(CO) POLYMER, MANUFACTURING ARTICLE, METHOD FOR APPLYING PHOTO-ALIGNMENT MATERIAL ON AN OPTICAL ELEM

专利摘要:
(co) polymer, article of manufacture, method for applying a photo alignment material to an optical element and (co) polymer composition the present disclosure provides new photo alignment (co) polymer materials demonstrating improved adhesion to a substrate . the (co) polymeric structure includes at least one photochemically active chromophore and at least one adhesion promoter group. Also disclosed are articles of manufacture, optical elements, ophthalmic elements and liquid crystal cells which include at least one photoalignment layer made of photoalignment (co) polymer materials and methods for forming.
公开号:BR112012013530B1
申请号:R112012013530-9
申请日:2010-12-06
公开日:2019-09-17
发明作者:Gobinda Saha；Anil Kumar
申请人:Transitions Optical, Inc.；
IPC主号:

专利说明:

History of the invention [0001] The present disclosure relates to new (co) polymeric materials suitable for use as photoalignment layers. The new photo-alignment materials comprise a structurally photo-orientable anisotropic polymer network that exhibits improved adhesion to substrate surfaces and can align thicker layers of monomeric and polymeric liquid crystals. Methods for making and applying new photo-alignment materials are also disclosed.
[0002] Liquid crystal materials are used in a variety of applications where the liquid crystal material is deposited as a layer on the surface of a substrate. The successful operation of a liquid crystal device depends, at least in part, on the ability of the liquid crystal molecules within the layer to adopt and maintain a particular alignment or orientation. These layers of liquid crystals can be aligned or oriented using various methods. One approach is to coat the surface of the substrate with an orientation layer before applying the liquid crystal layer. The orientation layer can then be used to orient the liquid crystal material on the substrate, for example, by friction or irradiation with polarized electromagnetic radiation. The orientation layer defines the direction of orientation of the liquid crystal molecules of the layer with the consequence that the longitudinal axes of the molecules become aligned with the direction
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2/84 orientation defined by the orientation layer. In addition to the directional alignment, the orientation layer can also provide an angle of inclination for the liquid crystal molecules, so that the molecules themselves align at an angle to the surface of the orientation layer instead of being parallel to the surface.
[0003] The orientation of polymeric layers by irradiation with polarized electromagnetic radiation is known. The radiation-based orientation overcomes certain disadvantages associated with uniaxial friction guidance, such as dust generation, heat generation, destruction of thin films and lack of structuring capacity. In addition, the orientation by irradiation also allows the possibility of providing different areas having different orientation in relation to the neighboring areas. Examples of photo-orientable alignment materials include polymer-bound photo-active cinnamic acid derivatives, coumarin derivatives, cis / trans isomerizable azo derivatives, and photochemically decomposable polyimide derivatives.
[0004] U.S. Patent No. 6,107,427 relates to cross-linkable photo-active polymeric materials comprising amides and esters of 3-aryl-acrylic acid as well as their use as guidance layers for layers of liquid crystals. Such materials find use in the production of optical elements and multilayer systems, such as liquid crystal displays.
[0005] International publication No. WO 2004/060861 A2 discloses photoreticulable copolymers of (a) at least one monomer from the group of acrylates, methacrylates, acrylamides and methacrylamides to which each is linked
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3/84 covalently, directly or via a bridge-forming group, a photochemically dimmable or isomerizable molecule, (b) at least one polyoxyalkyl ester or a polyoxyalkylamide of a dicarboxylic acid or ethylenically unsaturated monomer, or a polyoxyalkyl ether of an unsaturated alcohol ethylenically, and (c) optionally, other ethylenically unsaturated comonomers. Copolymers have a glass transition temperature of not more than 70 ° C, and preferably less than 70 ° C. Such materials are suitable as alignment layers for liquid crystals used in the production of electro-optical elements, for example, liquid crystal displays, compensating film optical delay filters, cholesteric filters, anti-reflection filters and the like.
[0006] International publication No. WO 2005/015298 A1 provides an alignment layer having improved adhesion on liquid crystal films, a precursor material used for the preparation of such a layer, a laminate comprising such a layer and at least one polymer film of liquid crystals, and the use of the alignment layer and the laminate in optical, electro-optical, decorative or security devices and uses. The alignment layer and the precursor material comprise at least one reactive mesogen in monomeric, oligomeric or polymeric form. Preferably, the reactive mesogen is incorporated into the solvated composition used to form an alignment film. Alternatively, the reactive mesogen can be used as a component in a composition used to form lead layers that are generally not polymeric layers, but monolayers or self-assembled multilayers. Promoting the alignment of
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4/84 liquid crystals by the command layer is generally not a volume effect, but actually a surface effect where the command layer molecules are attached to the surface, and are typically only one layer thick.
[0007] Although the aforementioned photo-alignment copolymers and resulting alignment layers exhibit slightly improved adhesion (to substrates to which they are applied and to subsequently applied liquid crystal layers), they still do not provide sufficient adhesion to any layer for some applications, for example, for use in the production of ophthalmic devices such as lenses. In general, these prior art alignment layer materials used in liquid crystal devices still demonstrate poor adhesion for such applications, and are often produced using high processing temperatures (200 ° C to 250 ° C) that are not compatible for certain substrates, for example, optical plastic substrates. As mentioned earlier, adhesion between layers is also required in applications where a layer of liquid crystals or another layer is deposited on the surface of the photoalignment layer. In applications where adhesion levels are sufficient, exfoliation of the photoalignment layer of the substrate surface and / or exfoliation of subsequent layers of the surface of the photoalignment layer can be observed.
[0008] In addition, certain applications, such as ophthalmic applications, use layers of liquid crystals greater than 20 microns in thickness. In these applications, photo-alignment layers that are capable of
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5/84 align layers of adherent liquid crystals with a thickness of up to 1,000 microns. Therefore, photoalignment materials that can be used to form layers having improved adhesion properties and thicker lined liquid crystal layers are desired. The photoalignment materials of the present invention overcome the deficiencies of the previously known photoalignment copolymers and the alignment layers comprising them, and provide the desired improved adhesion properties.
Brief summary of the disclosure [0009] This disclosure relates to a (co) polymer comprising a structure represented by the formula:
where: each of M ^a , M ^b , and M ^c independently represents residues of selected monomer units of substituted or unsubstituted acryloyl units, in which said acryloyl substituents are chosen from C1-C4 alkyl, phenyl, -O- and combinations thereof, substituted or unsubstituted styrene units, substituted or unsubstituted epoxy units, substituted or unsubstituted urethane units, substituted or unsubstituted polycarboxylic acid units, substituted or unsubstituted polyol units, units substituted or unsubstituted polyamine, or substituted or unsubstituted hydroxy alkanoic acid units; said substituents being selected from C1-C20 alkyl, C1-C20 alkoxy, C3-C10 cycloalkyl, alkyl of
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6/84
C ₁ -C ₂₀ alkyl (alkoxy of C ₁ -C ₂₀₎ haloalkyl C ₁ -C ₂₀ heterocycloalkyl C ₃ -C ₂₀ haloarila (haloalkyl C ₁ C ₂₀₎ aryl, (alkyl C ₁ -C ₂₀ ) aryl, (C ₁ -C ₂₀ alkoxy) aryl, heteroaryl, aryl (C ₁ -C ₂₀ alkyl), heteroaryl (C ₁ -C ₂₀ alkyl); L ^a , L ^b , and L ^c are spacer groups, each of which is selected independently of a single bond, (CH2) 2-, - (CF2) h-, -Si (Z ') 2 (CH2) g- or - (Si (CH3) 2O) h-, N (R) -, -C (R) = C (R) -, -C (R) = N-, -C (R ') 2-C (R ') ₂ -, -O-, C (O) -, -C ° C-, -N = N-, -S-, -S (O) -, -S (O) (O) -, - ( O) S (O) O-, O (O) S (O) O-, normal or branched chain C ₁ -C ₂₄ alkylene residue, arylene, C ₃ -C ₁₀ cycloalkylene, or various combinations thereof , being that, in each occurrence, Z 'is independently chosen from hydrogen, C ₁ -C ₁₈ alkyl, C3-C10 cycloalkyl or aryl; at each occurrence, R is independently chosen from Z ^b , hydrogen, C1C18 alkyl, C3-C10 cycloalkyl or aryl; at each occurrence R 'is independently chosen from Z ^b , C1-C18 alkyl, C3-C10 cycloalkyl or aryl; the C1C24 alkylene residue is mono-substituted by Z ^b , cyano, or halogen, or polysubstituted by Z ^b or halogen; in each occurrence g is independently chosen from 1 to 20, and h is an integer from 1 to 16 inclusive; each Z ^a is independently a photochemically active chromophore selected from dimerized substituted or unsubstituted cinnamate, dimerizable substituted or unsubstituted coumarin, cis / trans isomerizable or unsubstituted cis, trans substituted or unsubstituted polyimide, or aromatic ester substituted or unsubstituted capable of undergoing Photo-Fries rearrangement; each Z ^b is an adhesion promoting group selected independently from hydroxy, acid
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7/84 carboxylic, anhydride, isocyanate, blocked isocyanate, thioisocyanate, blocked thioisocyanate, amino, uncle, organofunctional silane, organofunctional titanate, organofunctional zirconate, or epoxy, with each organofunctional group being independently selected from vinyl, ally, radicals from hydrocarbons with vinyl functionality, hydrocarbon radicals with epoxy functionality, hydrocarbon radicals with ally functionality, hydrocarbon radicals with acryloyl functionality, hydrocarbon radicals with methacryloyl functionality, hydrocarbon radicals with styryl functionality, hydrocarbon radicals with mercapto functionality, or combinations of hydrocarbons. such organofunctional groups, said hydrocarbon radicals being selected from C1-C20 alkyl, alkenyl C ₂ -C ₂₀ alkynyl C ₂ -C ₂₀ alkoxy, C ₁ -C 20 (alkyl of C1-C20) alkoxy C1 -C20, (C1C20 alkoxy) C1-C20 alkyl, aryl, heteroaryl, and combinations of ta radical hydrocarbon ions; provided that when Z ^b is hydroxy or carboxylic acid, the (co) polymer will further comprise at least one other adhesion promoting group; Z ^c is a mesogenic structure selected from a group of liquid crystals as rigid straight rods, a group of liquid crystals as arched rigid rods, or groups of liquid crystals as hard disks; and x has a value greater than zero and less than or equal to 1 (0 <x <1), y has a value greater than or equal to zero and less than 1 (0 <y <1), and z has a value greater than or equal to zero and less than 1 (0 <z <1) where x + y + z = 1 and n has a value ranging from 10 to 10,000, where when x = 1, then at least one of L ^a and Z ^a is replaced yet with at least one adhesion promoting group Z ^b and when y = 0, then
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8/84 at least one of L ^a , Z ^a , L ^c and Z ^c is further replaced with at least one adhesion promoting group Z ^b .
[0010] According to an embodiment, the present disclosure provides a (co) polymer in which z is 0.
[0011] In another embodiment, the present disclosure provides a (co) polymer in which z is greater than 0.
[0012] Additional incorporations of this disclosure come from articles of manufacture. The manufacturing articles comprise at least a photo-alignable portion comprising a copolymer having a structure represented by the above formula in which the variables M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b ,
Z ^c , x, y, z, and n are described here.
[0013]
Other embodiments of the present disclosure also provide optical elements, such as ophthalmic elements, display elements, windows, mirrors, active liquid crystal elements, or passive liquid crystal elements.
The optical elements comprise a substrate and at least a partial layer on at least a portion of a substrate surface. The at least partial layer comprises a (co) polymeric material having a structure represented by
M ^c , L ^a , L ^b , L ^c , Z ^a , above formula
Z ^b , Z ^c , x, y, na z, which variables M ^a , M ^b , and n are described here.
In specific embodiments, the optical elements may further comprise one or more additional at least partial layers on at least a portion of a substrate surface.
[0014]
Still further embodiments of the present disclosure provide a liquid crystal cell. The liquid crystal cell comprises a first surface, a second surface opposite the first surface, a first surface
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At least partial layer on at least a first portion of the first surface facing the second surface, a second layer at least partial on at least a portion of the second surface facing the first surface, where the first layer at least partial and the second at least partial layer define a space, and a liquid crystal material in the space between the first at least partial layer and the second at least partial layer. The first at least partial layer and the second at least partial layer are alignment layers and at least one of the first at least partial layer and the second at least partial layer comprises a (co) polymer having a structure represented by the above formula in which the variables M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b , Z ^c , x, y, z, and n are described here. In specific embodiments, the liquid crystal material comprises at least one of a dichroic material or a photochromatic / dichroic material.
[0015] Still other embodiments of the present disclosure provide methods for applying a photo-alignment material to an optical element. The method comprises applying an at least partial layer of a photoalignment (co) polymer material over at least a portion of a substrate surface, forming an attractive bond between one or more adhesion promoting groups over the (co) material photo-alignment polymer and a compatible group on the substrate surface, and align at least partially at least a first portion of the photo-alignment (co) polymer material exposing the at least partial layer to polarized UV radiation. Photo (co) polymer material Petition 870190057778, of 06/24/2019, p. 11/26
10/84 alignment has a structure represented by the above formula in which the variables M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b , Z ^c , x, y, z, en are described in detail here.
Brief description of the various views of the drawings [0016] Several embodiments disclosed herein will be better understood when read together with the drawings, in which:
[0017] Figure 1 illustrates an incorporation of an optical element in accordance with the present disclosure;
[0018] Figure 2 illustrates a second embodiment of an optical element in accordance with the present disclosure; and [0019] Figure 3 illustrates an incorporation of a liquid crystal cell in accordance with the present disclosure. Detailed description of the invention [0020] The present disclosure relates to structures and methods for producing structurally photo-oriented anisotropic polymer networks suitable for deposition as layers on substrates and which can align thicker layers of monomeric or polymeric liquid crystals and exhibit adhesion. improved to commonly used substrates as well as subsequent layers on the surface of the polymeric layer.
[0021] Liquid crystal materials are used in a variety of applications. Liquid crystal (LC) molecules tend to align with one another in a preferred direction, producing a fluid material with anisotropic, electromagnetic and / or mechanical optical properties. The mesogen is the fundamental unit of an LC, which induces the structural order in the liquid crystal material. The mesogenic portion of the LC typically comprises a rigid portion
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11/84 that aligns with other mesogenic components in the LC composition, thus aligning the LC molecules in a specific direction. The rigid portion of the mesogen may consist of a rigid molecular structure, such as a mono or polycyclic ring structure, including, for example, a mono or polycyclic aromatic ring structure. Liquid crystal mesogens that are suitable for use in conjunction with the various embodiments disclosed herein include thermotropic liquid crystal mesogens and lyotropic liquid crystal mesogens. Examples of thermotropic liquid crystal mesogens that are suitable for use in conjunction with the various embodiments disclosed herein include column-shaped liquid crystal mesogens (or as rods), disk-shaped (or as disc) liquid crystal mesogens, and mesogens of cholesteric liquid crystals. Examples of potential mesogens are shown in detail, for example, in U.S. serial patent application no.
12 / 163,116, in paragraphs [0024] - [0047], and include those described by Demus, et al.,
Flussige
Kristalle in
Tabellen ”,
VEB
Deutscher
Verlag
Fur
Grundstoffindustrie, Leipzig,
Germany, 1974 and Flussige
Kristalle in Tabellen II ”,
VEB Deutscher
Verlag
Fur
Grundstoffindustrie, Leipzig, Germany, 1984.
[0022]
Liquid crystals (LC's) can exist in an unordered state or in an ordered (aligned) state.
LC molecules in the unordered state will adopt an essentially random orientation, that is, there will be no general orientation for LC molecules in an ordered state LC molecules. Or aligned will generally adopt an orientation where the mesogenic portions of the
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12/84 LC molecules are at least partially aligned from beginning to end of the aligned portion of the LC material. When used here, the terms align and align mean to place in an appropriate position or arrangement by interacting with another material, compound or structure. In certain cases, the mesogenic portions of the LC molecules will be aligned at least partially in a parallel orientation. In other cases, the mesogenic portions of the LC molecules may be at least partially aligned in a helical orientation.
[0023] Liquid crystal polymers (LCP's) are polymers capable of forming regions of very ordered structure while in a liquid phase. LCP's can be prepared from compounds of liquid crystal monomers (LCM's) which are then polymerized to form the LCP. Alternatively, LCP's can be formed by polymerizing a polymerizable material in the presence of a liquid crystal material, such that the liquid crystal material is trapped in the polymer. LC's, LCM's, and LCP's have a wide range of uses, ranging from use as strong engineering plastics to delicate gels for LC displays. These materials can also be used, for example, in optical elements, such as ophthalmic elements, elements of displays, windows, and mirrors. Liquid crystal materials can be used, for example, as at least partial layers, coatings, or films on at least a portion of a substrate and can impart certain desired characteristics to the substrate, such as for use in optical data storage applications. such as photomasks or decorative pigments; in cosmetics and for
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13/84 security applications (see, for example, U.S. patent no.
6,217,948); as curable resins for medical, dental, adhesive and stereolithographic applications (see, for example, U.S. Patent No. 7,238,831); as articles of manufacture, such as molded assembly, or castings for use in the aforementioned applications and in various similar devices. In certain cases, LC materials can be incorporated into optical elements, such as, for example, ophthalmic elements, display elements, mirror windows, active and passive liquid crystal cells, elements, and devices and other articles of interest containing LC or LCP, such as polarizers, optical compensators (see, for example, US patent No. 7,169,448), optical retarders (see, for example, US patent No. RE39,605E), color filters, and wave for light wave circuits (see, for example, US patent No. 7,058,249). Certain mesogenic compounds may find particular use as LCM's and LCP's for the formation of ophthalmic elements that further comprise a dichroic or photochromatic / dichroic compound or material.
Dichroic compounds are capable of preferentially absorbing one of two orthogonal components of flat polarized light.
[0024] Generally, it is to properly position or arrange the mesogenic or LC molecules, including, for example, dichroic compounds, in order to achieve the desired effect. That is, for linear mesogens or as a stem, it is generally necessary to align at least partially the molecules of the compound such that the long axes of the molecules aligned at least partially of the mesogenic compound are generally parallel to each other. Alignment with
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14/84 less partial of LC materials and other anisotropic materials can be effected by at least one of exposing at least a portion of the material to a magnetic field, exposing at least a portion of the material to a shear force, exposing at least a portion of the material to an electric field, exposing at least a portion of the material to flat polarized ultraviolet (UV) radiation, exposing at least a portion of the material to infrared radiation, drying at
any less an portion of material, cauterize at least an portion of material, friction fur any less a portion of material, and align at least an portion of material with another structure or material, such how one material in
at least partially ordered alignment. It is also possible to align LC materials or other anisotropic materials with an oriented surface, such as a surface coated with an at least partially ordered alignment material. That is, the liquid crystal molecules can be applied as a coating layer, or film on a surface that has been oriented, for example, by friction, notch or photo-alignment methods, and subsequently aligned such that the long axis of each one of the liquid crystal molecules acquires an orientation that is generally parallel to the general direction of orientation of the surface.
[0025] Alignment materials, such as photo-alignment material, can be used as a coating on a substrate surface or on a portion of the surface where the alignment material can be at least partially aligned and then can be used to align one or more liquid crystal materials in a layer
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15/84 which is applied over a portion of the alignment material layer. However, conventional photoalignment materials may exhibit poor adhesion to the surface and / or subsequent layers that can be coated on the surface of the photoalignment materials.
This can lead to exfoliation or detachment of the photo-alignment layer from the surface and / or subsequent layers and overall loss of utility and average product life. The various incorporations of this disclosure provide new photoalignment (co) polymeric materials. The (co) polymeric photo-alignment materials exhibit improved adhesion to a substrate surface on which the materials are coated and improved adhesion between the materials to a subsequent layer that is deposited on the surface of the photo-alignment materials layer. The improved adhesion characteristics are affected by the incorporation of an adhesion promoting group within the (co) polymeric structure of the photoalignment material.
[0026] In accordance with an embodiment, the present disclosure provides a copolymer comprising a structure represented by formula I.
| _a _L b
Z ^to Z ^b (I) [0027]
Referring to formula I, M ^a and M ^b represent residues from monomer units. Each M ^a and M ^b is selected
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16/84 of substituted or unsubstituted acryloyl units, said substituents being chosen from alkyl of
C ₁ -C ₄ , phenyl, -O- and combinations thereof. Examples of such acryloyl units include acryloyloxy, methacryloyloxy and cinnamate. Each M ^a and M ^b is also selected from substituted or unsubstituted styrene units, substituted or unsubstituted epoxy units, substituted or unsubstituted polycarboxylic acid units, substituted or unsubstituted polyol units, polyamine units of substituted or non-substituted or hydroxy substituted alkanoic acid units or non-substituted, wherein said substituents are selected from alkyl C ₁ -C ₂₀ alkoxy, C ₁ -C _20, cycloalkyl of C ₃ -C ₁₀ , C ₁ C20 alkyl (C1-C20 alkoxy), C1-C20 haloalkyl, C3-C20 heterocycloalkyl, haloaryl, (C1C20 haloalkyl) aryl, (C1-C20 alkyl) aryl, (alkoxy C1-C20) aryl, heteroaryl, aryl (C ₁ -C ₂₀ alkyl), heteroaryl (alkyl
C1-C20). When used herein, the term residues when used in reference to a monomer or monomeric unit means that it is left over from the monomeric unit after it has been incorporated into a polymeric chain.
When used herein, the term derived when used in reference to a carboxylic acid or polycarboxylic acid includes amides, esters, acyl halides, acyl anhydrides, and cyano derivatives.
Groups M ^to
M ^b in formula I form the polymer backbone of the (co) polymer. According to specific incorporations, each of the groups
M ^a
M ^b can independently be residues from substituted or unsubstituted acryloyloxy units or substituted or unsubstituted methacryloyloxy.
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17/84 [0028] As represented in formula I, the (co) polymer has pendant groups -L ^to -Z ^a and -L ^b -Z ^b , where groups L represent spacer groups between the monomeric residue (that is, M ^a and M ^b ) and the groups Z ^a and Z ^b . According to various embodiments, the groups L ^a and L ^b are spacer groups, each of which can be independently selected from a single bond, - (CH2) 2-, - (CF2) h-, -Si (Z ') 2 (CH2) g- or (Si (CH3) 2O) _h -, -N (R) -, -C (R) = C (R) -, -C (R) = N-, -C (R ' ) 2-C (R ') 2-, -O-, -C (O) -, -C ° C-, -N = N-, -S-, -S (O) -, -S (O) (O) -, - (O) S (O) O, -O (O) S (O) O-, normal or branched chain C ₁ -C ₂₄ alkylene residue, arylene, C ₃ -C cycloalkylene ₁₀ , or various combinations thereof. According to these structures, at each occurrence, Z 'can be independently chosen from hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₀ cycloalkyl or aryl; at each occurrence, R can be independently chosen from Z ^b , hydrogen, C1-C18 alkyl, C3-C10 cycloalkyl or aryl; at each occurrence R 'can be independently chosen from Z ^b , C1-C18 alkyl, C3-C10 cycloalkyl or aryl; the C1-C24 alkylene residue can be monosubstituted by Z ^b , cyano, or halogen, or poly-substituted by Z ^b or halogen. Additionally, according to the groups
spacers L ^a and L ^b , in each occurrence, g can to be regardless chosen of 1 to 20, for example, in 2 to 15 or from 5 to 10; and h can to be represented per one number integer from 1 to 16 including, per example of 2 to 12 or in 4 a
10.
[0029] Each group ^a represents a photochemically active chromophore. When used herein, the phrase photochemically active chromophore includes structures or portions of the chemically reacting molecule or polymer (such as with
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18/84 themselves or with another active portion, for example, another photochemically active chromophore) in response to the absorption of actinic radiation. When used here, the term actinic radiation means electromagnetic radiation that is capable of causing a response. Actinic radiation includes, for example, visible and ultraviolet radiation. The photochemically active chromophore may undergo a photochemical cis / trans isomerization, a photochemical cycloaddition [2 + 2] (leading to a crosslinking of the polymer or oligomer), a photochemical decomposition or a photochemical rearrangement. According to various embodiments, photochemically active chromophores include derivatives of dimerizable substituted or unsubstituted cinnamate, or dimerizable substituted or unsubstituted coumarin, cis / trans isomerizable or unsubstituted aomer, photochemically substituted or unsubstituted polyimides, and substituted or unsubstituted aromatic esters capable of undergoing Photo-Fries rearrangement. In specific embodiments, the photochemically active chromophore may be a dimerizable substituted or unsubstituted cinnamate or dimerizable substituted or unsubstituted coumarin.
Cinnamates and coumarins can react during exposure to actinic radiation and undergo dimerization [2 + 2] as described in Alignment Technologies and Applications of Liquid Crystal Devices, Kohki Takotah et al., Taylor and Francis, New York, 2005, pages 61-63 . Examples of suitable cinnamates can be found in U.S. patents.
paragraphs 5. 637,739, at column 6, lines 19 to 32 and 7. 173,114 gives column 3, line 13 column 5, row 2 and coumarins can to be found in patents U.S. No. 5,231,194 of column 1,
row 37 to column 3, row 50, 5,247,099 to column 1, row
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19/84 to column 4 row 28, 5,300,656 from column 1, row 13 to column 10, row 15, and 5,342,970 from column 1 to row 6 to column 7, row 34.
[0030] Additional examples of photochemically active chromophores may include: azocompounds such as poly ((n-butyl-co methacrylate — (E) -4- (phenyl diazenyl) phenylab-styrene methacrylate) described in Macromol. Chem. Phys. 2009, 210, pages 1484-1492; photodegradable polyimides such as poly (2-methyl-6- (4- (p-tolyloxy) phenyl) pyrrol [3,4-f] isoindole1,3,5,7 (2H, 6H ) -tetraone), poly (5- (2- (1,3-dioxo-2- (4- (ptolyloxy) phenyl) isoindolin-5-yl) -1,1,1,3,3,3-hexa fluorine propan-2-yl) -2-methyl isoindoline-1,3-dione), poly (5- (2- (1,3dioxo-2- (4- (2- (p-tolyl) propan-2-yl) phenyl) isoindolin-5-yl) 1,1,1,3,3,3-hexa fluorine propan-2-yl) -2-methyl isoindoline-1,3dione) and poly (5- (1,1,1, 3,3,3-hexa fluoro-2- (4- (1,1,1,3,3,3hexafluoro-2- (p-tolyl) propan-2-yl) phenyl-2,3-dioxo isoindolin5-yl ) propan-2-yl) -2-methyl isoindoline-1,3-dione) described in Macromolecules 1994, 27, pages 832-837; a photoreactive polyimide such as (2E, 2'E bis (3-phenyl acrylate) ) -4- (5 (1,1,1,3,3,3-hexafluoro-2-1,3-dioxo isoindolin-2-yl) -4'-met il [1,1'-biphenyl] -3,3'-diyl described in Macromolecules 2006, 36, pages 6527-6536; a photo-decomposable polyimide such as 7-methyl-2- (4- (4-methyl benzyl) phenyl) tetrahydro-1H-5,9 methane pyrido [3,4-d] azepine-1,3,6,8 (2H , 4H, 7H) -tetraone and 2methyl-5- (4- (4- (2- (4- (p-tolyloxy) phenyl) propan-2-yl) phenoxy) phenyl) hexahydrocyclobut [1,2-c: 3 , 4-c '] dipyrrol-1, 3- (2H, 3aH) diona described in The Liquid Crystal Book Series: Alignment
Technologies and Application of Liquid Crystal Devices, by
K. Takatoh et al., 2005, Taylor & Francis, page 63; and aromatic esters capable of undergoing PhotoPetição 870190057778 rearrangement, of 06/24/2019, p. 36/115
20/84
Fries include: poly (5-methacrylamido naphthalen-1-yl methacrylate), poly (4-methacrylamido naphthalen-1-yl methacrylate), poly (4-methacrylamido phenyl methacrylate), poly (4-methacrylamido methacrylate and phenethyl), poly (4- (2-ethyl methacrylamido) phenyl methacrylate) described in Molecular Crystal and Liquid Crystal, 2007, vol. 479, page 121.
[0031] Each Z ^b group represents an adhesion promoting group. When used herein, the term adhesion promoter means a group or structure that improves adhesion between the (co) polymeric structure and the substrate on which it is coated or polymeric films that are coated on the surface of the polymer containing the adhesion promoter. Adhesion promoters can act by forming an at least partial attractive force on a molecular or atomic level between the (co) polymer and the subsequent substrate or coating. Examples of attractive forces include covalent bonds, polar covalent bonds, ionic bonds, hydrogen bonds, electrostatic attractions, hydrophobic interactions, and Van der Waals attractions. That is, a feature in the adhesion promoting group Z ^b can form an attractive interaction with a feature on the surface or a feature on the subsequent coating. Within the copolymer structure according to the various embodiments here, the attractive interaction between a plurality of adhesion promoting groups Z ^c and the subsequent substrate or coating material surface results in improved adhesion between the copolymer and the substrate surface and / or the subsequent coating. Various incorporations of structures suitable for the adhesion promoting group Z ^b include hydroxy, carboxylic acid, anhydride, isocyanate,
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21/84 blocked isocyanate, thio-isocyanate, blocked thio-isocyanate, amino, uncle, organofunctional silane, organofunctional titanate, organofunctional zirconate, or epoxy, each organofunctional group being
selected
regardless vinyl, alila, radicals in Hydrocarbons with functionality vinyl, radicals in Hydrocarbons with functionality epoxy, radicals in Hydrocarbons with functionality alila, radicals in Hydrocarbons with functionality acryloyl, radicals in Hydrocarbons with methacryloyl functionality, radicals in Hydrocarbons with functionality styrene, radicals in
hydrocarbons having mercapto functionality, or combinations of such organofunctional groups, said hydrocarbon radicals being selected from alkyl from C ₁ -C _20, alkenyl C ₂ -C ₂₀ alkynyl C ₂ -C ₂₀ alkoxy, C ₁ -C ₂₀ , (C1-C20 alkyl) C1-C20 alkoxy, (C1-C20 alkoxy) C1-C20 alkyl, aryl, heteroaryl, and combinations of such hydrocarbon radicals; provided that when Z ^b is hydroxy or carboxylic acid, the (co) polymer will further comprise at least one other adhesion promoting group, such as those adhesion enhancers disclosed in US Patent No. 6,025,026 in column 6, line 5 a column 8, column 65, 6,150,430 from column 2, row 59 to column 5, row 44, and
7,410,691 from column 6, row 4 to column 8, row 19. When used herein, the term blocked in reference to isocyanate or thio isocyanate groups refers to a structure where the isocyanate or thio isocyanate group reacted reversibly with a group to protect the isocyanate or thio isocyanate group from reacting until the blocking group is removed. Generally, compounds used to block isocyanate or uncle groups
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22/84 isocyanates can be organic compounds that have active hydrogen atoms, for example, cetoximes, epsilocaprolactams and volatile alcohols. Examples of blocking groups include amines, hydroxamic esters, substituted or unsubstituted pyrazole groups, phenols, cresol, nonyl phenol, caprolactam, triazole, imidazoline, oxime, formate and diacetone, including those described in X. Tassel et al., The New Blocking Agent of Isocyanates, European Polymer Journal, 2000, 36, 1745-1751 and in ZW Wicks Jr., Progress in Organic Coatings, 1975, 3, 73-99.
[0032] Referring also to formula I, according to several incorporations, n can have a value ranging from 10 to 10,000, for example, from 100 to 5,000 or from 500 to 2,000. According to specific incorporations, x can have a value greater than zero and less than or equal to 1 (0 <x <l) and y can have a value greater than or equal to zero and less than 1 (0 <y <l), where x + y = 1. That is, according to these specific incorporations, the (co) polymer contains only residues of monomers M ^a and M ^b . In other embodiments, as described herein, the (co) polymer may comprise additional monomer residues. In those incorporations where x = 1 (that is, when y = 0), at least one of L ^a and Z ^a is still replaced with at least one adhesion promoting group Z ^b .
[0033] In still other embodiments of the (co) polymer described herein, the copolymer structure represented by formula I may further comprise residues of a substituted monomeric unit M ^c having the structure:
M G
L ^c
Z ^c
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23/84 where each M ^c can be independently a residue from selected monomer units of substituted or unsubstituted acryloyl units, said acryloyl substituents being chosen from C ₁ C ₄ alkyl, phenyl, -O- and combinations of the same substituted or unsubstituted styrene units, substituted or unsubstituted epoxy units, substituted or unsubstituted urethane units, substituted or unsubstituted polycarboxylic acid units, substituted or unsubstituted polyol units, substituted polyamine units or unsubstituted, or substituted or unsubstituted hydroxy alkanoic acid units;
wherein said substituents are selected from alkyl from C ₁ -C ₂₀ alkoxy, C ₁ -C _20, cycloalkyl C ₃ -C _10, alkyl of C1 -C20 (C1 -C20 alkoxy) C1 -C20 haloalkyl , C3-C2o heterocycloalkyl, haloaryl, (C1-C2o haloalkyl) aryl, (C1-C2o alkyl) aryl, (C1-C2o alkoxy) aryl, heteroaryl, aryl (C1-C2o alkyl), heteroaryl (C1 alkyl) -C2o). Each L ^c is a spacer group that can be independently chosen from those spacer groups described herein. According to various incorporations, the group Z ^c is a mesogenic structure that can be selected from a group of liquid crystals as rigid straight rods, a group of liquid crystals as arched rigid rods, or groups of liquid crystals as hard disks. According to these incorporations, z can have a value greater than zero and less than 1 (0 <z <1) such that x + y + z = 1. That is, the copolymer can consist of monomeric structures represented by M ^a , M ^b and M ^c . In those incorporations where y = 0, at least one of L ^a , Z ^a , L ^c , and Z ^c is still replaced with at least one group
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24/84 adhesion promoter Z ^b . That is, in all embodiments of the copolymer, the monomeric residues of the copolymer will have substituents having at least one adhesion promoting group Z ^b .
[0034] Yet other incorporations of this disclosure provide one comprising a
have ranges from 100 to 5,000 or shown. The value represented by formula II:
M ³ | ₇ ---- IX / F I ----- Ί IVF
in which groups M structures such as here at 10,000, for example,
According to formula II, x can have a
500 to 2,000.
value greater than zero and less than or equal to 1 (0 <x <l), y has a value greater than or equal to zero and less than 1 (0 <y <l), ez has a value greater than or equal to zero and less that 1 (0 <z <l) where x + y + z = 1, provided that when x = l at least one of L ^a and Z ^a is still replaced with at least one adhesion promoting group Z ^b and when y = The at least one of L ^a , Z ^a , L ^c and Z ^c is further substituted with at least one adhesion promoting group Z ^b .
[0035] In specific embodiments, each of M ^a , M ^b , and M ^c can be independently residues of substituted or unsubstituted acryloyloxy units or of substituted or unsubstituted methacryloyloxy units, and Z ^a can be a photochemically active chromophore selected from a
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25/84 dimerizable substituted or unsubstituted cinnamate or dimerizable substituted or unsubstituted coumarin.
[0036] According to the various incorporations of the (co) polymers described here, the mesogenic structure Z ^c can have a structure represented by:
R ^m - [G ¹ - [S ¹ ] j] j '- [G ² - [S ² ] d] d' - [G ³ - [S ³ ] e] e '- [S ⁴ ] f [0037] According to the mesogenic structure Z ^c , in each occurrence, each G, G, and G can be independently chosen from a divalent group chosen from a substituted or unsubstituted aromatic group, a substituted or unsubstituted alicyclic group, a group heterocyclic substituted or unsubstituted, and mixtures thereof, wherein the substituents are selected from: hydroxy, amino, halogen, alkenyl C ₂ -C _18, alkynyl of C ₂ -C _18, azido, silyl, siloxy, hydride silyl, (tetrahydro-2H-pyran-2yl) oxy, thio, isocyanate, thio isocyanate, acryloyloxy, methacryloyloxy, 2- (acryloyloxy) ethyl carbamyl, 2 (methacryloyloxy) ethyl carbamyl, aziridinyl, allyoxycarboxyloxy, carboxylic acid, carboxylic acid amino acryloyl, methacryloyl amino, amino carbonyl, (C1C18 alkyl) amino carbonyl, amino carbonyl (C1-C18 alkyl), (C1-C18 alkoxy) carbonyl, aryloxy carbonyloxy, perfluoro (alk C1-C18 uyl) amino; di- (perfluorine (C1C18 alkyl) amino), C1-C18 acetyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, (C1-C18 alkyloxy) carbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C1 alkyl -C18), C1-C18 alkyl, C1-C18 alkoxy, amino (C1-C18 alkyl), (C1-C18 alkyl) amino, di- (C1-C18 alkyl) amino, (C1- alkyl C18) (C1-C18 alkoxy), (C1-C18 alkoxy) (C1C18 alkoxy), nitro, poly (C1-C18 alkyl) ether, (C1 alkyl
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26/84
C ₁₈ ) (C ₁ -C ₁₈ alkoxy) (C ₁ -C ₁₈ alkyl), methacryloxy oxy (C ₁ -C ₁₈ alkyl), poly (C ₁ -C ₁₈ alkoxy), ethylene, acryloyloxy (alkyl (C ₁ -C ₁₈ ), methacryloyloxy (C ₁ C ₁₈ alkyl), 2-chloro acryloyloxy, 2-phenyl acryloyloxy, acryloyloxy phenyl, 2-chloro acryloyl amino, 2-phenyl acryloyl amino carbonyl, oxetanyl, glycidyl, cyano, C1-C18 alkyl isocyanate, itaconic acid ester, vinyl ether, vinyl ester, styrene derivative, main or side chain liquid crystal polymers, siloxane derivatives, ethylene imine derivatives, maleic acid derivatives, fumaric acid derivatives, normal or branched chain C1-C18 alkyl group that is mono-substituted with cyan, halogen, or C1-C18 alkoxy, or poly-substituted with halogen, unsubstituted cinnamic acid, cinnamic acids that are substituted with at least one of methyl, methoxy, cyano or halogen, monovalent or divalent groups that irais chiral or non-substituted or unsubstituted radicals selected steroid radicals, terpenoid radicals, alkaloid, or mixtures thereof, wherein the substituents are independently selected from alkyl from C ₁ -C ₁₈ alkoxy, C ₁ -C _18, amino, C ₃ -C ₁₀ cycloalkyl, (C1-C18 alkyl) (C1-C18 alkoxy), fluorine (C1-C18 alkyl), cyan, cyano (C1-C18 alkyl), cyan (C1 alkoxy -C18), or mixtures thereof; or a group comprising one of the following formulas: -M (T) _(ti) and -M (OT) _(ti) , in which M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from radicals organofunctional, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, et is the valence of M. Referring also to the
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27/84 mesogenic structure Z ^c , R ^m can be -H, hydroxy, amino, halogen, haloalkyl, aryl, C1-C18 alkyl, or C1-C18 alkoxy. In addition, each of the variables j, d, e and f independently has a chosen value from an integer ranging from 0 to 20, inclusive; each of j ', d', ee 'can independently be an integer from 0 to 4, provided that the sum of j' + d '+ e' is at least 1. Referring also to the mesogenic structure Z ^c , in each occurrence, each of S, S, S, and S and independently chosen from a spacer unit chosen from: (A) (CH2) g-, - (CF2) h-, -Si (Z ') 2 ( CH2) g-, or - (Si (CH3) 2O) h-, being that in each occurrence, Z 'is independently chosen from hydrogen, C1-C18 alkyl, C3-C10 cycloalkyl or aryl; in each occurrence, g is independently chosen from 1 to 20 and h is an integer from 1 to 16 inclusive; (B) -N (Y) -, -C (Y) = C (Y) -, -C (Y) = N-, -C (Y ') 2-C (Y') 2-, or a bond simple, being that in each occurrence Y is independently chosen from hydrogen, C1-C18 alkyl, C3-C10 cycloalkyl and aryl, and, in each occurrence, Y 'is independently chosen from C1-C18 alkyl, C3- cycloalkyl C10 or aryl; or (C) -O-, -C (O) -, -C ° C-, -N = N-, -S-, -S (O) -, S (O) (O) -, - (O ) S (O) O-, -O (O) S (O) O- or normal or branched chain C1-C ₂₄ alkylene residue, said C ₁ -C ₂₄ alkylene residue being unsubstituted, mono-substituted by cyan or halogen, or poly-substituted by halogen; provided that when two spacer units comprising heteroatoms are linked together with spacer units are linked so that the heteroatoms are not directly linked with each other and when S ¹ and S ⁴ are linked to another group, they will be linked in a similar way
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28/84 that two heteroatoms are not directly linked to each other.
[0038] Examples of other structures suitable for the mesogen Z ^c can be found, for example, in US serial patent application No. 12 / 489,811, in paragraphs [0018] [0040]; and include those described by Demus, et al., Flussige Kristalle in Tabellen ”, VEB Deutscher Verlag Fur Grundstoffindustrie, Leipzig, Germany, 1974 and Flussige Kristalle in Tabellen II”, VEB Deutscher Verlag Fur Grundstoffindustrie, Leipzig, Germany, 1984. Based in the present disclosure, a person skilled in the art will know how to incorporate the mesogenic structures shown in these references into the structure of the monomeric unit M ^c .
[0039] According to the various embodiments here, the (co) polymers can have a polymeric form of a random copolymer, a block copolymer, a grafted copolymer, a linear copolymer, a branched copolymer, a hyper-branched copolymer, a dendritic copolymer, or a star copolymer. In specific embodiments, (co) polymers can include a polymeric chain where different sections can have different shapes, such as, for example, a random polymeric section and a block polymeric section. Formation of (co) polymers having one or more of the forms mentioned can be performed using polymerization methods known in the art, including addition polymerization, condensation polymerization, controlled live polymerization, anionic polymerization, cationic polymerization, and radical polymerization.
[0040] The (co) polymers of the various embodiments described here may further comprise a residue of at least one
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29/84 of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a photosensitive material, and a non-photosensitive material. The (co) polymers described herein can be in a composition further comprising one or more additives. Additives can be selected from the group consisting of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a photosensitive material, a liquid crystal, a liquid crystal property additive, a nonlinear optical material, a dye, a promoter of alignment, a kinetic intensifier, a photoinitiator, a thermal initiator, a surfactant, a polymerization inhibitor, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology control agent, a gelator, a leveling agent, a free radical scavenger, a coupling agent, a tilt-controlling agent, a polymeric material in blocks or not in blocks, and an adhesion promoter. Examples of photochromatic compounds, dichroic compounds, photochromatic / dichroic compounds, photosensitive materials, appropriate non-photosensitive materials can be found, for example, in US serial application No. 12 / 329,197, filed and, December 8, 2008, entitled Alignment Facilities for Optical Dyes ”in paragraphs [0090] - [0102] and in the references cited here; and in U.S. serial patent application No. 12 / 163,180, filed June 27, 2008 entitled Formulations Comprising Mesogen Containing Compounds ”in paragraphs [0064] - [0084] and the references cited here. Other examples of dichroic dyes that can be used in conjunction with various incorporations here
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30/84 disclosed include those disclosed in U.S. Patent No. 7,044,599, in column 7, lines 18-56. Examples of photochromic / dichroic dyes that can be used in conjunction with various embodiments disclosed herein include those materials shown and described in US patent application publications No. 2005/0004361, from paragraph 27 to paragraph 158, and 2005/0012998 A1, from paragraph 89 to paragraph 251. Examples of appropriate compositions for the one or more additives are described in detail in US serial patent application No. 12 / 163,180, filed on June 27, 2008, entitled Formulations Comprising Mesogen Containing Compounds ”in paragraphs [0085 ] - [0108] and in the references cited here.
[0041] Still other embodiments of the present disclosure provide a manufacturing article comprising at least a photo-alignable portion. The photo-alignable portion may comprise a (co) polymer having the structure represented by formula I or formula II, in which the groups M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b , and Z ^c have the structures as shown here. The value of n ”ranges from 10 to 10,000 and the values of x”, y ”, and z” are as described herein.
[0042] The article of manufacture can be any type of commercial article that incorporates a photo-alignment layer in which the adhesion of the photo-alignment layer on a subsequent substrate and / or coating is important for the usefulness and life span of articles. For example, in certain embodiments, the article of manufacture may be an active liquid crystal cell, a passive liquid crystal cell, a display element, a window, a mirror, or an ophthalmic element. Examples of
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31/84 optical elements include ophthalmic devices and elements, displays devices and elements, windows, mirrors, active and passive liquid crystal cell devices and elements. Examples of ophthalmic elements include corrective and non-corrective lenses, including mono and multifocal lenses that can be multifocal, segmented or non-segmented lenses (such as bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect , or improve vision (cosmetically or differently), including contact lenses, intraocular lenses, magnifying lenses, and protective visors or lenses; and may also include partially formed lenses and blank lenses. When used here, the term display means the visible or machine-readable representation of words, numbers, symbols, plans or drawings. Examples of display devices and elements include screens, monitors, and security elements, including security tags and authentication tags. When used here, the term window means an opening adapted to allow the transmission of radiation through it. Examples of windows include automotive and aircraft transparencies, filters, shutters, and optical transparencies. When used here, the term mirror means a surface that speculatively reflects a large fraction of incident light. When used herein, the term liquid crystal cell refers to a structure containing liquid crystal material capable of being ordered. Active liquid crystal cells are cells in which the liquid crystal material is able to change from an ordered state to an disordered state and vice versa or to change from one ordered state to another.
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32/84 state ordered by the application of an external force, such as electric or magnetic hoods. Passive liquid crystal cells are cells in which the liquid crystal material maintains an ordered state. An example of an active liquid crystal cell device or element is a liquid crystal display.
[0043] As described here, in certain embodiments the optical element can be a security element. Examples of security elements include security marks or authentication marks that connect to at least a portion of a substrate, such as: cards and access passes, for example, tickets, badges, identification or membership cards, identity cards. debit and / or credit, etc .; negotiable instruments and non-negotiable instruments, for example, draft contracts, checks, policies, bank notes (cash), certificates of deposit, certificates of stock, etc .;
official documents, for example, money, licenses, identification cards, benefit cards, visas, passports, official certificates, property deeds, etc .;
consumer goods, for example, software,
CDs,
DVDs, furniture, electronic devices, sporting goods, etc .;
credit cards; and labels, tags and packaging.
[0044]
The security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, according to certain incorporations in which a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material can be applied in at least a portion
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33/84 of the substrate before applying the security mark on it. For example, a reflective aluminum coating can be applied to at least a portion of the substrate before the security element is formed on the substrate. Additionally, the security element can be connected to at least a portion of a substrate chosen from non-dyed substrates, dyed substrates, photochromatic substrates, dyed photochromatic substrates, linearly polarized substrates, circularly polarized substrates, and elliptically polarized substrates.
[0045] In addition, the security element according to the aforementioned embodiment may comprise one or more other coatings or sheets to form a reflective multilayer security element with angle-dependent characteristics as described in US patent no. 6,641,874.
[0046] According to other incorporations, this disclosure provides optical elements. According to these embodiments, the optical element may comprise a substrate and a first at least partial layer on at least a portion of the substrate. The at least partial first layer may comprise a copolymeric material as described herein, for example, a copolymer having a structure represented by any of formulas I or II, described herein.
As described herein, the optical element is an ophthalmic element, a display element, a window, a mirror, an active liquid crystal cell element, or a passive liquid crystal cell element.
[0047]
When used herein, the term layer or coating means a supported film derived from a
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34/84 composition capable of flowing, which may or may not have a uniform thickness, and specifically excludes polymeric sheets. The layer or coating can be cured after application to the surface of the optical element to form a cured layer or coating. When used herein, the term sheet means a pre-formed film having a generally uniform thickness and capable of self-support. Additionally, when used here, the term connected to means in direct contact with an object or in indirect contact with an object through one or more structures or materials, at least one of which is in direct contact with the object. Consequently, according to various embodiments disclosed herein, the at least partial coating may be in direct contact with at least a portion of the substrate or it may be in indirect contact with at least a portion of the substrate through one or more structures or materials. For example, the at least partial coating may be in contact with one or more other at least partial coatings, polymer sheets or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate. When used herein, the phrase at least partial when used in reference to a layer or coating means that the layer or coating covers 5% to 100% of the area of the mentioned coated area. When used herein, the phrase at least a portion when used in reference to a surface of a substrate means a surface area ranging from 1% to 100% of the total surface area of the substrate.
[0048] As discussed here, the copolymeric materials described here exhibit improved adhesion to a surface of
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35/84 substrate and / or provide improved adhesion of subsequent layers of coating material. One method of measuring adhesion of coating materials, for example, adhesion of a coating material to a surface of a substrate or adhesion of subsequent coatings on a surface of a coating material is by testing crosshatched tape. According to this method, the coating material is scratched, for example, with a knife, scalpel, razor blade, hatch cutter or other cutting device, in a hatched pattern. A pressure sensitive tape is applied to the covering surface over the hatched cuts and then the tape is quickly removed (as described by ASTM D3359). Then, the area is inspected with the hatched cuts to remove the coating and then classified. In various embodiments, the at least partial layer of copolymeric materials on the substrate surface described here will exhibit 10% to 100% adhesion, 50% to 100% adhesion, or in specific incorporations even 100% adhesion. As will be understood in the art, other methods of adhesion testing can be used to measure the adhesion of the copolymeric material to the substrate surface or the adhesion of coatings subsequent to the layer of copolymeric material. These methods include, for example, knife tests, take out tests, scrape tests, or other test methods. Alternative adhesion methods will produce results comparable to those observed with the hatch adhesion test.
[0049] According to certain incorporations, the first layer at least partially be aligned at least partially, as determined by application of a
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36/84 subsequent alignable coating and determination of the degree of alignment. When used here, the phrase at least partially when used in reference to the degree of alignment of materials alignable in a layer means that 10% to 100% of the alignable elements of the material are aligned. Other incorporations can exhibit 25% to 100% alignment, 50% to 100% alignment, or in specific incorporations even 100% alignment. The first at least partial layer can be at least partially aligned in a parallel, elliptical, skewed, vertical orientation, or in a helical orientation. Appropriate methods for at least partially aligning the first at least partial layer include at least one of exposing at least a portion of the composition to a magnetic cap, exposing at least a portion of the composition to a shear force, exposing to at least one portion of the composition to an electric field, exposing at least a portion of the composition to flat polarized ultraviolet radiation, exposing at least a portion of the composition to infrared radiation, drying at least a portion of the composition, cauterizing at least a portion of the composition, rubbing at least a portion of the composition, and aligning at least a portion of the composition with another structure or material, such as at least partially ordered alignment means. Appropriate alignment methods for layers are described in more detail in US Patent No. 7,097,303, from column 27, line 17 to column 28, line 45. In specific embodiments, the at least partial first layer can be at least partially aligned by exposure to polarized electromagnetic radiation.
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37/84 [0050] According to incorporations in which the first at least partial layer is at least partially aligned by exposure to polarized electromagnetic radiation, the photochemically active chromophore Z ^a in the (co) polymer represented in the structures of formulas I and II, it can undergo a photochemical reaction to form a structure at least partially aligned in the (co) polymer. For example, in those structures where Z ^a is dimmable coumarin or cinnamate, coumarin or cinnamate can undergo cycloaddition [2 + 2] / photochemical dimerization with cinnamate or coumarin in an adjacent polymer row or in an adjacent site in the same polymer row to form a structure at least partially aligned. Where Z ^a is cis / trans isomerizable azo, the structure can undergo photochemical cis / trans isomerization to provide at least partially aligned structure. Where Z ^a is a photochemically decomposable polyimide, the polyimide can undergo photochemical decomposition to provide an at least partially aligned structure. Where Z ^a is an aromatic ester capable of undergoing a photochemical rearrangement of Photo-Fries, the aromatic ester can undergo a photochemical rearrangement to provide at least partially aligned structure.
[0051] In specific embodiments, at least a portion of the first at least partial layer can be aligned in a first direction, for example, exposing the portion to polarized electromagnetic radiation and at least a second portion of the first at least partial layer can be aligned in one different direction from the first direction, for example, exposing the second portion to electromagnetic radiation that is polarized in a different direction. The expert in the art
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38/84 will understand that using this method, several portions of the at least partial first layer can be aligned in various directions desired by the user.
[0052] According to certain embodiments, optical elements having the first at least partial layer, which can be at least partially aligned as described herein, can further comprise one or more additional at least partial layers on at least a portion of the surface of the substrate. When used herein, the phrase on at least a portion of the substrate surface includes layers applied directly to the substrate surface and coating layers applied to one or more layers on the substrate surface. That is, one or more additional layers can be applied directly on the substrate surface or on one or more intermediate layers that were previously applied to the substrate surface, thus forming a multilayer laminar coating. According to various embodiments, at least one or more additional layers can be selected from a bonding layer, a primer layer, an abrasion resistant coating, a hard coating, a protective coating, a reflective coating, a photochromic coating , a dichroic coating, a photochromatic / dichroic coating, an anti-reflective coating, a linearly polarized coating, a circularly polarized coating, an elliptically polarized coating, a transient coating, a layer of liquid crystal material, a layer of alignment material , a compatibilizer coating, a functional organic coating, a retardant layer, or
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39/84 combinations of any of them. In another embodiment, the additional layers are selected from a primer layer, a protective coating, a transitional coating and a combination of such coatings. In an additional embodiment, the primer layer is a polyurethane.
[0053] According to the various embodiments disclosed herein, the functional organic coating may be a polarized coating comprising an aligned liquid crystal coating and an aligned dichroic dye. When used here, the term polarized coating refers to a coating that is adapted to confine the vibrations of the electromagnetic vector of light waves to a single direction or plane. Generally, although not required, polarized coatings comprising conventional dichroic dyes will have a constant (or fixed) color or hue due to the presence of the dichroic dye. For example, the polarized coating may have a brownish or bluish color or hue. Examples of polarized coatings comprising aligned liquid crystal materials and dichroic dyes that can be used in conjunction with various embodiments disclosed herein are described in U.S. Patent Application Publication No. 2005/0151926, from paragraph 10 to paragraph 159.
[0054] The polarized coating according to various incorporations disclosed herein may also comprise a photochromic material. According to these embodiments, the coating can be either a polarized coating or a photochromatic coating, i.e., one that exhibits both conventional polarization properties as well as conventional photochromatic properties.
For example, according to several incorporations disclosed here,
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40/84 polarized and photochromic coating, may have a first colored polarized state when not exposed to actinic radiation mainly due to the dichroic dye tone, a second colored polarized state when exposed to actinic radiation due to the combined effect of the dichroic dye tone and color photochromic material when exposed to actinic radiation.
For example, if the optical element is an ophthalmic lens comprising the photochromic polarized coating, the lens may change reversibly from a first colored polarized state when the user is not exposed to actinic radiation or
UV from sunlight, for a second colored polarized state when the user is exposed to actinic or UV radiation from sunlight.
[0055] Examples of conventional photochromic coatings include coating comprising any of the conventional photochromatic compounds which are discussed in detail below. For example, photochromic coatings can be photochromic polyurethane coatings, such as those described in U.S. Patent No. 6,187,444; photochromic coatings of aminoplastic resin, such as those described in U.S. Patent Nos. 4,756,973, 6,432,544 and 6,506,488; photochromic polysilane coatings, such as those described in U.S. Patent No. 4,556,605; photochromic poly (meth) acrylate coatings, such as those described in U.S. Patent Nos. 6,602,603, 6,150,430 and 6,025,026 and WO 01/02449; photochromic polyanhydride coatings, such as those described in U.S. Patent No. 6,436,525; photochromic polyacrylamide coatings, such as those described
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41/84 in U.S. Patent No. 6,060,001; photochromic epoxy resin coatings, such as those described in U.S. Patent Nos. 4,756,973 and 6,268,055; and photochromic poly (urea / urethane) coatings, such as those described in U.S. Patent No. 6,531,076.
[0056] Additionally, according to various embodiments disclosed herein, the functional organic coating may be a photochromic / dichroic coating comprising an aligned liquid crystal coating comprising an aligned photochromatic / dichroic material. When used herein, the term photochromatic / dichroic coating refers to a coating that is adapted to exhibit both photochromatic and polarizing properties in response to at least actinic radiation. For example, according to various embodiments disclosed herein, the functional organic coating may be a photochromatic / dichroic coating that is adapted to change reversibly from a first optically colorless non-polarized state to a second colored polarized state in response to at least actinic radiation. . For example, if the optical element is an ophthalmic lens comprising the photochromatic / dichroic coating, the lens may change reversibly from an optically colorless first non-polarized state when the user is exposed to actinic or UV radiation, for example, out of sunlight , for a second colored polarized state when the user is exposed to actinic or UV radiation, for example, from sunlight. Examples of such coatings are described in U.S. Patent Application Publication No. 2005/0012998, from paragraph 11 to paragraph 442.
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42/84 [0057] Examples of primer layers that can be used in conjunction with various embodiments disclosed herein include coatings comprising coupling agents, at least partial hydrolysates of coupling agents, and mixtures thereof. When used herein, the term coupling agent means a material having at least one group capable of reacting, bonding and / or associating with a group on at least one surface. In an embodiment, a coupling agent can serve as a molecular bridge at the interface of at least two surfaces that can be similar or different. In another embodiment, the coupling agents can be monomers, oligomers, prepolymers and / or polymers. Such materials include organometallic such as silanes, titanates, zirconates, aluminates, zirconium aluminates, hydrolysates thereof and mixtures thereof. When used herein, the phrase at least partial hydrolysates of coupling agents means that at least some even all hydrolyzable groups in the coupling agent are hydrolyzed. In addition to coupling agents and / or coupling agent hydrolysates, the primer layers may comprise other adherence-improving ingredients. For example, the primer layers may further comprise an amount of improved adhesion of an epoxy-containing material. Amounts of improved adhesion of an epoxy containing material when added to the coating composition containing coupling agent can improve the adhesion of a coating applied subsequently when compared to a coating composition containing coupling agent that is essentially free of the epoxy containing material. Others
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43/84 examples of primer layers that are suitable for use in conjunction with the various embodiments disclosed herein include those described in U.S. Patent Nos. 6,150,430, 6,042,737, and 6,025,026. Additional examples of primer layers include polyurethane coating compositions such as those described in US Patent No. 6,187,444 and poly (urea / urethane) coating compositions such as those described in US Patent No. 6,532,075, both of which coating compositions can be used with or without a photochromic material.
[0058] Other types of functional organic coatings that can be used in accordance with the various embodiments disclosed herein include: paints, for example, a paste or pigmented liquid for decoration, protection, and / or identification of a substrate; and printing inks, for example, a paste or pigmented liquid for writing and printing on substrates, such as the production of check marks on security documents, for example, documents such as banknotes (money), passports, and driving licenses , for which authentication or authenticity verification may be desired. In addition, as discussed above, the lined liquid crystal coating may comprise a material adapted to exhibit dichroism, and at least a portion of the material adapted to exhibit dichroism can be at least partially aligned with at least a portion of the liquid crystal material partially aligned.
[0059] When used here, the term transient coating refers to a coating that helps to create a gradient in properties between two coatings. For example, a transitional coating can assist in creating
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44/84 of a gradient in hardness between a relatively hard coating and a relatively soft coating. Examples of transient coatings (which may also be called bonding layers or bonding layer coatings) include thin radiation-cured acrylate films, for example, such as those shown in US patent application publications 2003 / 0165686 of paragraph 79 to paragraph 173; 2004/0207809 from paragraph 108 to paragraph 204; 2005/0196616 from paragraph 107 to paragraph 158; 2005/196617 from paragraph 24 to paragraph 129; 2005/196618 from paragraph 28 to paragraph 291; 2005/0196626 from paragraph 164 to paragraph 217; and 2005/196696 from paragraph 24 to paragraph 141.
[0060]
When used herein, the term anti-reflective coating refers to a coating that increases the transmittance of light through a substrate by reducing the amount of light that is reflected by the substrate.
Examples of anti-reflective coatings include a layer or multilayer of metal oxides, metal fluorides, or other such materials. Examples of suitable anti-reflective coatings can be found in the U.S. patent
No. 5,580,819 from column 2, line 50 to column 11, line 44.
[0061] Additionally, according to certain embodiments disclosed herein, the additional coating may be a protective coating such as an abrasion resistant coating, such as a hard coating, on its external surfaces. For example, commercially obtainable thermoplastic polycarbonate ophthalmic lens substrates are often sold with an abrasion resistant coating already applied to their
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45/84 external surfaces because these surfaces tend to be quickly scratched, worn or scratched. An example of such a lens substrate is the GENTEX ™ polycarbonate lens (obtainable from Gentex Optics). Therefore, when used herein, the term substrate includes a substrate having a protective coating, such as an abrasion resistant coating on its surfaces. Other examples of protective coatings include abrasion resistant coatings comprising organic silanes, abrasion resistant coatings comprising thin films based on radiation cured acrylate, abrasion resistant coatings based on inorganic materials such as silica, titania and / or zirconia, resistant coatings abrasion-type that are curable by ultraviolet, oxygen barrier coatings, UV shield coatings, and combinations thereof. For example, according to an embodiment, the protective coating may comprise a first coating of a thin film based on radiation cured acrylate having UV shielding properties and a second coating comprising an organic silane. Examples of commercial protective coatings include SILVUE® 124 and HI-GARD® coatings obtainable, respectively, from SDC Coatings, Inc. and PPG Industries, Inc.
[0062] According to various embodiments, the one or more at least additional partial layers may comprise a second at least partial layer on the surface of the first at least partial layer. In these embodiments, the at least partial second layer may comprise at least one liquid crystal material. In those incorporations where
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46/84 the at least partial first layer has been at least partially aligned, as described herein, the at least one liquid crystal material of the at least partial second coating can be at least partially aligned with the alignment of the at least partial first layer. According to these embodiments, the at least partial first layer can serve as a photo-alignment layer for the liquid crystal materials in the at least partial second layer. Examples of liquid crystal materials suitable for use with photo-alignment materials in accordance with the various embodiments disclosed herein include compounds containing mesogen or residues thereof, liquid crystal polymers, liquid crystal monomers, dichroic materials, and photochromic materials / dichroic. When used herein, the term prepolymer means partially polymerized materials.
[0063] According to several embodiments disclosed herein in which the at least partial second layer is an aligned liquid crystal layer, the aligned liquid crystal layer may comprise a material adapted to exhibit dichroism, and at least a portion of the material adapted for display dichroism can be aligned with at least a portion of the liquid crystal material aligned at least partially. When used herein, the term material adapted to exhibit dichroism means a material that is adapted to absorb one of two polarized components of the orthogonal plane of radiation at least transmitted more strongly than the other. Examples of materials that are adapted to exhibit dichroism include dichroic materials such as dyes of photochromic / dichroic materials such as
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47/84 dyes. In specific embodiments, the at least one liquid crystal material in the second layer can be at least one dichroic material and / or photochromatic / dichroic material, such as those described herein. When used herein, the term dichroic material means a material that has a generally constant absorption spectrum and that is adapted to absorb one of two polarized components of the orthogonal plane of radiation at least more strongly transmitted than the other. When used here, the term photochromatic / dichroic material means a material that has an absorption spectrum for at least visible radiation that varies in response to at least actinic radiation and that absorbs one of two polarized components from the orthogonal plane of at least transmitted radiation more strongly than the other, in response to at least actinic radiation.
[0064] Figure 1 illustrates the optical element 100 according to an embodiment described herein. In Figure 1, the at least partial coating 120 is applied to at least a portion of an upper substrate surface 110. The at least partial second layer 130 is coated on the coating surface 120 opposite substrate 110.
[0065] According to certain embodiments comprising a second at least partial layer comprising at least one liquid crystal material, the one or more at least additional partial layers may further comprise a at least partially aligned third layer at least partially comprising a second material of alignment and an at least partial fourth layer comprising at least a second liquid crystal material. In these incorporations, the third layer
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48/84 at least partially aligned can be aligned in a different direction from the first at least partially aligned layer. The at least a second liquid crystal material can then be aligned with the third layer at least partially aligned. The second alignment material can have a structure represented by any of the copolymeric materials (represented by formulas I and II), which can have the same structure or a different structure of the alignment material in the at least partial first layer. Alternatively, the at least partial third layer may comprise a different alignment material in structure than the copolymeric materials described herein. In addition, the at least one second liquid crystal material of the fourth layer may be the same or different from the at least one liquid crystal material of the second layer. Examples of the at least a second liquid crystal material in the fourth layer include at least one dichroic material and / or photochromatic / dichroic material, described herein.
[0066] In specific embodiments, the partial layers on at least a portion of the substrate surface can be arranged in a pile or laminated on the substrate surface. For example, the first at least partial layer, the second at least partial layer, the third at least partial layer and the fourth at least partial layer can form a pile on the substrate surface. Referring to Figure 2, which illustrates the optical element 200 according to this embodiment, the first at least partial layer 220 is coated on the upper surface of substrate 210. The second at least partial layer 230 is coated on the surface of the opposite layer 220 substrate 210. The third
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At least partial layer 240 is coated on the surface of the second layer 230 opposite the first layer 220 and the at least partial layer 250 is coated on the surface of the third layer 240 opposite the second layer 230. In other embodiments, one or more additional layers can be applied to at least a portion of the surface of the at least partial fourth layer.
[0067] Generally speaking, substrates that are suitable for use together with the various embodiments disclosed herein include substrates formed from organic materials, inorganic materials, or combinations thereof (for example, composite materials). Examples of materials that can be used in accordance with the various embodiments disclosed herein are described in more detail below.
[0068] Specific examples of organic materials that can be used to form the substrates disclosed herein include polymeric materials, such as those discussed in detail above, for example, homopolymers and copolymers prepared from monomers and mixtures of monomers disclosed in the US patent. No. 5,962,617 and US Patent No. 5,658,501 from column 15, line 28 to column 16, line 17. For example, such polymeric materials can be thermoplastic or thermoset polymeric materials, can be transparent or optically clear, and can have any required refractive index. Examples of such disclosed monomers and polymers include: polyol monomers (allyl carbonate), for example, allyl diglycol carbonates such as diethylene glycol bis (allyl carbonate), the monomer of which is sold under the trade name CR-39 by PPG Industries , Inc .; polyurea / polyurethane polymers (polymers of
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50/84 poly (urea / urethane)), which are prepared, for example, by the reaction of polyurethane prepolymer and a diamine curing agent, a composition for such polymer being sold under the trade name TRIVEX by PPG Industries, Inc .; carbonate comonomer terminated with (meth) acryloyl polyol, diethylene glycol dimethacrylate monomers; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomers; ethoxylated trimethylolpropane triacrylate monomers; ethylene glycol bis methacrylate monomers; poly (ethylene glycol) bis methacrylate monomers; urethane acrylate monomers; poly monomers (ethoxylated bisphenol A dimethacrylate); poly (vinyl acetate); poly (vinyl alcohol); polyvinyl chloride); poly (vinylidene chloride); polyethylene; polypropylene; polyurethanes; poly (thio-urethanes); thermoplastic polycarbonates; such as carbonate-bonded resin derived from bisphenol A and phosgene, such material being sold under the trade name LEXAN; polyesters, such as the material sold under the trade name MYLAR; poly (ethylene terephthalate); poly (vinyl butyral); poly (methyl methacrylate), such as the material sold under the trade name PLEXIGLAS, and polymers prepared by reacting polyfunctional isocyanates with polythiols or polyisulfide monomers, whether homopolymerized and / or copolymerized and / or terpolymerized with polythiols, polyisocyanates and polyisotopes and polyisotopes and polyisotopes ethylenically unsaturated or vinyl monomers containing halogenated aromatics. Copolymers of such monomers and mixtures of the described polymers and copolymers with other polymers are also considered to form block copolymers or
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51/84 interpenetrated network products.
[0069] According to several incorporations disclosed here, the substrate can be an ophthalmic substrate. When used here, the term ophthalmic substrate means lenses, partially formed lenses and blank lenses. Examples of organic materials suitable for use in forming ophthalmic substrates according to various embodiments disclosed herein include polymers recognized in the art that are useful as ophthalmic substrates, for example, organic optical resins that are used to prepare optically clear leaks for optical applications, such as like ophthalmic lenses.
[0070] Other examples of organic materials suitable for use in forming substrates according to the various embodiments disclosed herein include both synthetic and natural materials, opaque or translucent polymeric materials, including: natural and synthetic textile materials, and cellulosic materials such as wood paper .
[0071] Examples of inorganic materials suitable for use in forming substrates according to the various embodiments disclosed herein include glass, minerals, ceramics, and metals. For example, in an embodiment, the substrate comprises glass. In other embodiments, the substrate may have a reflective surface, for example, a ceramic substrate, metallic substrate, or polished mineral substrate. In other embodiments, a reflective layer or coating can be deposited or applied differently to a surface of an organic or inorganic substrate to make it reflective or to improve its reflection.
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52/84 [0072] In addition, the substrates according to various embodiments disclosed herein may be non-dyed, dyed, linearly polarized, circularly polarized, elliptically polarized, photochromatic, or dyed photochromatic substrates. When used herein with reference to substrates, the term undyed means substrates that are essentially free of coloring agent additions (such as conventional dyes) and have an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation. Additionally, with reference to substrates, the term dyed means substrates that have a coloring agent (such as conventional dyes) and an absorption spectrum for visible radiation that does not vary significantly in response to actinic radiation.
[0073] When used here with reference to substrates, the term linearly polarized refers to substrates that are adapted to polarize radiation linearly (that is, to confine the vibrations of the electric light wave vector in one direction). When used herein with reference to substrates, the term circularly polarized refers to substrates that are adapted to circularly polarize radiation. When used herein with reference to substrates, the term elliptically polarized refers to substrates that are adapted to polarize radiation elliptically.
Additionally, when used here with reference to substrates, the term dyed photochromatic means substrates containing added coloring agent as well as a photochromatic material, having an absorption spectrum for visible radiation that varies in response to at least radiation
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Actinic 53/84. Consequently, for example, the dyed photochromatic substrate may have a first color characteristic of the coloring agent and a second color characteristic of the combination of the coloring agent and the photochromatic material when exposed to actinic radiation.
[0074] Still other incorporations of this disclosure refer to liquid crystal cells. According to these embodiments, the liquid crystal cells may comprise a first substrate comprising a first surface, a second substrate comprising a second surface opposite the first surface of the first substrate, a first at least partial layer on at least a portion of the first surface facing the second surface, a second layer at least partial on at least a portion of the second surface facing the first surface, the first layer at least partial and the second layer at least partial defining a space between them , and a liquid crystal material in the space between the first at least partial layer and the second at least partial layer. According to various embodiments, the first at least partial layer and the second at least partial layer are alignment layers. In certain embodiments, at least one of the first at least partial layer and the second at least partial layer may comprise a (co) polymer having a structure represented by one of formulas I and II shown here, in which the groups M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b , and Z ^c have the structures as shown here. The value of n ranges from 10 to 10,000 and the values of x, y, and z are as described herein. Suitable substrates for the first
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54/84 substrate and for the second liquid crystal cell substrate can include any of the substrates described herein. In specific embodiments, the first substrate and the second substrate may be able to transmit electromagnetic radiation through the substrate material (that is, the substrates are optically clear, transparent, or translucent).
[0075] In specific embodiments both the first at least partial layer and the second at least partial layer can comprise a (co) polymer having the structure represented by one of formulas I and II. In specific embodiments, both the first layer and the second layer comprise a (co) polymer material as described herein, the copolymer of the first surface may have the same polymeric structure as the copolymer of the second surface.
That is, the copolymer on both the first and second surfaces has the same monomeric structures for M ^a , M ^b , M ^c , L ^a , L ^b , L ^c ,
Z ^a ,
Z ^b , and Z ^c . In other embodiments, the first surface structure may be polymeric of the (co) polymer polymer of the (co) polymer of being different from the structure of the second surface. That is, although the copolymer of both the first and second surfaces may have a structure that can be represented by one of formulas I and II, the polymeric structure on each surface may differ in structure from at least one of M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b , and Z ^c .
[0076] In certain incorporations, at least one of the first at least partial layer and the second at least partial layer is at least partially lined. Both the first at least partial layer and the second layer by
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Less partial 55/84 is aligned at least partially. The first and / or second layer can be aligned by any of the alignment methods described herein. In specific embodiments, surfaces can be aligned by exposure to polarized electromagnetic radiation, for example, flat polarized UV radiation. In an embodiment, the alignment of the at least partial first layer can be in the same direction as the alignment of the at least partial second layer. In other embodiments, the alignment of the at least partial first layer may be in a different direction from the alignment of the at least partial second layer.
[0077] In specific embodiments, the liquid crystal cell can be an active liquid crystal cell or a passive liquid crystal cell. According to various embodiments, the liquid crystal material in the liquid crystal cells described herein, can be any liquid crystal material known in the art, such as those mentioned herein. In specific embodiments, the liquid crystal material may be a liquid crystal material that is capable of being aligned by the alignment layer comprising the first layer, by the alignment layer comprising the second layer, by both alignment layers (i.e. first layer and the second layer). According to specific embodiments, the liquid crystal material may comprise at least one of a dichroic material or a photochromatic / dichroic material, including any of the dichroic materials or the photochromatic / dichroic materials described or mentioned herein.
[0078] The liquid crystal cell can be used, for example, as display elements, including screens,
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56/84 monitors, or security elements. According to certain embodiments, the liquid crystal cell can be a pixelated cell (in pixels). When used here, the term pixelated (a) means that an article, such as a display element or liquid crystal cell, can be broken into a plurality of individual pixels (ie, a single point occupying a specific place within a display, image or cell). In certain embodiments, the liquid crystal cell can be a pixelated cell, comprising a plurality of regions or compartments (i.e., pixels). The characteristics of individual pixels, such as color, polarization and the like, can be controlled in relation to other pixels in the display element, liquid crystal, or article.
[0079] Figure 3 illustrates an incorporation of a liquid crystal cell according to the present disclosure. According to this embodiment, the liquid crystal cell 300 comprises first surface 310 and second surface 320 opposite the first surface 310. The first surface 310 has a layer of an alignment material 330 which faces the second surface 320 and the second surface 320 has a layer of alignment material 340 which faces first surface 310. Cell 300 also comprises a bottom substrate 360 and will contain liquid crystal material 350 in the space defined by the first and second surface.
[0080] Additional embodiments of the present disclosure provide methods for applying a photo-alignment material to an optical element, such as any of the optical elements described herein. According to incorporations
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57/84 specific methods may comprise applying at least a partial layer of a photoalignment (co) polymer material on at least a portion of a substrate surface, forming an attractive bond between one or more adhesion promoting groups ( Z ^b ) in the polymeric structure of the photo-alignment (co) polymer material and a compatible group on the substrate surface, and align at least partially at least a first portion of the photo-alignment (co) polymer material exposing the layer at least partial to polarized UV radiation. According to these incorporations, the photo-alignment material can have a structure represented by the (co) polymeric structures described here, such as those represented by formulas I or II shown here, in which the groups M ^a , M ^b , M ^c , L ^a , L ^b , L ^c , Z ^a , Z ^b , and Z ^c have structures shown here. The value of n ranges from 10 to 10,000 and the values of x, y, and z are as described herein.
[0081] According to these incorporations, the substrate can be any of the substrates for optical elements described here in detail. When used here, the term compatible group means a functional group, parcel or molecular architecture that can form an attractive force with the adhesion group, including covalent bonds, polar covalent bonds, ionic bonds, hydrogen bonds, electrostatic attractions, hydrophobic interactions, and attractions
from Van . der Waals, or a combination two or more of these forces attractive.[0082] Methods specific to to apply the layer fur any less partial of (co photo-alignment polymer, such as how on here described himself, about at least one portion of an
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58/84 surface of a substrate, are described in detail in US patent No. 7,342,112 of column 83, line 16 to column 84, line 10. These disclosed methods include methods for forming articles, such as optical elements and ophthalmic elements, which may also include at least one of a dichroic compound or a photochromatic / dichroic compound, by a variety of methods known in the art, such as absorption, coating, overmoulding, rotating coating, spray coating, rotating and spray coating, coating / casting, reverse coating, transfer coating, surface compression coating, engraving coating, thin extruder die coating, blade coating, induction, rod / bar coating and wire coating. Various coating methods suitable for use in certain embodiments of the present disclosure are described in Coating Processes ”, Kirk-Othmer Encyclopedia of Chemical Technology, volume 7, pp 1-35, 2004. Absorption methods are described in US patent No. 6,433. 043 of column 1, line 31 to column 13, line 54. According to certain embodiments, the at least partially coated substrate may be part of an optical element, as described herein. In specific embodiments, the optical element can be an ophthalmic element, such as corrective and non-corrective lenses, including mono and multifocal lenses, which can be segmented or non-segmented multifocal lenses (such as bifocal lenses, trifocal lenses and progressive lenses) ), as well as other elements used to correct, protect, or improve vision (cosmetically or differently), including
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59/84 contact, intraocular lenses, magnifying lenses, and protective visors or lenses;
and may also include partially formed lenses and blank lenses. In other embodiments, the coated substrate at least partially may be incorporated into a manufacturing article, as described herein.
[0083]
In specific embodiments, the methods may further comprise at least partially aligning at least a second portion of the photoalignment (co) polymer material by exposing the at least partial layer of the photoalignment (co) polymer material in the second portion to UV radiation. polarized, the alignment direction of the first portion of the photoalignment (co) polymer material being different from the alignment direction of the second portion of the photoalignment (co) polymer material. For example, by selectively exposing the second portion of the photo-alignment (co) polymer material to polarized UV radiation that is polarized in a different direction from the polarized UV radiation used to align the first portion, the first and second (and subsequent portions) may have different alignments. You can perform the selective exposure of a portion, masking or blocking the exposure of the substrate section that is either not aligned or aligned in a different direction. Using this method, patterns can be formed in the photo-aligning (co) polymer material in which the alignments of the various portions of the photo-aligning (co) polymer material define the pattern.
[0084]
Still in accordance with other embodiments of the various methods described herein, the methods may further comprise applying a second at least partial layer comprising a liquid crystal material in at least a portion of
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60/84 a surface of the photoalignment (co) polymer material and at least partially align the liquid crystal material with an alignment of the photoalignment (co) polymer material of the photoalignment (co) polymer aligned least partially. The liquid crystal material can be any liquid crystal useful in the art, for example, any of the crystal materials
liquids here cited or indicated. In incorporations specific, the material in liquid crystal may be at least one of a dichroic material or a material photochromatic / dichroic. [0085] How on here if argued, in incorporations
Specific adhesion-promoting groups on the (co) polymer material can also form attractive bonds with the at least partial second layer. In many cases, it may be desirable to have not only improved adhesion between the photo-alignment material of the first layer and the substrate, but also to have improved adhesion between the photo-alignment material in the first layer and the material in the second layer. According to these specific embodiments, the methods may further comprise forming an attractive bond (such as those described herein) between one or more groups promoting adhesion on the surface of the photo-aligning (co) polymer material and a compatible group in the second at least partial layer. The compatible group can be in the structure of the material that forms the at least partial second layer, such as the coating or film material, for example, a polymeric material.
[0086] The various incorporations of the methods of this disclosure may also include applying at least one
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61/84 additional layer on at least a portion of a surface of the photo-aligning (co) polymer material. As described herein, the at least one additional layer can be applied directly to the surface of the photoalignment (co) polymer material or alternatively, be applied to the surface of a layer that has been applied to the surface of the (co) material photo-alignment polymer.
By this method, a stack or laminate of different layers can be applied to the surface of the photo-aligning (co) polymer material.
In various embodiments, the at least one additional layer can be selected from a bonding layer, a primer layer, an abrasion resistant coating, a hard coating, a protective coating, a reflective coating, a photochromic coating, a non- reflective, linearly polarized coating, circularly polarized coating, elliptically polarized coating, transient coating, liquid crystal material layer, alignment material layer, retardant layer, or combinations of any of them. a bonding layer, a primer layer, an abrasion resistant coating, a hard coating, a protective coating, a reflective coating, a photochromic coating, a non-reflective coating, a linearly polarized coating, a circularly polarized coating, a coating elliptically polarized, a transient coating, a layer of liquid crystal material, a layer of alignment material, a layer of retarder, or combinations of any of the same.
In those incorporations, where the additional layer is applied directly
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62/84 on the surface of the photoalignment (co) polymer material, the additional coating may comprise one or more compatible groups, such that the method may comprise forming an attractive bond between one or more adhesion promoting groups on the surface of the ( co) photo-alignment polymer and the one or more compatible groups in the additional layer.
[0087] In general, the thickness of the at least partial coatings can be any thickness necessary to achieve the desired thickness for the article of manufacture or optical element. For example, and according to various embodiments, the first at least partial coating can have a thickness ranging from: 0.005 to 1000 pm, 0.05 to 100 pm, 0.5 to 50 pm, or even from 2 to 8 pm. Additionally, according to certain embodiments, the thickness of the first at least partial coating may be greater or less than the thickness of the at least one additional at least partial coating. The second at least partial coating and any additional coating may have a thickness ranging from: 0.5 to 10 pm, 1 to 10 pm, or even from 0.5 to 5 pm. The thickness of the second at least partial coating may be the same as that of the first at least partial coating or, as described herein, in certain embodiments it may be greater or less than the thickness of the first at least partial coating.
[0088] In accordance with specific embodiments, the present disclosure provides the following photo-alignment materials: (a) poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co- (2 [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) of ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl]; (b)
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63/84 poly (4- (6- (methacryloyloxy) hexyloxy) benzoate) -co- (2 - [(3,5dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) -co- (gmethacryloxy propyl trimethoxysilane) from ((E) -2 -methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl]; (c) poly [4- (6 (methacryloyloxy) hexyloxy) benzoate) -co- (2-isocyanate ethyl methacrylate) from ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1enyl) phenyl]; (d) poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co- (2-isocyanate ethyl methacrylate) -co - ((E) -2-methoxy-4- (3methoxy-3-oxoprop-1-enyl) phenyl] (gmethacryloxy propyl trimethoxysilane); (e) poly [4- (6 (methacryloyloxy) hexyloxy) benzoate) -co - ((g-methacryloxy propyl trimethoxysilane) from ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1enyl) phenyl]; (f) poly [4- (6- (methacryloyloxy) hexyloxy) benzoate ) -co- (2-hydroxy ethyl methacrylate) -co- (g-methacryloxy propyl trimethoxysilane) from ((E) -2-methoxy-4- (3-methoxy-3oxoprop-1-enyl) phenyl]; (g) poly (4- (6 (methacryloyloxy) hexyloxy) benzoate) -co- (3-isopropenyl-a, adimethyl benzyl isocyanate) from ((E) -2-methoxy-4- (3-methoxy-3oxoprop-1-enyl) phenyl ]; (h) poly [4- (6 (methacryloyloxy) hexyloxy) benzoate) -co- (2- (terciobutylamino) ethyl methacrylate) from ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1enyl) ) phenyl]; (i) poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co- (2 - [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) -co- (4-methoxy phenyl- 4 - ((6- (acryloyloxy) hexyl) oxy benzoate) of ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1enyl) phenyl]; (j) poly [4- (6- ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl (methacryloyloxy) hexyloxy) benzoate) -co- (methyl methacrylate) -co- (glycidyl methacrylate); (k) poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co- (2- [3,5dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) -co- (hexyl
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64/84 of ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1enyl) phenyl].
[0089]
In view of the present disclosure, one of ordinary skill in the art will recognize that other polymeric materials having structures represented by formulas I and II may be used as photoalignment layers having improved adhesion properties.
[0090] The following examples describe more particularly various embodiments of the present invention, or aspects thereof.
Examples [0091] In Part 1 of the Examples, the preparation of the photo-alignment materials of this disclosure is described as
Examples 1-9 and Comparative Example (CE). In Part 2, liquid crystal coating components and dichroic dyes are described. Part 3 describes the preparation and coating application of photo-alignment material alone, with liquid crystal coating (LCCF) formulations on different substrates or with a stack of coatings on polycarbonate lenses. Part 4 describes adherence testing and results of photo-alignment materials separately and with a liquid crystal coating formulation (LCCF) applied in Table 1 and a stack of coatings in Table 2.
Part 1 - Photo-alignment materials
Example 1 [0092] Poly (4- (6- (methacryloyloxy) hexyloxy) benzoate) -co (2 - [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) of ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl]
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[0093] The following materials were added in a 50 ml Schenk tube: 4- (6- (methacryloyloxy) hexyloxy) (E) -2-methoxy-4- (3-methoxy-3-oxoprop-l-) benzoate enyl) phenyl (2.83 g, 0.0057 mol), 2 - [(3,5-dimethyl pyrazolyl) carboxyamino] methacrylate ethyl having CAS # 78279-10-4 obtainable from Showa Denko (0.478 g, 0.0019 mol), 2,2'-azo bis (2-methyl propionitrile) (0.0062 g, 0.000038 mol) and cyclopentanone (14.17 g). The tube was cooled in a dry ice / acetone bath and degassed by a vacuum pump followed by filling with N ₂ . This process was repeated five times. The tube was placed in an oil bath maintained at 60 ° C and stirred for 16 hours. The molecular weight of the polymer was analyzed by gel permeation chromatography (GPC) using a column calibrated with a polystyrene standard. The results were as follows: M _n = 43,864; M _w = 123,738; M _w / M _n = 2.82.
Example 2 [0094] Poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co (2 - [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) -co (γ-methacryloxy propyl trimethoxysilane) of (( E) -2-methoxy-4 (3-methoxy-3-oxoprop-1-enyl) phenyl]
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[0095] The procedure of Example 1 was followed except that the following materials were used in the specified amounts: 4- (6- (methacryloyloxy) hexyloxy) (E) - benzoate
2- methoxy-4- (3-methoxy-3-oxoprop-l-enyl) phenyl (1 g, 0.002 mol), 2 - [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate (0.1807 g, 0.00074 mol), γmethacryloxy propyl trimethoxysilane (0.0357 g, 0.0001 mol), 2.2'-azo bis (2-methyl propionitrile) (0.0047 g, 0.00003 mol) and the cyclopentanone solvent ( 5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 54,144; M _w = 116,402; M _w / M _n = 2.15.
Example 3 [0096] Poly (4- (6- (methacryloyloxy) hexyloxy) benzoate) -co (2-isocyanate ethyl methacrylate) from ((E) -2-methoxy-4- (3-methoxy)
3-oxoprop-1-en1) phenyl]
[0097] The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) 2-methoxy-4- (3-methoxy-3-) benzoate oxoprop-l-enyl) phenyl (1 g, 0.002
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67/84 mol), ethyl 2-isocyanate methacrylate (0.104 g, 0.00067 mol), 2,2'-azo bis (2-methyl propionitrile) (0.0044 g, 0.00003 mol) and the cyclopentanone solvent (5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 57,351; M _w = 149,825; M _w / M _n = 2.61.
Example 4 [((E) -2-Methoxy-4- ([E) -2-methoxy-4- ([((E) -2-methoxy-4- ([((E) -2-methoxy-4- (3-methoxy-3-oxoprop-lenyl) phenyl] [0099]
The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) 2-methoxy-4- (3-methoxy-3-oxoprop-l) benzoate -enyl) phenyl (1 g, 0.002 mol), ethyl 2-isocyanate methacrylate (0.104 g, 0.00067 mol), γ-methacryloxy propyl trimethoxysilane (0.033 g, 0.00013 mol), 2.2'-azo bis (2-methyl propionitrile) (0.0044 g, 0.00003 mol) and the cyclopentanone solvent (5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 58,015; M _w = 153,397; M _w / M _n = 2.64.
Example 5 [0100] Poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co ((γ-methacryloxy propyl trimethoxysilane) from ((E) -2-methoxy-4Petition 870190057778, 06/24/2019, pg. 84/115
68/84 (3-methoxy-3-oxoprop-1-enyl) phenyl]
[0101] The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) 2-methoxy-4- (3-methoxy-3-) benzoate oxoprop-l-enyl) phenyl (1 g, 0.002 mol), γ-methacryloxy propyl trimethoxysilane (0.150 g, 0.0006 mol), 2,2'-azo bis (2-methyl propionitrile) (0.0066 g, 0 , 00004 mol) and the cyclopentanone solvent (5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 56,498; M _w = 139,980; M _w / M _n = 2.47.
Example 6 [((E) -2-Methoxy-4- ([E) -2-methoxy-4- (6- (methacryloyl) hexyloxy) benzoate) -co ((E) -2-methoxy-4- (poly (4- (methacryloyl) hexyloxy) benzoate) -co ((E) -2-methoxy-4-) (3-methoxy-3-oxoprop-l-
[0103] The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) petition 870190057778, of 06/24/2019, p. 85/115
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2-methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl (1 g, 0.002 mol), 2-hydroxy ethyl methacrylate (0.131 g, 0.00101 mol), γ-methacryloxy propyl trimethoxysilane ( 0.150 g, 0.0006 mol), 2,2'-azo bis (2-methyl propionitrile) (0.0066 g, 0.00004 mol) and the cyclopentanone solvent (5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 70,329; M _w = 193,335; M _w / M _n = 2.74.
Example 7 (0) [0104] Poly (4- (6- (methacryloyloxy) hexyloxy) benzoate) -co (3-isopropenyl-a, α-dimethyl benzyl isocyanate) of (E) -2methoxy-4- (3-methoxy-3 -oxoprop-l-enyl) phenyl]
NCO [0105]
The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) 2-methoxy-4- (3-methoxy-3-oxoprop-l) benzoate -enyl) phenyl (0.5 g, 0.001 mol), 3-isopropenyl-a isocyanate, α-dimethyl benzyl (0.0608 g, 0.0003 mol), 2,2'-azo bis (2-methyl propionitrile ) (0.0033 g, 0.00002 mol) and the cyclopentanone solvent (2.5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 6,480; M _w = 8,702; M _w / M _n = 1.34.
Example 8 [0106] Poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co (2- (terciobutylamino) ethyl methacrylate) from ((E) -2-methoxy-4 (3-methoxy-3-oxoprop- 1-enyl) phenyl]
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ΊΟ / SA
[0107] The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) 2-methoxy-4- (3-methoxy-3-) benzoate oxoprop-l-enyl) phenyl (0.5 g, 0.001 mol), 2- (terciobutylamino) ethyl methacrylate (0.056 g, 0.0003 mol), 2,2'-azo bis (2-methyl propionitrile) (0 .0033 g, 0.00002 mol) and the cyclopentanone solvent (2.5 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 5,435; M _w = 10,793; M _w / M _n = 1.98.
Example 9 [0108] Poly [4- (6- (methacryloyloxy) hexyloxy) benzoate) -co (2 - [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate) co- (4-methoxy phenyl-4 - (( 6- (acryloyloxy) hexyl) oxy benzoate) ((E) -2-methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl]
[0109] The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6- (methacryloyloxy) hexyloxy) (E) 2-methoxy-4- (3-methoxy-3-) benzoate oxoprop-l-enyl) phenyl (4 g, 0.008
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71/84 mol), 2 - [(3,5-dimethyl pyrazolyl) carboxyamino] ethyl methacrylate (0.778 g, 0.003 mol), 4 - ((6 (acryloyloxy) hexyl) oxy) 4-methoxy phenyl benzoate (0 , 4069 g, 0.0012 mol), 2,2'-azo bis (2-methyl propionitrile) (0.0204 g, 0.00012 mol) and the cyclopentanone solvent (20 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 68,687; M _w = 310,178; M _w / M _n = 4.51.
Comparative Example (CE) [0110] (E) 2-Methoxy-4- (3-methoxy-3-oxoprop-1-enyl) phenyl poly [4- (6- (methacryloyloxy) hexyloxy) benzoate]
[0111] As a Comparative Example, a homopolymer without a group capable of serving as an adhesion promoter was prepared. The procedure of Example 1 was followed except that the following materials were used in the specified quantities: 4- (6 (methacryloyloxy) hexyloxy) (E) -2-methoxy-4- (3methoxy-3-oxoprop-l-enyl) benzoate ) phenyl (5 g, 0.010 mol), 2,2'-azo bis (2-methyl propionitrile) (0.0083 g, 0.00005 mol) and the cyclopentanone solvent (25 g). The molecular weight of the polymer was analyzed by GPC using a column calibrated with a polystyrene standard. The results were as follows: M _n = 78,058; M _w = 171,016; M _w / M _n = 2.19.
Part 2 - Liquid crystal coating components and formulations [0112] LCM represents liquid crystal monomers.
[0113] DD represents dichroic dye.
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72/84 [0114] PC represents photochromatic materials.
[0115] LCCF stands for liquid crystal coating formulation.
[0116] LCM-1 is 1- (6- (6- (6- (6- (6- (6- (6- (6- (8- (4- (4- (4- (8acryloyloxy hexyloxy) benzoyloxy) benzoyloxy ) phenyloxy carbonyl) phenoxy) octyloxy) -6-oxo hexyloxy) -6-oxo hexyloxy) -6oxo hexyloxy) -6-oxo hexyloxy) -6-oxo hexyloxy) -6-oxo hexyloxy) -6-oxo hexyloxy) -6 -oxo hexyloxy) -6-oxo hexan-1-ol which was prepared according to the procedures described in Example 17 of US patent publication No. 2009/0323011, the liquid crystal monomer of which is incorporated herein by reference.
[0117] LCM-2 is RM257 obtainable commercially reported as 4- (3-acryloyloxy propyloxy) -benzoic acid 2-methyl-1,4-phenylene ester, obtainable from EMD Chemicals, having the molecular formula C ₃₃ H ₃₂ Oi ₀ .
[0118] LCM-3 is RM105 obtainable commercially reported as 4- (6- (acryloyloxy) hexyloxy) 4-methoxy-3methyl phenyl benzoate, obtainable from EMD Chemicals, having the molecular formula C ₂₃ H ₂₆ O ₆ .
[0119] LCM-4 is RM23 obtainable commercially reported as 4- (6-acryloyloxy hexyloxy) -benzoic acid (4-cyano phenyl ester), obtainable from EMD Chemicals, having the molecular formula C ₂₃ H ₂₃ O ₅ .
[0120] LCM-5 is RM82 obtainable commercially reported as bis (4- (6- (acryloyloxy) hexyloxy) benzoate) of 2methyl-1,4-phenylene, obtainable from EMD Chemicals, having the molecular formula C ₃₉ H ₄₄ Oi ₀ .
[0121] DD-1 is reported to be 4 - (((4 - ((E) -phenyl diazenyl) naphthalen-1-yl) diazenyl) phenoxy) methyl) benzoate
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73/84 ethyl and was prepared as described in paragraph [0221] of U.S. patent application publication No. 2009 / 0146104A1, the disclosure of which is incorporated herein by reference.
[0122] PC-1 is reported to be 2-phenyl-2- {4- [4- (4methoxy phenyl) -piperazin-1-yl] -phenyl} -5- (2-methoxy ethyl oxy carbonyl) -6- methyl-8- (4- (4- (4- (trans) -pentyl cyclohexyl) benzoyloxy) -phenyl-2H-naphtho [1,2-b] pyran and was prepared following the procedures of US Patent No. 7,342 .112, the disclosure of which is incorporated herein by reference.
[0123] PC-2 is reported to be 3- (4-fluorine phenyl-3- (4piperazine phenyl) -13-ethyl-13-methoxy-6-methoxy-7- (4- (4- (4 (trans) -pentyl cyclohexyl) benzoyloxy) -phenyl) benzoyloxyindene [2 ', 3': 3,4] naphtho [1,2-b] pyran and was prepared following the procedures of US patent No. 7,342,112, which disclosure here is incorporated by reference.
LCCF-1 was prepared as follows:
[0124] Step 1- In an appropriate flask containing a mixture of anisole (3.5 g) and BYK®-346 additive (0.035 g, reported as poly (dimethyl siloxane) modified with polyether obtainable from BYK Chemie, USA), added LCM-2 (3.25 g), LCM-3 (3.25 g), DD-1 (0.39 g), 4-methoxy phenol (0.0098 g), and IRGACURE® 819 (0, 0975 g, photo-initiator obtainable from CibaGeigy Corporation). The resulting mixture was stirred for 2 hours at 80 ° C and cooled to about 26 ° C.
[0125] Step 2- Hydroxyethyl methacrylate (0.65 g) and dibutyl tin dilaurate (0.008 g) were added and the resulting mixture was stirred for 30 minutes at about 26 ° C. LCCF-2 was prepared as follows:
[0126] The procedure used to prepare LCCF-1 was followed except that DD-1 was not added to the mixture.
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LCCF-3 was prepared as follows:
[0127] Step 1- In an appropriate flask containing a mixture of anisole (3.4667 g) and BYK®-346 additive (0.0347 g, reported as poly (dimethyl siloxane) modified with polyether obtainable from BYK Chemie, USA) , LCM-2 (1.3 g), LCM-3 (1.3 g), LCM-4 (1.3 g), LCM-5 (1.3 g), 4-methoxy phenol (0) were added , 0078 g), and IRGACURE® 819 (0.078 g, photo-initiator obtainable from Ciba-Geigy Corporation). The resulting mixture was stirred for 2 hours at 80 ° C and cooled to about 26 ° C.
[0128] Step 2- Hydroxyethyl methacrylate (0.65 g) and dibutyl tin dilaurate (0.008 g) were added and the resulting mixture was stirred for 30 minutes at about 26 ° C.
LCCF-4 was prepared as follows:
[0129] The procedure used to prepare LCCF-3 was followed except that in Step 1 PC-2 (0.31 g) was also added to the reaction mixture.
LCCF-5 was prepared as follows:
[0130] The procedure used to prepare LCCF-3 was followed except that in Step 1 PC-1 (0.312 g) was also added to the reaction mixture.
LCCF-6 was prepared as follows:
[0131] In an appropriate flask containing a mixture of anisole (1.4808 g) and BYK®-346 additive (0.0148 g, reported as poly (dimethyl siloxane) modified with polyether obtainable from BYK Chemie, USA), if LCM-2 (1.0 g), LCM-3 (1.0 g), LCM-1 (1.0 g), DD-1 (0.165 g), 4-methoxy phenol (0.0041 g), and IRGACURE® 819 (0.0413 g, photo-initiator obtainable from Ciba-Geigy Corporation). The resulting mixture was stirred for 2 hours at 80 ° C.
LCCF-7 was prepared as follows:
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75/84 [0132] In an appropriate bottle containing a mixture of anisole (1.7407 g) and BYK®-346 additive (0.0174 g, reported as poly (dimethyl siloxane) modified with polyether obtainable from BYK Chemie, USA) , LCM-1 (0.5 g) was added,
LCM-2 (0.5 g), LCM-3 (0.5 g), LCM-4 (0.5 g), LCM-5 (0.5 g), PC-2 (0.156 g), 4- methoxy phenol (0.0039 g), and IRGACURE® 819 (0.0392 g, photo-initiator obtainable from Ciba-Geigy Corporation). The resulting mixture was stirred for 2 hours at 80 ° C.
Part 3 - Preparation of coatings for substrates coated with lined liquid crystals.
Part 3-1 - Primer preparation [0133] In a 250 ml amber glass bottle equipped with a magnetic stir bar, the following materials were added in the indicated quantities: polyacrylate polyol (15, 2334 g) (Composition D of Example 1 US Patent No. 6,187,444, the disclosure of which is incorporated herein by reference); poly (alkylene carbonate diol) (40,0000 g) T-5652 from Asahi Kasei Chemicals; DESMODUR® PL 340 (33, 7615 g) from Bayer
Material Science; TRIXENE® BI 7960 (24.0734 g) from Baxenden;
BYK®-333 polyether modified poly (dimethyl siloxane) (0.0658 g) from BYK Chemie, GmbH; KKAT® 348 urethane catalyst (0.8777 g) from King Industries; g-glycidoxy propyl trimethoxysilane A-187 (3.5109 g) from Momentive Performance
Materials; light stabilizer TINUVIN® 928 (7.8994 g) of
Ciba Specialty Chemicals; and 1-methyl-2-pyrrolidinone (74.8250 g) from Sigma-Aldrich.
[0134] The mixture was stirred at room temperature for 2 hours to produce a solution having 50% by weight of final solids based on the total weight of the solution.
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Part 3-2 - Preparation of photo-alignment coatings [0135] Solutions of each of the photo-alignment materials of Examples 1 and 9 and the Comparative Example were prepared by diluting to 4 weight percent in cyclopentanone, based on the total weight of the solution.
Part 3-3 - Liquid crystal coating formulations [0136] Liquid crystal coating formulations (LCCF) 1 to 7 were prepared as described above in Part 2 above.
Part 3-4 - Transitional layer coating formulation (TLCF)
TLCF was prepared as follows:
[0137] In a 250 ml amber glass bottle equipped with a magnetic stir bar, the following materials were added in the indicated amounts: hydroxyl methacrylate (1.242 g) of Sigma-Aldrich; neopentyl glycol diacrylate SR247 (13.7175 g) from Sartomer; trimethylolpropane trimethyl acrylate SR350 (2.5825 g) from Sartomer; DESMODUR® PL
340 (5.02 g) of Bayer Material Science; IRGACURE® 819 (0.0628 g) from Ciba Specialty Chemicals; DAROCUR® TPO (0.0628 g) from Ciba Specialty Chemicals; poly (butyl acrylate) (0.125 g); 3-aminopropyl propyl trimethoxysilane A-1100 (1.4570 g) of
Momentive Performance Materials; and Test 200 absolute anhydrous ethanol (0.4570 g) from Pharmaco-Aaper.
[0138] The mixture was stirred at room temperature for 2 hours.
Part 3-5 - Protective coating formulation (PCF) PCF (hard coating) was prepared as follows:
[0139] Charge 1 was added to a clean dry beaker and the beaker was placed in an ice bath at 5 ° C with stirring.
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Charge 2 was added and a release of heat raised the temperature of the reaction mixture to 50 ° C. The reaction mixture was cooled to 20-25 ° C and Charge 3 was added with stirring. Charge 4 was added to adjust the pH from about 3 to about 5.5. Charge 5 was added and the solution was mixed for half an hour. The solution was filtered through a nominal 0.45 micron capsule filter and stored at 4 ° C until use.
Charge 1 [0140] Glycidoxy propyl trimethoxysilane (32.4 g) [0141] Methyl trimethoxysilane (345.5 g)
Charge 2 [0142] Deionized water (DI) solution with nitric acid (1 g nitric acid / 7000 g) (292 g)
Charge 3 [0143] DOWANOL® PM solvent (228 g)
Charge 4 [0144] TMAOH (tetramethyl ammonium hydroxide in 25% methanol) (0.45 g)
Charge 5 [0145] BYK® 306 surfactant (2.0 g)
Part 3-6 - Procedures used to prepare coatings and pile of coatings reported in Tables 1 and 2
Part 3-6A - Substrate preparation [0146] Square substrates measuring 5.08 cm by 5.08 cm by 0.318 cm prepared with CR-39® monomer were obtained from Homalite, Inc. Finished monofocal lenses (6 bases, 70 mm) prepared with CR-39® monomer were also used as indicated. Each substrate prepared with CR-39® monomer was cleaned by rubbing with a tissue soaked in acetone and dried
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[0147] Finished monofocal lenses (6 bases, 70 mm) made of GENTEX OPTICS polycarbonate and semi-finished monofocal lenses (6 bases, 70 mm) without hard coating made of TRIVEX monomer were also used as indicated. These lenses were cleaned by rubbing with a cloth soaked in isopropanol and dried with an air stream.
[0148] Each of the aforementioned substrates was corona treated by passing on a conveyor belt in a HV 2000 series crown treatment equipment, serial energy production no. 020270 from Tantec EST Systems with a high voltage transformer. The substrates were exposed to the crown generated by 53.99 KV, 500 Watts during travel on the conveyor belt at a belt speed of 3 feet / min.
Part 3-6B - Primer coating procedure [0149] The primer solution was applied to the test substrates by rotating coating on a portion of the test substrate surface by distributing approximately 1.5 mL of the solution and rotating the substrates at 500 rpm per 3 seconds, followed by 1,500 rpm for 7 seconds, followed by 2,500 rpm for 4 seconds. For the rotating coating, a spinning processor from Laurell Technologies Corp. was used. (WS-400B6NPP / LITE). Then, the coated substrates were placed in an oven maintained at 125 ° C for 60 minutes. The coated substrates were cooled to about 26 ° C. The substrate was corona treated by passing on a conveyor belt in a HV 2000 series crown treatment equipment, serial energy production no. 020270 from Tantec EST Systems with a high voltage transformer. The primer layer
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79/84 dry was exposed to the crown generated by 53, 00 KV, 500 Watts during travel on the conveyor belt at a belt speed of 3 feet / min.
Part 3-6C - Coating procedure for photo-alignment materials [0150] The coating solutions of Examples 1-9 and CE prepared in Part 3-2 were applied to the test substrates by rotational coating on a portion of the substrate surface of test distributing approximately 1.0 mL of the solution and rotating the substrates at 800 rpm for 3 seconds, followed by 1,000 rpm for 7 seconds, followed by 4,000 rpm for 4 seconds. For the rotating coating, a spinning processor from Laurell Technologies Corp. was used. (WS-400B6NPP / LITE). Then, the coated substrates were placed in an oven maintained at 120 ° C for 30 minutes. The coated substrates were cooled to about 26 ° C.
[0151] The dry photo-alignment layer on each of the substrates was ordered at least partially by exposure to linearly polarized ultraviolet radiation using a DYMAX® UVC-6 UV / carrier system from DYMAX® Corp. having a 400 Watt power supply. The light source was oriented such that the radiation was linearly polarized in a plane perpendicular to the substrate surface. The amount of ultraviolet radiation to which each alignment layer was exposed was measured using an EIT Inc. Power Puck ™ high energy UV radiometer (serial No. 2066) and was as follows: UVA 0.126 W / cm ² and 5 , 962 J / cm ² ; UVB 0.017 W / cm ² and 0.078 J / cm ² ; UVC 0 W / cm ² and 0 J / cm ² ; and UVV 0.046 W / cm ² and 2.150 J / cm ² . After ordering at least a portion of the photoorientable polymeric network, the substrates were cooled to about 26 ° C
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80/84 and kept covered.
Part 3-6D - Coating procedure for liquid crystal coating formulations [0152] Each of the liquid crystal coating (LCCF) formulations reported in Table 1 was coated by rotation at a rate of 1,200 rpm / 15 seconds on the materials photo-alignment ordered at least partially from Part 3-6C on the test substrates. Each coated square substrate was placed in an oven at 50 ° C for 20 minutes and each coated lens was placed in an oven at 50 ° C for 30 minutes. Subsequently, substrates and lenses were cured in an ultraviolet lamp in the BS-03 irradiation chamber of Dr. Grobel UV-Elektronik GmbH in a nitrogen atmosphere for 30 minutes at a peak intensity of 11-16 Watts / m ² of UVA. The post-curing of the coated substrates was completed at 110 ° C for 3 hours.
[0153] Each of the liquid crystal coating (LCCF) formulations reported in Table 2 was coated by rotation at a rate of 400 rpm for 6 seconds, followed by 800 rpm for 6 seconds on the photo-alignment materials ordered at least partially Part 3-6C on the test substrates. Each coated lens was placed in an oven at 60 ° C for 30 minutes. The lenses were then cured under two ultraviolet lamps in the UV curing oven machine designed and built by Belcan Engineering in a nitrogen atmosphere during travel on a conveyor belt at a speed of 6 ft / min at a peak intensity of 445 Watts / m ² of UVA and 0.179 Watts / cm ² of UVV and UV dosage of 2.7 53 J / cm ² of UVA and 1.191 J / cm ² of UVV. The cured layer was exposed to the crown generated by 53.00 KV, 500
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Watts during travel on the conveyor at a speed of 3 feet / min.
Part 3-6E - Transitional coating procedure [0154] The transitional layer solution prepared in Part 3-4 was coated by rotation at a rate of 1,400 rpm for 7 seconds over the cured LCCF coated substrates. The lenses were then cured under two ultraviolet lamps in the UV curing oven machine designed and built by Belcan Engineering in a nitrogen atmosphere during travel on a conveyor belt at a speed of 6 ft / min at a peak intensity of 1.887 Watts / m ² of UVA and 0.694 Watts / cm ² of UVV and UV dosage of 4,699 J / cm ² of UVA and 1,787 J / cm ² of UVV. The cured connection layer was exposed to the crown generated by 53.00 KV, 500 Watts during travel on the conveyor belt at a belt speed of 3 feet / min.
Part 3-6F - Coating procedure for the protective coating (hard coating) [0155] The hard coating solution, prepared in Part 3-5, was coated by rotation at a rate of 2,000 rpm for 10 seconds over the substrates coated with a layer of bond healed. The post-curing of the coated substrates was completed at 105 ° C for 3 hours.
Part 4 - Adherence test and results [0156] The standardized test method ASTM D-335993 was used to measure adhesion by tape test - Method B to determine the adhesion of layers on the surfaces of test substrates. The coated substrates were cut with 11 blades in a hatched pattern to form about 200
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82/84 squares. Tape pull was performed 3 times in the same area using 3M # 600 clear tape. The test surfaces were examined with a Fisher Scientific STEREOMASTER II microscope at 3X magnification. The results indicated as APPROVED showed that most (that is, more than 75%) if not all the squares remained on the substrate surface and the results indicated as FAILED showed that they showed that most (that is, more than 75%) not all the squares were removed from the substrate by the tape. The results of the adhesion tests on the indicated substrates are shown in Tables 1 and 2. When the photo-alignment materials of Examples 1-9 and Comparative Example (CE) were used alone on a substrate (that is, without an LCCF), the LCCF # column indication was nonexistent since no liquid crystal coating formulation was applied. When LCCF was applied to the photo-alignment material layer of Examples 1-9 and Comparative Example (CE), the respective number of each LLCF's applied and tested individually was shown in Table 1. Table 2 includes the results adherence test for polycarbonate lenses having a stack of coatings indicated, ie the letter X means that the coating was present.
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Table 1 - Adherence test results on different substrates.
Example# LCCF # CR-39® monomer squares Monomer lensesCR-39® Polycarbonate lenses TRIVEX® monomer lenses CE No present DISAPPROVED DISAPPROVED DISAPPROVED DISAPPROVED CE 1,2,3,4,5.6 or 7 DISAPPROVED --- --- --- 1 No present APPROVED APPROVED APPROVED APPROVED 1 1,2,3,4,5.6 or 7 APPROVED APPROVED --- --- 2 No present APPROVED APPROVED APPROVED APPROVED 2 6 or 7 APPROVED APPROVED APPROVED APPROVED 3 No present APPROVED APPROVED --- --- 4 No present APPROVED APPROVED APPROVED --- 5 No present APPROVED --- APPROVED --- 6 No present APPROVED --- APPROVED --- 7 No present APPROVED --- APPROVED APPROVED 8 No present APPROVED --- APPROVED APPROVED 9 No present --- APPROVED --- --- 9 7 - APPROVED - -
Table 2 - Adhesion results for stacks of coatings on polycarbonate lenses
Example# Primer Alignment layer LCCF Connection layer Hard coating Adherence 1 X X 6 X X APPROVED 1 X X 7 X X APPROVED 9 X X 7 X X APPROVED CE X X 6 X X DISAPPROVED CE X X 6 X X DISAPPROVED
[0157] It is understood that the present description and examples illustrate relevant aspects of the invention for a clear
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84/84 understanding of the invention. Certain aspects of the invention that would be obvious to those of ordinary skill in the art and therefore would not facilitate a better understanding of the invention have not been presented in order to simplify the present description. Although the present invention has been described in conjunction with certain embodiments, the present disclosure is not limited to the particular embodiments or examples disclosed herein, but is intended to cover modifications that are within the spirit and scope of the invention, as defined by the appended claims.

权利要求:
Claims (15)
[1]
1. (Co) polymer, characterized by the fact that it comprises a structure represented by the formula:
- M ³V IVF y m = η.Λ
L ^a
L ^b
L ^c
Z® where: each of M ^a , M ^b , and M ^c independently represents residues of selected monomeric units of substituted or unsubstituted acryloyl units, in which said acryloyl substituents are chosen from C1-C4 alkyl, phenyl, -0- and combinations thereof, substituted or unsubstituted styrene units, substituted or unsubstituted epoxy units, substituted or unsubstituted urethane units, substituted or unsubstituted polycarboxylic acid units, substituted or unsubstituted polyol units , substituted or unsubstituted polyamine units, or substituted or unsubstituted hydroxy alkanoic acid units; said substituents being selected from C1-C20 alkyl, C1-C20 alkoxy, C3-C10 cycloalkyl, C1-C20 alkyl (C1-C20 alkoxy), C1-C20 haloalkyl, C3-C20 heterocycloalkyl , haloarila (haloalkyl CIC ₂₎ aryl, (alkyl of C1-C20) aryl, (alkoxy of C1-C20) aryl, heteroaryl, aryl (alkyl of C1-C20)> heteroaryl (alkyl of C1-C20) alkyl; L ^a , L ^b , and L ^c are spacer groups, each of which is selected independently of a single bond, (CH ₂ ) _g -, - (CF ₂ ) _h -, - Si (Z ') 2 (CH ₂ ) _g - or - (Si (CH ₃ ) ₂ O) _h -,
N (R) -, -C (R) = C (R) -, -C (R) = N-, -C (R ') ₂ -C (R') ₂ -, -0-, Petition 870190057778, of 06/24/2019, p. 102/115
[2]
11/11
C (O) -, -C ° C-, -N = N-, -S-, -S (O) -, -S (O) (O) -, - (O) S (O) O-, O (O) S (O) O-, normal or branched chain C ₁ -C ₂₄ alkylene residue, arylene, C ₃ -C ₁₀ cycloalkylene, or various combinations thereof, with Z occurring at each occurrence 'is independently chosen from hydrogen, C ₁ -C ₁₈ alkyl, C3-C10 cycloalkyl or aryl; at each occurrence, R is independently chosen from Z ^b , hydrogen, C1C18 alkyl, C3-C10 cycloalkyl or aryl; at each occurrence R 'is independently chosen from Z ^b , C1-C18 alkyl, C3-C10 cycloalkyl or aryl; the C1C ₂₄ alkylene residue is mono-substituted by Z ^b , cyano, or halogen, or polysubstituted by Z ^b or halogen; in each occurrence g is independently chosen from 1 to 20, and h is an integer from 1 to 16 inclusive; each Z ^a is independently a photochemically active chromophore selected from dimerized substituted or unsubstituted cinnamate, dimerizable substituted or unsubstituted coumarin, cis / trans isomerizable or unsubstituted cis, trans substituted or unsubstituted polyimide, or aromatic ester substituted or unsubstituted capable of undergoing Photo-Fries rearrangement; each Z ^b is an adhesion promoting group selected independently from hydroxy, carboxylic acid, anhydride, isocyanate, blocked isocyanate, thioisocyanate, blocked thioisocyanate, amino, uncle, organofunctional silane, organofunctional titanate, organofunctional zirconate, or epoxy, each of which organofunctional group is independently selected from vinyl, allyl, hydrocarbon radicals with vinyl functionality, hydrocarbon radicals with epoxy functionality, hydrocarbon radicals with alyl functionality,
Petition 870190057778, of 06/24/2019, p. 103/115
[3]
3/11 hydrocarbon radicals with acryloyl functionality, hydrocarbon radicals with methacryloyl functionality, hydrocarbon radicals with styryl functionality, hydrocarbon radicals with mercapto functionality, or combinations of such organofunctional groups, said hydrocarbon radicals being selected from C ₁ alkyl -C _20, alkenyl C ₂ -C ₂₀ alkynyl C ₂ -C ₂₀ alkoxy, C ₁ -C 20, (C1C20 alkyl) C1C20 alkoxy, (C1C20 alkoxy) C1C20 alkyl, aryl, heteroaryl, and combinations of such hydrocarbon radicals; provided that when Z ^b is hydroxy or carboxylic acid, the (co) polymer will further comprise at least one other adhesion promoting group; Z ^c is a mesogenic structure selected from a group of liquid crystals as rigid straight rods, a group of liquid crystals as arched rigid rods, or groups of liquid crystals as hard disks; and x has a value of 0 <x <1, y has a value of 0 <y <1, and z has a value of 0 <z <1 where x + y + z = 1 and n has a value ranging from 10 to 10,000, where x = 1, then at least one of L ^a and Z ^a is still replaced with at least one adhesion promoting group Z ^b and when y = 0, then at least one of L ^a , Z ^a , L ^c and Z ^c is further substituted with at least one adhesion promoting group Z ^b .
2. (Co) polymer according to claim 1, characterized by the fact that it also comprises a residue of at least one of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a photosensitive material, and a non- photosensitive.
3. (Co) polymer according to either of claims 1 or 2, characterized by the fact that it is in the
Petition 870190057778, of 06/24/2019, p. 104/115
[4]
4/11 form of a random copolymer, a block copolymer, a grafted copolymer, a linear copolymer, a branched copolymer, a hyper-branched copolymer, a dendritic copolymer, or a star copolymer.
4. (Co) polymer according to any one of claims 1 to 3, characterized in that each of M ^a, M ^b, M ^c and independently be residues units acryloyloxy or methacryloyloxy units and Z ^to be a photochemically active chromophore selected from a dimerizable substituted or unsubstituted cinnamate or dimerizable substituted or unsubstituted coumarin.
[5]
5. (Co) polymer according to any one of claims 1 to 4, characterized in that the mesogenic structure Z ^c has a structure represented by:
R ^m - [G ¹ - [S ¹ ] j] j '- [G ² - [S ² ] d] d' - [G ³ - [S ³ ] e] e '- [S ⁴ ] source:
(I) at each occurrence, each G, G, and G is independently chosen from: a bivalent group chosen from: a substituted or unsubstituted aromatic group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted heterocyclic group substituted and mixtures thereof, wherein the substituents are selected from: hydroxy, amino, halogen, alkenyl C ₂ -C _18, alkynyl of C ₂ -C _18, azido, silyl, siloxy, silyl hydride (tetrahydro- 2H-pyran-2yl) oxy, thio, isocyanate, thio isocyanate, acryloyloxy, methacryloyloxy, 2- (acryloyloxy) ethyl carbamyl, 2 (methacryloyloxy) ethyl carbamyl, aziridinyl, allyloxy carbonyloxy, carboxylic acid, amino carboxylic acid, amino carboxylic ester, , amino carbonyl, (C1C18 alkyl) amino carbonyl, amino carbonyl (C1-C18 alkyl),
Petition 870190057778, of 06/24/2019, p. 105/115
5/11 (C ₁ -C ₁₈ alkoxy) carbonyl, aryloxy carbonyloxy, perfluorine (C ₁ -C ₁₈ alkyl) amino; di- (perfluoro (C ₁ C ₁₈ alkyl) amino), C ₁ -C ₁₈ acetyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkoxy, (C ₁ -C ₁₈ alkyloxy) carbonyloxy, halocarbonila, hydrogen, aryl, hydroxy (alkyl of C ₁ -C _18), alkyl C ₁ -C ₁₈ alkoxy, C ₁ -C _18, amino (alkyl of C ₁ -C ₁₈₎ (C 1 -C 18 alkyl ) amino, di- (C1-C18 alkyl) amino, (C1-C18 alkyl) (C1-C18 alkoxy), (C1-C18 alkoxy) (C1C18 alkoxy), nitro, poly (C1- alkyl) C18) ether, (C1C18 alkyl) (C1-C18 alkoxy) (C1-C18 alkyl), methacryloxy oxy (C1-C18 alkyl), poly (C1-C18 alkoxy), ethylene, acryloyloxy (C1 alkyl -C18), methacryloyloxy (C1C ₁₈ alkyl), 2-chloro acryloyloxy, 2-phenyl acryloyloxy, acryloyloxy phenyl, 2-chloro acryloyl amino, 2-phenyl acryloyl amino carbonyl, oxetanyl, glycidyl, cyano, C1- alkyl isocyanate C18, itaconic acid ester, vinyl ether, vinyl, styrene, liquid crystal polymers ester of main chain or side chain, deri siloxane, ethylene imine, maleic acid, fumaric acid, normal or branched chain C1-C18 alkyl group that is monosubstituted with cyan, halogen, or C1-C18 alkoxy, or poly-substituted with halogen, unsubstituted cinnamic acid, cinnamic acids that are substituted with at least one of methyl, methoxy, cyano or halogen, substituted or unsubstituted chiral or non-chiral monovalent or divalent groups chosen from steroidal radicals, terpenoid radicals, alkali radicals, or mixtures thereof, the substituents are independently chosen from C1-C18 alkyl, alkoxy from
C1-C18, amino, C3-C10 cycloalkyl, (alkyl of
C1Petition 870190057778, of 06/24/2019, p. 106/115
[6]
6/11
C _i8 ) (C _i -C _i8 alkoxy), fluorine (C _i -C _i8 alkyl), cyan, cyan (C _i -C _i8 alkyl), cyan (C _i -C _i8 alkoxy), or mixtures of the same; or a group comprising one of the following formulas: -M (T) _(ti) and -M (OT) ( _ti ), in which M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from radicals organofunctional, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, et is the valence of M;
(II) R ^m is -H, hydroxy, amino, halogen, haloalkyl, aryl, C _i -C _i8 alkyl, or C _i -C _i8 alkoxy;
(III) each of j, d, e and f is independently chosen from an integer ranging from 0 to 20, inclusive; each of j ', d', ee 'is independently an integer from 0 to 4 as long as the sum of j' + d '+ e' is at least i; and (IV) in each occurrence, each of S, S, S, and S is independently chosen from a spacer unit chosen from: (A) - (CH ₂ ) g-, - (CF ₂ ) h-, - Si (Z ') ₂ (CH ₂ ) g-, or (Si (CH ₃ ) ₂ O) _h -, being that in each occurrence, Z' is independently chosen from hydrogen, C1-8 alkyl, C3- cycloalkyl C10 or aryl; in each occurrence, g is independently chosen from ia 20 and h is an integer from ia i6 inclusive; (B) -N (Y) -, -C (Y) = C (Y) -,
-C (Y) = N-, -C (Y ') ₂ -C (Y') ₂ -, or a single bond, and in each occurrence Y is independently chosen from hydrogen, C1-8 alkyl, C1-8 cycloalkyl C3-C10 and aryl, and, at each occurrence, Y 'is independently chosen from C1 -C8 alkyl, C3-C0 cycloalkyl or aryl; or (C) -O-,
-C (O) -, -C ° C-, -N = N-, -S-, -S (O) -, -S (O) (O) -, - (O) S (O) O- , Petition 870190057778, of 06/24/2019, p. 107/115
[7]
7/11
O (O) S (O) O- or alkylene residue of from C ₁ -C ₂₄ normal or branched alkylene residue of said C ₁ -C ₂₄ unsubstituted and mono-substituted by cyano or halogen, or poly-substituted by halogen; provided that when two spacer units comprising heteroatoms are linked together with spacer units are linked so that the heteroatoms are not directly linked with each other and when S ¹ and S ⁴ are linked to another group, they will be linked so that two heteroatoms are not directly linked to each other.
6. Article of manufacture, characterized in that it comprises: a substrate, an at least partial first layer on at least a portion of a substrate surface, the layer comprising a (co) polymer, as defined in any of the claims of 1 to 5, the first at least partial layer being optionally at least partially aligned by exposure to polarized electromagnetic radiation; and, optionally, one or more additional at least partial layers on at least a portion of the substrate surface, the one or more additional layers being selected from a bonding layer, a primer layer, an abrasion resistant coating, a hard coating, a protective coating, a
coating reflective, a photochromic coating, a coating non-reflective, polarized coating linearly, a circularly polarized coating, a coating elliptically polarized, a coating transitional, a layer of liquid crystal material, a
layer of alignment material, a layer of retarder, or combinations of any of them.
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[8]
11/11
7. Manufacturing article according to claim 6, characterized by the fact that it is an optical element selected from an active liquid crystal cell, a passive liquid crystal cell, a display element, a window, a mirror, or a ophthalmic element.
8. Article of manufacture according to any one of claims 6 and 7, characterized in that one or more additional at least partial layers are present and comprise: a second layer at least partial on a surface of the first layer at least partial the at least partial second layer comprising at least one liquid crystal material optionally comprising at least one dichroic material or photochromatic / dichroic material; optionally, a third layer at least partially aligned at least partially comprising a second alignment material; and optionally, a at least partial fourth layer comprising at least a second liquid crystal material, the third layer being at least partially aligned, if present, is aligned in a different direction the first layer at least partially aligned and the first, second, at least partial third and fourth layers optionally form a pile on the substrate surface.
[9]
Manufacturing article according to any of claims 6 and 7, characterized in that it is a liquid crystal cell comprising: a first substrate having a first surface; a second substrate having a second surface opposite the first surface;
an at least partial first layer over at least one
Petition 870190057778, of 06/24/2019, p. 109/115
9/11 portion of the first surface facing the second surface; a second at least partial layer on at least a portion of the second surface facing the first surface, the first at least partial layer and the second at least partial layer defining a space; and a liquid crystal material optionally comprising at least one dichroic material or a photochromatic / dichroic material in the space between the first at least partial layer and the second at least partial layer, the first layer being at least partial and the second layer at least the least partial are alignment layers and at least one of them, preferably both, comprises a (co) polymer, as defined in any one of claims 1 to 4, and at least one of the first layer being at least partial and the second the at least partial layer is optionally at least partially aligned and the alignment of the first at least partial layer is preferably in a different direction from the alignment of the at least partial second layer.
[10]
10. Method for applying a photo-alignment material to an optical element, characterized in that it comprises: applying at least a partial layer of a photoalignment material comprising a (co) polymer, as defined in any one of claims 1 to 5 , on at least a portion of a substrate surface; forming an attractive bond between one or more groups promoting adhesion on the photoalignment (co) polymer material and a compatible group on the substrate surface; and at least partially align at least a first portion of the photo (co) polymer material Petition 870190057778, of 6/24/2019, p. 110/115
10/11 alignment exposing the at least partial layer to polarized UV radiation.
[11]
11. Method according to claim 10, characterized by the fact that it further comprises: aligning at least partially at least a second portion of the photo-alignment (co) polymer material exposing the at least partial layer to polarized UV radiation, being that the alignment direction of the first portion of the photoalignment (co) polymer material is different from the alignment direction of the second portion of the photoalignment (co) polymer material.
[12]
Method according to any one of claims 10 and 11, characterized in that it further comprises: applying a second at least partial layer comprising a liquid crystal material to at least a portion of the (co) polymeric photo-material alignment; and at least partially aligning the liquid crystal material with an alignment of the photoalignment (co) polymer material at least partially aligned, the liquid crystal material comprising at least one dichroic material or a photochromatic / dichroic material.
[13]
13. Method according to claim 12, characterized in that it further comprises forming an attractive bond between one or more groups promoting adhesion on the surface of the photo-aligning (co) polymer material and a group compatible in the second layer by less partial.
[14]
Method according to any one of claims 10 and 11, characterized in that it further comprises applying at least an additional layer to at least a portion of a surface of the photo (co) polymer material
Petition 870190057778, of 06/24/2019, p. 111/115
11/11 alignment, at least one additional layer selected from a bonding layer, a primer layer, an abrasion resistant coating, a hard coating, a protective coating, a reflective coating, a photochromic coating, a non-reflective coating , a linearly polarized coating, a circularly polarized coating, an elliptically polarized coating, a transient coating, a layer of liquid crystal material, a layer of alignment material, a retardant layer, or combinations of any of the same.
[15]
15. Composition of (co) polymer, as defined in any one of claims 1 to 5, characterized by the fact that it comprises one or more additives selected from the group consisting of a photochromatic compound, a dichroic compound, a photochromatic / dichroic compound, a photosensitive material, a liquid crystal, a liquid crystal property additive, a nonlinear optical material, a dye, an alignment promoter, a kinetic intensifier, a photoinitiator, a thermal initiator, a surfactant, a polymerization inhibitor, a solvent, a light stabilizer, a thermal stabilizer, a release agent, a rheology controlling agent, a gelling agent, a leveling agent, a free radical purger, a coupling agent, a slope controlling agent, a polymeric material in blocks or not in blocks, and an adhesion promoter.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-07-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-07-16| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C08F 220/30 , C08F 220/62 , C08G 65/331 , C09K 9/02 , G02B 1/04 Ipc: C08F 220/30 (1974.07), C08F 220/62 (1974.07), C08F |

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2019-09-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/12/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/12/2010, OBSERVADAS AS CONDICOES LEGAIS |

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