权利要求：
1. A method for manufacturing a deflection member, the method comprising the steps of:
a. incorporating a monomer;
b. incorporating a photoinitiator system;
c. incorporating a photoinhibitor;
d. incorporating a reinforcing member;
e. combining the monomer, photoinitiator system, and photoinhibitor to form a photopolymer resin;
f. exposing the photopolymer resin to a first wavelength;
g. exposing the photopolymer resin to a second wavelength; and
h. polymerizing the monomer to form a protuberance extending from the reinforcing member.
2. The method of claim 1, wherein the protuberance is locked-on to the reinforcing member.
3. The method of claim 1, wherein the monomer comprises one or more materials selected from the group consisting of di-functional monomers, tri-functional monomers, multi-functional monomers, monomethacrylates, dimethacrylates, trimethacrylates, multi-functional methacrylates, monoacrylates, diacrylates, triacrylates, multi-functional acrylates, epoxy acrylates, acrylate functional polyether polyols, methacrylate functional polyether polyols, acrylate functional polyester polyols, methacrylate functional polyester polyols, acrylate functional polyurethanes, methacrylate functional polyurethanes, prepolymers, oligomers, and combinations thereof.
4. The method of claim 1, wherein the photoinitiator system comprises one or more materials selected from the group consisting of acylphosphine oxides, bis-acyl phospine oxides, camphorquinone, benzophenone, 7-diethylamino-3-thenoylcoumarin, alkyl ethers of benzoin, diphenoxy benzophenone, benzildimethylketal, halogenated functional benzophenones, amino functional benzophenones, benzils, benzimidazozles, 2-hydroxy-2-methylphenol-1-propanone, fluorenone, fluorenone derivatives, 2,2-diethoxyacetophenone, benzoin, 9,10-phenanthrenequinone, anthraquinone derivatives, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)butanone, zanthone, zanthone derivatives, halogenated acetophenone, halogenated acetophenone derivatives, thioxanthone, thioxanthone derivatives, sulfonyl chlorides of aromatic compounds, diacetyl, furil, anisil, 4,4′-dichlorobenzil, 4,4′-dialkoxybenzil, phenylpropanedione, acylphosphine oxides, 2-(dimethylamino)ethyl methacrylate, diphenyliodonium hexafluorophosphate, diphenyliodonium chloride, ethyl-4-(dimethylamino)benzoate, and combinations thereof.
5. The method of claim 1, wherein the photoinhibitor comprises one or more materials selected from the group consisting of 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole; hexaarylbiimidazole (HABI); bridged HABI; 2-(2-methoxyphenyl)-1-[2-(2-methoxyphenyl)-4,5-diphenyl-2H-imidazol-2-yl]-4,5-diphenyl-1H-imidazole; 2-(2-ethoxyphenyl)-1-[2-(2-ethoxyphenyl)-4,5-diphenyl-2H-imidazol-2-yl]-4,5-diphenyl-1H-imidazole; 2,2′,4-tris-(2-Chlorophenyl)-5-(3,4-dimethoxyphenyl)-4′,5′-diphenyl-1,1′-biimidazole; zinc dimethyl dithiocarbamate; zinc diethyl dithiocarbamate; zinc dibutyl dithiocarbamate; nickel dibutyl dithiocarbamate; zinc dibenzyl dithiocarbamate; tetramethylthiuram disulfide; tetraethylthiuram disulfide (TEDS); tetramethylthiuram monosulfide; tetrabenzylthiuram disulfide; tetraisobutylthiuram disulfide; dipentamethylene thiuram hexasulfide; N,N′-dimethyl N,N′-di(4-pyridinyl)thiuram disulfide; 3-Butenyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate; 4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid; 4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol; Cyanomethyl dodecyl trithiocarbonate; Cyanomethyl [3-(trimethoxysilyl)propyl] trithiocarbonate; 2-Cyano-2-propyl dodecyl trithiocarbonate; S,S-Dibenzyl trithiocarbonate; 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid; 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid N-hydroxysuccinimide; Benzyl 1H-pyrrole-1-carbodithioate; Cyanomethyl diphenylcarbamodithioate; Cyanomethyl methyl(phenyl)carbamodithioate; Cyanomethyl methyl(4-pyridyl)carbamodithioate; 2-Cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate; Methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate; 1-Succinimidyl-4-cyano-4-[N-methyl-N-(4-pyridyl)carbamothioylthio]pentanoate; Benzyl benzodithioate; Cyanomethyl benzodithioate; 4-Cyano-4-(phenylcarbonothioylthio)pentanoic acid; 4-Cyano-4-(phenylcarbonothioylthio)pentanoic acid N-succinimidyl ester; 2-Cyano-2-propyl benzodithioate; 2-Cyano-2-propyl 4-cyanobenzodithioate; Ethyl 2-(4-methoxyphenylcarbonothioylthio)acetate; 2-Phenyl-2-propyl benzodithioate; Cyanomethyl methyl(4-pyridyl)carbamodithioate; 2-Cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate; Methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate; 1,1′-Bi-1H-imidazole; functional variants of any of the one or more materials; and combinations thereof.
6. The method of claim 1, wherein the reinforcing member comprises one or more materials selected from the group consisting of woven fabric, nonwoven fabric, natural fibers, synthetic fibers, metallic fibers, carbon fibers, silicon carbide fibers, fiberglass, mineral fibers, polymer fibers, polyethylene terephthalate (“PET”), PBT polyester, phenol-formaldehyde (PF), polyvinyl chloride fiber (PVC), polyolefins (PP and PE), acrylic polyesters, aromatic polyamids (aramids), polytetrafluoroethylene, polyethylene (PE), polyphenylene sulfide (“PPS”), elastomers, and combinations thereof.
7. The method of claim 1, wherein the monomer, photoinitiator system, photoinhibitor, and optionally a solvent form a solution.
8. The method of claim 1, wherein the first wavelength has a first range within from about 100 nm to about 1400 nm and results in photoinitiation of the photopolymer resin.
9. The method of claim 1, wherein the second wavelength has a second range within from about 100 nm to about 1400 nm and results in photoinhibition of the photopolymer resin.
10. The method of claim 9, wherein the first range is different from the second range.
11. The method of claim 9, wherein the first range and second range at least partially overlap.
12. The method of claim 1, wherein the method further comprises a third wavelength, wherein the third wavelength has a third range within from about 100 nm to about 1400 nm and results in photoinhibition of the photopolymer resin.
13. The method of claim 1, wherein a viscosity of the photopolymer resin is from about 100 cP to about 2000000 cP.
14. The method of claim 1, further comprising polymerizing the monomer to form a plurality of protuberances to form a resinous framework.
15. The method of claim 14, wherein a first portion of the plurality of protuberances are at a first elevation and wherein a second portion of the plurality of protuberances are at a second elevation, and wherein the first elevation is a greater distance than the second elevation.
16. The method of claim 15, wherein the first and second portions are separated from each other along an X axis and/or a Y axis of the deflection member.
17. The method of claim 1, wherein the method further comprises incorporating a photoabsorber comprising one or more materials selected from the group consisting of 2,3,5-t-amyl tetrahydro benzotriazole; benzotriazoles; polymerizable benzotriazoles; benzotriazole substituted in the 5-position of the benzo ring by a thio ether; benzotriazole substituted in the 5-position of the benzo ring by a alkylsulfonyl; benzotriazole substituted in the 5-position of the benzo ring by a phenylsulfonyl moiety; benzotriazole substituted in the 5-position of the benzo ring by an electron withdrawing group; 2-(2-hydroxy-3,5-di-alpha-cumylphenyl)-2H-benzotriazole; 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl)-2H-benzotriazole; mixtures of benzotriazoles; titanium dioxide; yellow dyes; blue dyes; red dyes; green dyes; dyes; non-reactive dyes; food grade dyes; cosmetic dyes; azo dyes; 4-Chloro-7-nitrobenzofurazan; and combinations thereof.
18. The method of claim 17, wherein a first photoabsorber is functional with the first wavelength, and wherein a second photoabsorber is functional with the second wavelength.
19. The method of claim 1, wherein the reinforcing member and a radiation source, when producing at least one of the first and second wavelengths, is in movement relative to the other.
20. The method of claim 1, wherein the protuberance has a cross-sectional shape having curved sidewalls.
21. The method of claim 1, wherein the photopolymer resin is in a vat and wherein the vat and/or the reinforcing member is in movement during the polymerizing step (h).
22. The method of claim 1, the method further comprising forming a dead zone between the photopolymer resin and a vat comprising the photopolymer resin.
23. The method of claim 1, wherein the protuberance comprises multiple build layers comprising defined seams therebetween.
24. The method of claim 1, wherein the protuberance comprises a plurality of continuous undefined layers.
25. The method of claim 1, wherein the photopolymer resin further comprises a stabilizer comprising one or more materials selected from the group consisting of antioxidants; co-stabilizers; hindered amines; hindered phenolics; 2,6-di-tert-butylphenol; DTBP; methyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate; [Pentaerythrityl-tetrakis(3-(3′,5′-di-tert. butyl-4-hydroxyphenyl)-propionate]; Irganox 1010 (BASF); bis(2,4-di-tert.-butyl-6-methylphenyl)-ethyl-phosphite; phosphoric acid, (2,4-di-butyl-6-methylphenyl)ethylester; Irgafos 38 (BASF); flame retardants; thermal stabilizers; N,N′-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide], Irganox 1098 (BASF); and combinations thereof.
26. The method of claim 1, wherein the photopolymer resin further comprises an excipient comprising one or more materials selected from the group consisting of volatile fluids; isoparaffin fluids; oils, mineral oils, metal oxides; fumed metal oxides; colloidal silicas, silicas, silicone dioxide; titanium dioxide; cellulose; nanocellulose; cellulosic nanoparticles; cellulosic nanofibers; bacterial cellulose; calcium sulfate particles; calcium sulfate whiskers; modified calcium sulfate particles; modified calcium sulfate whiskers, and combinations thereof.
27. The method of claim 1, wherein the first and second wavelengths are produced by a single radiation source.
28. The method of claim 1, wherein the first wavelength is produced by a first radiation source, and the second wavelength is produced by a second radiation source.
具体实施方式：
[0036]Various non-limiting examples of the present disclosure will now be described to provide an overall understanding of the principles of the deflection members, and methods of manufacturing such deflection members, disclosed herein. One or more non-limiting examples are illustrated in the accompanying drawings. Those of ordinary skill in the art will understand that the deflection members, and methods of manufacturing such deflection members, described herein and illustrated in the accompanying drawings are non-limiting examples. The features illustrated or described in connection with one non-limiting example can be combined with the features of other non-limiting examples. Such modifications and variations are intended to be included within the scope of the present disclosure.
[0037]The present disclosure is directed to processes of using three dimensional printing technology to produce deflection members with a non-unitary reinforcing member that are intended for use in fibrous structure production (e.g., paper products and nonwovens). The process involves using computer control (which may be programmed to move reinforcing member(s) and/or radiation source(s) between or along predefined coordinates) to print a framework of polymers of specific material properties onto, into and/or around a separately manufactured reinforcing member in an additive manner to create durable deflection members with a long lifespan and unique structural and topographical profiles. The terms “three dimensional printing technology”, “three dimensional printing system,”“three dimensional printer,”“3-D printing”, “printing,”“additive manufacturing”, “additive manufacturing apparatus”, “AM” and the like all generally describe various solid freeform fabrication techniques for using a build material or a print material to make three dimensional (3-D) objects by stereolithography (SLA), continuous liquid interface production (CLIP), selective deposition, jetting, fused deposition modeling (FDM, as marketed by Stratasys Corp., Eden Prairie, Minn.), also known as fused filament fabrication (FFF), bonded deposition modeling, selective laser melting (SLM), direct metal laser sintering (DMLS), selective laser sintering (SLS), laminated object manufacturing (LOM), and other techniques now known in the art, or that may be known in the future. Stereolithography may include the use of lasers, DLP projectors, DMD digital micro-mirror devices, SLM spatial light modulators, laser LED and DLP systems (as described in U.S. Pat. No. 10,409,148 by O. Shkurikhin et al.) and/or combinations thereof. Digital masks may be used to control the distribution and localized control of radiation exposure either as from a source such as a display (e.g., LCD, LED) or displays that regulate the passage of curing radiation from a source. The computers may be programmed to move radiation source(s) and/or reinforcing member(s) (or components housing or holding the reinforcing member(s)) to move between or along predefined coordinates to form protuberance(s)/resinous framework.
[0038]Additive manufacturing is widely used in both research and industry, such as, for example, the automotive and aviation industries, for creating components that require a high level of precision. Traditional additive manufacturing processes involve the use of CAD (Computer Aided Design) software to generate a virtual 3-D model, which is then transferred to process preparation software where the model is virtually disassembled into individual slices or layers. The model is then sent to an additive manufacturing apparatus, where the actual object in printed layer by layer. As previously detailed in the Background, current methods for additively manufacturing deflection members are unitary in nature (i.e., the deflection member does not constitute a unit comprised of previously separate components joined together) and/or don't include methods of manufacture that provide for a strong bond (i.e., “lock-on”) between the resinous framework and the reinforcing member. Accordingly, currently available additively manufactured deflection members do not have the strength or longevity to be economically utilized in current papermaking or nonwoven production processes.
[0039]Deflection Member
[0040]An example of a traditional deflection member of the general type useful in the present disclosure, but made according to the disclosure of U.S. Pat. No. 4,514,345, is shown in FIGS. 1-3. As illustrated, a deflection member 2 includes a resinous framework 4 attached to a permeable reinforcing member 6. Deflection members 2 may comprise elevated portions (e.g., protuberance 7) that are built from the reinforcing member 6. The elevated portions may be separated in the machine direction (MD) and/or the cross direction (CD), which is advantageous for creating knuckles and pillows in a fibrous sheet formed therefrom—the knuckles formed against the protuberances and the pillows formed between the protuberances. As shown in FIG. 3, protuberances 7 making up the resinous framework 4 may be at different elevations or heights, such that a first portion of the protuberances 7 may be at a first elevation or height “X” and a second portion of the protuberances 7 may be at a second elevation or height “Y,” such that “X” is less than “Y,” and more particularly, that the first portion of protuberances extend from a surface such as a reinforcing member less than the second portion of protuberances. Resinous framework 4 may comprise cross-linkable polymers or alternatively composite materials that include cross-linkable polymers and filler materials. For example, in some forms detailed herein, the resinous framework 4 includes cross-linkable polymers selected from light activated polymers (e.g., UV light activated, e-beam activated, etc.), heat activated polymers, multipart polymers, moisture activated polymers, chemically activated polymers, and combinations thereof. In some deflection members, the utilized resinous framework may include any of the cross-linkable polymers as described in U.S. Pat. No. 4,514,345 issued Apr. 30, 1985 in the name of Johnson et al., and/or as described in U.S. Pat. No. 6,010,598 issued Jan. 4, 2000 in the name of Boutilier et al. In other deflection members, the utilized resinous framework may include any of the cross-linkable polymers as described in U.S. Pat. No. 7,445,831 issued Nov. 4, 2008 in the name of Ashraf et al. Other suitable cross-linkable and filler materials known in the art may also be used as resinous framework.
[0041]The pattern of resinous framework 4 can be structured in any decorative pattern known in the art of papermaking belts (micro patterns, i.e., the structure of an individual protuberance 7 within the resinous framework and/or macro patterns, i.e., a pattern including multiple protuberances 7, or the overall deflection member belt pattern including many protuberances 7). In particular, patterns that are not able to be manufactured in traditional deflection member production processes, such as taught by Johnson et al., are of the most interest. For example, the resinous framework patterns taught by Manifold et al. in U.S. patent application Ser. No. 15/132,291 are of high interest.
[0042]Reinforcing Member
[0043]Reinforcing member 6 can be made of woven filaments 8 as are known and are common in the art of papermaking belts. In such non-limiting forms, woven filaments can be made of natural fibers, cotton fibers, coated fibers, genetically engineered fibers, synthetic fibers, metallic fibers, carbon fibers, silicon carbide fibers, fiberglass, mineral fibers, and/or polymer fibers including polyethylene terephthalate (“PET”) or PBT polyester, phenol-formaldehyde (PF); polyvinyl chloride fiber (PVC); polyolefins (PP and PE); acrylic polyesters; aromatic polyamides (aramids) such as Twaron®, Kevlar® and Nomex®; polytetrafluoroethylene such as Teflon® commercially available from DuPont®; polyethylene (PE), including with extremely long chains/HMPE (e.g. Dyneema or Spectra); polyphenylene sulfide (“PPS”); and/or elastomers. In one non-limiting form, the woven filaments of the reinforcing member are filaments as disclosed in U.S. Pat. No. 9,453,303 issued Sep. 27, 2016 in the name of Aberg et al.
[0044]The woven filaments may be translucent, partially translucent, or opaque to assist and/or deter curing of the resinous framework. The reinforcing member may include woven filaments that exhibit a diameter of about 0.20 mm to about 1.2 mm, or about 0.20 mm to about 0.55 mm, or about 0.35 mm to about 0.45 mm. The reinforcing member may be manufactured by traditional weaving processes, or may be manufactured through other processes such as additive manufacturing, e.g., 3-D printing—but in such embodiments, the reinforcing member is not made in a unitary manner with the resinous framework.
[0045]The reinforcing member may also be made of any other permeable material known in the art. The term “permeable” may be used to refer generally to a material or structure that allows a liquid state cross-linkable polymer being utilized to build the resinous framework of the deflection member to pass at least partially through or be at least partially absorbed. Such permeable materials can be a porous material such as textiles, fabrics, knits, woven materials, mesh, polymers, rubbers, foams, etc. The porous materials can be in the form of a flexible cloth, a sheet, a layer and other structures.
[0046]Whether formed or woven filaments, reinforcing members may be of an endless or seamless design. Optionally, the reinforcing member may be cut or from stock of finite or infinite length. Once made, the deflection member may need to be seamed, sewn, fastened or fixed as is common in the art of papermaking or non-woven manufacture.
[0047]Whether formed of woven filaments and/or other permeable materials, reinforcing member 6 may include voids (i.e., spaces naturally occurring in a woven product between filaments) and/or foramina (i.e., perforations formed in a previously non-perforated reinforcing member). Reinforcing member 6 may also be formed from impermeable or semi-impermeable materials known in the art, such as various plastics, metals, metal impregnated plastics, etc., that include voids and/or foramina. Whether permeable, impermeable, or semi-impermeable, the reinforcing member may be translucent, partially translucent, or opaque to assist and/or deter curing of the resinous framework.
[0048]The particular deflection member structure shown in FIG. 1 includes discrete cured resin elements 10 and a continuous deflection conduit 12 (i.e., the space between the cured resin elements that allows a pressure differential to flow through voids 18 in woven reinforcing member 6). The particular deflection member structure shown in FIG. 2 includes a resinous framework 4 that is structured in a continuous pattern with discrete deflection conduits 12 (i.e., the space surrounded by the continuous cured resin element that allows a pressure differential to flow through voids 18 in woven reinforcing member 6). In non-illustrated embodiments, the resinous framework can also be structured to be a semi-continuous pattern on reinforcing member 6. The illustrated patterns include a resinous framework that includes either discrete cured resin elements or deflection conduits in a hexagon shape when viewed from above or below. The deflection members created by the additive manufacturing processes detailed herein may have an identical or similar resinous framework structure. However, the deflection members created by the additive manufacturing processes detailed herein may have a resinous framework that may have any shape or structure known in the art of papermaking and nonwoven making belts.
[0049]FIG. 4 illustrates a close up of a nonlimiting embodiment of a woven reinforcing member 6. Filaments 8 are woven together to form voids 18 between the filaments. As can be observed, each void 18 is framed by four surrounding filaments 8. Accordingly, in the non-limiting illustrated embodiment, each void has four side surfaces 30, with each side surface being formed by the portion of the filament that faces inward towards the void. In other non-illustrated embodiments, the woven filaments may be woven in a different pattern, and thus, voids 18 may have more than four side surfaces, or as few as three or substantially two side surfaces.
[0050]In other non-illustrated embodiments, the reinforcing member can be a material that is not a woven reinforcing member (e.g., a permeable or non-permeable material as detailed above). Such material may be a sheet or film and may be translucent, partially translucent, or opaque to assist and/or deter curing of the resinous framework. Such reinforcing member may include foramina. The foramina will function like the voids in a woven reinforcing member by also allowing a pressure differential to flow through the deflection conduits during the papermaking and/or nonwoven making processes. The voids/foramina provide an open area in the reinforcing member sufficient to allow water and/or air to pass through during papermaking and nonwoven making processes, but nevertheless preventing fibers from being drawn through. As fibers are molded into the deflection member during production of fibrous substrates, the reinforcing member serves as a “backstop” to prevent or minimize fiber loss through the deflection member.
[0051]FIG. 5 illustrates a close up of a nonlimiting embodiment of a reinforcing member 6 that is not a woven reinforcing member and includes foramina 40. Foramina 40 may be included in reinforcing member 6 in any number and/or size and/or regular or irregular shape (e.g., circles, ovals, triangles, squares, hexagons, octagons, etc.) and/or pattern. Foramina 40 each include at least one sidewall surface 42. The side wall surface(s) 42 is/are the surface(s) that extend between the substantially planar upper surface 20 and the substantially planar lower surface 22 of reinforcing member 6. For example, in foramina 40 that are of a circular or oval shape when viewed from above, there is a single continuous sidewall surface 42. In foramina that are square in shape when viewed from above, there are four sidewall surfaces 42.
[0052]FIG. 3 is a cross-sectional view of FIG. 2 taken along line 3-3. As illustrated, overall deflection member 2, as well as resinous framework 4, have a substantially planar upper surface 14 and a substantially planar lower surface 16. In some embodiments, the deflection member and the resinous framework may have an upper surface and a lower surface that are not substantially planar. In such embodiments, the upper surface is considered to be an X-Y plane, wherein X and Y can correspond generally to the cross-direction (CD) and the machine direction (MD) respectively, that intersects the portion of the resinous framework that is the furthest distance above the reinforcing member in the Z direction. In the same embodiment, the lower surface is considered to be an X-Y plane that intersects the portion of the resinous framework that is the furthest distance below the reinforcing member in the Z direction.
[0053]One skilled in the art will appreciate that the symbols “X,”“Y,” and “Z” designate a system of Cartesian coordinates, wherein mutually perpendicular “X” and “Y” define a reference plane formed by a flat, level surface upon which lower surface 16 of deflection member 2 sits, and “Z” defines a direction orthogonal to the X-Y plane. Accordingly, the term “X-Y plane” used herein refers to a plane that is parallel to the reference plane formed by the flat, level surface upon which lower surface 16 of deflection member 2 sits. The person skilled in the art will also appreciate that the use of the term “plane” does not require absolute flatness or smoothness of any portion or feature described as planar. In fact, the lower surface 16 of deflection member 2 can have texture, including so-called “backside texture” which is helpful when the deflection member is used as a papermaking belt on vacuum rolls in a papermaking process as described in Trokhan or Cabell et al. As used herein, the term “Z direction” designates any direction perpendicular to the X-Y plane. Analogously, the term “Z dimension” means a dimension, distance, or parameter measured parallel to the Z-direction and can be used to refer to dimensions such as the height of protuberances 7 or the thickness, or caliper, of the unitary deflection member. It should be carefully noted, however, that an element that “extends” in the Z-direction does not need itself to be oriented strictly parallel to the Z-direction; the term “extends in the Z direction” in this context merely indicates that the element extends in a direction which is not parallel to the X-Y plane. Analogously, an element that “extends in a direction parallel to the X-Y plane” does not need, as a whole, to be parallel to the X-Y plane; such an element can be oriented in the direction that is not parallel to the Z direction.
[0054]When viewed in cross-section, the illustrated deflection members include a resinous framework that includes either discrete cured resin elements or discrete deflection conduits with substantially planar upper and lower surfaces in common with the substantially planar upper and lower surfaces of the deflection member. Further, the wall surfaces that span the distance between the upper and lower surfaces of the resinous framework are substantially flat and perpendicular to both the upper and lower surfaces. The deflection members created by the additive manufacturing processes detailed herein may have an identical or similar resinous framework structure. However, the deflection members created by the additive manufacturing processes detailed herein may have a resinous framework that can have any shape or structure known in the art of papermaking and nonwoven making belts. For example, the wall surfaces can be straight or curved, perpendicular or angled to the upper and lower surfaces, and the upper and lower surfaces can be flat, textured, patterned, consistent, irregular, stepped, cantilevered, overhanging, porous and/or angled. FIG. 2A is a deflection member comprising a plurality of bulbous shaped protuberances 7. FIG. 3A is cross-section view of one of the protuberances 7 of FIG. 2A along line 3A-3A. Each protuberance 7 of FIG. 2A may be discrete, unattached to any other protuberance 7 or may be attached to each other along the Y axis and/or the X axis. In FIG. 2A, the individual protuberances 7 are discrete from each other along the X axis. FIGS. 3B-3D illustrate cross-sections of shapes of the protuberances 7 that may be substituted for the protuberance 7 shapes illustrated in FIGS. 2, 2A, 3, and 3A. The shapes of the protuberances 7 in FIGS. 3A-D may be referred to as complex shapes and may be formed using various 3-D printing techniques explained in more detail below, some of which include the emission of two different wavelengths, one that cures a photopolymer resin and one that inhibits curing of the photopolymer resin. As used herein, “different wavelengths” may be different by at least 1 nm. “Different wavelength ranges” may also be different by at least 1 nm. A “wavelength range” can be as small as 0.1 nm or 0.01 nm or 0.001 nm and may be larger.
[0055]Further, as illustrated in FIG. 3, reinforcing member 6 may have a substantially planar upper surface 20 and a substantially planar lower surface 22. In embodiments that have a woven reinforcing member, such reinforcing member may have macroscopically substantially planar upper and lower surfaces, while also having a microscopically non-substantially planar upper and lower surfaces. As used herein, the terms containing “macroscopical” or “macroscopically” refer to an overall geometry of a structure under consideration when it is placed in a two-dimensional configuration. In contrast, “microscopical” or “microscopically” refer to relatively small details of the structure under consideration, without regard to its overall geometry. For example, in the context of the reinforcing member, the term “macroscopically substantially planar” means that the reinforcing member, when it is placed in a two-dimensional configuration, has—as a whole—only minor deviations from absolute planarity, and the deviations do not adversely affect the reinforcing member's performance. At the same time, the reinforcing member can have a microscopical non-substantially planar upper and lower surfaces due to the three-dimensional pattern of woven filaments, as illustrated herein in FIGS. 1, 2, and 3.
[0056]In embodiments of deflection member that include a woven reinforcing member, upper surface 20 of reinforcing member 6 is considered to be an X-Y plane (i.e., a plane that is parallel to a reference plane formed by the flat, level surface upon which lower surface 16 of deflection member 2 sits) that intersects with the portion of the reinforcing member that is the furthest distance in the Z direction above lower surface 16 of deflection member 2. Lower surface 22 of reinforcing member 6 is considered to be an X-Y plane that intersects the portion of the reinforcing member that is the furthest distance in the Z direction below upper surface 14 of deflection member 2.
[0057]Process for Making Deflection Members
[0058]The additive manufacturing processes detailed below may be used to produce deflection members of the general type (including specific deflection members disclosed in the incorporated references) detailed above that include a resinous framework and a non-unitary reinforcing member. The types of additive manufacturing apparatuses that are employable in the methods detailed here are any type now known in the art, or that may be known in the future. Non-limiting examples of applicable additive manufacturing apparatuses include SLA, CLIP, LAMP, HARP, DLP-SLA, 3D-nanoprinting, 3D-fabrication by tomographic back projection techniques and g-DLP as are currently known in the art of additive manufacturing and described as stereolithography apparatus (SLA) in U.S. Pat. No. 5,236,637 by C. W. Hull et. al.; continuous liquid interface printing (CLIP) as described in U.S. Pat. No. 10,144,181B2 by J. M. DeSimone et. al., U.S. Pat. No. 9,205,601B2 by J. M. DeSimone et. al., and U.S. Publication No. 2018/0243976A1 by B. Feller; large area maskless photopolymerization (LAMP) as described in WO 2019/161299A1 by S. Das et. al.; high area rapid printing (HARP) as described in U.S. Publication No. 2019/0160733A1 by C. Mirkin et. al.; two wavelength negative imaging with DLP-SLA as described in U.S. Publication No. 2020/0001531A1 by B. D. Moran; continuous 3D-nanoprinting as described in U.S. Publication No. 2018/0015661A1 by X. Xu et. al.; computed axial lithography (CAL) as described in U.S. patent Ser. No. 10/647,061B2 by B. Kelly et. al.; tomographic back projection as described in WO 2019/043529A1 by D. Loterie et. al.; and grayscale digital light projection (g-DLP) as described in Grayscale digital light processing 3D printing for highly functionally graded materials, Science Advances 5(5): eaav5790 by X. Kuang et. al. on May 9, 2019. Regardless of the particular type of additive manufacturing apparatus employed, the apparatus may include at least one radiation source and a vat containing a photopolymer resin.
[0059]Radiation Sources
[0060]The at least one radiation source may include one, two, three, four, five, six, seven, eight, nine, ten, or more individual radiation sources. The at least one radiation source may include between 1 and about 50 individual radiation sources, between 1 and about 20 individual radiation sources, or between 1 and about 15 individual radiation sources, or between 1 and about 10 individual radiation sources, or between 1 and about 5 individual radiation sources, or between 1 and about 3 individual radiation sources. In some embodiments detailed below, such as methods for continually printing deflection members, the at least one radiation source may include 50 or more individual radiation sources, or between about 50 and about 50,000 individual radiation sources, or between about 50 and about 900 individual radiation sources, or between about 50 and about 220 individual radiation sources, or between about 50 and about 100 individual radiation sources, or between about 50 and about 75 individual radiation sources. These radiation sources may be oriented in the cross-direction (CD) and/or machine direction (MD) at one or more locations along the length of a deflection member. The at least one radiation source may include one or more individual radiation sources located at an upper location on the additive manufacturing apparatus (i.e., upper radiation source(s)) and/or include one or more individual radiation sources located at a lower location on the additive manufacturing apparatus (i.e., lower radiation source(s)). The radiation may be directed orthogonally towards the surface of the deflection member and/or reinforcing member, or may be angled towards, or may be reflected towards the surface of the deflection member and/or reinforcing member (i.e., directed in a non-orthogonal manner).
[0061]The at least one radiation source emits radiation that is utilized in the curing and/or prevention of curing when the photopolymer resin is exposed to it. The at least one radiation source can generate actinic radiation from an ultraviolet (UV) laser, a visible (VIS) laser, an infrared (IR) laser, a DLP projector, an LED array or display, an LCD panel or display, fiber optic bundles or assemblies thereof, or any other radiation type now known in the art, or that may be known in the future. In additive manufacturing apparatuses that include multiple radiation sources, the radiation sources may be all be of the same type, wavelength, and/or output strength, or the radiation sources may be any combination of types, wavelength, and/or output strengths. A non-limiting example of a UV laser can be constructed starting with a laser diode, such as a 375 nm (70 mW maximum power) available from ThorLabs (part number L375P70MLD) or less expensive VIS lasers operating at 405 nm (available in 20 mW to 1W maximum power, L405P20 and L405G1 respectively from ThorLabs). Other non-limiting examples may include argon-ion lasers which can, depending on the type, emit at a variety of wavelengths in UV, VIS and IR: 351.1 nm, 363.8 nm, 454.6 nm, 457.9 nm, 465.8 nm, 476.5 nm, 488.0 nm, 496.5 nm, 501.7 nm, 514.5 nm, 528.7 nm, 1092.3 nm. Commercial examples of applicable 405 nm lasers include the Form series of SLA printers available from FormLabs such as the Form 1+ and Form 2 (250 mW maximum power with a 140 micron spot size). Still another example of a laser applicable to the methods detailed herein is a VIS laser (532 nm, maximum 6W), as detailed by M. Shusteff et al. in U.S. Patent Publication No. 2018/001567, taught to be effective at volumetric curing of resin via multiple orthogonal beams when interested in shapes from intersecting extruded profiles. Energy is provided and/or controlled in sufficient quantity to promote curing and thereby exceeding thresholds provided by dissolved oxygen or other photoinhibitors such as those consistent with the publications: Continuous AM by Volumetric Polymerization Inhibition Patterning, Jan. 11, 2019 by M. P. de Beer et al.; Science Adv. 5:eaau8723+Supplementary Materials; WO 2019/164808A1; U.S. patent Ser. No. 10/213,956B2 and U.S. patent Ser. No. 10/667,525B2 to K. Willis and B. J. Adzima; and U.S. Patent Publication Nos. 2019/0134888 and 2019/0126534 to DeSimone et al. and WO2014/126837 to DeSimone et al. and U.S. Patent Publication No. 2017/0120515 to J. P. Rolland et al.
[0062]Radiation sources of the present disclosure may move relative to a vat and/or over a reinforcing member to emit radiation to form protuberance(s)/resinous framework. The movement(s) of the radiation source may include rotating around the vat and/or the reinforcing member, and/or moving in the X, Y, and/or Z directions relative to the reinforcing member. More particularly, radiation sources may move between or along predefined coordinates (which may be programmed).
[0063]Vat
[0064]The vat containing photopolymer resin may be of any size to accommodate the printing of deflection members. The vat may be clear, translucent, or opaque, and constructed of plastic, stainless steel or any other material known in the art that is deep enough to hold the required amount of photopolymer resin. The vat may be lined with a minimally or non-reflective surface such black Formica. The volume of resin in the vat is controlled to incrementally or wholly deliver the final thickness in the finished deflection member. Vats of the present disclosure may move relative to the radiation sources. For example, the vat may rotate while the radiation source(s) remain stationary or the vat may rotate while the radiation source(s) counter rotate or while the radiation source(s) move in an X, Y, and/or Z direction relative to a reinforcing member within the vat. The vat may move in an X, Y, and/or Z direction relative to a reinforcing member within the vat to bring the reinforcing member closer to radiation source(s). More particularly, the vat may move between or along predefined coordinates (which may be programmed). Multiple vats may be used or the resin in the vat may be replaced to deliver different material properties or control depth of cure due to resin absorption properties at the radiation wavelength.
[0065]Dead Zone
[0066]A dead zone may be created between the actinic source and the build surface to prevent curing, partially cure, slow curing, weaken adhesion, provide a barrier to adhesion, or combinations thereof. The volumetric shape of the dead zone may be of uniform thickness (i.e., a static or moving solid film or liquid; molecularly or chemically balanced with photoinhibitors such as dissolved solids, liquids or gases). Similar mechanisms can be employed to affect a non-uniform volume or three-dimensional shape of the dead zone with designs or patterns that are can be symmetric, random or repeating. The dead zone may be oriented near a top, side or bottom plane of a build surface. In some cases, a dead zone may be formed from a group as described in Continuous AM by Volumetric Polymerization Inhibition Patterning, Jan. 11, 2019 by M. P. de Beer et. al.; Science Adv. 5:eaau8723+Supplementary Materials; a group as described in WO 2019/164808A1; U.S. patent Ser. No. 10/213,956B2 and U.S. patent Ser. No. 10/667,525B2 to K. Willis and B. J. Adzima; and U.S. Patent Publication Nos. 2019/0134888 and 2019/0126534 to DeSimone et al.; WO2014/126837 to DeSimone et al. and U.S. patent Ser. No. 10/647,873B2 issued May 12, 2020 to J. P. Rolland et. al.; and barriers such as those described as a dewetting phase (e.g. solid, aqueous solid, ice, solid tetraethylene glycol, solid PEG-200, solid PEG-400, solid PEG-600, solid polyethylene glycol, per-fluorinated solid, per-fluorinated solid comprising a solid perfluoropolyether, fluoro-gel comprises 2-(per-fluoroheyxl)ethyl acrylate swelled with perfluoropolyether, fluorinated based liquids, perfluoro-n-alkanes, perfluoropolyethers, perfluoralkylethers, co-polymers of substantially fluorinated molecules, fluid with contact angle above 60° or above 90°, silicone liquids, liquid polymerized siloxanes, silicon oils, fluorinated oils, organic oils, oils, immiscible fluids with respect to photopolymer resin, insoluble fluids with respect to the photopolymer resin, densified salt solutions, densified sugar solutions, silicon-gel, organo-gel, aqueous hydro-gel, fluoro-gel, agar, agarose gels, polyacrylamide gels, starch gels, cationic gels, anionic gels, surfactants, fluorinated acrylic polymers (such as Capstone FS-22 and Capstone FS-83 from Dupont (Wilmington, Del., USA)), ionic surfactants, CTAB (hexadecyl-trimethylammonium bromide), CPC (cetylpyridinium chloride), DOAB (dimethyldioctadecylammonium bromide), SDS (sodium dodecyl sulfonate), SDBS (sodium dodecyl-benzenesulfonate), non-ionic surfactants, hexaethylene glycol mono-n-dodecyl ether, polyoxyethylene (2) sorbitan monolaurate (Tween-20; Polysorbate 20), Tyloxapol, or when present as liquid, optionally mobile or flowing; and combinations thereof) that is optionally optically transparent allowing 1% to 100% transmittance of actinic radiation, that is optionally cooled, that is optionally oxygenated; and combinations thereof)