatic-purpose-like fashion. Use—Stainless steel sieve with coffee bean holes, and print the white I decoration composition in the temperature range from step to starvation. The printed bottle is then hardened in a forced air supply box at / 80 C for one hour. The surface gloss of the package is based on the N__Curve small area gloss meter (Rhopoint from East Sussex, UK)

Instmmentation Ltd.), which uses the procedures of ASTM D523 and is recorded in Table 1. The surface gloss of the composition of the present invention (Examples 1-3) is better than that of Example 4. Table 1 Example gloss, 60 ° — 1 43 2 34 _ 3 37 1 _ 4 23-28 Example 7 The clothing is a 250 mesh as in Example 2 White decorative composition containing organic particles and inorganic particles +, with the following components: 96457.doc -29- 200530146 Ingredient weight, g% by weight Epon 880 50.00 25.5 Epon 1001F 55.00 28.1 Stearyl alcohol 10.00 5.1 Epon 1001F 5.00 2.6 R -706 Ti02 32.00 16.3 Coloring agent 0.1355 0.1 Coloring agent 0.9184 0.5 Sphericel 110P8 10.00 5.1 Doverphos S-680 1.01 0.5 Vestosint 2070 20.02 10.2 Modaflow powder 111 (65%) 4.00 2.0 Dyhard 100M 7.73 3.9 Aerosil R974 1.00 0.5 Total 196.8 100.0 according to In a specific embodiment of the present invention, a 250-mesh substantially transparent coating composition is prepared, which contains the following J points: ingredient weight, g% by weight Epon 1 00 1 F 40.00 41.6 Epon 880 40.00 41.6 stearyl alcohol 10.00 10.4 Modaflow 1.00 1.0 BYK 405 0.20 0.2 Dyhard 100S 4.37 4.5 Aerosil R-974 0.50 0.5 Add soft drink bottle (250ml volume) at 325 ° C For 7 hours to remove any preexisting polyethylene coating. All heat-cleaned empty bottles were fitted with a 250 mesh stainless steel screen with the decorative composition as in Example 5. Half of the white decorated bottles use a 250 mesh stainless steel screen, 96457.doc -30- 200530146 with a substantially transparent coating composition on the white ink decorative area (" clear coating film "example), and The remaining half did not get a clear coating film ("Control Pi Example"). The two compositions were baked and hardened in a single step as in Example 5. Half of each group of bottles was essentially sprayed with polyethylene cold-seal coating ("CEC"), while the remaining half did not get cold-seal coatings without CEC "). Subject the coated bottles to accelerated corrosive conditions and measure such as Loss of the following white decorative composition. Three coated bottles were filled with cold water in a corrosive bath stirred at 70 ° C (2.5% by weight iNaOH, 0.3% by weight of Diversylever anti-burst sword and parts per million 50 CaCO3) immersed for 7 minutes. Remove the bottle from the bath for inspection. Any small printing loss is considered a failure of the entire group. The bottle is then emptied and refilled with cold water, and the test cycle is repeated Until failure is observed. The data recorded in Table 2 indicate that the durability of the white decorative composition is due to surface coating with a transparent coating composition, and bottles with or without polyethylene CEC with the decorative white composition. It is significantly enhanced. This data also indicates that the polyethylene CEC coated on the bottle contains a substantially transparent coating composition, which has no effect on the durability of the white decorative composition. Table 2 Test cycle control without CEC Controlled CEC-containing clear coating film without CEC Clear coating film with CEC 1-9 Pass through Pass pass Pass pass Pass pass Pass pass Pass 10 Pass pass Pass pass Pass pass Pass pass Pass pass Pass pass Pass pass Pass pass Pass Pass 25 Pass Pass Pass Pass Pass Pass Pass 26-45 Pass Pass Pass Pass 46 Pass Pass Pass 47 Pass Failure fail 96457.doc -31-200530146 Although the present invention has been The specific details of some specific embodiments are described, and these details are not intended to be a limitation of the field of the present invention, except that they are all included in the scope of the accompanying patent application. 96457.doc 32-

Claims (1)

200530146 10. Scope of patent application: 1. A method for coating ceramic substrate, comprising: ~ part of the substrate machine adhesive and using at least one colored coating composition on at least one, and the composition contains at least one There is at least one kind of coloring agent that can be hardened; then use a transparent coating composition on the at least one standing material. This composition contains a kind of hardenable organic spotting agent. The basis of the two blades is: Coating composition and substance: the adhesive in group a hardens; among them, whether it is a pigmented coating or a substantially transparent coating composition, it can be used for the first coating, and = the first use in The coating composition further contains many particles. / 8 2. The method according to claim i, wherein a colored coating composition is used. From 3. · According to the method of # 未 项 1, in which the real coating composition is used, the transparent coating composition on the shell is used for the first time. 4. The method of claim 2, wherein the substantially transparent coating composition is coated on all colored coating compositions on the substrate. The method according to the term 2 of the month, wherein the substantially transparent coating composition is applied only to the edges of the colored coating composition. 6_ According to the method of claim i of the patent scope, the coating composition used for the first time in 纟 contains many particles, which are okay at the first temperature or lower!丨 生 ’and softened at or below the second temperature at which the adhesive hardens. 0 96457.doc 200530146 8. 9. At or below the temperature of the coating composition used more than once and according to the method of claim 1, the first one has many particles, which do not soften when the adhesive is hardened. According to the method of the monthly term, each colored coating composition in # and essentially: the bright coating composition further contains many particles, in which the binder in each coating composition is the same or different ', and Many of the particles in each coating composition are the same or different. : According to the method of term 8 of the month, 'the particles are rigid at the first temperature or below this temperature', and when the adhesive is hardened at the second temperature or below this temperature, which is between the first temperature and the second temperature 10. The method according to claim 6 has a difference of at least 30 ° C. 11. 12. 13. 14. 15. The method according to item 9 of the scope of patent application, wherein the difference between the first temperature and the second temperature is at least 30 ° c. The method according to claim 8, wherein at least some of the particles contain an organic material. The method according to claim 12, wherein the organic material is polyamine. According to the method requested, at least one of the hardenable organic adhesives contains a reactive resin having a polyepoxy functional group. The method according to claim 14, wherein the hardenable organic adhesive further contains an amine-functional hardener. 16. The method according to # 15, wherein the hardenable organic adhesive further contains a polyisocyanate. A method according to the scope of patent application, wherein the step of using comprises hot-melt silk-screening the composition on a substrate. 96457.doc 200530146 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. The method according to claim 1, wherein the coloring agent comprises an organic pigment. The method according to claim 1, wherein the coloring agent comprises an inorganic pigment. The method according to claim i, wherein the color-imparting agent comprises a pigment of double fruit. According to the method of Yong Yong, the ceramic substrate is broken glass. The method according to claim 6, wherein the ceramic substrate is broken glass. A ceramic substrate is coated according to the method of claim 1. A ceramic substrate coated according to the method of claim 2. A ceramic substrate coated according to the method of claim 3. The 勹 k substrate is coated according to the method of claim 6. The method according to claim 1, further comprising treating the substrate with the composition before coating the coating composition to enhance the peelability of the hardened composition from the substrate. According to the method of claim 3, the method further comprises coating a second substantially transparent coating composition on at least a part of at least a part of the one or more colored coating compositions on the substrate. 96457.doc 200530146 VII. Designated representative map: (1) The designated representative map of this case is: (none) (II) The component symbols of this representative map are briefly explained: 8. If there is a chemical formula in this case, please disclose the one that can best show the characteristics of the invention. Chemical formula: (none) 96457.doc