WO2007040493A1 - Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor - Google Patents
Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor Download PDFInfo
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- WO2007040493A1 WO2007040493A1 PCT/US2005/034299 US2005034299W WO2007040493A1 WO 2007040493 A1 WO2007040493 A1 WO 2007040493A1 US 2005034299 W US2005034299 W US 2005034299W WO 2007040493 A1 WO2007040493 A1 WO 2007040493A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/04—Thixotropic paints
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2005—Treatments with alpha, beta, gamma or other rays, e.g. stimulated rays
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Definitions
- compositions, methods, processes and assemblages for rendering paper and fiber-based products resistant to water are Described herein.
- a variety of consumer, scientific, and industrial products are composed of natural fibers, such as paper. When exposed to water, these products exhibit reduced structural strength which can lead to tearing or breaks. In addition, ink or pencil writing on these products fades, bleeds, or streaks when exposed to water.
- porous and/or fiber products that have and retain desirable aesthetic, performance and durability properties when exposed to water, including exposure for prolonged periods of time.
- the present fiber products exhibit at least one of the following characteristics after exposure to water for at least 1 day: (a) retention of structural integrity; (b) retention of structural strength; (c) retention of ink or pencil writing; (d) retention of print; (e) retention of brightness; and (f) resistance to mold, algae, mildew, bacterial, and/or fungal growth.
- fiber products that exhibit at least two of the aforementioned characteristics, at least three of the aforementioned characteristics, at least four of the aforementioned characteristics, at least five of the aforementioned characteristics, or all of the aforementioned characteristics.
- fiber products that exhibit or retain at least one of the following characteristics after exposure to water for at least 2 days, at least 3 days, at least 7 days and at least 10 days. Also described are fiber products wherein exposure to water includes soaking, misting, spraying, seeping, or combinations thereof. Also described herein are compositions, methods, strategies, techniques, assemblages and factories for waterproofing porous and/or fiber products. In further embodiments, the waterproofed porous and/or fiber products retain desirable aesthetic, performance and durability properties when exposed to water, including exposure for prolonged periods of time. [0004]
- the present fiber products comprise compositions, partially cured compositions, and fully cured compositions provided herein. Also presented herein are compositions that can be applied to a fiber substrate, optionally followed by a curing process, to produce a fiber product having at least one of the aforementioned characteristics.
- compositions comprising:
- the present composition is applied to a fiber substrate, optionally followed by a curing process, to manufacture fiber products having at least one of the aforementioned characteristics.
- porous and/or fiber products comprising (a) a porous and/or fiber substrate; and (b) a composition comprising:
- porous and/or fiber products that exhibit at least one characteristic: (a) retention of writability of pen and/or ink; (b) retention of print; (c) retention of brightness; and/or (d) ability to block absorption of organic solvents (e.g., alcohol, methyl ethyl ketone, etc.).
- organic solvents e.g., alcohol, methyl ethyl ketone, etc.
- porous and/or fiber products that resist the growth of mold, mildew, algae, bacteria and/or fungus.
- fiber and/or porous products comprise a cured composition that has been impregnated, at least in part, into the porous and/or fiber product.
- porous and/or fiber products that exhibit at least one characteristic after exposure to water for at least 1 day: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- methods of manufacturing the present porous and/or fiber products comprising (a) providing a fiber and/or porous substrate; (b) applying a composition to said fiber and/or porouse substrate to produce a fiber and/or porous product; and (c) curing said fiber and/or porous product, wherein said composition comprises:
- assemblages for manufacturing the present porous and/or fiber products comprising (a) means for providing a porous and/or fiber substrate; (b) means for applying a composition to said porous and/or fiber substrate to produce a porous and/or fiber product; and (c) means for curing said porous and/or fiber product, wherein said composition comprises:
- Porous and/or fiber products produced by the above assemblages for manufacturing are also presented.
- Exemplary applications for the present porous and/or fiber products include labels, books, newspaper, magazines, maps, field manuals, envelopes, paper plates, clothes, shipping materials, vapor barriers, garden markers, underwater markings, sports equipment, gym bags, business cards, cardboard, shower curtains and the like. Additional applications include use of the present porous and/or fiber products to block absorption of aqueous-based solutions, including water from any source, including mudwater, lake water, stream water, tap water, ocean water, sewage water and purified water. Additional applications include use of the present porous and/or fiber products to block absorption of organic solvents, such as alcohol, methyl ethyl ketone, and the like.
- Figure 1 is a flowchart of one possible process for applying the compositions described herein to a fiber substrate.
- Figure 2 is an illustration of one representative method and assemblage for applying the compositions described herein to a fiber substrate, and curing the composition.
- Figure 3 is an illustration of another representative method and assemblage for applying the compositions described herein to a fiber substrate, and curing the composition.
- actinic radiation refers to any radiation source which can produce polymerization reactions, such as, by way of example only, ultraviolet radiation, near ultraviolet radiation, and visible light.
- co-photoinitiator refers to a photoinitiator which may be combined with another photoinitiator or photoinitiators.
- cure refers to polymerization, at least in part, of a coating composition.
- curable refers to a coating composition which is able to polymerize at least in part.
- curing booster refers to an agent or agents which boost or otherwise enhance, or partially enhance, the curing process.
- fiber substrates refers to any object which is, contains, or is derived from a natural fiber; such objects encompass:
- marker such as, but not limited to, garden markers, underwater markers, soil markers, and the like;
- various types of natural fiber knits such as, but not limited to, cotton, wool, linen, hemp, rampie, silk, and the like; and
- fiber substrates which have non-fiber components such as, but not limited to, buttons, zippers, pins, staples, clips, rods, and the like.
- filler refers to a relatively inert substance, added to modify the physical, mechanical, thermal, or electrical properties of a coating.
- inorganic pigment' refers to ingredients which are particulate and substantially nonvolatile in use, and includes those ingredients typically labeled as inerts, extenders, fillers or the like in the paint and plastic trade.
- the term "irradiating,” as used herein, refers to exposing a surface to actinic radiation.
- milling refers to the processes of premixing, melting and grinding a powder coating formulation to obtain a powder suitable for spraying.
- photoinitiators refers to compounds that absorb ultraviolet light and use the energy of that light to promote the formation of a dry layer of coating.
- polymerizable pigment dispersions refers to pigments attached to polymerizable resins which are dispersed in a coating composition.
- polymerizable resin or "activated resin,” as used herein, refers to resins which possess reactive functional groups.
- pigment refers to compounds which are insoluble or partially soluble, and are used to impart color.
- retention of brightness refers to the ability of a material to retain at least about 90% of its brightness. Retention of brightness prevents discoloration, such as darkening or yellowing, of a material.
- retention of ink or pencil writing refers to the ability of ink or pencil writing to be at least about 90% retained on a material. Retention of ink or pencil writing prevents bleeding, fading, and/or streaking on a material.
- Representative tests for determining retention of ink or pencil writing include spectrophotometric tests, such as the Ink Elimination (IE) test and the Effective Residual Ink Concentration (ERIC) test, for example
- retention of print refers to the ability of print to be at least about 90% retained on a material.
- Representative prints include various ink prints, such as labels, logos, and the like. Retention of print prevents bleeding, fading, and/or streaking on a material.
- Representative tests for determining retention of print include various spectral photometric tests.
- retention of structural strength refers to the ability of a material to retain at least about 90% of its physical and structural integrity, strength, or durability. Retention of structural strength prevents tearing, ripping, or breaks. Representative mechanical tests for determining retention of structural strength include manual inspection, folding endurance, and tensile strength, for example. Spectral photometric tests may also be employed to determine retention of structural strength.
- retention of writability of pencil and/or ink refers to the ability of a material to retain at least about 90% of its ability to be written upon by any type of pencil or any source of ink, such as a pen or printer. Writability depends on the absorbency of a material.
- vehicle refers to the liquid portion of solvent based formulations, and can incorporate both the solvent and the resin.
- compositions comprising:
- compositions provided herein are applied to fiber substrates to produce fiber products having desirable properties.
- the present composition comprises nano-fillers in an amount of 20-60% by weight of the total weight of the composition (wt/wt).
- the present composition comprises at least one photo-initiator in an amount of 0.5-10% wt/wt.
- the present composition comprises at least one mono-functional monomer in an amount of 2-80% wt/wt.
- the present composition comprises a diluent in an amount of 2-22% wt/wt.
- the present composition comprises a surfactant in an amount of 0.01-2.0% wt/wt.
- the present composition comprises a pigment dispersion in an amount of 1- 12% wt/wt and a second photoinitiator in an amount of 0.5-5% wt/wt.
- compositions described herein can be applied to various fiber substrates to produce fiber products.
- Compositions described herein are curable by various sources of visible radiation, near visible radiation, ultra-violet (UV) radiation, and combinations thereof.
- UV radiation can be selected from the group consisting of UV-A radiation, UV- B radiation, UV-B radiation, UV-C radiation, UV-D radiation, or combinations thereof.
- Coating flexibility may be an important characteristic for compositions herein when applied to objects which flex, distort, or otherwise change shape, such as, but not limited to, fabrics and cloths. Coating flexibility allows the composition to flex or distort without cracking when the object flexes, distorts or changes shape; whereas coating adhesion properties allows the coating to remain attached to the object when the object flexes, distorts or changes shape. Certain embodiments of the compositions described herein may be used to obtain and optimize desirable properties.
- the present composition comprises nano-fillers.
- Nano-fillers can be either insoluble inorganic particles, or insoluble organic particles.
- the inorganic nano-fillers are generally metal oxides, although other inorganic compounds can be used.
- Examples of inorganic nano-fillers include aluminum nitrides, aluminum oxides, antimony oxides, barium sulfates, bismuth oxides, cadmium selenides, cadmium sulfides, calcium sulfates, cerium oxides, chromium oxides, copper oxides, indium tin oxides, iron oxides, lead chromates, nickel titanates, niobium oxides, rare earth oxides, silicas, silicon dioxides, silver oxides, tin oxides, titanium dioxides, zinc chromates, zinc oxides, zinc sulfides, zirconium dioxides, and zirconium oxides.
- organic nano-fillers are generally polymeric materials ground into appropriate sized particulates.
- examples of nanometer sized organic nano-fillers include, but are not limited to, nano- polytetrafluoroethylene, acrylate nanosphere colloids, methacrylate nanosphere colloids, and combinations thereof, although micron sized fillers of the polytetrafluoroethylene, acrylate, methacrylate, and combinations thereof may be used.
- the present compositions comprise nano-alumina.
- Nano- alumina is composed of high purity aluminum oxide that is of nanometer size, including by way of example less than 200 nm, and within the range of approximately 5-40 nanometer discrete spherical particles. Nano-alumina imparts excellent optical clarity, gloss and physical properties. Nano-alumina-based compositions find use in abrasion resistant coating applications requiring superior optical transparency such as eye glasses; fine polishing applications, including semiconductors; and nanocomposite applications, including improved thermal management, hi addition, incorporation of nano-alumina can give rise to compositions with improved impact resistance, abrasion resistance and scratch resistance.
- the present compositions comprise nano-silicon dioxide.
- Nano-silicon dioxides having a nanometer size including by way of example less than about 200 nm, and by way of further example, with an average particle size 5 to 40 nm, can be incorporated into compositions. Addition of nano-silicon dioxides may impart improved toughness, hardness and abrasion and scratch resistance.
- nano-silicon dioxides include those sold under the name
- Nanocryl ® C by Hanse Chemie (Geesthacht, Germany), such as Nanocryl ® C 350, Nanocryl ® C 130, Nanocryl ® C 140, Nanocryl ® C 145, Nanocryl ® C 146, Nanocryl ® C 150, Nanocryl ® C 153, Nanocryl ® C 155, Nanocryl ® C 165.
- Nanocryl ® C 155 is included in the present compositions.
- nano-fillers include: oxides, carbides, nitrides, borides, silicates, ferrites and titanates.
- examples of such nano- fillers are, but not limited to, nano-zirconium oxide, nano-zirconium dioxides, nano- silicon carbide, nano-silicon nitride, nano-sialon (silicon aluminum oxynitride), nano- aluminum nitrides, nano-bismuth oxides, nano-cerium oxides, nano-copper oxides, nano- iron oxides, nano-nickel titanates, nano-niobium oxides, nano-rare earth oxides, nano- silver oxides, nano-tin oxides, and nano- titanium oxides. These materials have relatively high mechanical strength at high temperatures.
- nano-fillers used in the composition described herein include amorphous silicon dioxide prepared with polyethylene wax, synthetic amorphous silica with organic surface treatment, untreated amorphous silicon dioxide, alkyl quaternary bentonite, colloidal silica, acrylated colloidal silica, alumina, zirconia, zinc oxide, niobia, titania aluminum nitride, silver oxide, cerium oxides, and combinations thereof.
- the silicon dioxides are chosen from a group consisting of both synthetic and natural silicon dioxides with surface treatments including polyethylene wax or waxes and IRGANOX® from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.
- the average particle size of nano-fillers in the compositions described herein includes by way of example less than about 20 ⁇ m, and by way of further example, with an average particle size 1 to 10 ⁇ m discrete particles; whereas, the average particle size of nano-f ⁇ ller particles includes by way of example less than about 200 nm, and by way of further example, with an average particle size 5 to 50 nm discrete particles.
- nano-filler particles have an average diameter of 10, 20, 30, or 40 nm.
- the particle size distribution of nano-filler particles ranges from lnm to 60 nm, such as from 5 nm to 30 nm.
- Nano-fillers are present in the compositions in an amount ranging from 20 to 60% wt/wt, such as from 25 to 55% wt/wt, 30 to 50% wt/wt, or 30 to 40% wt/wt. In an embodiment, the present compositions comprise from 33-36% wt/wt.
- fillers imparts certain rheological properties to the composition, such as viscosity; however, the addition of nanoscale fillers imparts dramatically different effects on the coating mechanical properties in comparison to micron scale fillers.
- the mechanical properties of the composition can be manipulated by varying the amount of micron sized fillers and nano-fillers.
- Improved properties attributable to nano-fillers include improved tensile strength, modulus, heat distortion temperature, barrier properties, UV resistance, abrasion and scratch resistance, and conductivity.
- the incorporation of certain nano-fillers, such as nano-alumina and nano-silicon, can provide favorable long-term coating without significantly effecting optical clarity, gloss, color or physical properties. These improved properties may be in large part due to the small size and large surface area of the nanoscale fillers.
- the present composition comprises at least one photo-initiator. In a further or alternative embodiment, the present composition comprises at least two photo-initiators, m a further or alternative embodiment, the present composition comprises at least three photo-initiators.
- photo-initiators are added to initiate rapid polymerization of monomers in the composition upon exposure to a source of actinic radiation, such as ultraviolet light.
- the photo-initiator can be matched to the spectral properties of the UV source, such as medium pressure mercury arc lights which produce intense UV-C (200-280 nm) radiation, doped mercury discharge lamps which produce UV-A (315-400 nm) radiation, or UV-B (280-315 nm) radiation depending on the dopant, or combination of lamp types.
- varying UV source(s) may be employed.
- photo-initiator Any suitable type of photo-initiator may be used in the composition, including those categorized as free radicals.
- the photo-initiator may be in liquid or solid form.
- combinations of photo-initiators may be used which encompass different spectral properties of the UV sources used to initiate polymerization.
- the photo-initiator may be selected from a group consisting of diphenyl (2, 4, 6 - trimethylbenzoyl) phosphine oxide, benzophenone, ESACURE ® KTO, IRGACURE ® 184, IRGACURE ® 500, DARACUR ® 1173, Lucirin ® TPO, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phenyl-propan-l-one, 2, 4, 6,-trimethylbenzophenone, 4- methylbenzophenone, oligo (2 -hydroxy-2 -methyl - l-(4-(l- methylvinyl)phenyl)propanone), and combinations thereof.
- the photo- initiators may be selected from a group consisting of phosphine oxide type photoinitiators, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzophenone, 1- hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phenyl-propan-l-one (DAROCUR ® 1173 from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.)), 2,4,6-trimethylbenzophenone and 4-methylbenzophenone, ESACURE ® KTO 46 (Lamberti S.p.A., Gallarate (VA), Italy), oligo(2-hydroxy-2- methyl-l-(4-(l-methylvinyl)phenyl)propanone), amine acrylates, thioxanthones, benzyl methyl ketal, and mixtures thereof.
- phosphine oxide type photoinitiators di
- the photo-initiators may be selected from 2-hydroxy-2-methyl-l-phenyl-propan-l-one (DAROCUR ® 1173 from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.), phosphine oxide type photoinitiators, IRGACURE (D 500, 819, or 1700 (Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.), amine acrylates, thioxanthones, benzyl methyl ketal, and mixtures thereof.
- DAROCUR ® 1173 from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.
- IRGACURE IRGACURE
- amine acrylates thioxanthones
- benzyl methyl ketal 2-hydroxy-2-methyl-phenyl-propan-l-one
- photo-initiators which are suitable for use in the practice of the present invention include, but are not limited to, l-phenyl-2-hydroxy-2-methyl-l-propanone, oligo ⁇ 2-hydroxy-2 methyl- l-4-(methylvinyl)phenylpropanone) ⁇ , 2-hydroxy 2-methyl-l- phenyl propan-1 one, bis (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone and benzophenone as well as mixtures thereof.
- Still other useful photoinitiators include, for example, bis(n,5,2,4- cyclopentadien -l-yl)-bis 2,6 -difluoro-3-(lH-pyrol-l-yl) phenyl titanium and 2-benzyl -2-N,N-dimethyl amino -1- (4-morpholinophenyl) -1- butanone.
- IRGACURE ® 784 and IRGACURE ® 369 are useful photoiniators.
- useful photoiniators include, for example, 2-methyl-l-4(methylthio)-2- morpholinopropan-1-one, 4-(2 -hydroxy) phenyl - 2-hydroxy-2-(methylpropyl)ketone, 1 -hydroxy cyclohexyl phenyl ketone benzophenone, (cyclopentadienyl)( 1 -methylethyl)benzene-iron hexafluorophosphate, 2,2-dimemoxy-2- phenyl-1-acetophen-one 2,4,6- trimethyl benzoyl-diphenyl phosphine oxide, benzoic acid, 4-(dimethyl amino)-ethyl ether, as well as mixtures thereof.
- the present composition comprises at least one photo-initiator comprising ce-hydroxyketone, such as 1-hydroxy-cyclohexyl-phenyl- ketone.
- the present composition comprises at least one photo-initiator comprising benzophenone.
- the present composition comprises at least one photo-initiator comprising a benzoyl diaryl phosphine, such as 2,4,6-trimethylbenzoyl)diphenylphosphine oxide.
- the present composition comprises a combination of photo- initiators.
- the present composition comprises IRGACURE ® 184 and IRGACURE ® 500.
- the present composition comprises IRGACURE ® 184, IRGACURE ® 500, and Lucirin ® TPO.
- the photo-initiator(s) are present in the compositions in an amount ranging from
- wt/wt 0.5-10% wt/wt, such as from 1 to 9% wt/wt, 3 to 8% wt/wt, or 4 to 6% wt/wt.
- the present composition comprises a combination of photo-initiators, wherein each photo-initiator is present in an amount ranging from 0.5- 5% wt/wt, such as from 1 to 4% wt/wt or 2 to 3% wt/wt.
- the present composition comprises IRGACURE ® 184 in an amount ranging from 2 to 6% wt/wt, such as about 2, 3, 4, 5, or 6% wt/wt and IRGACURE ® 500 in an amount ranging from 0.5 to 4% wt/wt, such as about 0.5, 1, 2, 3, or 4% wt/wt.
- the present compositions comprise a pigment dispersion and a second photo-initiator comprising benzoyl diaryl phosphine oxide.
- phosphine oxide type photo- initiators are effective in pigmented composition, including, by way of example only, black and UV-curable coating materials.
- Phosphine oxides also find use as photo- initiators for white coatings, hi an embodiment, compositions comprise a pigment dispersion and a photoinitiator comprising 2,4,6-trimethylbenzoyl)diphenylphosphine oxide, such as Lucirin ® TPO.
- the present composition comprises a photo-initiator comprising benzoyl diaryl phosphine oxide that is present in an amount ranging from 0.5- 5% wt/wt, such as from 1 to 4% wt/wt or 2 to 3% wt/wt.
- the photo- initiator comprising benzoyl diaryl phosphine oxide may be present in the composition in an amount of about 0.5, 1, 2, 3, or 4% wt/wt.
- the present composition comprises at least one mono-functional monomer, hi an embodiment, the present composition comprises a combination of monomers.
- a source of actinic radiation such as ultraviolet light
- monomers in the composition are rapidly polymerized to form oligomers.
- compositions herein may comprise monomers, oligomers, or monomers and oligomers.
- the mechanical properties of the present compositions depend upon the type of monomers and oligomers provided.
- polyester acrylates combine good abrasion resistance with toughness
- urethane acrylates and polyether acrylates can provide flexibility, elasticity and hardness.
- the composition described herein combine oligomers and monomers which impart various properties to obtain compositions that are hard, abrasion resistant, scratch resistant, and impact resistant.
- the monomers are chosen from a group consisting of 2-phenoxyethyl acrylate, isobornyl acrylate, acrylate ester derivatives, methacrylate ester derivatives, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, 2-phenoxyethyl acrylate esters, and cross-linking agents, such as, but not limited to, propoxylated glyceryl triacrylate, tripropylene glycol diacrylate, and mixtures thereof.
- the monomer(s) are present in the compositions in an amount ranging from 2-
- the present composition comprises 2-phenoxyethyl acrylate in an amount ranging from 4-40% wt/wt, such as from 10 to 30% wt/wt, 10 to 25% wt/wt, or 10 to 15% wt/wt.
- the present composition comprises 1,4- butanediol dimethacrylate in an amount ranging from 4-40% wt/wt, such as from 10 to 30% wt/wt, 10 to 25% wt/wt, or 10 to 15% wt/wt.
- the present composition comprises tetxahydrofurfuryl acrylate in an amount ranging from 10-40% wt/wt, such as from 15 to 30% wt/wt or 20 to 25% wt/wt.
- the present composition comprises a combination of mono-functional monomers, hi yet another embodiment, the present composition comprises at least one mono-functional monomer selected from the group consisting of 2- phenoxyethyl acrylate, 1,4- butanediol dimethacrylate, tetrahydrofurfuryl acrylate, and mixtures thereof. In a further or alternative embodiment, the present composition comprises 2-phenoxyethyl acrylate, 1,4- butanediol dimethacrylate, and tetrahydrofurfuryl acrylate.
- the present composition comprises a combination of monomers, each present in an amount ranging from 4-40% wt/wt, such as from 10 to 30% wt/wt, 10 to 25% wt/wt, or 10 to 15% wt/wt.
- the present composition comprises 2-phenoxyethyl acrylate, 1,4- butanediol dimethacrylate, and tetrahydrofurfuryl acrylate, each present in an amount ranging from 4-40% wt/wt.
- Surfactants are examples of surfactants.
- compositions comprise at least one surfactant.
- Surfactants are employed to impart desirable properties to compositions, such as improved slip, scratch resistance, flow, levelling, release, and defoaming.
- surfactants include, but are not limited to, polymers such as polystyrene, polypropylene, polyesters, styrene-methacrylic acid type copolymers, styrene-acrylic acid type copolymers, polytetrafluoroethylene, polychlorotrifluoroethylene, polyethylenetetrafluoroethylene type copolymers, polyaspartic acid, polyglutamic acid, and polyglutamic acid- ⁇ -methyl esters, and modifiers such as silane coupling agents and alcohols.
- Additional surfactants include olefins, such as polyethylene, polypropylene, polybutadiene, and the like; vinyls, such as polyvinylchlori.de, polyvinylesters, polystyrene; acrylic homopolymers and copolymers; phenolics; amino resins; alkyds, epoxys, siloxanes, nylons, polyurethanes, phenoxys, polycarbonates, polysulfones, polyesters (optionally chlorinated), polyethers, acetals, polyimides, and polyoxyethylenes.
- Further exemplary surfactants include cross-linked as well as non-crosslinked acrylates that are compatible with UV curing compositions, such as crosslinkable silicone acrylate.
- Exemplary surfactants include those manufactured under the name TEGO® Rad by Degussa AG (Essen, Germany) and include TEGO® Rad 2100, 2200, 2250, 2300, 2500, 2600, 2650, and 2700.
- the surfactant(s) are present in the compositions in an amount ranging from 0.01-
- 2.0% wt/wt such as about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0 % wt/wt.
- the present composition comprises at least one diluent.
- the diluent is appropriate for diluting oligomers.
- the present composition comprises a reactive diluent that produces polymers through the formation of free radicals when exposed to a source of actinic radiation, such as ultraviolet light.
- Reactive diluents suitable for addition to the present composition exhibit at least one of the following properties: (a) high UV reactivity; (b) low shrinkage; (c) good balance of hardness and flexibility; (d) high UV stability after polymerization; (e) good viscosity reduction; and/or (f) low toxicity and irritancy.
- Representative diluents include, but are not limited to, isobornyl acrylate, isodecyl acrylate, trimethylolpropane triacrylate (TMPTA), di-trimethylolpropane triacrylate (Di-TMPTA), propoxylated TMPTA (PO6-TMPTA), and combinations thereof.
- TMPTA trimethylolpropane triacrylate
- DI-TMPTA di-trimethylolpropane triacrylate
- PO6-TMPTA propoxylated TMPTA
- diluents that may be employed in the present composition are also categorized as mono-functional or multi-functional monomers, described and listed herein.
- the present composition comprises at least one diluent in an amount ranging from
- the present composition comprises isobornyl acrylate in an amount ranging from 2-20% wt/wt, such as from 5 to 18% wt/wt, 7 to 15% wt/wt, or 10 to 12% wt/wt.
- the present compositions may optionally comprise at least one pigment or pigment dispersion.
- Pigments are insoluble white, black, or colored material, typically suspended in a vehicle for use in a paint or ink, and may also include effect pigments such as micas, metallic pigments such as aluminum, and opalescent pigments.
- Pigments are used in coatings to provide decorative and/or protective functions however, due to their insolubility, pigments may be a possible contributing factor to a variety of problems in liquid coatings and/or dry paint films.
- Examples of some film defects thought to be attributable to pigments include: undesirable gloss due to aggregates, blooming, pigment fading, pigment flocculation and/or settlement, separation of pigment mixtures, brittleness, moisture susceptibility, fungal growth susceptibility, and/or thermal instability.
- organic pigments can be used in the compositions described herein, including, but not limited to, carbon black, azo-pigment, phthalocyanine pigment, thioindigo pigment, anthraquinone pigment, flavanthrone pigment, indanthrene pigment, anthrapyridine pigment, pyranthrone pigment, perylene pigment, perynone pigment and quinacridone pigment.
- Various inorganic pigments can be used in the compositions described herein, for example, but not limited to, titanium dioxide, aluminum oxide, zinc oxide, zirconium oxide, iron oxides: red oxide, yellow oxide and black oxide, Ultramarine blue, Prussian blue, chromium oxide and chromium hydroxide, barium sulfate, tin oxide, calcium, titanium dioxide (rutile and anatase titanium), sulfate, talc, mica, silicas, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, clays such as kaolin clay, muscovite and sericite.
- the present composition comprises polymerizable pigment dispersions that comprise of at least one pigment attached to an activated resin; wherein the activated resin is selected from a group consisting of acrylate resins, methacrylate resins, and vinyl resins, and the pigment is selected from a group consisting of carbon black, rutile titanium dioxide, organic red pigment, phthalo blue pigment, red oxide pigment, isoindoline yellow pigment, phthalo green pigment, quinacridone violet, carbazole violet, masstone black, light lemon yellow oxide, light organic yellow, transparent yellow oxide, diarylide orange, quinacridone red, organic scarlet, light organic red, and deep organic red.
- the activated resin is selected from a group consisting of acrylate resins, methacrylate resins, and vinyl resins
- the pigment is selected from a group consisting of carbon black, rutile titanium dioxide, organic red pigment, phthalo blue pigment, red oxide pigment, isoindoline yellow pigment, phthalo green pigment, quinacridone violet, carbazole violet
- pigment dispersions are distinguishable from other pigment dispersions which disperse insoluble pigment particles in some type of resin and entrap the pigment particles within a polymerized matrix.
- the pigment dispersions used in the compositions and methods described herein have pigments treated such that they are attached to acrylic resins; consequently the pigment dispersion is polymerizable upon exposure to UV irradiation.
- An "ideal" dispersion consists of a homogeneous suspension of primary particles.
- inorganic pigments are often incompatible with the resin in which they are incorporated, and this generally results in the failure of the pigment to uniformly disperse.
- a milling step may be required as dry pigments comprise a mixture of primary particles, aggregates, and agglomerates which must be wetted and de- aggregated before the production of a stable, pigment dispersion is obtained.
- the level of dispersion in a particular pigment-containing coating composition affects the application properties of the composition as well as the optical properties of the cured film. Improvements in dispersion result in improvements in gloss, color strength, brightness, and gloss retention.
- the present composition optionally comprises at least one pigment or pigment dispersion in an amount ranging from 1-12% wt/wt, such as from 3 to 10% wt/wt, or 5 to
- compositions herein may optionally comprise adhesion promoters, corrosion inhibitors, curing boosters, and/or fillers to obtain desirable chemical and mechanical properties.
- Compositions may further comprise additional fillers that are not necessarily nano-fillers, such as amorphous silicon dioxide prepared with polyethylene wax, synthetic amorphous silica with organic surface treatment, IRGANOX ®, untreated amorphous silicon dioxide, alkyl quaternary bentonite, colloidal silica, acrylated colloidal silica, alumina, zirconia, zinc oxide, niobia, titania aluminum nitride, silver oxide, cerium oxides, and combinations thereof. Further, the average size of the filler particles is less than 10 micrometers, or less than 5 micrometers, or even less than 1 micrometer. III. Methods of Using Compositions
- compositions described herein may be applied to fiber substrates to produce fiber products.
- Fiber substrates comprising the present compositions can be exposed to a source of actinic radiation, such as ultraviolet light, to effect curing.
- a source of actinic radiation such as ultraviolet light
- one aspect of the methods described herein is drawn to methods of manufacturing fiber products, said method comprising (a) providing a fiber substrate; (b) applying a composition to said fiber substrate to produce a fiber product; and (c) curing said fiber product, wherein said composition comprises: (i) nano-fillers; (ii) at least one photo-initiator; (iii) at least one mono-functional monomer; (iv) a surfactant; (v) a diluent; and
- any type of substrate that is, composed of, or derived from natural fibers is a suitable fiber substrate.
- the fiber substrates are articles of manufacture.
- the fiber substrates are part of articles of manufacture. Fiber substrates compatible with the present invention possess sufficient wicking action (capillary action) such that when applied, compositions will adhere to the fiber substrate.
- Exemplary fiber substrates include all types of natural fabrics, such as cotton and wool fabrics; natural knits such as cotton and wool knits; paper of all thicknesses, such as tissue, envelopes, newspaper, magazine paper, book paper, business cards, writing paper and cardboard.
- paper substrates may optionally contain writing, such as pencil, staples, clips, perforations, and/or folds.
- Fabric substrates may optionally contain writing, folds, buttons, zippers, and the like.
- Fiber substrates may be of any size or shape, including but not limited to, square, rectangular, angular features, circular, etc.
- Fiber substrates may be provided in any manner sufficient to facilitate applying the present compositions to the fiber substrate, hi an embodiment, fiber substrates may be provided on a spindle or in a roll. In another embodiment, fiber substrates may be laid flatly on a conveyor belt or on a tray. In yet another embodiment, fiber substrates are hung on a moving line. [0093] Fiber substrates encompass:
- paper products such as, but not limited to, stationary paper, writing paper, construction paper, cardboard paper, envelopes, paper bags, paper boxes, packages, paper labels, paper signs, newspaper, book paper, magazine paper, business cards, paper suitable for holding or containing food; freezerwrap, paper drinking cups, cardstock, and the like;
- markers such as, but not limited to, garden markers, underwater markers, soil markers, and the like;
- fiber substrates which have non-fiber components, such as, but not limited to, buttons, zippers, pins, staples, clips, rods, and the like
- compositions are applied to fiber substrates so as to produce fiber products.
- Compositions maybe applied to fiber substrates by means of spraying, brushing, rolling, dipping, blade coating, curtain coating or a combination thereof.
- the means of spraying can include, but is not limited to, the use of a High Volume Low Pressure (HVLP) spraying systems, air-assisted/airless spraying systems, or electrostatic spraying systems.
- HVLP High Volume Low Pressure
- the compositions described herein are sprayed at high- pressure onto a fiber product, including pressures up to 25 psi, up to 30 psi, up to 35 psi, up to 40 psi, up to 45 psi, up to 50 psi, up to 55 psi, up to 60 psi, up to 65 psi, up to 70 psi, up to 80 psi, up to 90 psi, and up to 100 psi.
- Such high-pressure application of the compositions facilitates impregnation of the composition within the fiber product.
- the paper is passed through rollers to assist in the distribution and/or the impregnation of the composition.
- the rollers are hard acrylic rollers.
- the rollers produce a nice, even product.
- the fiber product is paper, card stock, or cardboard. In a further embodiment, such a method allows the use of no more than 0.02 grams of composition per square inch of fiber product.
- the composition is forcibly applied or centrifugally applied onto the fiber substrate, such as by means of a rotating lens.
- the lens is rotated by means of a spinner or reciprocator.
- Application of the composition by means of a rotating lens is advantageous over application by soaking, a wired down rod, or other drawing down methods.
- Application of the composition by means of a rotating lens produces fiber products having more desirable properties than fiber products where compositions are applied by soaking, wired down rod, and other drawing down methods.
- the lens may be made of poly(methyl methacrylate), polyacrylamide, fluoropolymers, silicone polymers, CR-39 polycarbonate, or combinations thereof.
- the lens is composed of polycarbonate, such as a polycarbonate contact lens.
- the lens can be rotated by any acceptable means of achieving rotation, including but not limited to, a spinner or reciprocator.
- the lens is rotated by means of a reciprocator.
- the lens can rotate at any speed suitable to effect application to the fiber substrate.
- the lens can be rotated at about 10, 20, 30, 40, 50, 60, 80, 100, 120, 150, or 200 rotations per minute (RPM).
- assemblages and means for effecting rotation may have standardized speed settings, e.g. slow, medium, high, etc.
- Compositions may be applied to fiber substrates under any standardized speed setting on an assemblage or means for effecting rotation, such as a spinner or reciprocator.
- a metered amount of the composition is delivered to the lens for application to the fiber substrate.
- Compositions may be delivered to the lens via a syringe or pump.
- a syringe or pump that steadily delivers the composition to the lens is employed.
- compositions delivered to the lens depends on the type, shape, and size of the lens as well as the fiber substrate utilized. A larger amount of the composition will be applied to fiber substrates that are larger in size and have higher wicking action in comparison to smaller substrates that have lower wicking action. By way of example only, compositions may be applied to fiber substrates in an amount ranging from 0.01 to 2.0 grams per square inch of substrate, such as about 0.02-1.5, 0.05-1.0, or 0.05-0.1 g/in 2 .
- Fiber substrates may be coated with varying amounts of the present compositions.
- fiber substrates may be partially coated or wholly coated with the present compositions.
- compositions described herein are applied to both sides of a fiber product, using any of the methods described herein, m another embodiment, the compositions described herein are applied to one side of a fiber product, using any of the methods described herein; to prevent curling of the product following and/or during curing, the composition is preferably applied to the back side of the fiber product.
- a roll of paper substrate is drawn out and passed around a lens that is rotating by means of a reciprocator.
- the rotating lens comprises the composition and the composition is outwardly applied to the surface of the paper substrate via the rotating lens.
- paper substrate with an uncured coated surface comprises non- fiber objects such as, but not limited to, metal objects, fiber glass objects, ceramic objects, glass objects, plastic objects, or combinations thereof.
- non-fiber objects such as, but not limited to, metal objects, fiber glass objects, ceramic objects, glass objects, plastic objects, or combinations thereof.
- the surfaces of non-fiber objects become partially covered, or become fully covered by the uncured coating.
- the composition is applied in a single application, or in multiple applications, hi further or alternative embodiments, the composition is applied by a single lens or by multiple lenses. Li further or alternative embodiments, multiple compositions are applied to the fiber substrate. Li further or alternative embodiments, multiple compositions are applied simultaneously or sequentially to the fiber substrate.
- the composition is applied to fiber substrates at ambient temperature, or at temperatures higher or lower than ambient temperature.
- An aspect of the invention is drawn to assemblages for manufacturing fiber products, wherein said assemblages comprise means for applying the present composition to fiber substrates.
- assemblages comprise means for spraying, curtain coating, dipping, rolling, brushing, or throwing the present composition onto the surface of a fiber substrate.
- forcible application or centrifugal application by way of a lens is the most efficacious methods of application, and can be accomplished by delivering a measuring dosed of the composition via a rotating lens.
- An aspect described herein are methods, processes, devices and assemblages for curing fiber substrates comprising the present compositions. Curing can be achieved by exposure to heat or actinic radiation.
- the actinic radiation is selected from the group consisting of visible radiation, near visible radiation, ultra-violet (UV) radiation, and combinations thereof.
- the UV radiation is selected from the group consisting of UV-A radiation, UV-B radiation, UV-C radiation, UV-D radiation, or combinations thereof.
- UV-curable compositions are prepared using a single or mixture of photo-initiators sufficient to encompass all necessary frequencies of light. These are used to work with the lights or light pairs, arranged to ensure complete cure of an object. Polymerization, in particular acrylate double bond conversion and induction period, can be affected by the choice of oligomers, photo-initiators, inhibitors, and pigments, as well as UV lamp irradiance and spectral output. In comparison to clear coat formulations, the presence of pigments may make curing much more complex due to the absorption of the UV radiation by the pigment. Thus, the use of variable wavelength UV sources, along with matching of absorption characteristics of photo-initiators with UV source spectral output, allows for curing of pigmented formulations.
- Light sources used for UV curing include arc lamps, such as carbon arc lamps, xenon arc lamps, mercury vapor lamps, tungsten halide lamps, lasers, the sun, sunlamps, and fluorescent lamps with ultra-violet light emitting phosphors.
- arc lamps such as carbon arc lamps, xenon arc lamps, mercury vapor lamps, tungsten halide lamps, lasers, the sun, sunlamps, and fluorescent lamps with ultra-violet light emitting phosphors.
- Medium pressure mercury and high pressure xenon lamps have various emission lines at wavelengths which are absorbed by most commercially available photo-initiators.
- mercury arc lamps can be doped with iron or gallium.
- lasers are monochromatic (single wavelength) and can be used to excite photo-initiators which absorb at wavelengths that are too weak or not available when using arc lamps.
- medium pressure mercury arc lamps have intense emission lines at 254 nm, 265 nm, 295 nm, 301 nm, 313 nm, 366 nm, 405/408 nm, 436 nm, 546 nm, and 577/579 nm. Therefore, a photo-initiator with an absorbance maximum at 350 nm may not be a efficiently excited using a medium pressure mercury arc lamp, but could be efficiently initiated using a 355 nm Nd:YVO4 (Vanadate) solid-state lasers.
- UV/Visible light sources with varied spectral output in the range of 250-450 nm may be used directly for curing purposes; however wavelength selection can be achieved with the use of optical bandpass or longpass filters. Therefore, as described herein, the user can take advantage of the optimal photo-initiator absorbance characteristics.
- the emission spectra of the lamp must overlap the absorbance spectrum of the photo-initiator. Two aspects of the photo-initator absorbance spectrum need to be considered. The wavelength absorbed and the strength of absorption (molar extinction coefficient).
- the photo-initiators HMPP (2- hydroxy-2- methyl- 1-phenyl-propan-l -one) and TPO (diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide) in DAROCUR ® 4265 (from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.) have absorbance peaks at 270-290 nm and 360-380 nm
- DAROCUR ® 1173 from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.
- ESACURE ® KTO-46 from Lamberti S.p.A., Gallarate (VA), Italy
- IRGACURE ® 907 from Ciba Specialty Chemicals 540 White Plains Road, Tarrytown, New York, U.S.A.
- the addition of pigment to a formulation increases the opacity of the resulting coating and can have an effect on curing abilities. Furthermore, the added pigment can absorb the incident curing radiation and thereby affect the performance of the photo- initiator.
- the curing properties of opaque pigmented coatings can depend on the pigment present, individual formulation, irradiation conditions, and substrate reflection. Therefore consideration of the respective UV/vis absorbance characteristics of the pigment and the photo-initiator can be used to optimize UV curing of pigmented coatings.
- photo-initiators used for curing pigmented formulations have a higher molar extinction coefficient between the longer wavelengths (300 nm-450 nm) than those used for curing clear formulations.
- phosphine oxide type photo-initiators for example but not limited to bis acylphosphine oxide, are effective in pigmented, including, by way of example only, black, UV-curable coating materials. Phosphine oxides also find use as photo-initiators for white coatings, and enable an effective through cure for the compositions described herein.
- the mercury gas discharge lamp is the UV source most widely used for curing, as it is a very efficient lamp with intense lines UV-C (200-280 nm) radiation, however it has spectral emission lines in the UV-A (315-400 nm) and in the UV-B (280-513 nm) regions.
- the mercury pressure strongly affects the spectral efficiency of this lamp in the UV-A, UV-B and UV-C regions.
- the mercury spectrum can be strongly changed mainly in the UV-A, but also in the UV-B and UV-C regions.
- Doped gallium gives intensive lines at 403 and 417 nm; whereas doping with iron raises the spectral radiant power in the UV-A region of 358-388 nm by a factor of 2, while because of the presence of iodides UV-B and UV-C radiation are decreased by a factor of 3 to 7.
- the presence of pigments in a coating formulation can absorb incident radiation and thereby affect the excitation of the photo-initiator.
- an iron doped mercury arc lamp (emission 358-388 nm) is ideal for use with photo- initiator ESACURE ® KTO-46 (from Lamberti S. p. A., Gallarate (VA), Italy) (absorbance between 245 and 378 nm).
- Multiple lamps with a different spectral characteristics, or sufficiently different in that there is some spectral overlap, can be used to excite mixtures of photo-initiator or mixtures of photo-initiators and co-initiators.
- a iron doped mercury arc lamp emission 358-388 nm
- a pure mercury arc lamp emission 200-280 nm
- the order in which the excitation sources are applied can be adventitiously used to obtain enhanced coating characteristic, such as, by way of example only, hardness, smoothness, shine, adhesion, abrasion resistance, scratch resistance, impact resistance and corrosion resistance.
- Initial exposure of the coated surface with the longer wavelength source is beneficial, as it traps the nano-filler particle in place and initiates polymerization near the surface, thereby imparting a smooth and adherent coating.
- shorter wavelength radiation enables for a fast cure of the remaining film that has been set in place by the initial polymerization stage.
- the time of exposure to each lamp type can be manipulated to enhance the curing of the compositions described herein.
- One approach used for curing of the compositions described herein used to coat surfaces of wooden objects is to expose the coated surface to the longer wavelength doped mercury arc lamps for a shorter time than exposure to the shorter wavelength mercury arc lamp.
- this exposure scheme may cause the cured coatings to wrinkle/crmkle. Therefore, other exposure schemes involve identical exposure time for both the short wavelength mercury arc lamp, and the longer wavelength doped mercury arc lamps, or alternatively the exposure time to the longer wavelength doped mercury arc lamp can be longer than the time of exposure for the short wavelength mercury arc lamps.
- fiber substrates comprising the present compositions are exposed to a mercury arc lamp.
- the time period for exposing fiber products to actinic radiation is less than 2 minutes. In further embodiments, the time period for exposing fiber products to actinic radiation is less than 1 minute. In further embodiments, the time the time period for exposing fiber products to actinic radiation is less than 15 seconds.
- Fiber products can optionally be exposed to two sources of actinic radiation.
- the time between the first actinic radiation step and the second actinic radiation step is less than 2 minutes. In further embodiments, the time between the first actinic radiation step and the second actinic radiation step is less than 1 minute. In further embodiments, the time between the first actinic radiation step and the second actinic radiation step is less than 15 seconds.
- the length of time of the first actinic radiation step is shorter than the length of time of the second actinic radiation step. In further or alternative embodiments, the length of time of the first actinic radiation step is longer than the length of time of the second actinic radiation step, m further or alternative embodiments, the length of time of the first actinic radiation step is identical to the length of time of the second actinic radiation step.
- Embodiments include fiber products comprising the present compositions which exhibit at least one, two, or three of the following characteristic upon curing: (a) retention of writability of pen and/or ink; (b) retention of print; and/or (c) retention of brightness.
- cured fiber products exhibit at least one, two, three, or four of the following characteristics after exposure to water for at least 1 day: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- assemblages for manufacturing fiber products, wherein said assemblages comprise means for curing fiber substrates comprising the present composition.
- assemblages comprise an irradiation station that includes at least one light capable of providing actinic radiation selected from the group consisting of visible radiation, near visible radiation, ultra-violet (UV) radiation, and combinations thereof.
- the irradiation station includes at least one light source capable of providing actinic radiation selected from the group consisting of UV-A radiation, UV-B radiation, UV-B radiation, UV-C radiation, UV-D radiation, or combinations thereof.
- compositions for instance, by way of example only, at least one nano-filler, at least one photo-initiator, at least one mono- functional monomer, at least one surfactant, a diluent, and optionally at least one pigment dispersion and a second photo-initiator, and using a means for mixing the components together to form a smooth composition, hi further or alternative embodiments, the composition may be mixed in or transferred to a suitable container, such as, but not limited to, a can.
- a suitable container such as, but not limited to, a can.
- Fiber products produced by the present methods and assemblages exhibit at least one, two, or three of the following characteristis: (a) retention of writability of pen and/or ink; (b) retention of print; and/or (c) retention of brightness.
- fiber products produced by the present methods and assemblages exhibit at least one, two, three, or four of the following characteristics after exposure to water for at least 1 day: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- assemblages comprise means for mixing components of the present compositions, hi a further or alternative embodiment, assemblages comprise means for providing a fiber substrate. In a further or alternative embodiment, assemblages comprise means for applying the present composition to a fiber substrate. In a further or alternative embodiment, assemblages comprise means for curing fiber substrates comprising applied compositions.
- Fiber substrates may be provided in any manner sufficient to facilitate applying the present compositions to the fiber substrate.
- fiber substrates are provided on a spindle or in a roll, hi another embodiment, fiber substrates may be laid flatly on a conveyor belt or on a tray. In yet another embodiment, fiber substrates are hung on a moving line.
- Means for curing the fiber substrates may comprise irradiating substrates comprising the present composition so as to partially or completely cure the surface at an irradiation station, hi an embodiment, irradiation and curing is accomplished at a single station so as to not require the transport of the object, hi still a further embodiment, the means for applying the composition is located at an application station, wherein the object must be moved from the application station to the irradiation station. In yet a further embodiment, such assemblages further comprise a means for moving the object from the application station to the irradiation station. In still yet a further embodiment, the means for moving comprises a conveyer belt.
- the irradiation station comprises a means for limiting the exposure of actinic radiation to the application station.
- assemblages further comprise a means for rotating the substrate around at least one axis, hi yet further or alternative embodiment, assemblages further comprise a mounting station wherein the substrate to be applied with the composition is attached to a movable unit, hi further embodiments, the movable unit is capable of rotating the substrate around at least one axis. In further or alternative embodiments, the movable unit is capable of moving the substrate from the application station to the irradiation station.
- such assemblages further comprise a removal station wherein the completely cured fiber product is removed from the movable unit, hi further embodiments, the completely cured fiber product does not require cooling prior to removal from the movable unit.
- the application station further comprises a means for reclaiming composition that is non-adhering to the surface of the fiber substrate.
- the reclaimed composition is subsequently applied to a different substrate.
- the assemblage comprise a source of actinic radiation selected from the group consisting of visible radiation, near visible radiation, ultra-violet (UV) radiation, and combinations thereof.
- the assemblage comprise multiple sources of actinic radiation.
- the irradiation station includes an arrangement of mirrors.
- processes further comprise attaching the fiber substrate to a rotatable spindle prior to the application step.
- processes further comprise moving the conveying means after attaching the object to the rotatable spindle so as to locate the object near an application station.
- processes further comprise applying the present composition at the application station as the spindle holding the object rotates.
- the conveying means comprises a conveyer belt.
- the irradiation station comprises a curing chamber containing a first actinic radiation source and a second actinic radiation source.
- such processes further comprise moving the completely cured product via the conveying means outside the curing chamber wherein the product is packed for storage or shipment.
- the irradiation station includes an arrangement of mirrors such that the applied surface is cured in three dimensions, hi further or alternative embodiments, the irradiation station includes an arrangement of light sources such that the coated surface is cured in three dimensions, hi further embodiments, each light source emits different spectral wavelength ranges, hi further embodiments, the different light sources have partially overlapping spectral wavelength ranges.
- production lines for applying at least a portion of a surface of a fiber substrate with the present composition comprising a process which comprises attaching the substrate onto a conveying means; applying the present composition at an application station onto the surface of the fiber substrate; moving the applied substrate via the conveying means to an irradiation station; irradiating and partially or wholly curing the applied surface at the irradiation station with actinic radiation; wherein the fiber product upon curing exhibit at least one, two, or three of the following characteristics: (a) retention of writability of pen and/or ink; (b) retention of print; and/or (c) retention of brightness.
- fiber products produced by the present production lines exhibit at least one, two, three, or four of the following characteristics after exposure to water for at least 1 day: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- facilities or factories for producing fiber products comprising at least one process line for applying at least a portion of a surface of a fiber substrate with the present composition comprising a process which comprises attaching the substrate onto a conveying means; at least one process line for applying the present composition at an application station onto the surface of the fiber substrate; at least one process line for moving the applied substrate via the conveying means to an irradiation station; and at least one process line for irradiating and partially or wholly curing the applied surface at the irradiation station with actinic radiation; wherein the fiber product upon curing exhibit at least one, two, or three of the following characteristics: (a) retention of writability of pen and/or ink; (b) retention of print; and/or (c) retention of brightness.
- fiber products produced by the present production lines exhibit at least one, two, three, or four of the following characteristics after exposure to water for at least 1 day: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- Fiber products provided herein are fiber substrates comprising the present compositions, hi further or alternative embodiments, the entire surface or just a portion of the surface of fiber products comprise the present compositions.
- the present composition may be sparingly applied or heavily applied to the fiber substrate.
- fiber products that comprise the present compositions may be uncured, partially cured, or completely cured.
- the present composition upon curing provides at least one, two, or three of the following characteristics to the fiber product: (a) retention of writability of pen and/or ink; (b) retention of print; and/or (c) retention of brightness.
- fiber product exhibits at least one, two, or three of the following characteristics: (a) retention of writability of pen and/or ink; (b) retention of print; and/or (c) retention of brightness.
- the present composition upon curing provides at least one, at least two, at least three, or at least four of the following characteristics to the fiber product after exposure to water: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- fiber product exhibits the following characteristics after exposure to water for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 40, 45, 50, 55, and 60 days: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- fiber product exhibits the following characteristics after exposure to water for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 40, 45, 50, 55, and 60 days: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and/or (d) retention of brightness.
- Exposure to water can constitute partial or complete exposure to water.
- exposure to water can include exposure to moisture, such as mist, fog, and pressurized water vapor.
- exposure to water can constitute exposure to water-containing weather, such as rain, drizzle, snow, sleet, fog, hail, and the like.
- exposure to water can constitute partial or complete submersion of an object in water.
- exposure to water can be continuous, consecutive, or intermittent.
- objects exposed to water can be submerged underwater or laying in a pool of water.
- newspaper-grade paper is impregnated/coated and cured with the compositions described herein using the methods described herein.
- the newspaper is then printed using standard techniques.
- the resulting newspaper retains (a) structural strength; (b) print; and (d) brightness, even upon continuous exposure to water for several days or weeks.
- a similar procedure produces magazine, books (including cookbooks), maps, field guides, business cards, envelopes, packaging material and cardboard with similar properties.
- the resulting fiber product is paper suitable for further printing using a standard laser printer, ink-jet printer, or typewriter. Further, the applied print can be black ink, white ink or any color ink (and combinations thereof).
- the resulting printed paper product retains (a) structural strength; (b) print; and (d) brightness, even upon continuous exposure to water for several days or weeks.
- compositions described herein are coated/impregnated as described herein onto food grade paper as described herein and the resulting product used to wrap a food product.
- the resulting food grade paper retains (a) structural strength; (b) print; and (d) brightness, even upon continuous exposure to the food product for several days or weeks.
- a food product includes water, drinks, ice cream, beer, wine, soup, and coffee.
- compositions described herein are coated/impregnated as described herein onto paper as described herein and the resulting product used as a reliable, portable, dry-erase board. That is, dry-erase markers can readily write on the paper product, and the resulting writing can be erased using a standard dry-erase eraser.
- the reliable, portable, dry-erase board can be used multiple times without loss of structural strength, writability or durability.
- compositions described herein are coated/impregnated as described herein onto a shower curtain as described herein and the resulting product used as a shower curtain.
- the resulting shower curtain resists the growth of mold and mildew.
- compositions possess excellent durability and are suitable for surfaces of fiber products which encounter physical wearing or exposure to various weather conditions.
- Various mechanical properties of solid coatings and the various testing methods for them is described in "Mechanical Properties of Solid Coatings" Encyclopedia of Analytical Chemistry, John Wiley & Sons, 2000, which is herein incorporated by reference in its entirety. Descriptions for the following tests are provided by way of example only.
- compositions and methods described herein provide an improved cured product that exhibits improvement in at least one of the following properties: (a) retention of writability of pen and/or ink; (b) retention of print; and (c) retention of brightness.
- compositions and methods described herein provide an improved cured product that exhibits improvement in at least one of the following properties: (a) retention of structural strength; (b) retention of ink or pencil writing; (c) retention of print; and (d) retention of brightness.
- Retention of brightness prevents discoloration, such as darkening or yellowing, of a material.
- Retention of ink or pencil writing refers to the ability of ink or pencil writing to be retained on a material. Retention of ink or pencil writing prevents bleeding, fading, and/or streaking on a material.
- Representative tests for determining retention of ink or pencil writing include spectrophotometric tests, such as the Ink Elimination (IE) test and the Effective Residual Ink Concentration (ERIC) test, for example
- Retention of print refers to the ability of print to be retained on a material.
- Representative prints include various ink prints, such as labels, logos, and the like. Retention of print prevents bleeding, fading, and/or streaking on a material.
- Representative tests for determining retention of print include various spectral photometric tests.
- Retention of structural strength refers to the ability of a material to retain its physical and structural integrity, strength, or durability. Retention of structural strength prevents tearing, ripping, or breaks. Representative mechanical tests for determining retention of structural strength include manual inspection, folding endurance, and tensile strength, for example. Spectral photometric tests may also be employed to determine retention of structural strength.
- Retention of writability of pencil and/or ink refers to the ability of a material to retain its ability to be written upon by any type of pencil or any source of ink, such as a pen or printer. Writability depends on the absorbency of a material.
- Resistance to the growth of mold, bacteria, and/or fungus refers to the ability of the material to inhibit or slow down the growth of these of mold, bacteria, and/or fungus. This characteristic can be tested by streaking a mold, bacteria, and/or fungus on the coating and/or cured fiber product and comparing the growth of the mold, bacteria, and/or fungus relative to an uncoated and/or uncured fiber product.
- an embodiment for a clear composition is prepared by mixing 21.45% tetrahydofurfuryl acrylate; 11.98% isobornyl acrylate; 12.56% 1,4- butanediol dimethacrylate; 13.62% 2-phenoxyethyl acrylate; 34.91% Nanocryl C-155 (available from Hansiechemie, Germany) ; 2.00% Irgacure 500 (available from Ciba Specialty Chemicals); 3.43% Irgacure 184 (available from Ciba Specialty Chemicals); and 0.05% Tego Rad 2100 (available from Tego Chemie). These components are thoroughly mixed by the helical mixer until a homogeneous composition is produced.
- Irgacure 500 0.5-10 wt/wt%
- Example 2 Formulation for pigmented composition.
- An embodiment for a pigmented composition is prepared by mixing 21.45% tetrahydofurfuryl acrylate; 11.98% isobornyl acrylate; 12.56% 1,4-butanediol dimethacrylate; 13.62% 2-phenoxyethyl acrylate; 34.91% Nanocryl C-155 (available from Hansiechemie, Germany) ; 2.00% Irgacure 500 (available from Ciba Specialty Chemicals); 3.43% Irgacure 184 (available from Ciba Specialty Chemicals); 0.05% Tego Rad 2100 (available from Tego Chemie); 1-12% PC 9003, and 0.5 - 5.0% Lucerin TPO. These components are thoroughly mixed by the helical mixer until a homogeneous composition is produced.
- Example 3 Procedure used for making clear compositions.
- a further embodiment is the procedure used for making the present compositions.
- the components of the composition are mixed under air, as the presence of oxygen prevents premature polymerization. It is desired that exposure light be kept to a minimum, in particularly the use of sodium vapor lights should be avoided. However, the use of darkroom lighting may be an option.
- the components used in the manufacture of the composition which come in contact with monomers and coating mixture should be made of stainless steel or plastic, preferably polyethylene or polypropylene. Polystyrene and PVC should be avoided, as the monomers and mixture will dissolve them. In addition, contact of the monomers and mixture with mild steel, alloys of copper, acids, bases, and oxidizers should be avoided. Furthermore, brass fittings must be avoided, as they will cause premature polymerization or gelling.
- Adequate mixing of the composition can be obtained after 1-3 hours using a 1/3 horse power (hp) mixer and a 50 gallon cylindrical tank. Smaller quantities, up to 5 gallons, can be adequately mixed after 3 hours using a laboratory mixer (1/15 - 1/10 hp). Round walled vessels are desired as this avoids accumulation of materials in corners and any subsequent problems associated with incomplete mixing.
- Another parameter is that the mixers blades should be placed off of the bottom of the mixing vessel, at a distance of one half of the diameter of the mixer. The monomers are added to the mixing vessel first, and if necessary the monomers are gently warmed to aid in handling. Monomers should not be heated over 120 0 F, therefore if warming is needed the use of a temperature controlled heating oven or heating mantle is recommended.
- Example 4 Procedure used for making pigmented compositions
- a further embodiment is the manufacture procedure for pigmented compositions.
- a mixer of sufficient power and configuration is used to create laminar flow and efficiently bring the pigment dispersions against the blades of the mixer.
- a laboratory mixer or blender is sufficient, however for quantities of up to half of a gallon a 1/15 - 1/10 hp laboratory mixer can be used, but mixing will take several days.
- a helical or saw-tooth mixer of at least 30 hp with a 250 gallon round walled, conical bottomed tank may be used.
- a clear composition is mixed first, see Example 3. The pigment dispersion mixtures are premixed prior to addition to the clear composition as this ensures obtaining the correct color.
- the premixing of the pigments dispersions is easily achieved by shaking the pigments dispersion in a closed container, while wearing a dust mask.
- the fillers, the premixed pigments/pigment dispersions, and solid photo- initiator are then added to the clear composition and mixed for 1 1 A to 2 hours.
- Completeness of mixing is determined by performing a drawdown and checking for un- dissolved pigment. This is accomplished by drawing off a small quantity of the pigmented mixture from the bottom of the mixing tank and applying a thin coating onto a surface. This thin coating is then examined for the presence of any pigment which had not dissolved. The mixture is then run through a 100 mesh filter. A thoroughly mixed pigmented composition will show little or no un-dissolved pigment.
- Example 5 Process for applying compositions to the surface of paper and curing the paper.
- composition Applying composition to a sheet of paper
- FIG. 2 An embodiment for applying the composition as described in Examples 1 and 2 to the surface of a sheet of paper is illustrated in Figure 2.
- the sheet of paper is positioned proximately to a rotating lens that contains the composition, hi this embodiment, the lens is rotated in a counter-clock wise direction by a rotating spindle. As the lens rotates, the composition is thrown onto the sheet of paper. A metered amount of the composition is continuously added to the lens, via a syringe or pump, until the surface of the paper is covered with the composition.
- an 8.5" x 11" sheet of stationary paper was heavily coated with the composition of Example 1 and weighed. The difference in weight between the coated paper and an uncoated paper was calculated. An amount of 0.057g of composition was applied per square inch of the paper, which corresponded to about 5.55g of composition for an 8.5" x 11" sheet.
- an 8.5" x 11" sheet of stationary paper was coated with a smaller amount of the composition of Example 1 and weighed. The difference in weight between the coated paper and an uncoated paper was calculated. An amount of 0.04425 g of composition was applied per square inch of the paper, which corresponded to about 4.14 of composition for an 8.5" x 11" sheet.
- an 8.5" x 11" sheet of stationary paper was coated with the composition of Example 2, wherein said composition comprised 9.3% white pigment dispersion.
- the difference in weight between the coated paper and an uncoated paper was calculated.
- An amount of 0.04025g of composition was applied per square inch of the paper, which corresponded to about 3.74 g of composition for an 8.5" x 11" sheet.
- Other sheets having less composition applied to the surface was also obtained.
- FIG. 3 An embodiment for applying the composition as described in Examples 1 and 2 to the surface of paper in a roll is illustrated in Figure 3.
- the roll of paper is positioned proximately to a rotating lens and drawn past the lens.
- the lens contains the composition and a metered amount of the composition is continuously added to the lens, via a syringe or pump.
- the lens can rotate in a clockwise or counter-clock wise direction by a rotating spindle. As the lens rotates, the composition is thrown onto the roll of paper. A metered amount of the composition is continuously added to the lens and applied to the paper until the surface of the paper is covered with the composition.
- compositions of Example 1 exposure to the coated paper to one mercury arc lamp is sufficient to effect curing.
- compositions of Example 2 exposure to the coated paper to two mercury arc lamps is sufficient to effect curing, where one lamp can be a mercury arc lamp and the other lamp can be a mercury arc lamp doped with iron, to ensure proper curing.
- the time of exposure to the doped mercury arc lamp is less than the time of exposure to the pure mercury arc lamp. Both lamps are turned off and the cured paper is then removed.
- Example 6 Representative Properties of Cured Paper.
- Cured paper made according to Example 5 exhibited comparable writability for both pencil and ink as paper not comprising the composition. The presence of the composition did not impair the ability of pencil or ink to be absorbed onto the cured paper. Cured paper made according to Example 5 exhibited comparable brightness and luminosity in comparison to paper not comprising the composition. In comparison to paper not comprising the composition, printed paper cured according to Example 5 retained the print after the composition was applied and after the paper was cured.
- the print of the cured paper was retained after soaking in water for 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 25, 30, 35, 40, 45, 50, 55, and 60 consecutive days. No apparent bleeding, streaking, or fading of the print had occurred.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2005336938A AU2005336938A1 (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
BRPI0520559-0A BRPI0520559A2 (en) | 2005-09-23 | 2005-09-23 | composition, paper product, and papermaking process |
CNA200580052019XA CN101304872A (en) | 2005-09-23 | 2005-09-23 | Combination for impregnating paper articles and natural fibre, as well as method, technique and apparatus thereof |
EP05801000A EP1945447A1 (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
PCT/US2005/034299 WO2007040493A1 (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
EA200800906A EA200800906A1 (en) | 2005-09-23 | 2005-09-23 | COMPOSITIONS FOR IMPLEMENTATION OF PAPER PRODUCTS AND NATURAL TISSUES AND METHODS, METHODS AND MEANS USING THESE COMPOSITIONS |
MX2008003799A MX2008003799A (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor. |
CA002622992A CA2622992A1 (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
JP2008532199A JP2009509023A (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fibers, methods, processes and assembly therefor |
IL190356A IL190356A0 (en) | 2005-09-23 | 2008-03-20 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2005/034299 WO2007040493A1 (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
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WO2007040493A1 true WO2007040493A1 (en) | 2007-04-12 |
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PCT/US2005/034299 WO2007040493A1 (en) | 2005-09-23 | 2005-09-23 | Compositions for impregnating paper products and natural fabrics and methods, processes and assemblages therefor |
Country Status (10)
Country | Link |
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EP (1) | EP1945447A1 (en) |
JP (1) | JP2009509023A (en) |
CN (1) | CN101304872A (en) |
AU (1) | AU2005336938A1 (en) |
BR (1) | BRPI0520559A2 (en) |
CA (1) | CA2622992A1 (en) |
EA (1) | EA200800906A1 (en) |
IL (1) | IL190356A0 (en) |
MX (1) | MX2008003799A (en) |
WO (1) | WO2007040493A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012085879A1 (en) | 2010-12-22 | 2012-06-28 | Fondazione Istituto Italiano Di Tecnologia | A process for providing hydrorepellent properties to a fibrous material and thereby obtained hydrophobic materials |
WO2012176126A1 (en) * | 2011-06-21 | 2012-12-27 | Basf Se | Printing diffraction gratings on paper and board |
US20130292279A1 (en) * | 2012-05-04 | 2013-11-07 | R.J. Reynolds Tobacco Company | Transparent moisture barrier coatings for containers |
WO2015049262A1 (en) * | 2013-10-04 | 2015-04-09 | Basf Se | High gloss metal effect papers |
US9358576B2 (en) | 2010-11-05 | 2016-06-07 | International Paper Company | Packaging material having moisture barrier and methods for preparing same |
US9365980B2 (en) | 2010-11-05 | 2016-06-14 | International Paper Company | Packaging material having moisture barrier and methods for preparing same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103669110B (en) * | 2013-11-14 | 2017-01-11 | 华南理工大学 | Luminous plant fiber and preparation method thereof |
CN106544927B (en) * | 2016-11-23 | 2018-06-19 | 宁波弘泰包装新材料科技有限公司 | PaperTray and preparation method thereof |
EP3695724A4 (en) * | 2017-10-12 | 2021-06-09 | Ibiden Co., Ltd. | Antiviral substrate, antiviral composition, method for manufacturing antiviral substrate, antimicrobial substrate, antimicrobial composition and method for manufacturing antimicrobial substrate |
CN112647359A (en) * | 2020-12-14 | 2021-04-13 | 台州市路桥瑞康家庭用品厂 | Antibacterial paper cup and production method thereof |
WO2023171023A1 (en) * | 2022-03-08 | 2023-09-14 | Dic株式会社 | Active energy ray-curable resin composition, cured product, laminate ,and article |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020149659A1 (en) * | 2001-01-08 | 2002-10-17 | Dong Wu | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
US20050171227A1 (en) * | 2004-02-04 | 2005-08-04 | Ecology Coatings, Inc. | Environmentally friendly, 100% solids, actinic radiation curable coating compositions and coated surfaces and coated articles thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4224008B2 (en) * | 2003-09-19 | 2009-02-12 | 株式会社リコー | Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and image forming process cartridge |
-
2005
- 2005-09-23 EA EA200800906A patent/EA200800906A1/en unknown
- 2005-09-23 CA CA002622992A patent/CA2622992A1/en not_active Abandoned
- 2005-09-23 JP JP2008532199A patent/JP2009509023A/en active Pending
- 2005-09-23 AU AU2005336938A patent/AU2005336938A1/en not_active Abandoned
- 2005-09-23 WO PCT/US2005/034299 patent/WO2007040493A1/en active Application Filing
- 2005-09-23 EP EP05801000A patent/EP1945447A1/en not_active Withdrawn
- 2005-09-23 CN CNA200580052019XA patent/CN101304872A/en active Pending
- 2005-09-23 BR BRPI0520559-0A patent/BRPI0520559A2/en not_active IP Right Cessation
- 2005-09-23 MX MX2008003799A patent/MX2008003799A/en unknown
-
2008
- 2008-03-20 IL IL190356A patent/IL190356A0/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020149659A1 (en) * | 2001-01-08 | 2002-10-17 | Dong Wu | Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles |
US20050171227A1 (en) * | 2004-02-04 | 2005-08-04 | Ecology Coatings, Inc. | Environmentally friendly, 100% solids, actinic radiation curable coating compositions and coated surfaces and coated articles thereof |
Non-Patent Citations (2)
Title |
---|
"Achieving Adhesion Using a Low Skin and Eye Irritation Tetrahydrofurfuryl Acrylate Based Monomer", SARTOMER APPLICATION BULLETIN, XX, XX, 1 March 2003 (2003-03-01), XX, pages 1 - 3, XP003011364 * |
"Adhesion of Radiation Cured Coatings to Plastics", SARTOMER APPLICATION BULLETIN, XX, XX, 1 March 2003 (2003-03-01), XX, pages 1 - 7, XP003011363 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9358576B2 (en) | 2010-11-05 | 2016-06-07 | International Paper Company | Packaging material having moisture barrier and methods for preparing same |
US9365980B2 (en) | 2010-11-05 | 2016-06-14 | International Paper Company | Packaging material having moisture barrier and methods for preparing same |
WO2012085879A1 (en) | 2010-12-22 | 2012-06-28 | Fondazione Istituto Italiano Di Tecnologia | A process for providing hydrorepellent properties to a fibrous material and thereby obtained hydrophobic materials |
WO2012176126A1 (en) * | 2011-06-21 | 2012-12-27 | Basf Se | Printing diffraction gratings on paper and board |
US8993219B2 (en) | 2011-06-21 | 2015-03-31 | Basf Se | Printing diffraction gratings on paper and board |
US10322603B2 (en) | 2011-06-21 | 2019-06-18 | Basf Se | Printing diffraction gratings on paper and board |
US10625534B2 (en) | 2011-06-21 | 2020-04-21 | Basf Se | Printing diffraction gratings on paper and board |
US20130292279A1 (en) * | 2012-05-04 | 2013-11-07 | R.J. Reynolds Tobacco Company | Transparent moisture barrier coatings for containers |
WO2015049262A1 (en) * | 2013-10-04 | 2015-04-09 | Basf Se | High gloss metal effect papers |
EP3052701B1 (en) | 2013-10-04 | 2017-06-28 | Basf Se | High gloss metal effect papers |
US10494766B2 (en) | 2013-10-04 | 2019-12-03 | Basf Se | High gloss metal effect papers |
Also Published As
Publication number | Publication date |
---|---|
AU2005336938A2 (en) | 2008-05-08 |
EP1945447A1 (en) | 2008-07-23 |
CA2622992A1 (en) | 2007-04-12 |
BRPI0520559A2 (en) | 2009-06-13 |
CN101304872A (en) | 2008-11-12 |
MX2008003799A (en) | 2008-09-30 |
AU2005336938A1 (en) | 2007-04-12 |
IL190356A0 (en) | 2009-09-22 |
EA200800906A1 (en) | 2008-10-30 |
JP2009509023A (en) | 2009-03-05 |
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