Continuous additive manufacturing method

Abstract

A continuous method of making an adhesive is provided. The method includes obtaining a photochemically polymerizable adhesive precursor composition disposed on a major surface of a photochemically transparent substrate; and irradiating a first portion of the photochemically polymerizable adhesive precursor composition through the photochemically transparent substrate with a first irradiance dose. The method further includes moving the photochemically transparent substrate; and irradiating a second portion of the photochemically polymerizable adhesive precursor composition through the photochemically transparent substrate with a second irradiance dose. Optionally, the method further includes irradiating a third portion of the photochemically polymerizable adhesive precursor composition through the photochemically transparent substrate prior to moving the substrate. The first irradiance dose and the third irradiance dose are generally different, thereby forming a unitary adhesive having a variable thickness in an axis normal to the photochemically transparent substrate.

Description

Technical Field

[0001] This disclosure relates to a continuous method for preparing an additive for adhesives. Background Technology

[0002] In various industries, adhesives such as pressure-sensitive adhesives, hot-melt adhesives, or structural adhesives are used to join components together. Due to the miniaturization of devices, the demand for more precise adhesive delivery is increasing. Furthermore, certain adhesive shapes, such as wedge shapes, cannot be produced by die-cutting. Summary of the Invention

[0003] This disclosure relates to the preparation of additives for adhesives. Additional methods, such as continuous methods, have been identified for the preparation of adhesives.

[0004] In a first aspect, a continuous method for preparing an adhesive is provided. The method includes: obtaining a photoradioactive polymerizable adhesive precursor composition disposed on a main surface of a photoradioactive transparent substrate; and irradiating a first portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a first irradiation dose to form a first adhesive; the method further includes: moving the photoradioactive transparent substrate; and irradiating a second portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a second irradiation dose to form a second adhesive.

[0005] In a second aspect, another continuous method for preparing an adhesive is provided. The method includes: obtaining a photoradioactive polymerizable adhesive precursor composition disposed on a main surface of a photoradioactive transparent substrate; and irradiating a first portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a first irradiation dose. The method further includes: irradiating a second portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a second irradiation dose; and moving the photoradioactive transparent substrate. The first and second portions are adjacent to or overlap each other, and the first and second irradiation doses are different, thereby forming a monolithic adhesive with a variable thickness in an axis orthogonal to the photoradioactive transparent substrate.

[0006] The foregoing overview of this disclosure is not intended to describe every aspect of this disclosure or every implementation thereof. The following description illustrates exemplary embodiments in more detail. Guidance is provided at several points throughout this application by way of a list of examples that can be used in various combinations. In each case, the cited list is used only as a representative group and should not be construed as an exclusive list. Attached Figure Description

[0007] Figure 1 A schematic cross-sectional view of a device used for an exemplary method according to this disclosure.

[0008] Figure 2 A schematic cross-sectional view of a device used in another exemplary method according to this disclosure.

[0009] Figure 3 A schematic cross-sectional view of an apparatus for yet another exemplary method according to this disclosure.

[0010] Figure 4 A schematic cross-sectional view of a device for yet another exemplary method according to this disclosure.

[0011] Figure 5 A schematic cross-sectional view of a device used in another exemplary method according to this disclosure.

[0012] Figure 6 A schematic cross-sectional view of a device used for an additional exemplary method according to this disclosure.

[0013] Figure 7 A schematic cross-sectional view of an apparatus for yet another exemplary method according to this disclosure.

[0014] Figure 8 A schematic cross-sectional view of a device for yet another exemplary method according to this disclosure.

[0015] Figure 9 A schematic cross-sectional view of a device for use in another additional exemplary method according to this disclosure.

[0016] Figure 10 A schematic cross-sectional view for use with an exemplary irradiation source according to this disclosure.

[0017] Figures 11a and 11b are schematic cross-sectional views of another exemplary irradiation source according to this disclosure.

[0018] Figure 12 This is a schematic cross-sectional view for yet another exemplary irradiation source according to this disclosure.

[0019] Figure 13 A schematic cross-sectional view for use with an additional exemplary irradiation source according to this disclosure. Detailed Implementation

[0020] This disclosure provides methods for preparing additives for adhesives, such as the continuous preparation of adhesives. In some embodiments, a monolithic adhesive with varying thickness is formed, while in other embodiments, multiple adhesives with substantially the same thickness are formed.

[0021] For the terminology listed below, unless a different definition is provided elsewhere in the claims or description, these definitions shall apply to the entire application.

[0022] Glossary

[0023] While most terms used throughout the specification and claims are well-known, some interpretation may still be necessary. It should be understood that, as used herein:

[0024] As used in this specification and the accompanying embodiments, unless the content clearly indicates otherwise, the singular forms “a,” “an,” and “the” include multiple referents. As used in this specification and the accompanying embodiments, unless the content clearly indicates otherwise, the term “or” is generally used in its meaning including “and / or.”

[0025] As used in this specification, a range of values ​​expressed by endpoints includes all values ​​included in that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0026] Unless otherwise specified, all figures used in this specification and embodiments, including expressions or measurements of components, properties, etc., should in all cases be understood to be modified by the term "about". Therefore, unless stated to the contrary, the numerical parameters shown in the foregoing specification and the appended list of embodiments may vary according to the desired properties sought by those skilled in the art using the teachings of this disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalence to the embodiments protected by the claims, each numerical parameter should be interpreted at least according to the significant digits of the reported value and by applying conventional rounding.

[0027] The term "comprising" and its variations are not intended to be limiting in the places where they appear in the specification and claims.

[0028] The terms "preferred" and "ideally" refer to embodiments of this disclosure that provide certain benefits in certain circumstances. However, other embodiments may also be preferred in the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0029] The term "photochemical radiation" refers to electromagnetic radiation that can produce photochemical reactions.

[0030] The term "dose" refers to the degree of exposure to photochemical radiation.

[0031] The term "whole" refers to a whole composed of parts that together form a whole.

[0032] The term “(co)polymer” includes both homopolymers containing a single monomer and copolymers containing two or more different monomers.

[0033] The terms “(meth)acrylate” or “(meth)acrylate” include both acrylic and methacrylate (or acrylate and methacrylate). Acrylate and methacrylate monomers, oligomers or polymers are collectively referred to herein as “acrylates”.

[0034] The term "aliphatic group" refers to a saturated or unsaturated straight-chain or branched hydrocarbon group. This term is used to encompass, for example, alkyl, alkenyl, and alkynyl groups.

[0035] The term "alkyl group" refers to a saturated hydrocarbon group that is straight-chain, branched, cyclic, or a combination thereof and typically has 1 to 20 carbon atoms. In some embodiments, the alkyl group comprises 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, isopropyl, tert-butyl, heptyl, dodecyl, octadecyl, pentyl, 2-ethylhexyl, etc. The term "alkylene group" refers to a divalent alkyl group.

[0036] The term "alicyclic group" refers to a cyclic hydrocarbon group whose properties are similar to those of an alicyclic group. The term "aromatic group" or "aryl group" refers to a monocyclic or polycyclic aromatic hydrocarbon group.

[0037] In contrast to adhesive, the term "pattern" refers to the design of an adhesive that defines at least one orifice in the adhesive.

[0038] The term "solvent" refers to a substance that dissolves another substance to form a solution.

[0039] The term "total monomers" refers to the combination of all monomers in an adhesive composition, including both polymerization products and optional additional materials.

[0040] Throughout this specification, the terms "an embodiment," "certain embodiments," "one or more embodiments," or "implementation," whether or not preceded by the term "exemplary," mean that a particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one of the exemplary embodiments of this disclosure. Therefore, expressions such as "in one or more embodiments," "in some embodiments," "in certain embodiments," "in one embodiment," "in many embodiments," or "in an embodiment" appearing throughout this specification do not necessarily refer to the same embodiment of the exemplary embodiments of this disclosure. Furthermore, specific features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0041] Various exemplary embodiments of this disclosure will now be described. Various modifications and alterations may be made to the exemplary embodiments of this disclosure without departing from the spirit and scope of this disclosure. Therefore, it should be understood that the embodiments of this disclosure are not limited to the exemplary embodiments described below, but are subject to the limiting factors shown in the claims and any equivalents.

[0042] In a first aspect, a continuous method is provided. The method includes: acquiring a photoradioactive polymerizable adhesive precursor composition disposed on a main surface of a photoradioactive transparent substrate; and irradiating a first portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a first irradiation dose to form a first adhesive; the method further includes: moving the photoradioactive transparent substrate; and irradiating a second portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a second irradiation dose to form a second adhesive.

[0043] In a second aspect, another continuous method for preparing an adhesive is provided. The method includes: obtaining a photoradioactive polymerizable adhesive precursor composition disposed on a main surface of a photoradioactive transparent substrate; and irradiating a first portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a first irradiation dose. The method further includes: irradiating a second portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a second irradiation dose; and moving the photoradioactive transparent substrate. The first and second portions are adjacent to or overlap each other, and the first and second irradiation doses are different, thereby forming a monolithic adhesive with a variable thickness in an axis orthogonal to the photoradioactive transparent substrate.

[0044] The following disclosure relates to both the first aspect and the second aspect.

[0045] Such continuous methods are applicable to the preparation of various adhesive structures. For example, continuous methods can form a series or array of individual adhesives, each spaced apart from the others by a distance the substrate travels between irradiations of the individual adhesive. In some embodiments, the individual adhesives have the same height, length, and width as each other. In contrast, in other embodiments, the individual adhesives differ from each other in at least one of height (i.e., in the z-direction from the main surface of the substrate), length, and width. Advantageously, the methods of this disclosure provide the ability to readily prepare individual adhesives with a variety of unique shapes due to the use of an adaptable photochemical radiation source from which the boundaries and dose of the photochemical radiation determine the specific shape of the individual adhesive. For example, digital light projectors, laser scanning devices, and liquid crystal displays can be controlled to vary the area and intensity of the photochemical radiation that leads to the curing of the photochemically polymerizable adhesive precursor composition.

[0046] As mentioned above, die-cutting of adhesives cannot easily form adhesives with wedge shapes. Similarly, die-cutting is not suitable for forming adhesives with height gradients or other unique shapes. The (continuous) method disclosed herein not only provides a variety of shapes and gradients, but also enables the fabrication of a variety of different shapes and heights on the same substrate.

[0047] Therefore, in some embodiments, the method of the first aspect further includes irradiating a third portion of the photochemically radiolucent adhesive precursor composition through the photochemically radiolucent substrate before moving the substrate, wherein the first and third portions are adjacent to or overlap each other. When the first and third irradiation doses are not the same, a monolithic adhesive with variable thickness is formed in an axis orthogonal to the photochemically radiolucent substrate. In some embodiments, the irradiation time of the first dose is shorter or longer than the irradiation time of the third dose. In some embodiments, the photochemical radiation intensity of the first dose is lower or higher than the photochemical radiation intensity of the third dose. In some embodiments, the irradiation of the first portion occurs before, simultaneously with, or in combination with the irradiation of the third portion.

[0048] Optionally, the method of the first aspect further includes irradiating a fourth portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate. When the second and fourth portions are adjacent to or overlap each other and the second and fourth irradiation doses are not the same, the second integral adhesive has a variable thickness in an axis orthogonal to the main surface of the photochemically radioactive transparent substrate. In some embodiments, the irradiation time of the second dose is shorter or longer than the irradiation time of the fourth dose. In some embodiments, the photochemical radiation intensity of the second dose is lower or higher than the photochemical radiation intensity of the fourth dose. In some embodiments, the irradiation of the second portion occurs before, simultaneously with, or in combination with the irradiation of the fourth portion.

[0049] Alternatively, in some embodiments, the method includes applying the same irradiation dose to multiple different portions (e.g., to both a first portion and a third portion) of a photochemically radiopolymerizable adhesive precursor composition, thereby forming a pattern of adhesive with the same thickness in an axis orthogonal to the main surface of the photochemically radiotransparent substrate. This pattern includes one or more separate adhesives that can be integral with or separate from one or more other separate adhesives of the same height.

[0050] In some embodiments, the second aspect of the method further includes irradiating a third portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate after moving the substrate. Optionally, the first and third irradiation doses may be the same or different. Furthermore, the second aspect of the method may also include irradiating a fourth portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate with a fourth irradiation dose. The third and fourth portions are adjacent to or overlap each other, and the third and fourth irradiation doses are different, thereby forming a monolithic adhesive. In such embodiments, the photochemically radioactive transparent substrate is moved after irradiating the fourth portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate.

[0051] In most embodiments, the (e.g., monolithic) adhesive is a pressure-sensitive adhesive (PSA), a structural adhesive, a structural hybrid adhesive, a hot-melt adhesive, or a combination thereof. For example, the adhesive is typically prepared from a photochemically irradiable polymerizable adhesive precursor composition comprising acrylates, two-component acrylate and epoxy resin systems, two-component acrylate and urethane systems, or combinations thereof. In some embodiments, the photochemically irradiable polymerizable adhesive precursor composition is 100% polymerizable precursor composition, while in other embodiments, the photochemically irradiable polymerizable adhesive precursor composition contains at least one solvent, such as, but not limited to, C4-C12 alkanes (e.g., heptane), alcohols (e.g., methanol, ethanol, or isopropanol), ethers, and esters.

[0052] For example, the acrylic polymer may be a non-tertiary alcohol acrylate having 1 to 18 carbon atoms. In some embodiments, the acrylate comprises a carbon chain having 4 to 12 carbon atoms and terminating at a hydroxyl oxygen atom, the chain comprising at least half of the total number of carbon atoms in the molecule.

[0053] Certain available acrylates can be polymerized into sticky, stretchable, and elastic adhesives. Examples of acrylates include, but are not limited to, 2-methylbutyl acrylate, isooctyl acrylate, lauryl acrylate, 4-methyl-2-pentyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, isodecyl acrylate, isodecyl methacrylate, and isononyl acrylate. Suitable non-tertiary alcohol acrylates include, for example, 2-ethylhexyl acrylate and isooctyl acrylate.

[0054] To enhance the strength of the adhesive, acrylates can be copolymerized with one or more mono-olefinically unsaturated monomers having highly polar groups. Such mono-olefinically unsaturated monomers include acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide, N-substituted acrylamides (e.g., N,N-dimethylacrylamide), acrylonitrile, methacrylonitrile, hydroxyalkyl acrylate, ethyl ethyl cyanoacrylate, N-vinylpyrrolidone, N-vinylcaprolactam, and maleic anhydride. In some embodiments, these copolymerizable monomers are used in amounts less than 20% by weight of the adhesive matrix, such that the adhesive is tacky at normal room temperature. In some cases, tackiness can be maintained at up to 50% by weight of N-vinylpyrrolidone.

[0055] Particularly usable are acrylate copolymers, which contain at least 6% by weight of acrylic acid based on the total weight of the monomers in the acrylate copolymer, and in other embodiments, at least 8% by weight or at least 10% by weight of acrylic acid. The adhesive may also include small amounts of other useful copolymerizable monoolefin unsaturated monomers, such as alkyl vinyl ethers, vinylidene chloride, styrene, and vinyltoluene.

[0056] In some embodiments, the adhesive according to this disclosure comprises a two-component acrylate and epoxy resin system. For example, suitable acrylate-epoxy resin compositions are described in detail in U.S. Patent Application Publication 2003 / 0236362 (Bluem et al.). In some embodiments, the adhesive according to this disclosure comprises a two-component acrylate and urethane system. For example, suitable acrylate-urethane compositions are described in detail in U.S. Patent No. 4,950,696 (Palazotto et al.).

[0057] The cohesive strength of the adhesive can also be enhanced by using crosslinking agents such as those containing 1,6-hexanediol diacrylate, and photosensitive triazine crosslinking agents (such as those taught in U.S. Patent Nos. 4,330,590 (Vesley) and 4,329,384 (Vesley et al.), or thermally activated crosslinking agents (such as amine formaldehyde condensates with C1-4 alkyl groups oxidized to alkyl groups—for example, hexamethoxymethylmelamine, or tetraethoxymethylurea or tetramethoxymethylurea). Crosslinking can be achieved by irradiating the composition with electron beam (or “e-beam”) radiation, gamma radiation, or X-ray radiation. The diamide crosslinking agent can be used with acrylic adhesives in solution.

[0058] In typical photopolymerization methods, a monomer mixture can be irradiated with photochemical radiation (such as ultraviolet (UV) rays) in the presence of a photopolymerization initiator (i.e., a photoinitiator). Suitable exemplary photoinitiators are those available from BASF (Ludwigshafen, Germany) under the trade names IRGACURE and DAROCUR, and include 1-hydroxycyclohexyl benzophenone (IRGACURE 184), 2,2-dimethoxy-1,2-diphenylethyl-1-one (IRGACURE 651), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one (IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone (IRGACURE 369), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one (IRGACURE 369). 907), oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone]ESACURE ONE (Lamberti SpA, Gallararate, Italy), 2-hydroxy-2-methyl-1-phenylprop-1-one (DAROCUR 1173), 2,4,6-trimethylbenzoyl diphenylphosphine (IRGACURE TPO), and 2,4,6-trimethylbenzoyl phenylphosphinate (IRGACURE TPO-L). Suitable photoinitiators include, for example, but not limited to, benzyl dimethyl ketal, 2-methyl-2-hydroxyphenylacetone, benzoin methyl ether, benzoin isopropyl ether, anisolein methyl ether, aromatic sulfonyl chlorides, photoactive oximes, and combinations thereof. When used, the photoinitiator is typically present in an amount of about 0.01 to about 5.0 parts by weight, or 0.1 to 1.5 parts by weight, per 100 parts by weight of total monomers.

[0059] In many embodiments, the method includes post-curing one or more molding adhesives (e.g., a first adhesive, a second adhesive, a monolithic adhesive, etc.), for example, using photochemical radiation or heat for post-curing. In such embodiments, the radiation variable can be focused on polymerization to form the desired shape and size by not requiring the adhesive to cure to the full extent required for a particular application during initial irradiation.

[0060] Optionally, a thermal initiator is used to initiate the post-curing of the adhesive. Suitable thermal initiators include, for example, but not limited to, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobisisobutyronitrile (VAZO 64, available from DuPont), and 2,2'-azobis(2,4-dimethylpentanonitrile) (VAZO 64). 52, obtained from DuPont), 2,2'-azobis-2-methylbutyronitrile, (1,1'-azobis(1-cyclohexanenitrile), 2,2'-azobis(methyl isobutyrate), 2,2'-azobis(2-amidinylpropane) dihydrochloride, 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), 4,4'-azobis(4-cyanopentanoic acid) and their soluble salts (e.g., sodium, potassium), benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, dicetyl peroxydicarbonate (4-tert-butylcyclohexyl) ester, di(2-ethylhexyl) peroxydicarbonate, tert-butyl peroxyneoplastate, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, combinations of persulfates with sodium metabisulfite or sodium bisulfite, benzoyl peroxide plus dimethylaniline, cumene hydroperoxide plus cobalt naphthenate, and combinations thereof. When used, the thermal initiator is typically present in an amount of about 0.01 to about 5.0 parts by weight, or 0.1 to 0.5 parts by weight, per 100 parts by weight of total monomers.

[0061] This method typically also includes removing the photochemically polymerizable adhesive precursor composition that has come into contact with the adhesive (e.g., a first adhesive, a second adhesive, a bulk adhesive, etc.). Removal of the unpolymerized precursor composition after irradiation may involve the use of gravity, gas, vacuum, fluid, or any combination thereof. Optionally, suitable fluids for removing excess adhesive precursor composition include solvents. When the adhesive is to be post-cured, it may be particularly desirable to keep the residual precursor composition away from the adhesive in order to minimize or prevent the addition of adhesive material to the desired shape and size of the adhesive during post-curing.

[0062] There are no particular limitations on the temperature at which the methods according to this disclosure are performed. For methods employing photoradiopolymerizable adhesive precursor compositions that are liquid at room temperature (e.g., 20-25°C), for simplicity, at least some of the various steps of the method are typically performed at room temperature. For methods employing photoradiopolymerizable adhesive precursor compositions that are solid at room temperature, at least some of the various steps of the method may be performed at a high temperature above room temperature, such that the photoradiopolymerizable adhesive precursor composition is in liquid form. High temperatures may be used throughout the method or in such steps as adhesive formation, removal of unpolymerized photoradiopolymerizable adhesive precursor compositions, and / or optional post-curing of the adhesive. In some embodiments, certain portions of the method are performed at different temperatures, while in some other embodiments, the entire method is performed at a single temperature. Suitable high temperatures include, for example, but not limited to, 25°C and up to 150°C, up to 130°C, up to 110°C, up to 100°C, up to 90°C, up to 80°C, up to 70°C, up to 60°C, up to 50°C, or up to 40°C. In some embodiments, the method is performed at temperatures between 20°C and 150°C (ends included); between 30°C and 150°C (ends included); between 25°C and 100°C (ends included); and between 25°C and 70°C (ends included). The temperatures employed are generally limited to the lowest maximum temperature at which the materials used in the method (e.g., substrate, device components, etc.) remain thermally stable.

[0063] In some embodiments, the method is performed on equipment separate from other materials used for the final application of one or more molding adhesives. In such embodiments, the method further includes removing a first bulk adhesive from the substrate, as discussed in more detail below.

[0064] The resulting adhesive is called an adhesive because of its ability to bond two materials together. Properties such as specific peel strength and tack are not particularly limited, as long as the formed adhesive bonds two materials together (e.g., two layers in a multilayer structure, two components of a device, etc.). Typically, this test involves depositing the formed adhesive between two substrates (one or both of which can be polymers, glass, ceramics, or metals), pulling the article up through the edge of one substrate, and observing whether the second substrate remains attached to the article.

[0065] In some embodiments, the adhesive incorporates a variation in refractive index. Such a variation is typically formed as an artifact of irradiating the photochemically polymerizable adhesive precursor composition with various irradiation sources. For example, for monolithic adhesives with variable thickness, there is often a variation in refractive index between monolithic adhesive portions subjected to different doses to create the variability in thickness.

[0066] refer to Figure 1 The document provides a schematic diagram of an apparatus 100 for an exemplary method of this disclosure. The apparatus includes a photochemically transparent substrate 10 having a main surface 11 and an irradiation source 12 configured to guide photochemical radiation through the photochemically transparent substrate 10 at a predetermined dose at a predetermined location. The apparatus 100 also includes means 14 for depositing a composition 16 onto the main surface 11 of the photochemically transparent substrate 10, and means 18 for conveying the photochemically transparent substrate 10 or the irradiation source 12 relative to each other. Figure 1 In the illustrated apparatus, the means 14 for depositing composition 16 onto the main surface 11 of a photochemically transparent substrate 10 includes an open container that holds the volume of composition 16 positioned adjacent to the substrate 10 such that a portion of the main surface 11 of the substrate 10 contacts composition 16. This contact causes composition 16 to be deposited on the main surface 11 of the substrate 10, and then, as the means 18 for conveying the substrate 10 rotates, composition 16 continues to be deposited on the portion of the main surface 11 of the substrate 10 that is in contact with composition 16 held in the container 14.

[0067] In some embodiments, the device 100 also includes an air knife 20 configured to remove the composition from a substrate. Air knives are well known in the art and use compressed air to blow out contaminants, excess material, etc., from a product or device.

[0068] The device optionally also includes a second substrate 22. The substrate is not particularly limited in terms of material or surface structure; for example, Figure 1 The second substrate 22 shown comprises a structured sheet, wherein at least one main surface 25 of the sheet is structured (as opposed to flat and featureless). Suitable sheet materials include, for example, but not limited to, polymers selected from: polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, cycloolefin film, poly(methyl methacrylate), or combinations thereof. The second substrate may be a film, such as a single-layer or multilayer film having a smooth or structured surface. Suitable structured surfaces include microstructured or embossed surfaces. Typically, the second substrate is used so that the adhesive can be removed from the photochemically transparent substrate after irradiation from photochemical radiation. The second substrate 22 may be fixed adjacent to or separate from the photochemically transparent substrate 10 using rollers 23 or other suitable means.

[0069] In some embodiments, the device 100 further includes a scraper 24 configured to scrape the substrate and / or a sticky roller 26 configured to clean the substrate. Alternatively, other cleaning mechanisms for removing adhesives and / or unpolymerized compositions from the substrate may be used, for example, to prepare the substrate for depositing additional compositions on its main surface using solvent washing. Furthermore, in some embodiments, the substrate includes a release material coated on the main surface of the substrate to enhance the ease of removing adhesives formed on the substrate. Suitable release materials include, for example, but not limited to, silicone materials and low-adhesion coatings. An example of a suitable low-adhesion coating is a solution of a blend of polyvinyl-N-octadecylcarbamate and silicone resin, as described in U.S. Patent No. 5,531,855 (Heinecke et al.).

[0070] In many embodiments, the photochemically transparent substrate 10 is in the form of a cylinder. The means 14 for depositing the composition 16 onto the cylindrical substrate 10 may include rotating the cylinder (e.g., the photochemically transparent substrate) through the volume of the composition 16 to apply the composition 16 onto the main surface 11 of the substrate 10. Advantageously, it is not always necessary to strictly control the thickness of the composition deposited on the substrate, because the irradiation dose from the irradiation source is selected to polymerize the composition of a predetermined shape and size, rather than polymerizing through the entire thickness of the composition regardless of its specific depth.

[0071] In certain embodiments of the method according to this disclosure, during use, Figure 1 The apparatus shown operates as follows: a device 18 for conveying a photoradiotransparent substrate 10 rotates the substrate 10 through a device 14 for depositing a composition 16, thereby depositing the composition 16 onto the main surface 11 of the substrate 10 in contact with it. An irradiation source 12 guides radiation through the photoradiotransparent substrate 10 at one or more predetermined locations and at one or more predetermined doses. The irradiated composition 16 is at least partially polymerized to form at least one adhesive, such as adhesive 17 and adhesive 19, as... Figure 1As shown. For example, adhesive 17 includes a thickness variation due to the specific irradiation provided by irradiation source 12. As substrate 10 continues to rotate (e.g., in the direction of the arrow), air knife 20 directs air toward the main surface 11 of substrate 10 to assist in removing unpolymerized composition 16 held on the main surface 11 of substrate 10 to form adhesive. Once no longer deposited on substrate 10, excess composition 16 preferably returns to container 14 by gravity. Once the formed adhesive (e.g., adhesives 27 and 29) reaches the second substrate 22 via the rotation of photochemically irradiated transparent substrate 10, adhesives (27, 29) are transferred from the main surface 11 of substrate 10 to the main surface 25 of the second substrate 22. As substrate 10 continues to rotate, scraper 24 contacts the main surface 11 of substrate 10 and removes residual adhesive from substrate 10. Additionally, adhesive roller 26 contacts the main surface 11 of substrate 10 and removes residual adhesive from substrate 10. It should be understood that not every device 100 will include both or either of the scraper 24 and the sticky roller 26, as these may be optional components.

[0072] For example, referring to the first aspect, the method may include: obtaining a photoradioactive polymerizable adhesive precursor composition 16 disposed on a main surface 11 of a photoradioactive transparent substrate 10; and irradiating a first portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate 10 with a first irradiation dose to form a first adhesive 19. The method further includes: moving the photoradioactive transparent substrate 10; and irradiating a second portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate 10 with a second irradiation dose to form a second adhesive 17. In embodiments where the method further includes irradiating a third portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate 10 with a third irradiation dose before moving the substrate, and the first and third portions are adjacent to or overlap each other, when the first and third irradiation doses are not the same, the overall adhesive 19 is formed to have a variable thickness in an axis orthogonal to the photoradioactive transparent substrate 10.

[0073] Referring to the second aspect, the method may include: obtaining a photoradioactive polymerizable adhesive precursor composition 16 disposed on a main surface 11 of a photoradioactive transparent substrate 10; and irradiating a first portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate 10 with a first irradiation dose. The method further includes: irradiating a second portion of the photoradioactive polymerizable adhesive precursor composition through the photoradioactive transparent substrate with a second irradiation dose; and moving the photoradioactive transparent substrate. The first and second portions are adjacent to or overlap each other, and the first and second irradiation doses are different, thereby forming a monolithic adhesive 19 with a variable thickness in an axis orthogonal to the photoradioactive transparent substrate 10.

[0074] Now for reference Figure 2 The present invention provides a schematic diagram of an apparatus 200 for an exemplary method of the present disclosure. The apparatus includes a photochemically transparent substrate 210 having a main surface 211 and an irradiation source 212 configured to guide photochemical radiation through the photochemically transparent substrate 210 at a predetermined dose at a predetermined location. The apparatus 200 also includes means 214 for depositing a composition 216 onto the main surface 211 of the photochemically transparent substrate 210, and means 218 for conveying the photochemically transparent substrate 210 or the irradiation source 212 relative to each other. Figure 2 The schematic diagram of the illustrated device 200 also includes an air knife 220 configured to remove the nonpolymer composition 216 from the substrate 210. Additionally, in some embodiments, the device 200 includes a second irradiation source 232 configured to irradiate one or more adhesives (e.g., adhesives 227 and 229) through the second substrate 222 as the second irradiation source 232 passes. Typically, the use of the second irradiation source 232 is effective for post-curing one or more adhesives. The second substrate 222 is typically a consumable material obtained separately from the device, and in the illustrated embodiment, it comprises a structured sheet wherein at least one main surface 225 of the sheet is structured (as opposed to flat and featureless). The second substrate 222 can be fixed to the photochemically irradiated transparent substrate 210 adjacent to or separate from it using a roller 223 or other suitable means. Figure 2 The illustrated device 200 also includes a photochemical radiation transparent film 230 having a main surface 231. The photochemical radiation transparent film 230 at least partially wraps around the photochemical radiation transparent substrate 210 and serves to protect the main surface 211 of the substrate 210 from the effects of residual composition 216 and cleaning-resistant adhesive materials.

[0075] In use, device 200 is similar to the above. Figure 1 The device 100 is operated to include the irradiated composition 216, which is at least partially polymerized to form at least one adhesive, such as adhesive 217 and adhesive 219. Once the formed adhesives (e.g., adhesives 227 and 229) reach the second substrate 222 via rotation of the photochemically irradiated transparent substrate 210, the adhesives (227, 229) are transferred from the main surface 211 of the substrate 210 to the main surface 225 of the second substrate 222. Alternatively, in some embodiments, the adhesives (227, 229) formed are irradiated by a second irradiation source 232 so that the adhesives are cured before and after transfer from the (first) substrate 210 to the second substrate 222.

[0076] refer to Figure 3The present invention provides a schematic diagram of an apparatus 300 for an exemplary method of the present disclosure. The apparatus includes a photochemically transparent substrate 310 having a main surface 311 and an irradiation source 312 configured to guide photochemical radiation through the photochemically transparent substrate 310 at a predetermined dose at a predetermined location. The apparatus 300 also includes means 314 for depositing a composition 316 onto the main surface 311 of the photochemically transparent substrate 310, and means 318 for conveying the photochemically transparent substrate 310 or the irradiation source 312 relative to each other. Figure 3 The schematic diagram of the illustrated device 300 also includes an air knife 320 configured to remove a nonpolymer composition 316 from a substrate 310, and a plurality of second irradiation sources 332 configured to irradiate one or more adhesives (e.g., adhesives 327 and 329) through a second substrate 322 as one or more adhesives pass through a second irradiation source 332. Typically, the use of at least one second irradiation source 332 is effective for post-curing one or more adhesives. The second substrate 322 is typically a consumable material obtained separately from the device, and in the illustrated embodiment, it comprises a smooth sheet. The second substrate 322 can be secured to the photochemically transparent substrate 310 adjacent to or separate from it using a roller 323 or other suitable means. In some embodiments, the device 300 also includes a scraper 324 configured to scrape the substrate 310 and / or a sticky roller 326 configured to clean the substrate 310.

[0077] In use, device 300 is similar to the above. Figure 1 The device 100 is operated to include at least partially polymerizing the irradiated composition 316 to form at least one adhesive, such as adhesive 317 and adhesive 319. Once the formed adhesives (e.g., adhesives 327 and 329) reach the second substrate 322 via rotation of the photochemically irradiated transparent substrate 310, the adhesives (327, 329) are transferred from the main surface 311 of the substrate 310 to the main surface 325 of the second substrate 322. Additionally, in some embodiments, the formed adhesives (327, 329) are irradiated by one or more second irradiation sources 332 to post-cur the adhesives before transfer from the (first) substrate 310 to the second substrate 322.

[0078] refer to Figure 4The present invention provides a schematic diagram of an apparatus 400 for an exemplary method of the present disclosure. The apparatus includes a photochemically transparent substrate 410 having a main surface 411 and an irradiation source 412 configured to guide photochemical radiation through the photochemically transparent substrate 410 at a predetermined dose at a predetermined location. The apparatus 400 also includes means 414 for depositing a composition 416 onto the main surface 411 of the photochemically transparent substrate 410, and means 418 for conveying the photochemically transparent substrate 410 or the irradiation source 412 relative to each other. Optionally, an air knife 420 configured to remove non-polymerized composition 416 from the substrate 410 is provided with the apparatus. Figure 4 The schematic diagram of the device 400 also includes a mechanism 440 configured to remove one or more adhesives (e.g., adhesive 429) as one or more adhesives pass through the second substrate 422. For example, the mechanism could be a robotic mechanism with a movable arm 442 and a replaceable end effector 444 configured to detach one or more adhesives 429 from the photochemically transparent substrate 410. Figure 4 In the illustrated embodiment, the end effector 444 includes a main surface 445 configured to be shaped opposite to the upper main surface of the adhesive 429. The mechanism 440 is generally configured to place the adhesive 429 in a location separate from the device 400, such as on another substrate, on a device, on a release liner, in a storage container, etc. In some embodiments, the device 400 also includes a scraper 424 configured to scrape the substrate 410 and / or an adhesive roller 426 configured to clean the substrate 410.

[0079] In use, device 400 is similar to the above. Figure 1 The device 100 is operated to include at least partially polymerizing the irradiated composition 416 to form at least one adhesive such as adhesive 417 and adhesive 419. However, once the formed adhesives (e.g., adhesives 427 and adhesive 429) reach the mechanism 440 via rotation of the photochemically irradiated transparent substrate 410, the adhesives (427, 429) are transferred from the main surface 411 of the substrate 410 to the main surface 445 of the end effector 444 of the mechanism 440.

[0080] refer to Figure 5The present disclosure provides a schematic diagram of an apparatus 500 for an exemplary method of the present disclosure. The apparatus includes at least two rollers 552 and 518 (at least one roller being configured to convey a photochemically transparent substrate 510), and an irradiation source 512 configured to guide photochemical radiation through the photochemically transparent substrate 510 at a predetermined location and a predetermined dose. The apparatus 500 also includes means 514 for depositing a composition 516 onto a main surface 511 of the photochemically transparent substrate 510, and means 518 for conveying the photochemically transparent substrate 510 or the irradiation source 512 relative to each other. The means 514 for deposition includes a container configured to dispense the composition 516 as a pool on the main surface 511 of the substrate 510. The photochemically transparent substrate 510 is typically a consumable material obtained separately from the apparatus, rather than a component of the apparatus. Optionally, an air knife 520 configured to remove non-polymerized composition 516 from the substrate 510, in which one or more adhesives 517 and 519 are formed, is provided with the apparatus 500.

[0081] In some implementations, during use, Figure 5 The apparatus shown operates as follows: a device 518 for conveying a photoradiotransparent substrate 510 drives the web of the photoradiotransparent substrate 510 via a plurality of rollers 550, which form a receiving area to hold the composition 516 supplied by a device 514 for depositing the composition 516 on the main surface 511 of the substrate 510 in contact with it. In this embodiment, the device 514 for deposition is a container disposed above the photoradiotransparent substrate 510. An irradiation source 512 guides radiation through the photoradiotransparent substrate 510 at one or more predetermined locations with one or more predetermined doses. The irradiated composition 516 is at least partially polymerized to form at least one adhesive such as adhesive 517 and adhesive 519, as... Figure 5 As shown. For example, adhesive 517 includes a width variation compared to adhesive 519 due to the specific irradiation provided by irradiation source 512. While continuing to drive substrate 510 from unwinding roller 552 to conveying device 518 (e.g., as shown) Figure 5 As shown on the winding roller, the air knife 520 directs air toward the main surface 511 of the substrate 510 to assist in removing unpolymerized composition 516 held on the main surface 511 of the substrate 510 to form an adhesive. Excess composition 516 is preferably returned to a receiving area defined by the plurality of rollers 550. Once the formed adhesive (e.g., adhesives 527 and 529) reaches the winding roller 518, the web of the photochemically radiant transparent substrate 510 is wound.

[0082] refer to Figure 6The present disclosure provides a schematic diagram of an apparatus 600 for an exemplary method of the present disclosure. The apparatus includes at least two rollers 652 and 618 (where at least one roller is configured to convey a photochemically transparent substrate 610), and an irradiation source 612 configured to guide photochemical radiation through the photochemically transparent substrate 610 at a predetermined dose at a predetermined location. The apparatus 600 also includes means 614 for depositing a composition 616 onto a main surface 611 of the photochemically transparent substrate 610, and means 618 for conveying the photochemically transparent substrate 610 or the irradiation source 612 relative to each other. The photochemically transparent substrate 610 is typically a consumable material obtained separately from the apparatus, rather than a component of the apparatus. The means 614 for deposition includes a container configured to dispense the composition 615 through a funnel 615 and dispense the composition 616 as a pool on the main surface 611 of the substrate 611. The apparatus also includes a dam roller 645 comprising a pair of spaced-apart edges (not shown) configured to contact the photochemically transparent substrate 610 and define a receiving area between the edges to provide space for a pool of composition 616 disposed on the photochemically transparent substrate 610.

[0083] The additional device can be configured to contact the embankment roller 645 with the photochemically transparent substrate 610 to help minimize leakage of the composition 616 from the photochemically transparent substrate 610. Figure 6 The illustrated device includes three pressure rollers 646, 647, and 648 and a belt 649. Two of the pressure rollers 646 and 647 are positioned adjacent to a third pressure roller 645, and the third pressure roller 648 is positioned at a distance from the first two pressure rollers 646 and 647. The belt 649 is configured to be in contact with a photochemically transparent substrate 610 within a loop surrounding the three pressure rollers 646, 647, and 648. The three pressure rollers 646, 647, and 648 are configured to apply force to the belt to maintain it in contact with the photochemically transparent substrate 610. When conveying the photochemically transparent substrate 610, the belt 649 passes around the three pressure rollers 646, 647, and 648.

[0084] In use, device 600 is similar to that described above. Figure 5 The equipment 500 is operated, including when the substrate 610 continues to be driven from the unwinding roller 652 (and below the embankment roller 645) to the conveying device 618 (e.g., as...). Figure 6As shown on the winding roller, the air knife 620 directs air toward the main surface 611 of the substrate 610 to assist in removing unpolymerized composition 616 held on the main surface 611 of the substrate 610 to form an adhesive by irradiation from the photochemical irradiation source 612. Excess composition 616 is preferably returned to the receiving area defined by the embankment roller 645. Once the formed adhesive (e.g., adhesives 627 and 629) reaches the winding roller 618, the web of the photochemically irradiated transparent substrate 610 is wound.

[0085] refer to Figure 7 The present disclosure provides a schematic diagram of an apparatus 700 for an exemplary method of the present disclosure. The apparatus includes at least two rollers 752 and 718 configured to convey a photochemically transparent substrate 710 (at least one roller being configured to convey the photochemically transparent substrate 710), and an irradiation source 712 configured to guide photochemical radiation through the photochemically transparent substrate 710 at a predetermined dose at a predetermined location. The apparatus 700 also includes means 714 for depositing a composition 716 onto a main surface 711 of the photochemically transparent substrate 710, and means 718 for conveying the photochemically transparent substrate 710 or the irradiation source 712 relative to each other. The photochemically transparent substrate 710 is typically a consumable material obtained separately from the apparatus 700, rather than a component of the apparatus. The apparatus also includes a dam roller 745 comprising a pair of spaced-apart edges (not shown) configured to contact a photochemically transparent substrate 710 and define a receiving area between the edges to provide space for a pool of composition 716 disposed on the photochemically transparent substrate 710. A device 714 for deposition includes a container configured to dispense composition 716 as a thin layer onto the surface of the dam roller 745, the composition 716 traveling around the dam roller 745 and forming a pool on the main surface 711 of the substrate 710.

[0086] The additional device can be configured to contact the embankment roller 745 with the photochemically transparent substrate 710 to help minimize leakage of the composition 716 from the photochemically transparent substrate 710. Figure 7 In the illustrated apparatus, such a device includes two tension rollers 754 and 756, wherein a photochemically transparent substrate 710 is fed above one tension roller 756, below a dam roller 745, and above the other tension roller 754. This configuration allows the tension rollers 754 and 756 to be configured to apply force to the photochemically transparent substrate 710 so as to keep the substrate 710 in contact with the dam roller 745 as the substrate 710 is conveyed through the apparatus.

[0087] In use, device 700 is similar to that described above. Figure 5The equipment 500 is operated, including when the substrate 710 continues to be driven from the unwinding roller 752 (and above the first tension roller 756, below the embankment roller 745, and above the second tension roller 754) to the conveying device 718 (e.g., such as...). Figure 7 As shown on the winding roller, the air knife 720 directs air toward the main surface 711 of the substrate 710 to assist in removing unpolymerized composition 716 held on the main surface 711 of the substrate 710 to form an adhesive through irradiation from the photochemical irradiation source 712. Excess composition 716 is preferably returned to the receiving area defined by the embankment roller 745. Once the formed adhesive (e.g., adhesives 727 and 729) reaches the winding roller 718, the web of the photochemically irradiated transparent substrate 710 is wound.

[0088] refer to Figure 8 The present disclosure provides a schematic diagram of an apparatus 800 for an exemplary method of the present disclosure. The apparatus includes at least two rollers 852 and 818 configured to convey a photochemically transparent substrate 810 (at least one roller being configured to convey the photochemically transparent substrate 810), and an irradiation source 812 configured to guide photochemical radiation through the photochemically transparent substrate 810 at a predetermined dose at a predetermined location. The apparatus 800 also includes means 814 for depositing a composition 816 onto a main surface 811 of the photochemically transparent substrate 810, and means 818 for conveying the photochemically transparent substrate 810 or the irradiation source 812 relative to each other. The photochemically transparent substrate 810 is typically a consumable material obtained separately from the apparatus 800, rather than a component of the apparatus. The apparatus also includes a dam roller 845 comprising a pair of spaced-apart edges (not shown) configured to contact a photochemically transparent substrate 810 and define a receiving area between the edges to provide space for a pool of composition 816 disposed on the photochemically transparent substrate 810. A device 814 for deposition includes a container configured to dispense composition 816 as a thin layer onto the surface of the dam roller 845, the composition 816 traveling around the dam roller 845 and forming a pool on the main surface 811 of the substrate 810.

[0089] The additional device can be configured to contact the embankment roller 845 with the photochemically transparent substrate 810 to help minimize leakage of the composition 816 from the photochemically transparent substrate 810. Figure 8In the illustrated apparatus, such a device includes two tension rollers 854 and 856, wherein a photochemically transparent substrate 810 is fed above one tension roller 856, below a dam roller 845, and above the other tension roller 854. This configuration allows the tension rollers 854 and 856 to be configured to apply force to the photochemically transparent substrate 810 so as to maintain contact between the substrate 810 and the dam roller 845 as the substrate 810 is conveyed through the apparatus. Figure 8 In the device shown, the tension roller is positioned adjacent to the dam roller 845 such that the photochemically transparent substrate 810 has more than 50% circumferential contact with the dam roller 845, in order to further assist in minimizing the leakage of the composition 816 from the photochemically transparent substrate 810.

[0090] In use, device 800 is similar to that described above. Figure 5 The equipment 500 is operated, including, for example, continuing to drive the substrate 810 from the unwinding roller 852 (and above the first tension roller 856, below the embankment roller 845, and above the second tension roller 854) to the conveying device 818 (e.g., such as...). Figure 8 (See the winding roller shown). Additionally, in some embodiments, the formed adhesive (e.g., 827, 829) is irradiated by one or more second irradiation sources 832 to post-cure the adhesive before winding the substrate 810. Optionally, an air knife 820 directs air toward the main surface 811 of the substrate 810 to assist in removing unpolymerized composition 816 held on the main surface 811 of the substrate 810 to form the adhesive by irradiation from the photochemical irradiation source 812. Excess composition 816 is preferably returned to the receiving area defined by the embankment roller 845. Once the formed adhesive (e.g., adhesives 827 and 829) reaches the winding roller 818, the web of the photochemically irradiated transparent substrate 810 is wound.

[0091] refer to Figure 9The present disclosure provides a schematic diagram of an apparatus 900 for an exemplary method of the present disclosure. The apparatus includes at least two rollers 952 and 918 (at least one roller being configured to convey a photochemically transparent substrate 910), and an irradiation source 912 configured to guide photochemical radiation through the photochemically transparent substrate 910 at a predetermined location and a predetermined dose. The apparatus 900 also includes means 914 for depositing a composition 916 onto a main surface 911 of the photochemically transparent substrate 910, and means 918 for conveying the photochemically transparent substrate 910 or the irradiation source 912 relative to each other. The means 914 for deposition includes a die configured to dispense the composition 916 onto the main surface 911 of the substrate 910. In such embodiments, the composition 916 is preferably sufficiently viscous to remain on the main surface 911 of the substrate 910 without leaking from the side edges of the substrate 910. The photochemically transparent substrate 910 is typically a consumable material obtained separately from the apparatus 900, rather than a component of the apparatus. Optionally, an air knife 920 configured to remove a nonpolymerized composition 916 from a substrate 910 in which one or more adhesives 917 and 919 are formed is provided together with the device 900.

[0092] Another optional component of the device 900 is a blade 960 that slices portions of the substrate 910 on which one or more adhesives (e.g., 927 and / or 929) are applied. Figure 9 The illustrated embodiment shows a stack 961 of multiple substrates 910 comprising one or more formed adhesives. In an alternative embodiment, the substrate 910 on which one or more adhesives (e.g., 927 and / or 929) are formed is wound on a winding roller (not shown).

[0093] In some implementations, during use, Figure 9 The apparatus shown operates as follows: a die 914 deposits composition 916 onto the main surface 911 of a photoradioactive transparent substrate 910. An irradiation source 912 guides radiation through the photoradioactive transparent substrate 910 at one or more predetermined locations and with one or more predetermined doses. The irradiated composition 916 polymerizes at least partially to form at least one adhesive, such as adhesive 917 and adhesive 919, as... Figure 9As shown. For example, adhesive 917 includes a width variation compared to adhesive 919 caused by the specific irradiation provided by irradiation source 912. A device 918 for conveying the photochemically transparent substrate 910 drives the web of the substrate 910 above roller 952 to allow gravity to begin separating the unpolymerized composition 916 to form adhesives (e.g., 917 and 919). As the substrate 910 continues to be driven from the first roller 918 to the second roller 952, an air knife 920 directs air toward the main surface 911 of the substrate 910 to assist in removing the composition 916 retained on the main surface 911 of the substrate 910. Excess composition 916 is preferably deposited in container 958 for recycling or reuse. Once a specific portion of the substrate 910 retaining at least one of the formed adhesives (e.g., adhesive 927 and / or adhesive 929) reaches the blade 960, the blade 960 is used, and that portion of the photochemically transparent substrate 910 is cut off (and optionally added to the stack 961 of each substrate 910 piece including at least one of the formed adhesives 927).

[0094] See Figure 1-9 In each of the figures, the photochemically transparent substrate includes glass (e.g., in...). Figure 1-4 (in any of the figures) or polymer materials (e.g., in Figure 1-9 (As shown in any of the figures). When the photochemically transparent substrate comprises a polymeric material, the substrate typically comprises a polymeric material selected from: polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, cycloolefin film, poly(methyl methacrylate), or combinations thereof. When the photochemically transparent substrate comprises glass, the substrate typically comprises a glass selected from: borosilicate glass, soda-lime glass, and quartz glass. In some embodiments, the substrate comprises a multilayer structure, such as a polymer sheet, an adhesive layer, and a backing. In embodiments where the adhesive is intended to be transferred from the multilayer structure to another surface or substrate, the multilayer structure comprises a coating (e.g., a release coating) on ​​which a monolithic adhesive is disposed.

[0095] Figure 1-9 Each figure in the diagram is referred to as a device for transferring a photochemically irradiated transparent substrate or irradiation source relative to each other. The device for transfer typically includes mechanical devices as known in the manufacturing industry, such as electric motors, servo motors, stepper motors, or any combination thereof. Typically, the electric motor ultimately drives one or more rollers that transfer the substrate (e.g., a cylinder or web of indefinite length) and / or the irradiation source.

[0096] Reference Figure 1-9In each of the diagrams, photochemical radiation is typically provided by an irradiation source, which can be a digital light projector (DLP) with light-emitting diodes (LEDs), a DLP with lamps, a laser scanning device with lasers, a liquid crystal display (LCD) panel with a backlight, a photomask with lamps, or a photomask with LEDs. More specifically, Figure 10 The diagram provides a schematic of a DLP with LEDs or lamps, and Figures 11a and 11b provide schematics of photomasks with lamps or LEDs. Figure 12 The document provides a schematic diagram of an LCD panel with a backlight, and... Figure 13 The diagram provided is a schematic of a laser scanning device with a laser.

[0097] See now Figure 10The present disclosure provides a schematic diagram of an irradiation source 1000 for an exemplary method of the present disclosure, comprising a DLP 1065 having an LED or lamp 1066 (1066 represents an LED or lamp). The DLP 1065 includes a plurality of individually movable reflectors, such as a first reflector 1062, a second reflector 1063, and a third reflector 1064. Each reflector is positioned at a specific angle to direct irradiation from the LED or lamp 1066 toward a predetermined location of the composition 1016 disposed on the main surface 1011 of a photochemically transparent substrate 1010. In use, the intensity and duration of irradiation from the LED or lamp 1066 during the formation of one or more adhesives 1017 and 1019 will affect the curing (e.g., polymerization) depth of the composition 1016 in a direction orthogonal to the main surface 1011 of the substrate 1010. For example, a portion 1017b of the monolithic adhesive 1017 has a greater thickness than another portion 1017a of the same monolithic adhesive 1017. This can be achieved by irradiating part 1017b with a larger dose than part 1017a. In contrast, adhesive 1019 has a single thickness across its width because it receives the same dose across its width. The advantage of using a DLP is that individual reflectors can be easily adjusted (e.g., using computer control) to change the irradiation location and dose, and thereby change the shape of the resulting molded adhesive as needed without significant equipment modifications. DLPs are well known in the art, for example and not limited to U.S. Patent Nos. 5,658,063 (Nasserbakht), 5,905,545 (Poradish et al.), 6,587,159 (Dewald), 7,164,397 (Pettitt et al.), 7,360,905 (Davis et al.), 8,705,133 (Lieb et al.), and 8,820,944 (Vasquez). Suitable DLPs are commercially available, such as those from Texas Instruments (Dallas, TX). As indicated above, LEDs or lamps may be used in conjunction with DLP. Suitable lamps may include flashlights, low-pressure mercury lamps, medium-pressure mercury lamps, and / or microwave-driven lamps. A skilled technician may select a suitable LED or lamp source to provide the photochemical radiation required to initiate polymerization of a particular polymerizable composition, such as the UV LED CBT-39-UV available from Luminus Inc. (Sunnyvale, CA).

[0098] Referring now to Figures 11a and 11b, a schematic diagram is provided including an irradiation source 1100 comprising at least one photomask 1170a and 1170b having an LED or lamp 1166 (1166 denotes an LED or lamp) for use in the exemplary method of this disclosure. A lens 1167 having a convex surface 1168 is employed together with the LED or lamp 1166 to diffuse irradiation onto at least a portion of one or more photomasks 1170a and 1170b. As shown in Figure 11a, a first photomask 1170a is employed to direct irradiation from the LED or lamp 1166 toward a predetermined position of a composition 1116 disposed on a main surface 1111 of a photochemically irradiated transparent substrate 1110. In use, when forming one or more adhesives 1117 and 1119, the intensity and duration of irradiation from the LED or lamp 1166 will affect the curing (e.g., polymerization) depth of composition 1116 in a direction orthogonal to the main surface 1111 of substrate 1110. For example, a portion 1117b of the monolithic adhesive 1117 has a greater thickness than another portion 1017a of the same monolithic adhesive 1117. This can be achieved by using more than one photomask. For example, referring to Figure 11a, which shows photomask 1170a, in which multiple portions 1171a of composition 1116 are provided for irradiation that can be guided therethrough to cure composition 1116. Referring now to Figure 11b, which shows a second photomask 1170b, in which a portion 1171b of composition 1116 is provided for irradiation that can be guided therethrough to further cure composition 1116. In the illustrated embodiment, portion 1117b has a greater thickness than portion 1117a due to being irradiated twice; once using a first photomask 1170a and once using a second photomask 1170b; resulting in portion 1117b being irradiated with a greater dose than portion 1117a. In contrast, adhesive 1119 has a single thickness across its width because it receives the same dose across its width only through exposure to irradiation via the first photomask 1170a. Although the photomasks in Figures 11a and 11b are shown as having opaque and transparent portions, those skilled in the art will understand that photomasks including grayscale can be used to achieve a gradient of curing at different locations of the composition. Suitable photomasks are commercially available, such as nano-engraved photomasks from Infinite Graphics (Minneapolis, MN). Similar to the use of DLPs, LEDs, or lamps can be employed in conjunction with the photomask.

[0099] See Figure 12The present invention provides an irradiation source 1200 (e.g., an LCD with a backlight 1266) including a digital photomask 1272, wherein the backlight includes an LED or lamp 1266 (1266 represents an LED or lamp) for use in the exemplary methods of this disclosure. A lens 1267 having a convex surface 1268 is employed together with the backlight 1266 to diffuse irradiation over at least a portion of the digital photomask 1272. In use, the intensity and duration of irradiation from the backlight 1266 will affect the curing (e.g., polymerization) depth of the composition 1216 in a direction orthogonal to the main surface 1211 of the substrate 1210 when forming one or more adhesives 1217 and 1219. For example, a portion 1217b of the monolithic adhesive 1217 has a greater thickness than another portion 1217a of the same monolithic adhesive 1217. This can be achieved by irradiating portion 1217b with a larger dose than portion 1217a. In contrast, adhesive 1219 has a single thickness across its width because it receives the same dose across its width. The advantage of using a digital photomask is that individual pixels can be easily adjusted (e.g., using computer control) to change the irradiation position and dose, and thus the shape of the resulting molded adhesive can be changed as needed without significant equipment modifications. Suitable LCDs are commercially available, such as LCD LQ043T1DG28 from Sharp Corporation (Osaka, Japan).

[0100] See Figure 13The present invention provides a schematic diagram of an irradiation source 1300 including a laser scanning device 1362 having a laser 1366 for use in an exemplary method of the present disclosure. The laser scanning device 1362 includes at least one individually movable mirror. Each mirror is positioned at a specific angle to guide irradiation from the laser 1366 toward a predetermined position of the composition 1316 disposed on the main surface 1311 of a photochemically transparent substrate 1310. In use, the intensity and duration of irradiation from the laser 1366 will affect the curing (e.g., polymerization) depth of the composition 1316 in a direction orthogonal to the main surface 1311 of the substrate 1310 when forming one or more adhesives 1317 and 1319. For example, a portion 1317b of the monolithic adhesive 1317 has a greater thickness than another portion 1317a of the same monolithic adhesive 1317. This can be achieved by irradiating portion 1317b with a larger dose than portion 1317a. In contrast, adhesive 1319 has a single thickness across its width because it receives the same dose across its width. The advantage of using a laser scanning device is that one or more individual reflectors can be easily adjusted (e.g., using computer control) to change the irradiation position and dose, and thereby change the shape of the resulting molded adhesive as needed, without significant equipment modifications. Suitable laser scanning devices are commercially available, such as the JS2808 galvanometer scanner from Sino-Galvo (Beijing) Technology Co.,LTD. (Beijing, China). Technicians can select a suitable laser to provide the photochemical radiation required to initiate polymerization of a particular polymerizable composition, such as the CUBE 405-100C diode laser system from Coherent Inc. (Santa Clara, CA).

[0101] Therefore, any of the above-described irradiation sources of this disclosure are applicable to each device of the embodiments disclosed herein. The advantage of these irradiation sources is that they are easily configured to provide one or more predetermined doses of irradiation at one or more predetermined locations, thereby allowing the preparation of adhesives with variations in size and shape (especially in thickness perpendicular to the substrate).

[0102] Exemplary Implementation

[0103] Implementation Scheme 1 is a method for preparing an adhesive. The method includes: obtaining a photochemically radioactive polymerizable adhesive precursor composition disposed on the main surface of a photochemically radioactive transparent substrate; and irradiating a first portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate with a first irradiation dose to form a first adhesive; the method further includes: moving the photochemically radioactive transparent substrate; and irradiating a second portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate with a second irradiation dose to form a second adhesive.

[0104] Embodiment 2 is the method according to Embodiment 1, further comprising irradiating a third portion of the photochemically irradiated polymerizable adhesive precursor composition through a photochemically irradiated transparent substrate prior to moving the substrate to form a third adhesive.

[0105] Implementation scheme 3 is the method according to implementation scheme 1 or implementation scheme 2, wherein the first part and the third part are adjacent to or overlap each other.

[0106] Implementation scheme 4 is the method according to any one of implementation schemes 1 to 3, wherein the first irradiation dose and the third irradiation dose are different, thereby forming an integral adhesive comprising a first adhesive and a third adhesive, the integral adhesive having a variable thickness in an axis orthogonal to the photochemical radiation transparent substrate.

[0107] Implementation scheme 5 is the method according to any one of implementation schemes 1 to 4, further comprising post-curing the first adhesive.

[0108] Implementation scheme 6 is the method according to implementation scheme 5, wherein the post-curing includes photochemical radiation or heating.

[0109] Embodiment 7 is the method according to any one of Embodiments 1 to 6, further comprising irradiating a fourth portion of the photochemically irradiated polymerizable adhesive precursor composition through the photochemically irradiated transparent substrate to form a fourth adhesive.

[0110] Embodiment 8 is the method according to Embodiment 7, wherein the second portion and the fourth portion are adjacent to or overlap each other, thereby forming a second integral adhesive including the second adhesive and the fourth adhesive, the second integral adhesive having a variable thickness in an axis orthogonal to the main surface of the photochemical radiation transparent substrate.

[0111] Embodiment 9 is a method according to any one of Embodiments 1 to 8, further comprising using a gas, vacuum, fluid, or a combination thereof to remove from the first adhesive the photochemically irradiable polymerizable adhesive precursor composition that remains in contact with the adhesive after irradiation.

[0112] Implementation scheme 10 is the method according to any one of implementation schemes 1 to 9, further comprising removing the first adhesive from the substrate.

[0113] Implementation scheme 11 is the method according to implementation scheme 10, wherein the first adhesive is removed together with the second substrate.

[0114] Implementation scheme 12 is the method according to implementation scheme 11, wherein the second substrate comprises a microstructured sheet.

[0115] Implementation scheme 13 is the method according to implementation scheme 10, which includes using a robot to remove the first monolithic adhesive from the substrate.

[0116] Implementation scheme 14 is the method according to any one of implementation schemes 10 to 13, and further includes cleaning the substrate.

[0117] Implementation scheme 15 is the method according to any one of implementation schemes 1 to 14, wherein the substrate is coated with a release material.

[0118] Implementation scheme 16 is the method according to any one of implementation schemes 1 to 15, wherein the substrate comprises a glass or polymer material.

[0119] Implementation scheme 17 is the method according to any one of implementation schemes 1 to 16, wherein the substrate is in the form of a cylinder.

[0120] Embodiment 18 is the method according to Embodiment 17, comprising rotating a cylinder through a container holding a photochemically irradiable polymerizable adhesive precursor composition to place the photochemically irradiable polymerizable adhesive precursor composition on a substrate.

[0121] Implementation scheme 19 is the method according to any one of implementation schemes 1 to 16, wherein the precursor composition is disposed on a pool on the main surface of the substrate.

[0122] Implementation scheme 20 is the method according to any one of implementation schemes 1 to 19, wherein the irradiation time of the first dose is shorter than the irradiation time of the second dose.

[0123] Implementation scheme 21 is the method according to any one of implementation schemes 1 to 20, wherein the photochemical radiation intensity of the first dose is lower than that of the second dose.

[0124] Implementation scheme 22 is the method according to any one of implementation schemes 1 to 21, wherein the first part is irradiated before the second part is irradiated.

[0125] Implementation scheme 23 is the method according to any one of implementation schemes 1 to 22, wherein irradiation of the first part and irradiation of the second part occur simultaneously.

[0126] Implementation scheme 24 is the method according to any one of implementation schemes 1 to 23, wherein the first adhesive is a pressure-sensitive adhesive (PSA), a structural adhesive, a structural hybrid adhesive, a hot melt adhesive, or a combination thereof.

[0127] Embodiment 25 is the method according to any one of Embodiments 1 to 24, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises acrylate, a two-component acrylate and epoxy resin system, a two-component acrylate and urethane system, or a combination thereof.

[0128] Implementation scheme 26 is the method of any one of implementation schemes 1 to 25, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises acrylate.

[0129] Embodiment 27 is the method according to any one of Embodiments 1 to 26, wherein the photoinitiator is selected from 1-hydroxycyclohexylbenzophenone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1-one.

[0130] Implementation scheme 28 is a method according to any one of implementation schemes 1 to 27, wherein photochemical radiation is provided by a digital light projector (DLP) having light-emitting diodes (LEDs), a DLP having lamps, a laser scanning device having lasers, a liquid crystal display (LCD) panel having a backlight, a photomask having lamps, or a photomask having LEDs.

[0131] Implementation scheme 29 is the method according to implementation scheme 28, wherein the lamp is selected from flash lamps, low-pressure mercury lamps, medium-pressure mercury lamps, and microwave-driven lamps.

[0132] Implementation scheme 30 is a method according to any one of implementation schemes 1 to 29, wherein the first adhesive adheres the two materials together.

[0133] Implementation scheme 31 is the method according to any one of implementation schemes 1 to 30, wherein the first adhesive includes a change in refractive index.

[0134] Implementation scheme 32 is the method according to any one of implementation schemes 1 to 31, wherein the substrate comprises a multilayer structure.

[0135] Embodiment 33 is the method according to Embodiment 32, wherein the multilayer structure includes a polymer sheet, an adhesive layer, and a liner.

[0136] Implementation scheme 34 is the method according to implementation scheme 32 or implementation scheme 33, wherein the multilayer structure includes a coating thereon on which a first adhesive is disposed.

[0137] Embodiment 35 is the method according to any one of Embodiments 1 to 34, wherein the photochemically irradiated polymerizable adhesive precursor composition is 100% polymerizable precursor composition.

[0138] Implementation Scheme 36 Weibo The method according to any one of Implementation Schemes 1 to 35, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises at least one solvent.

[0139] Implementation scheme 37 is the method according to implementation scheme 15, wherein the release material comprises silicone resin.

[0140] Implementation scheme 38 is the method according to any one of implementation schemes 1 to 37, wherein the method is performed at a temperature between 20°C and 150°C (endpoints included).

[0141] Embodiment 39 is a method for preparing an adhesive. The method includes: obtaining a photoradiopolymerizable adhesive precursor composition disposed on a main surface of a photoradiotransparent substrate; and irradiating a first portion of the photoradiopolymerizable adhesive precursor composition through the photoradiotransparent substrate with a first irradiation dose. The method further includes: irradiating a second portion of the photoradiopolymerizable adhesive precursor composition through the photoradiotransparent substrate with a second irradiation dose; and moving the photoradiotransparent substrate. The first and second portions are adjacent to or overlap each other, and the first and second irradiation doses are different, thereby forming a monolithic adhesive with variable thickness in an axis orthogonal to the photoradiotransparent substrate.

[0142] Embodiment 40 is the method according to Embodiment 39, further comprising irradiating a third portion of the photochemically irradiated polymerizable adhesive precursor composition through a photochemically irradiated transparent substrate after moving the substrate, to deliver a third irradiation dose.

[0143] Implementation scheme 41 is the method according to implementation scheme 40, wherein the first irradiation dose and the third irradiation dose are the same.

[0144] Embodiment 42 is the method according to Embodiment 40 or Embodiment 41, further comprising irradiating a fourth portion of the photochemically irradiated polymerizable adhesive precursor composition through a photochemically irradiated transparent substrate with a fourth irradiation dose. The third portion and the fourth portion are adjacent to or overlap each other, and the third irradiation dose and the fourth irradiation dose are not the same.

[0145] Embodiment 43 is the method according to Embodiment 42, further comprising moving the photochemically radioactive transparent substrate after irradiating a fourth portion of the photochemically radioactive polymerizable adhesive precursor composition through the photochemically radioactive transparent substrate.

[0146] Implementation scheme 44 is the method according to any one of implementation schemes 39 to 43, further comprising post-curing the integral adhesive.

[0147] Implementation scheme 45 is the method according to implementation scheme 44, wherein the post-curing includes photochemical radiation or heating.

[0148] Embodiment 46 is the method according to any one of embodiments 39 to 45, further comprising using a gas, vacuum, fluid, or a combination thereof to remove the photochemically irradiable polymerizable adhesive precursor composition that remains in contact with the bulk adhesive after irradiation.

[0149] Implementation scheme 47 is the method according to any one of implementation schemes 39 to 46, further comprising removing the bulk adhesive from the substrate.

[0150] Implementation scheme 48 is the method according to implementation scheme 47, wherein the integral adhesive is removed together with the second substrate.

[0151] Implementation scheme 49 is the method according to implementation scheme 48, wherein the second substrate comprises a microstructured sheet.

[0152] Implementation scheme 50 is the method according to implementation scheme 47, which includes using a robot to remove the monolithic adhesive from the substrate.

[0153] Implementation scheme 51 is the method according to any one of implementation schemes 47 to 50, and further includes cleaning the substrate.

[0154] Implementation scheme 52 is the method according to any one of implementation schemes 39 to 51, wherein the substrate is coated with a release material.

[0155] Embodiment 53 is a method according to any one of embodiments 39 to 52, wherein the substrate comprises a glass or polymer material.

[0156] Implementation scheme 54 is the method according to any one of implementation schemes 39 to 53, wherein the substrate is in the form of a cylinder.

[0157] Embodiment 55 is the method according to Embodiment 54, comprising rotating a cylinder through a container holding a photoradiopolymerizable adhesive precursor composition to place the photoradiopolymerizable adhesive precursor composition on a substrate.

[0158] Implementation scheme 56 is the method according to any one of implementation schemes 39 to 53, wherein the precursor composition is disposed on a pool on the main surface of the substrate.

[0159] Implementation scheme 57 is the method according to any one of implementation schemes 39 to 56, wherein the irradiation time of the first dose is shorter than the irradiation time of the second dose.

[0160] Implementation scheme 58 is the method according to any one of implementation schemes 39 to 57, wherein the photochemical radiation intensity of the first dose is lower than that of the second dose.

[0161] Implementation scheme 59 is the method according to any one of implementation schemes 39 to 58, wherein the first part is irradiated before the second part is irradiated.

[0162] Implementation scheme 60 is the method according to any one of implementation schemes 39 to 59, wherein irradiation of the first part and irradiation of the second part occur simultaneously.

[0163] Embodiment 61 is a method according to any one of Embodiments 39 to 60, wherein the integral adhesive is a pressure-sensitive adhesive (PSA), a structural adhesive, a structural hybrid adhesive, a hot melt adhesive, or a combination thereof.

[0164] Embodiment 62 is the method according to any one of Embodiments 39 to 61, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises acrylate, a two-component acrylate and epoxy resin system, a two-component acrylate and urethane system, or a combination thereof.

[0165] Implementation scheme 63 is the method of any one of implementation schemes 39 to 62, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises acrylate.

[0166] Embodiment 64 is a method according to any one of Embodiments 39 to 63, wherein the photoinitiator is selected from 1-hydroxycyclohexylbenzophenone, 2,2-dimethoxy-1,2-diphenylethyl-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1-one.

[0167] Implementation scheme 65 is a method for LEDs according to any one of embodiments 39 to 64, wherein photochemical radiation is provided by a digital light projector (DLP) having light-emitting diodes (LEDs), a DLP having lamps, a laser scanning device having lasers, a liquid crystal display (LCD) panel having a backlight, a photomask having lamps, or a photomask having LEDs.

[0168] Implementation scheme 66 is the method according to implementation scheme 65, wherein the lamp is selected from flash lamps, low-pressure mercury lamps, medium-pressure mercury lamps, and microwave-driven lamps.

[0169] Implementation scheme 67 is a method according to any one of implementation schemes 39 to 66, wherein the integral adhesive adheres the two materials together.

[0170] Implementation scheme 68 is a method according to any one of implementation schemes 39 to 67, wherein the integral adhesive includes a change in refractive index.

[0171] Implementation scheme 69 is a method according to any one of implementation schemes 39 to 68, wherein the substrate comprises a multilayer structure.

[0172] Implementation scheme 70 is the method according to implementation scheme 69, wherein the multilayer structure includes a polymer sheet, an adhesive layer and a liner.

[0173] Implementation 71 is the method according to implementation 69 or implementation 70, wherein the multilayer structure includes a coating on which an integral adhesive is disposed.

[0174] Embodiment 72 is the method according to any one of Embodiments 39 to 71, wherein the photochemically irradiated polymerizable adhesive precursor composition is 100% polymerizable precursor composition.

[0175] Embodiment 73 is a method according to any one of embodiments 39 to 72, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises at least one solvent.

[0176] Implementation scheme 74 is the method according to implementation scheme 73, wherein the stripping material comprises silicone resin.

[0177] Implementation scheme 75 is the method according to any one of implementation schemes 39 to 74, wherein the method is performed at a temperature between 20°C and 150°C (endpoints included).

[0178] Example

[0179] These embodiments are for illustrative purposes only and are not intended to unduly limit the scope of the appended claims. While the numerical ranges and parameters illustrating the broad scope of this disclosure are approximations, the values ​​shown in the specific examples are recorded as precisely as possible. However, any numerical value inherently contains some error, which is necessarily caused by the standard deviation present in their respective test measurements. At a minimum, and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should at least be interpreted according to the significant digits of the reported value and by applying conventional rounding.

[0180] Material Summary

[0181] Unless otherwise stated, all parts, percentages, ratios, etc., in the embodiments and the remainder of this specification are by weight. Table 1 provides the role and source of the materials used in the following embodiments:

[0182] Table 1. Materials

[0183]

[0184] Experimental equipment

[0185] like Figure 1 The diagram broadly depicts an apparatus for the continuous manufacture of additives for adhesives. The photochemically transparent substrate 10 is constructed from an optically transparent cast acrylate tube with an outer diameter of 8 inches (20.32 cm) × an inner diameter of 7-3 / 4 inches (19.7 cm), cut to a length of 6 inches (15.24 cm). This tube, obtained as item 8486K735 from McMaster-Carr, Chicago, 11, is wound with a 5-mil (127-micron) thick transparent PET silicone release liner of type RF12N, available from SKC Haas in Seoul, South Korea. Thus, the siliconeized side of the release liner forms the main surface 11 of the photochemically transparent substrate 10.

[0186] A sidewall made of flat cast acrylic sheet, with a 2-inch (5.08 cm) center hole and smaller access holes, is inserted into a clear cast acrylic tube. A bearing with a 2-inch outer diameter and a 1-inch inner diameter is inserted into the 2-inch (5.08 cm) hole, allowing the clear cast acrylic tube to rotate around a fixed, hollow steel tube with a diameter of 1 inch (2.54 cm). The steel tube is attached to a frame constructed of extruded aluminum. The drive system consists of a 3D-printed gear attached to the acrylic sidewall and a matching gear on a 12V DC geared motor, model ZGA25RP83i, manufactured by Wenzhou Zhengke Electromotor Co., Ltd. in Yueqing, China.

[0187] A 10mm hole is drilled in the center of the steel pipe, and two LEDs (one emitting 390nm UV light, model UV3TZ-390-15, and the other emitting 405nm UV light, model UV3TZ-405-15, both available from Bivar Inc., Irvine, California) with 40cm cable leads and 82ohms resistors are inserted through the hole and mounted to the fixed hollow steel pipe using small acrylic rods. The LEDs face downwards towards the inside of the transparent cast acrylic pipe and are approximately 5mm away from the inner surface of the pipe.

[0188] A DC motor and two LEDs are connected to an Arduino R3 microcontroller with Arduino motor shielding, available from SparkFun Electronics, Niwot, CO. The microcontroller is programmed to rotate the transparent cast acrylic tube approximately 30 degrees, then stop and illuminate the LEDs for 2 hours; this program is set to repeat this sequence a total of 10 times.

[0189] The container 16, which has a substrate measuring 6.5 inches (16.51 cm) × 4.5 inches (11.43 cm) and sidewalls 0.5 inches (1.27 cm) high, is made of optically fluorescent cast acrylate Amber (thickness 3 / 32") purchased as McMaster-Carr, Chicago, IL as 85635K471 and is placed on a lifting platform below a transparent cast acrylate tube.

[0190] The "Ultra-High Efficiency Compressed Air Knife, Aluminum, 6" with an air gap width, purchased from McMaster-Carr, Chicago, IL as Project 6069K12, is assembled into the frame so that during the rotation of the drum, it blows excess composite material from the main surface 11 back into the container 16.

[0191] The intensity and energy of the LED at the main surface 11 were measured using a UV intensity analyzer (model 356) from OAI Instruments in San Jose, California. A 400 nm broadband sensor was attached to the analyzer with the sensor surface centered below the LED, and the sensor housing contacting the main surface 11. For a 390 nm LED, 39.3 mW / cm² was measured within 2 seconds of illumination. 2 Its strength and 79.1 mJ / cm 2 Energy dose. For a 405nm LED, 31.3mW / cm² was measured within 2 seconds of illumination. 2 Its strength and 63.7 mJ / cm 2 Energy dose.

[0192] Example 1

[0193] A photochemically polymerizable composition was prepared by filling a 100ml amber-colored wide-mouth glass flask with 6.25g of AA, 21.9g of iOA and 21.9g of iBOA, 0.156g of HDDA, 0.05g of TINOPALOB CO, 0.05g of BHT, and 0.75g of IRGACURE TPO. The flask was sealed and rotated on a top roller MX-T6-S on a laboratory bench at approximately 10 RPM for 2 hours.

[0194] The composition is poured into container 16 of the experimental apparatus and the container is lifted by means of a lifting platform so that the composition contacts the main surface 11 directly below the LED.

[0195] The experimental equipment was switched on and went through the sequence of rotating the drum and turning on the LEDs.

[0196] It was observed that dots of the cured adhesive composition formed at the spots illuminated by the LEDs. As the drum rotated, these dots emerged from the liquid composition, and excess liquid composition flowed out from the main surface 11 and returned to the container 16. The dots had a diameter of approximately 3 mm and a width of 0.5 mm.

[0197] Microscope slides were pressed onto the spots, and their adhesion to the slides was observed. The spots were then post-cured for 10 minutes in an Asiga flash UV post-curing chamber, available in Anaheim Hills, California, USA. This chamber contained four 9W fluorescent lamps with a peak wavelength of 365nm, arranged approximately 2 inches (5.08cm) away from the 5.5-inch (13.97cm) × 5.75-inch (14.61cm) substrate. UV intensity was measured using a UV intensity analyzer (Model 356) from OAI Instruments, San Jose, California, with a wide-band sensor of 400nm. Approximately 5.3mW / cm² was found across the entire substrate. 2 UV intensity.

[0198] After post-curing, touch the points, and they feel sticky and adhere to your fingers (like pressure-sensitive adhesive). Press a piece of paper onto the points, and observe that the paper and the glass slide adhere together.

[0199] While certain exemplary embodiments have been described in detail in this specification, it should be understood that modifications, variations, and equivalents of these embodiments will readily occur to those skilled in the art upon understanding the foregoing. Furthermore, all publications and patents cited herein are incorporated herein by reference in their entirety, as if each individual publication or patent were specifically and individually indicated to be incorporated by reference. Various exemplary embodiments have been described. These embodiments, as well as other embodiments, are within the scope of the following claims.

Claims

1. A method for preparing an adhesive, comprising: Obtain a photoradioactive polymerizable adhesive precursor composition disposed on the main surface of a photoradioactive transparent substrate; A first irradiation dose is applied to a first portion of the photochemically irradiated polymerizable adhesive precursor composition through the photochemically irradiated transparent substrate to form a first adhesive; Move the photochemically radiated transparent substrate; as well as A second portion of the photochemically irradiated polymerizable adhesive precursor composition is irradiated through the photochemically irradiated transparent substrate to form a second adhesive. The third portion of the photochemically irradiated polymerizable adhesive precursor composition is irradiated through the photochemically irradiated transparent substrate before being moved to form a third adhesive. Wherein, the first adhesive and the second adhesive are separate adhesives spaced apart from each other by the distance the photochemically transparent substrate moves, and The first portion and the third portion are adjacent to or overlap each other, and the first irradiation dose and the third irradiation dose are different, so that the curing depth of the portion receiving the larger irradiation dose in the direction orthogonal to the surface of the photochemically transparent substrate is greater than the curing depth of the portion receiving the smaller irradiation dose in the direction orthogonal to the surface of the photochemically transparent substrate, thereby forming an integral adhesive including the first adhesive and the third adhesive, the integral adhesive having a variable thickness in an axis orthogonal to the photochemically transparent substrate.

2. The method of claim 1, wherein the integral adhesive comprises a change in refractive index.

3. The method according to claim 1, further comprising post-curing the first adhesive.

4. The method of claim 1, further comprising using a vacuum, a fluid, or a combination thereof to remove the photochemically irradiable polymerizable adhesive precursor composition that remains in contact with the first adhesive after irradiation.

5. The method of claim 4, wherein the fluid comprises a gas.

6. The method of claim 1, further comprising removing the first adhesive from the substrate.

7. The method of claim 1, wherein the substrate is in the form of a cylinder, and the method further comprises rotating the cylinder through a container holding the photochemically radiopolymerizable adhesive precursor composition to dispose the photochemically radiopolymerizable adhesive precursor composition on the substrate.

8. The method of claim 1, wherein the precursor composition is disposed as a pool on the main surface of the substrate.

9. The method according to claim 1, wherein the irradiation time of the first irradiation dose is shorter than the irradiation time of the second irradiation dose.

10. The method according to claim 1, wherein the photochemical radiation intensity of the first irradiation dose is lower than the photochemical radiation intensity of the second irradiation dose.

11. The method of claim 1, wherein the first portion is irradiated before the second portion is irradiated.

12. The method of claim 1, wherein the first adhesive is a pressure-sensitive adhesive, a structural adhesive, a structural hybrid adhesive, a hot melt adhesive, or a combination thereof.

13. The method of claim 1, wherein the photochemically polymerizable adhesive precursor composition comprises acrylate, a two-component acrylate and epoxy resin system, a two-component acrylate and urethane system, or a combination thereof.

14. The method according to any one of claims 1 to 13, wherein the photochemical radiation is provided by a digital light projector with lamps, a laser scanning device with lasers, a liquid crystal display panel with a backlight, or a photomask with lamps.

15. The method of claim 14, wherein the photochemical radiation is provided by a digital light projector having light-emitting diodes or a photomask having light-emitting diodes.

16. The method of claim 1, wherein the substrate comprises a multilayer structure.

17. The method of claim 1, wherein the photochemically irradiable polymerizable adhesive precursor composition comprises at least one solvent.

18. The method of claim 1, wherein the method is performed at a temperature greater than or equal to 20 degrees Celsius and less than or equal to 150 degrees Celsius.

19. A method for preparing an adhesive, comprising: Obtain a photoradioactive polymerizable adhesive precursor composition disposed on the main surface of a photoradioactive transparent substrate; A first irradiation dose is applied to a first portion of the photoradiatively polymerizable adhesive precursor composition through the photoradiatively transparent substrate. A second portion of the photochemically irradiated polymerizable adhesive precursor composition is irradiated through the photochemically irradiated transparent substrate before the substrate is moved, wherein the first portion and the second portion are adjacent to or overlap each other, and the first irradiation dose and the second irradiation dose are different, such that the portion receiving the larger irradiation dose has a greater curing depth in a direction orthogonal to the surface of the photochemically irradiated transparent substrate than the portion receiving the smaller irradiation dose in a direction orthogonal to the surface of the photochemically irradiated transparent substrate, thereby forming an integral adhesive with a variable thickness in an axis orthogonal to the photochemically irradiated transparent substrate; as well as Move the photochemically radiated transparent substrate.

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