TW200903570A - Method of molding barrier ribs with hygroscopic polymeric molds - Google Patents

Abstract

The present invention relates to a method of making a flexible mold with a hygroscopic support, the flexible mold, and methods of using the mold to make microstructures.

Description

200903570 IX. Invention Description: [Prior Art] Progress in display technology (including the development of plasma display panels (pDp) and plasma-addressed liquid crystal (PALC) displays) has attracted attention in the formation of electrically insulating barrier ribs on glass substrates. A barrier rib separation unit, wherein the inert gas is excited by an electric field applied between the opposite electrodes. The gas discharge emits ultraviolet (UV) radiation within the unit. In the case of PDp, the inside of the unit is coated with a scale, which emits red, green or blue visible light when excited by uv light. The size of the cell determines the size of the pixels (pixels) in the display. For example, PDP and PALC displays can be used as displays for high definition television (HDTv) or other digital electronic display devices. One way to form the barrier ribs on the glass substrate is by direct molding. This involves laminating a mold onto a substrate with a glass or ceramic forming composition therebetween. Suitable compositions are described, for example, in U.S. Patent No. 6,3,52,763. The glass or ceramic is then cured to form a composition and the mold is removed. Finally, the barrier ribs are fused or sintered by firing at a temperature of about 55 (TC to about I600 t. The glass or ceramic forming composition has glass powder of micron-sized particles dispersed in an organic binder. Organic bonding The use of the agent allows the barrier ribs to be cured in the green state so that the firing fuses the glass particles in place on the substrate. See, for example, w〇2〇〇4/ 010452, WO 2004/043664, and Japanese application. No. 2004_108999. The mold for producing the barrier ribs may be a flexible mold. The flexible mold may comprise a support member and a shaping layer, as described in WO 2006/113412, which has at least one of (the 127318.doc 200903570) A reaction product of a methyl) propylene sulfhydryl oligomer and at least one (meth) propylene monomer. The flexible mold can be produced from a transfer mold having substantially the same microstructured pattern as the final barrier rib. US 2005/0212182 describes a flexible mold comprising a support member containing moisture that saturates at a temperature and relative humidity during use due to pre-applied moisture absorption treatment. As described in paragraph 〇〇31, when film P E T sufficient to allow absorption of moisture to stabilize its dimension and then it

When the mold is used to manufacture, the dimensional change of the mold after manufacture can be suppressed. [Embodiment] The present invention relates to a method of manufacturing a flexible mold, the flexible mold, and a method of manufacturing a microstructure using the mold. In the following, reference will be made to an embodiment of the invention which is suitable for the manufacture of flexible moulds such as microstructures which block ribs. Polymerizable resins and flexible molds can be utilized with other (e.g., microstructured) equipment and articles such as 'electrophoretic panels having capillary channels and lighting applications. The range of values recited by the endpoints includes all numbers included in the _ (for example, ranges 1 through 10 include bl, 15, 33, and 1 〇). Unless otherwise indicated, the quantities and properties of the indicated components are to be understood as all the numbers of the measurements and their analogs that can be used in the claims and in the scope of the patent application in all examples, which should be modified by the term "about". . The methacrylate '(meth) acrylonitrile group, refers to a functional group including acrylate acrylamide and methacrylamide. Methyl)acrylic acid (tetra) acrylic acid acrylate and (meth)acrylic acid S compound 0 127318.doc 200903570

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a partial perspective view showing an illustrative (e.g., flexible) mold. The flexible mold 1 has a two-layer structure having a planar support layer U and a microstructured surface referred to herein as a shaped layer 120 provided on the support. The flexible mold 1 丨 is adapted to produce a barrier rib having a grid-like rib pattern (also referred to as a lattice pattern) on a back panel of a plasma display panel (e.g., electrode patterned). Another commonly used barrier rib pattern (not shown) includes a plurality of (non-intersecting) ribs, also referred to as linear patterns, arranged in parallel with one another. The flexible mold is appropriately set to be large depending on the size of the finished article (e.g., display panel). For example, the flexible mold may be rectangular in shape (700 mm x 400 mm). The depth, spacing and width of the microstructure of the shaped layer may vary depending on the desired article. The depth of the microstructured (e. g., 'groove) pattern 125 (corresponding to the height of the barrier ribs) is generally at least 1 () 〇 μ η, and typically at least 15 〇 μπι. In addition, the depth is usually no more than 5 〇〇 μιη, and is usually less than 3 〇〇. The distance between the micro-deposition (e.g., grooves) patterns may be different in the longitudinal direction than in the lateral direction. The spacing is large w ^ / V V / ΧΑΧ Ρ "Ι - _Ϊ.ΓΤ3 fTJ -|> 2/0 μιη. § The pitch of the sea is usually not more than 6 〇〇 μηι, and preferably less than _ _. The width of the microstructured (e.g., groove) pattern 4 can be different between the upper and lower surfaces, especially when the barrier ribs so formed are wedge shaped. The width is generally at least 1 〇 and is usually at least 5 〇 often not more than 1 〇〇 μηη, and usually less than 8 〇 μιη μιη. Moreover, the width of the representative shaped layer has a thickness of at least 5 μηη, typically at least 1 〇, and more typically at least 50 μηη. Moreover, the thickness of the shaped layer is no greater than 1,000, typically less than 800 μηι' and more typically less than 7 arrays. When the thickness of the shaping layer 127318.doc 200903570 is less than 5 μm, the desired rib height is usually not obtained. When the thickness of the shaped layer is more than 1,000 μm, warpage of the mold and dimensional accuracy are lowered due to excessive shrinkage. The thickness of the polymeric support film is usually at least 毫米25 mm, and usually at least 0.075 mm. Further, the thickness of the polymeric support film is substantially less than 〇5 mm, and is usually less than 0.300 mm. The polymeric support film has a tensile strength of at least about 5 kg/mm2, and usually at least about 1 〇 kg/mm2. The polymeric support film typically has a glass transition temperature (Tg) of from about 6 (TC to about 2 Torr.) The flexible mold is typically prepared from a transfer mold or master mold that has a corresponding opposite to the flexible mold. Microstructured surface pattern. For example, a perspective view of an illustrative transfer mold or master mold 200 suitable for use in fabricating a flexible mold of the figure is depicted in Figure 2. Figure 2A depicts Figure 2 taken along line -... A cross-sectional view of the transfer mold 200. As described in the published U.S. Application Serial No. 205/02-34, the #-printing mold may have a microstructured surface composed of a cured (e.g., polyoxymethylene rubber) polymeric material. A master mold (e.g., having a metal support layer) can be prepared as described in WO 2005/013308. A flexible mold is fabricated in a transfer mold (e.g., transfer mold of Figure 2) as depicted in Figures 3A-3C In the embodiment of the flexible mold (for example, the flexible mold of Fig.), the polymerizable resin composition 35 is provided in at least the concave portion of the microstructured surface of the polymer transfer mold or the mother mold 200. Such as a knife coater or scraping The known coating member of the bar coater is completed by stacking a building member comprising a flexible polymerizable film on a mold filled with a polymerizable tree 127318.doc 200903570, so that the resin is in contact with the support. When cured in this manner, the curing of the polymerizable resin composition is generally preferred. For this embodiment, the support and the polymerizable composition are preferably sufficiently optically transparent to allow illumination to be cured. Passing through the support. Typically, the flexible mold has a haze of less than 1 5%, typically less than 10% and more typically no more than 5% (as measured by the test methods described in the examples). Once cured, once cured Adjusting the moisture absorption of the flexible mold 100 (in which the support film 38 is integrally bonded to the shaped layer formed of the cured polymerizable resin) and the transfer mold 2 are separated from the mold of the invention a polymeric support member, and the (i.e., first) temperature and/or relative humidity utilized during the method of preparing the mold in a suitable environment having a first temperature and a relative humidity is different from The temperature at which the mold is placed (i.e., the second) temperature and/or relative humidity during the method of making the ceramic microstructure. In this case, the size of the microstructure of the mold can be adjusted during the mold manufacturing process (for example, by thinning to form This aspect is especially useful when the mother mold or transfer mold of the flexible mold has a size (eg, pitch) greater than two of the target size, the target gauge is @@ amps for subsequent flexible molds The formation is as follows: 'ceramic barrier ribs, immersed on A &, size. If the conditions used during the mold manufacturing operation are the same conditions 楹 ^flexible and ' ', ρ, temperature and relative humidity Under the use of visual chess to mold ceramics, the microstructure size of the mold (such as 'pitch') is the same when it is manufactured. /, When the cookware is used to mold the ceramic paste, the first temperature is the same as that of the first phase, and the first temperature is substantially the same (that is, 127318.doc 200903570 does not make the adjustable mold size). Due to the second relative humidity. When, for example, the mother mold = humidity target is different, the mold manufacturing environment (that is, the distance between the molds is greater than the mold used to make the ceramics, the humidity is usually greater than the second temperature) and/or the relative temperature is used. (The distance between the molds is also in the manufacturing mold, the microstructure is expanded, so that the method of the cookware can be reduced to the target ♦. Conversely, when the mother mold or transfer mold, and the production plant..., When the distance between the distances is less than the target, the temperature of the mold manufacturing % and/or the relative temperature is reduced to shrink the microstructure, thereby increasing the pitch to the target size. The relative humidity between the first relative humidity and the second relative humidity The difference can vary from about 5% to about 4 G% RH. Typically, the mold environment is prepared and has the same or relatively close (i.e., first) temperature as the temperature and relative humidity used to pre-adjust the hygroscopic support. And relative humidity. For example, the difference is typically no greater than about 10% RH (eg, '9% RH, 8% RH, 7% RH, 6% RH, 5% RH, 4% RH) and can be as small as 1% Fat, 2% rh or 3 / i > RH. The first dish and relative humidity are also opposite But not equal to the second temperature and relative humidity. In this case, the adjustment of the microstructure during the method of manufacturing the mold is usually on the order of about 5 ppm per percent relative humidity. 0 Various hygroscopic plastic film materials can be used for flexibility. Branches for molds, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), ductile polypropylene, polycarbonate, and cellulose triacetate. The plastic film can be used as a single layer film, or as a composite or laminate film in which two or more combinations are combined. The surface of the support member can be treated to promote adhesion to the 127318.doc 200903570 polymeric wax composition. Appropriate based on vinegar

Photographically graded polyethylene terephthalate (IV) and a method described in U.S. Patent No. 4,340,276, the disclosure of which is incorporated herein by reference. G Preconditioning of the absorbent building member may include applying moisture to the plastic film prior to use in the manufacture of the mold. Suitable means for applying moisture include immersing the film in (e.g., hot) water, or by passing the film through a high temperature, high humidity atmosphere such as a plug. Typically, the plastic film is conditioned in a temperature and humidity controlled chamber to achieve the desired first humidity. The flexible mold H) 0 can be used to create (e.g., block rib) microstructures on a substrate such as a (e.g., electropolymer) display panel. Prior to use in the process, the transfer mold and support film are typically adjusted in a humidity and temperature controlled chamber (e.g., T' 22. 〇/55. /. relative humidity) to minimize any dimensional changes. In view of the sizing of the microstructures by using a different (i.e., 'first' relative humidity) used during the manufacture of the flexible mold, the mold typically has a target size, I therefore does not need to be as in WO 2004/043664 Further adjustments as described. Referring to Figures 4A through 4C, a flat transparent (e.g., glass) substrate 41 having a (e.g., strip-like) electrode pattern is provided. The flexible mold of the present invention is positioned, for example, by using an inductor such as a charge coupled device camera such that the barrier pattern of the mold is aligned with the electrode pattern of the substrate. A barrier rib precursor 45, such as a curable ceramic paste, can be provided in a variety of ways between the substrate and the shaped layer of the flexible mold. The curable material can be directly placed in the pattern of the mold, and then the mold and the material are placed on the substrate, and the material can be placed on the substrate, and then the mold is pressed against the material on the substrate. Alternatively, the material may be introduced into the gap between the mold and the substrate when the mold is placed together with the substrate by mechanical or other means. As depicted in Figure 4A, a (e.g., rubber) roller 43 can be used to engage the flexible substrate 100 by blocking the rib precursor. The rib precursor 45 is spread between the glass substrate 41 and the shaped surface of the mold to fill the groove portion of the mold. In other words, the rib precursor 45 sequentially replaces the air of the groove portion. Subsequently, the rib precursor is cured. As depicted on Figure 4B, the rib precursor is preferably cured by radiant exposure through the transparent substrate "and/or through the (e.g., UV) light of the mold 1" as shown in Figure 4C. The flexible mold 1 is removed and the resulting cured rib 45 remains bonded to the substrate 41. Although the mold may comprise other (eg, cured) polymeric material, at least the molded surface of the mold (eg, 'microstructured' a photopolymerization reaction product comprising a polymerizable composition, the composition generally comprising at least one ethylenically unsaturated oligomer and at least one ethylenically unsaturated diluent. The ethylenically unsaturated diluent can be combined with a dilute saturated oligomer Polymer copolymerization. The oligomer generally has at least a ruthenium, as defined by gel permeation chromatography (described in more detail in the real economy), and is generally less than 50,000 g/mole of weight average molecular weight (complement The ethylenically unsaturated diluent generally has a mw of less than !, 〇〇〇g/mole, and more typically less than 800 g/mole. The merging polymer and monomer have a reaction upon exposure to light (eg, crossover) G) This is the nature of photopolymerizable groups. Illustrative examples include epoxy groups, (meth) acrylate groups, olefin carbon double bonds, diloxy propoxy groups, α-methyl styryl groups, (meth) acrylamide groups, cyanate groups, Vinyl ether groups, combinations of such groups of 127318.doc 200903570, and analogs thereof. Free radically polymerizable groups are preferred. Among such groups, (meth) propyl sulfhydryl functional groups are typical And (meth) acrylate functionality is more typical. Typically, at least one of the components of the polymerizable composition, and more typically the oligomer, comprises at least two (meth) acrylonitrile groups. Various known oligomers having (meth)acryloyl functional groups. Suitable oligomers include (meth)acrylated urethanes (ie, amino phthalate (meth) acrylates) Ester), (meth)acrylated epoxy group (ie, 'epoxy (meth) acrylate vinegar), (meth) acrylate g liquefied (ie, polyester (A) (meth)acrylate, (meth)acrylated (meth)acrylic, (meth)acrylated The mystery (ie, poly(meth)acrylic acid) and (meth)acrylated polyolefin. The polymer and monomer preferably have a glass transition temperature of about -80 ° C to about 60 ° C, respectively. (Tg), which means that its homopolymer has such glass transition temperatures. The oligomer is generally combined with a monomer in an amount of from 5% by weight to 90% by weight of the total polymerizable composition of the mold. The amount of the polymer is at least 2% by weight, more usually at least 30% by weight, and more usually at least 4% by weight. In at least some preferred embodiments, the amount of the oligomer is at least 5% by weight, % by weight, 70% by weight or 8 〇 by weight 0 / 〇. In some embodiments, the polymerizable composition of the flexible mold may comprise one or more urethane (meth) acrylate merging agents, Such as self-sufficient

Daicel UCB Co., Ltd. under the trade names "EB 270" and "EB 8402," purchased oligomers. In other embodiments, the polymerizable composition of the prismatic mold can be 13 or a polyolefin of the kind (A Acrylate condensate, such as available from 127318.doc •14- 200903570

Osaka Organic Chemical Industry Ltd. under the trade name "SpDBA", other suitable flexible mold compositions are known. Various (mercapto) acrylonitrile-based single systems are known, including (for example ): aromatic (meth)acrylic acid vinegar 'includes the present milk methyl ethyl acrylate acid, phenoxy odor b, its polyethylene glycol acrylate, nonyl phenoxy polyethylene glycol, 3 _ benzene ^ (meth) acrylate of propyl acrylate and ethoxylated ethyl modified bisphenol; hydroxyalkyl (meth) acrylate, such as 4-butyl hydroxy acrylate; alkyl diol ( Mercapto acrylate and alkoxyalkylene glycol acrylates, such as decyloxy polyethylene glycol monoacrylate and polypropylene glycol diacrylate; polycaprolactone (fluorenyl) acrylate vinegar; Alkyl carbitol (meth) acrylates such as ethyl carbitol acrylate and 2-ethylhexyl carbitol acrylate; and various polyfunctional (fluorenyl) propylene fluorenyl monomers, including 2- Butyl-2-ethyl-1,3-propanediol diacrylate and trishydroxypropylpropane tris(methyl)propane A preferred polymerizable composition for making a flexible mold is described in the published U.S. Patent Application Serial No. 2006/023 1728. Photocurable rib precursor (also known as "polymer" or , paste, and) contain at least three components in addition to the photoinitiator just described. The first component is a particulate material (eg, powder) formed of glass or ceramic. The powder will eventually be fused by firing 2 Or sintering to form a microstructure. The second component is a curable organic binder that can be formed and then hardened by curing, heating or cooling. The bonding pair I allows the water body to be formed into a hard or semi-rigid state. "Microstructure. The adhesive usually volatilizes during debonding and firing, so it can also be called short-acting viscosity CF. The second component is thinner. The thinner is usually hardened. 127318.doc 200903570 Mixture material Thereafter, the release from the mold may be promoted. Alternatively or in addition, prior to firing the microstructured ceramic material, the diluent may promote rapid and substantially complete depletion of the binder during debonding. Good to maintain Liquid, such that the diluent is phase separated from the binder material during hardening. The rib rib precursor composition preferably has a viscosity of less than 2 〇, 〇〇〇cps and more preferably less than 1 〇, 〇〇〇cps, to All of the microstructured groove portions of the flexible mold are uniformly filled with entrained air. The rib rib precursor composition preferably has a flow rate of about 2 〇 Pas to _ Pa s at a shear rate of M/sec. Viscosity 'and viscosity at i Pa ^ 2 煎 at 100/sec.. Various curable organic binders can be used. Curable organic binders can be cured, for example, by exposure to radiation or heat. The binder may comprise any combination of monomers and agglomerates as long as it has a mixture of inorganic particulate materials and has an appropriate viscosity. Usually, the binder is preferably curable by radiation in an isothermal condition, i.e., without temperature change. This reduces the risk of displacement or expansion due to the different thermal expansion characteristics of the mold and the substrate. This allows the precise placement and alignment of the mold to be maintained as the rib precursor is hardened. The release agent is not only a solvent compound of the resin. Preferably, the diluent is bathable for incorporation into the sigma in an uncured state. After curing the binder of the slurry, the diluent should be phased with the monomer and/or oligomer of the eight compartments of the tray, the wheat and the crosslinking process. Preferably, the diluent phase is divided into a liquid material to form a liquid material: the cans of the glass powder or the powder of the body of the ceramic powder is too strong. In this way, the physical integrity of the cured green state microstructure is not greatly increased even when using a slightly higher level of dilution 127318.doc 200903570 (i.e., a ratio of diluent to resin greater than about 1:3) damage. This provides two advantages. First, the diluent reduces the risk of adhering the cured adhesive material to the mold by maintaining a liquid state while the adhesive is being cured. Second, by maintaining a liquid state while hardening the binder, the diluent is phase separated from the binder material, thereby forming a diluent sac or droplets dispersed throughout the network of the cured binder matrix. And promote the debonding process. Optionally, the photocurable rib precursor composition may comprise a dispersing agent and/or a thixotropic agent. Each of these additives can be used in an amount of from about 0.05% by weight to about 2.0% by weight of the total ribbed precursor composition. Typically, the amount of each of these additives is no greater than about 〇·5 weight ❶/〇. In addition, the rib precursor may comprise a tackifier such as a smouldering coupler to promote adhesion to a substrate (e.g., a glass panel of a PDP). The rib precursors may also optionally include various additives including, but not limited to, surfactants, catalysts, and the like, which are known in the art. The substantially s ' inorganic thixotrope gum may comprise clay (e.g., bentonite), shixi stone 'mica, montmorillonite, and the others' having a particle size less than 〇·1 μπι. In general, 'organic thixotropes can include fatty acids, fatty acid amines, hydrogenated sesame oil, casin, gums, gelatin, gluten, soy protein, alginic acid money, potassium alginate, sodium alginate. , gum arabic, guar gum (guar gUm), soy lecithin, pectin acid, starch, agar, ammonium polyacrylate, sodium polyacrylate, ammonium polythiolate, potassium salt (eg 'modified Acrylic polymers and copolymers), polyhydroxycarboxylic acid amines and brewed women (such as the trade name BYK-Chemie Co. "BYK 405"), 127318.doc -17- 200903570 polyvinyl alcohol, vinyl Polymer (vinyl mercapto ether / maleic anhydride), vinyl pyrrolidone copolymer, polypropylene decylamine, fatty acid decylamine or other aliphatic decylamine compound, carboxylated methyl cellulose, hydroxymethyl fiber , hydroxyethyl cellulose, cellulose xanthate, carboxylated starch, urethane urea, oleic acid and sodium alginate. In some aspects, the dispersing agent is an inspective polymer, i.e., a homopolymer, a valence polymer or a copolymer having at least one medium to strong polar Lewis basic functional copolymerizable monomer. Polarity (eg, hydrogen or ionic binding capacity) is often described by the use of terms such as "strong", "medium," and "weak". Describes this and other solubility techniques. "S〇ivents paint testing manual", 3rd edition, GG Seward, Ed., American

Society for Testing and Materials, Philadelphia, Pennsylvania and "A three-dimensional approach to solubility" ’ Journal of Paint Technology, Vol. 38, 496 5 Tiger, 269-280 pages. Various anionic polymeric dispersants are known, such as anionic polyamine-based polymeric dispersants available under the trade designation "Ajisper PB 821 " from Ajinomoto-Fine-Techno Co. In other embodiments, an acidic polymer can be used as a dispersing agent. For example, the rib precursor may comprise from 1 to 1 part by weight of the phosphorus-based compound' having at least one phosphate group, either alone or in combination with from 0.1 to 1 part by weight of the sulfonate-based compound. These compounds are described in W〇 2005/0 19934. Other acidic polymers used as dispersants are commercially available, such as from Noveon under the trade name "SolPlus D520." The amount of curable organic binder in the rib precursor composition is typically up to 127318.doc • 18- 200903570 2% by weight, more usually at least 5% by weight, and more usually at least 丨〇% by weight. The amount of diluent in the rib rib precursor composition is typically at least 2% by weight 'more usually at least 5% by weight' and more Usually at least 丨〇% by weight. The total set of organic group damage is usually at least 10% by weight, at least 15% by weight or at least 20% by weight. Further, the total amount of organic compounds is usually not more than 50% by weight. Inorganic test material The amount is usually at least 40% by weight, at least 5% by weight, or at least 60% by weight. The amount of the inorganic particulate material is not more than % by weight. The amount of the additive is substantially less than 1% by weight. Preparing a paste. For example, a glass or ceramic-forming particulate material (eg, a powder) may be combined with a diluent and a dispersant in a diluent ratio of from about 1 Torr to 15 parts by weight; Ingredients. The paste is typically filtered to 5 microns. In a preferred embodiment, the flexible mold can be reused. The number of times the flexible mold can be reused is combined with the rib precursor used in the method of fabricating the microstructure. Depending on the preferred embodiment, the ribbed precursor composition gamma flexible mold can be reused at any number of times from at least one re-use to at least five re-uses. Medium, polymerizable transfer mold = can be reused at least 1 () times, at least 15 times, at least 2 times or at least 3 times. The microstructure of the Tianke's I1 mold is less than 丄 (4). And more than 5% (if it can be determined by visual inspection with a microscope, the transfer mold can be reused. For the rib precursor to be cured by the Gu M @ a τ* cutting 可 flexible mold In an embodiment, the flexible mold is suitable for reuse when the prismatic M is sufficiently permeable, and the flexible core is sufficiently transparent to have less than (10), preferably 127318.doc • 19·200903570 after the use. 10% and more preferably no more than 5% turbidity, turbid, 1, and 1 The test method described in the examples is to measure.) Even more preferably, the mold can have the turbidity criterion just described after at least 5 re-uses. After use, in the preferred embodiment, the rib precursor is used. The material contains a diluent having a solubility parameter smaller than that of the curable organic binder. The solubility parameter of each monomer δί # x / 偬 塔 ) can be calculated by the following formula: δ = (ΔΕν / ν) 1 / 2, where ΔΕν is the steam servant ηΛ at a given temperature, and r is/flying here, and ν is the corresponding molar volume. According to the Fedors method, the chemical structure can be used to calculate sp (RFFedors, P 〇lym. Eng. Set,14(2),M147W > 1974 «

Polymer Handbook 4th Edition, "Solubility Parameter Values" edited by j.Brandrup, E H Jmmergut and E.A. Grulke). The difference between the solubility parameters of the curable binder and the diluent is at least i [MJ/m3] 1'2 ' and usually at least 2 [MJ/m3] w2. The difference between the solubility parameters of the curable binder and the diluent is preferably at least 3 [Μ"〆]!/2, 4 [MJ/m3]"2 or 5 [MJ/m3] 1/2. The difference between the solubility parameters of the curable binder and the diluent is preferably at least 6 [MJ/m3] 1, 2, 7 [MJ/m3] " 2 or 8 [MJ/m3] 1/2. Various organic diluents can be used depending on the choice of curable organic binder. In general, suitable diluents include various alcohols and diols such as alkylene glycols (eg, 'ethylene glycol, propylene glycol, tripropylene glycol), alkyl diols (eg, 1,3 butanediol), and alkoxylates. Alcohol (for example, 2-hexyloxyethanol 2-(2-hexyloxy)ethanol, 2-ethylhexyloxyethanol); ether, such as di-alkyl diol alkyl ether 127318.doc -20- 200903570 (for example, diethylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether); esters such as lactate and acetate, and in detail dialkyl glycol alkyl hydrazine Acetate (eg, diethylene glycol monoethyl carboxy acetate); alkyl stearate (eg, diethyl succinate), alkyl glutarate (eg, pentane monoacetate) And hexanoic acid ester (for example, diethyl adipate). The glass or ceramic is selected to form a particulate material (e.g., a powder) based on the final application of the microstructure and the nature of the microstructure to which the microstructure will adhere. A consideration is the coefficient of thermal expansion (CTE) of the substrate material (e.g., the glass panel of the 'PDP). Preferably, the CTE of the glass or ceramic forming material of the slurry of the present invention differs from the cte of the substrate material (e.g., the electrode patterned glass panel of the PDP) by no more than 10%. When the substrate material has a CTE that is much smaller or much larger than the CTE of the ceramic material of the microstructure, the microstructure may warp, burst, crack, shift, or completely fall off the substrate during processing. In addition, the substrate may be warped due to high CTE differences between the substrate and the fired microstructure. The inorganic particulate material suitable for use in the excimer of the present invention preferably has a coefficient of thermal expansion of from about 5 X 10_6 to i3xi (r6/°c. L) is generally used in the glass and/or ceramic materials of the present invention. A softening temperature of less than about 600 t and usually greater than 4 〇〇 t. The softening gamma of a ceramic powder refers to the temperature that must be achieved without fusing or sintering the powder material. The substrate generally has a ceramic material that is higher than the rib precursor. Softening temperature softening temperature. Selection of glass and/or ceramic powders having a low softening temperature allows the use of substrates which also have a relatively low softening temperature. Suitable compositions include, for example, i) ZnO and B2〇3; ii) Ba〇 With B2〇3;

Ui)Zn〇 ' Ba〇^B2〇3 ; iv)La2〇3^B2〇3 ; A ν)Α12〇3 . ZnO 127318.doc -21 · 200903570 and P2〇5. A lower softening temperature ceramic material can be obtained by incorporating a certain amount of mis, silk or phosphorus into the material. Other low softening temperature ceramic materials are known in the art. Other fully soluble, insoluble or partially soluble components can be incorporated into the human slurry of the Tauman material to obtain or modify various properties. The preferred size of the particulate glass or ceramic forming material of the rib precursor depends on the size of the microstructure formed and aligned on the patterned substrate. The average size of the particles is often no greater than about 1% to ls% of the size of the smallest characteristic size to be formed and aligned to the microstructure. For example, for PDP barrier ribs, the average particle size is typically no greater than about 2 or 3 microns. The photocurable polymerizable composition for use in the manufacture of a mold or as a binder in the manufacture of a ceramic microstructure preferably comprises one or more photoinitiators at a concentration of from 0.05% by weight to 5 parts by weight of the polymerizable resin composition. Within the range of %. Suitable photoinitiators include, for example, 2·hydroxy-2-methyl-1-phenylpropanone; ^[4 (2-based ethyl lactyl)-benzyl]_2_trans-base_2_mercapto-_ι _丙院_ι__ ; 2,2_ monomethoxy _, 2-- phenyl Ethylene-1-yl; 2-methyl-1-[4-(methylthio)phenyl]-2-? Lolinyl _ 1 _ acetone; and mixtures thereof. A suitable photoinitiator combination is described in U.S. Patent Application Serial No. 1 1/538,933, the entire disclosure of which is incorporated herein by reference.

Various other aspects that may be used in the present invention as described herein are known in the art including, but not limited to, each of the following patents: U.S. Patent No. 6,247,986; U.S. Patent No. 6,537,645; US Patent No. 6,352,763; US 6,843,952, US 6,306,948; WO 99/60446; WO 2004/062870; WO 2004/007166; WO

WO 03/032353; WO 2004/010452; WO 127318.doc • 22·200903570 2004/064104; U.S. Patent No. 6,761,607; U.S. Patent No. 6,821,178; WO 2004/043664; WO 2004/062870; W02005/042427; W02005/019934; W02005/021260; and W02005/013308. The invention is illustrated by the following non-limiting examples. Example: Hygroscopic polymeric support pre-conditioning As a hygroscopic polymeric support for the manufacture of molds, 4 different samples of 250 micron thick polyester film (trade name: Tetron film HS250, by Teijin Dupont Film) The manufacturing) was preconditioned for 24 hours using 3 different preconditioning environments. Support pre-adjustment A : 22°C/55%RH Support pre-adjustment B : 22°C/58%RH Support pre-adjustment C : 22°C/61%RH Master tool preparation with lattice-type PDP barrier The mother tool of the rib pattern. A rectangular transfer mold is fabricated from a metal master tool using a polyoxyxylene material and a stainless steel substrate as described in WO 2005/013308 and U.S. Patent Application Serial No. U.S. The cell pitch is 0.270 mm in the direction of the longer side and 0.808 mm in the direction of the shorter side. Preparation of Flexible Mold The photocurable resin used as the shaped layer of the mold was prepared as follows: 80 parts of aliphatic amide phthalate oligomer (Ebecryl (EB) 8402 manufactured by Daicel UCB) 127318.doc -23- 200903570 20 parts of lactone-modified monomer (FA2D manufactured by Daicel UCB) 1 part of photoinitiator (Irgacure 2959 by Chiba-Geigy) The viscosity of the resin is l〇,000 CPS (Brookfield viscometer with a 5th axis, rotating at 2 rpm). This resin was applied to the surface of the micro-structure of the tool in four separate experiments so that the recess of the microstructured surface was filled. The preconditioned polyester film is laminated to the surface of the tool filled with the photocurable resin in an environment having the same temperature and relative humidity as the temperature and relative humidity for preconditioning the PET support film. . By using a low-pressure mercury lamp (chemical lamp, radiation wavelength: 300 nm to 4 〇〇 nm Mitsubishi Osram), by irradiating 3,000 mJ/cm2 of UV through a preconditioned polyester film support. Light curing resin. Then remove the mold from the tool. The first temperature and RH (ie, the temperature of the mold manufacturing environment and RH) are between 22 ° C / 55% RH (ie, the second temperature and RH) microstructure comparison between the examples - 22 ° C / 55% RH a __ same transfer mold and master tool 22 〇C/58%RH - 9 ppm pitch in the length direction - 14 ppm pitch in the width direction 22 〇 C / 61% RH - in the length direction - 28 ppm Spacing - Shows -33 ppm pitch in the width direction. The spacing can be adjusted to approximately 5 ppm per degree of relative humidity. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a perspective view of an illustrative flexible mold suitable for use in the manufacture of barrier ribs. 127318.doc -24- 200903570 Figure 2 is a perspective view of an illustrative transfer mold suitable for use in making flexible molds of the drawings. 3A to 3C are cross-sectional views sequentially showing an illustrative method of manufacturing a flexible mold from a transfer mold. 4A through 4C are, in order, cross-sectional views of an illustrative method of fabricating a fine structure (e.g., 'blocking rib) using a flexible mold. [Major component symbol description] 41 Substrate 43 Roller 45 Barrier rib precursor 100 Flexible mold 110 Planar support layer 120 Shaped layer 125 Test structure pattern 200 Transfer mold or master mold 350 Polymerizable resin composition 380 Support /Support film 127318.doc •25-

Claims (1)

200903570 X. Patent application scope: 1 · A method for producing a microstructured article, which comprises the following steps: a mold containing a sucking *拎, w tooth piece, wherein the mold is first/ Prepared under the degree of dish and relative humidity; at the temperature of the first temperature and relatively thirsty; θ: π # 母主', and under a substrate and the microstructured surface of the mold to provide _ open & ', ceramic paste a bulk material, the second temperature and relative humidity are different from the first temperature and humidity in temperature, humidity, or combination; curing the material to form a microstructure integrally bonded to the substrate; The microstructured article removes the mold. 2. The method of claimant, wherein preparing the mold comprises providing a polymeric transfer mold or master mold having a microstructured surface; A polymerizable resin composition is provided in the recess of the microstructured surface of the mold; the pre-adjusted cake is spread 2P #日? The dent is stacked onto the microstructured surface of the mold; the polymerizable resin composition is cured; and the cured polymerizable resin composition is removed from the mold together with the support' thereby forming a flexible mold. 3. The method of claim 2, wherein the microstructured surface of the transfer mold or master mold comprises microstructures disposed at a pitch, and the first temperature or relative humidity adjusts the pitch of the microstructures. 4_ The microjunction of the transfer mold or the master mold in the method of the second aspect of the present invention. 127318.doc 200903570 The structured surface has a microstructure having a pitch greater than a target pitch. 5. The method of claim 4, wherein the first relative humidity is between 1% and 40% higher than the second relative humidity. 6. The method of claim 4, wherein the first relative humidity is between 1% and 1% by weight of the second relative humidity. 7. The method of claim 4, wherein the first relative humidity is 1 °/ higher than the second relative humidity. To 5 . 8. The method of claim 2, wherein the transfer mold or the master mold has a microstructure having a distance less than a target pitch. 9. The method of claim 8, wherein the first relative humidity is 1% to 4 低 lower than the second relative humidity. 10. The method of claim 8, wherein the first relative humidity is between 1% and 1% lower than the second relative humidity. 11. The method of [Section 8] wherein the first relative humidity is 1% to 5% lower than the second relative humidity. The method of Moon Length 2, wherein the polymerizable composition comprises at least one type of olefinic system Reaction of a saturated oligomer with at least one ethylenically unsaturated monomer. 13. The method of claim 12 wherein the polymer comprises an aminomethyl acrylate oligomer. And, wherein the curing comprises passing light through the mold, through the substrate, or a combination thereof. 15. The method of claim [wherein the substrate is a display panel member and the microstructures 127318.doc 200903570 弟一温相相1 6. The method of claim 1, wherein the first temperature is the same as 127318.doc