TW201540815A - Depositing polymer solutions to form optical elements - Google Patents

Abstract

Provided are methods of depositing polymer solutions on substrates to form various optical elements. A polymer solution may include about 0.1% - 0% by weight of a specific polymer having rigid rod-like molecules. The molecules may include various cores, spacers, and sides groups to ensure their solubility, viscosity, and cross-linking ability. The deposition techniques may include slot die, spray, molding, roll coating, and so forth. Pre-deposition techniques may be used to improve wettability and adhesion of substrates. Post-deposition techniques may include ultraviolet cross-linking, specific drying techniques, evaporation of solvent, treating with salt solutions, and shaping. The disclosed polymers and deposition processes may yield optical elements with high refractive index values, such as greater than 1.6. These optical elements may be used as +A plates, -C plates, or biaxial polymers and used as retarders in LCD active panels or as light collimators and light guides.

Description

Depositing a polymer solution to form an optical component

The present invention relates generally to the field of organic chemistry, and more particularly to methods for forming various optical elements using various birefringent films.

Optical polymers have unique properties, such as higher and/or anisotropic refractive indices, which make these polymers suitable for a variety of optical applications. For example, glass type polymethyl methacrylate (PMMA) and polystyrene are used as optical fiber core materials, backlighting applications for LCDs, plastic lenses and films, and enamel resins and cerium oxide are used as fiber coatings. However, the refractive index of PMMA is about 1.49, and the refractive index of polystyrene is about 1.59. These values are not sufficient to fully control the light, and many studies have attempted to develop polymers with higher refractive index values to reduce the working distance by starting "faster (high refractive index) optics, and to obtain optical components. Better geometry. Another exemplary application is liquid crystal displays (LCDs) that utilize optically anisotropic birefringent films, particularly in polarizing stacks, or obtain programmable phase differences in three-dimensional applications. Such polymeric films can be prepared from a variety of polymeric materials that are capable of obtaining optical anisotropy by uniaxial or biaxial intrinsic double reflection of the refractive index of the material, or by polymer orientation techniques. For example, triethylenesulfonyl cellulose (TAC) can be used as a weak negative C plate with a low double reflection inherent value. Another example is by stretching by the ring An olefin polymer (COP) produces a retardation film. Other examples of making optical components may also include the use of polycarbonate, polymethyl methacrylate (PMMA), and polyamine. These polymers can be used as alignment films or optical waveguides in LCDs or other optical devices. Optical components based on polyethylene terephthalate (PET) and polycarbonate (PC) have very inherent double reflections, which makes them difficult to stretch to produce TAC-like stretches unless special orientation techniques are used. The base of the phase difference plate. Furthermore, it is highly desirable to develop new and inexpensive processing techniques that can be controlled. Many existing polymers are difficult to process, and some processing techniques may have a negative impact on the optical properties of the polymer. For example, the use of a temperature gradient to fabricate a thermotropic crystal is also used as a phase difference plate, however, the orientation is obtained in a predetermined manner by grinding the polyamine structure in a certain direction, increasing processing costs and preparation steps. Since the screen size continues to increase, and the large-sized stretched film is difficult to process, it becomes more important.

This "Summary of the Invention" introduces the selection of concepts in a simple form, which will be further described in the "Embodiment" described later. This Summary is not intended to limit the scope of the claimed subject matter, and the scope of the subject matter to be protected.

Methods of depositing a polymer solution to form various optical components are provided. The solution may comprise from about 0.1% to about 30% by weight of a particular polymer having rigid rod-like molecules. The molecules may contain various cores, linkers, and pendant groups to ensure their solubility, viscosity, cross-linking ability, and other related processability. The deposition techniques may include slot die coating, spray coating, molding at various temperatures, roll-to-roll coating, Meyer bar coating, extrusion, casting, pressing, and the like. Various pre-deposition techniques and post-deposition techniques can be used. At least a portion of the pre-deposition technique can be used to increase the wettability and adhesion of the substrate on which the polymer solution is deposited. Some predeposition techniques may include Saponification, washing, oxidation, elution, corona treatment or plasma treatment, deposition of a primer layer, and the like. At least some of the post deposition techniques may include ultraviolet (UV) illumination, infrared (IR) illumination, cross-linking of the compound to the substrate, specific drying techniques, solvent evaporation, treatment with a salt solution, and structural shaping. This specially designed polymer and deposition process is capable of obtaining optical elements having a high refractive index value, for example greater than 1.6 or even greater than 1.7 in the visible region. These optical elements can be used as positive A plates, negative C plates or biaxial plates, and as phase difference plates, for example, in LCD active boards or as optical collimators and optical waveguides in backlight stacking applications. Other applications, such as lenses, optical security films are also included within the scope of the invention.

According to various aspects of the present disclosure, the polymer solution comprises a solvent and a polymer. The polymer comprises n organic units having the following structural formula.

[-(Core(S) _m ) _k -G _l -] _n

Wherein the organic unit comprises a rigid conjugated organic component Core, wherein the G system is selected from the group consisting of -C(O)-NR1-=(C(O))2=N-, -O-NR1-linear and a linking group of a group of (C1-C4)alkylene-CR1R2-OC(O)-CR1R2-, -C(O)-O-, -O-, -NR1-, wherein R1 and R2 are independently selected from the group consisting of a list of H, alkyl, alkenyl, alkynyl, aryl; wherein S is a hydrophilic pendant group that provides solubility to the polymer in a solvent, the same or different, independently selected from the group consisting of the following groups List of one or more: COOX, -SO3X (X is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, alkali metal, NW4 (W is H or alkyl or any combination thereof) List), -SO2NP1P2, -CONP1P2 (P1 and P2 are independently selected from the list comprising H, alkyl, alkenyl, alkynyl, aryl); and, m is 0, 1, 2 or 3, k Is 1, 2 or 3. In a certain embodiment, the n organic units can be capped with any suitable UV-curable component, such as alkenyl, alkynyl, acrylic, and the like. Core, linker and S-group can be independently selected Choose.

The above solvent may include one or more of the following solvents: a polar protic solvent, a polar aprotic solvent, and a non-polar solvent. More specifically, the above solvent may include one or more of the following solvents: water, ketone, ketone/alcohol binary mixture, hydroxyketone, tetrahydrofuran (THF), methyl acetate (MA), MIBK. In various embodiments, the above polymer solution may include one or more additives such as nonylphenoxy glycidyl ether, alcohols, acids, plasticizers, stabilizers, antioxidants, and hindered phenols. In a further embodiment of the invention, the above method steps can be implemented using various systems, devices and mechanisms. Other features, embodiments, and embodiments are detailed below.

100‧‧‧Optical components

102, 202, 1000, 1001‧‧‧ base

204‧‧‧ polymer film

300‧‧‧Process of depositing a polymer solution onto a substrate

302‧‧‧Providing polymer solution

304‧‧‧Predeposition substrate treatment

306‧‧‧Deposited polymer solution

308‧‧‧Remove solvent

600‧‧‧ mould

602‧‧‧ first surface

603‧‧‧ cavity

604‧‧‧ second surface

606‧‧‧ polymer solution

608‧‧‧Water Vapor

702‧‧‧Formed polymer coating

800‧‧‧Display system

801‧‧‧ optical compensator stack

810‧‧‧j-phase difference plate

820‧‧‧First liquid crystal layer

825‧‧‧Second liquid crystal layer

830‧‧‧Polarization layer

840‧‧‧Reflective polarizing layer

850‧‧‧Light Modulator

900‧‧‧Stacking

905‧‧‧Base

910‧‧‧PVA layer

915, 920‧‧‧ phase difference layer

925‧‧‧PSA layer

930‧‧‧VA battery layer

935‧‧‧PET layer

940‧‧‧Protective film

1002‧‧‧Slit mode

1003‧‧‧ Coating direction

1004‧‧‧embossing roller

1005‧‧‧ final structure

The embodiments are illustrated by the embodiments, but are not limited to the drawings in the drawings, in which like elements are referenced, wherein FIG. 1 is a high-order diagram of the coordinate system associated with the optical elements.

Figure 2 is a high level diagram showing a substrate having a surface coated with a polymer film.

Figure 3 is a schematic illustration of a method for depositing an aqueous polymer solution on a substrate in various embodiments of the present disclosure.

Fig. 4A shows an example of the dependence of the dry thickness and the wet thickness of the polymer solution deposited on the substrate.

Fig. 4B shows an example of the dependence of the thickness phase difference of the polymer solution deposited on the substrate on the dry thickness.

Figure 5 shows the dependence of viscosity (cP) as a function of shear rate (s ^-1 ) measured for different polymer concentrations (N).

6A-6C illustrate a molding process example of forming an optical element.

7A, 7B illustrate a grooving process example of a polymer solution layer deposited on a substrate.

Fig. 8 is a view showing an example of a schematic cross section of an example of a display system.

9A-9B are schematic cross-sectional views showing various stacks of display systems.

Figure 10 shows a slot die deposition technique.

In the following description, numerous specific details are set forth in order to provide a The concept of the invention is not premised on the implementation of some or all of these details. In other instances, well known processing steps have not been described in detail to prevent unnecessarily obscuring the inventive concept. Some of the concepts are described in terms of specific embodiments, and it should be understood that these embodiments do not limit the inventive concept.

Foreword

Polymers can be used to fabricate various optical components such as plastic optical fibers, optical coatings, lenses, phase difference plates, polarizers, optical collimators, optical waveguides, optical films (diffusers, collimating structures, optically enhanced films). , anti-glare and anti-reflective structures), illuminators and many other types of devices. However, such applications require specific optical properties and, in many cases, require specific processing characteristics, with very few polymers having sufficiently high values of refractive index and/or double reflection. For example, optically anisotropic birefringent films can be used in liquid crystal displays (LCDs) or other backlight stacking applications, such as phase difference plates, optical films, collimators, optical films, illuminators, light boxes, optical waveguides, light. Collimator and so on. These films can be adapted to the optical properties of each LCD type. The above films are capable of obtaining optical anisotropy by uniaxial stretching and biaxial stretching, applying shear stress to the polymer, casting, molding, and other suitable techniques. For example, TAC, PC, PMMA, polyamine, ring Olefin polymers (COP) can be used to make negative A, C, AC plates or other optical components for LCDs. Another polymer orientation technique utilizes a thermotropic liquid crystal polymer and is heated above its phase transition point or using a pre-stretched or rubbed substrate to provide the desired orientation as in the electrical field application.

As described above, many conventional optical films are manufactured by stretching to obtain a certain characteristic. Stretching produces various stresses and damages these conventional films, which adversely affect their performance. In addition, it may be difficult to stretch in two perpendicular directions, which typically require performance that is necessary for LCD stacking. A larger display format leads to another level of complexity and quality. The methods described herein deposit different types of optical films that do not need to be stretched, or perform heat treatment to achieve orientation, with the result that stress and damage are substantially avoided when integrated into an optical component, such as an LCD. The orientation of the polymer molecules in these films is obtained in the deposition process because the molecules are oriented under shear stress as compared to conventional methods.

In accordance with one or more embodiments of the present disclosure, a deposition method uses a polymer solution to form various optical components. Suitable polymer solutions can include from about 0.1 wt% to 30 wt%, or even from 1 wt% to 10% wt, of a particular polymer having rigid rod-like molecules. The solvent used in the polymer solution may include a wide range of substances such as polar protic solvents, polar aprotic solvents, and non-polar solvents. The polymer molecule may have a uniform atomic mass unit with a chain length of between about 5,000 and 100,000. It should be noted that the optimum chain length and molecular weight generally depend on the polymer concentration, viscosity, temperature, and many other depositions in the polymer solution. Physical and chemical parameters of post deposition processing. The size of the polymer chain is such that the above polymer molecules are oriented at least in the coating direction to obtain a desired refractive index for the optical element. As described later, the positive A plate, the negative C plate, and the biaxial polymer can be formed based, at least in part, on the orientation or stretching of the polymer chains.

The above polymer solution can be deposited using the following techniques: slot die, spray, molding, roll-to-roll coating, Meyer bar coating, roll coating, gravure coating, micro gravure coating, comma coating, knife coating, extrusion Out, printing, dip coating, and the like. For example, slot die technology is capable of forcing a polymer solution from a reservoir through a slit to a moving substrate under pressure. The slit may have a cross section that is much smaller than the reservoir and may be oriented perpendicular to the direction of movement of the substrate. The combination of pressure, slit width, slit and substrate gap, substrate movement speed, and various polymer solution characteristics described above provides a specific orientation of the molecules (e.g., these parameters can define the characteristics of the positive A-plate).

Substrates for polymer solution deposition may include polymeric substrates, glass substrates, TAC substrates, polypropylene substrates, polycarbonate substrates, PET, polyacrylic substrates, PMMA substrates, and the like. The substrate may be treated with one or more techniques prior to depositing the polymer solution to increase the wettability and/or adhesion of the polymer solution deposited onto the substrate. In particular, the above processing techniques may include one or more of the following: cleaning (eg, ultrasonic cleaning), elution, and/or oxidation with a moderately alkaline aqueous solution, saponification, deposition of a primer layer (eg, decane or Polyethyleneimine), which is modified by corona discharge or plasma discharge using various gases and vapors to modify irregularities, electron beams or ion beams on the surface of the substrate. The above predeposition techniques can also include the addition of additives to the polymer solution. The above additives may include plasticizers, antioxidants, surfactants, moldability agents, stabilizers, nonylphenoxy glycidyl ethers, alcohols, acids and hindered phenols or other low molecular weight materials and polymers.

Generally, polymer solutions may be identical before deposition and do not have the desired orientation for molecular orientation. However, various post deposition techniques can be used to achieve the desired molecular orientation or specific optical properties. Post deposition techniques may include, for example, ultraviolet (UV) crosslinking, specific drying techniques Evaporation of solvent technology from polymer solutions, infrared (IR) irradiation, heating, application of a dry gas stream, molding, and the like.

The specially designed polymers and deposition processes described above can achieve optical components having high refractive index values, such as greater than 1.6 or even greater than 1.7 in the partially visible region. These optical elements can be used, for example, as positive A plates, negative C plates or biaxial polymers, and as phase difference plates, for example, in LCD active plates or as optical collimators and optical waveguides in backlight stacking applications. Other applications, such as lenses and optical security films, are also included within the scope of the invention.

definition

The term "visible spectral range" refers to a spectral range with a lower limit of about 400 nm and an upper limit of about 700 nm.

The term "phase difference layer" refers to an optically anisotropic layer capable of changing the polarization state of light waves passing through the anisotropic layer by Descartes associated with a layer of deposited polymer solution or a corresponding optical element based thereon. The three principal refractive indices (n _x , n _y and n _z ) of the coordinate system are characterized. The two principal directions of the refractive indices n _x and n _y belong to the xy-plane coincident with the plane of the phase difference layer, and one main direction of the refractive index (n _z ) coincides with the normal of the phase difference layer. Further shown in Fig. 1, a first diagram shows an optical element 100 comprising a substrate with a deposited polymer solution and a shaft system having a vertical axis x, y and z (e.g., a Cartesian coordinate system). In various embodiments, at least two of the refractive indices of n _x , n _{y ,} and n _z have different values. The term "phase difference layer" may also refer to an optical element that splits incident monochromatic polarized light into a plurality of components and introduces a relative phase difference or phase shift therebetween.

The term "biaxial phase difference layer" refers to an optical layer having refractive indices n _x , n _{y ,} and n _z in the visible spectral range that satisfy the following conditions: n _x ≠n _z , n _x ≠n _{y ,} and n _x ≠n _z .

The term "uniaxial retardation layer" refers to an optical layer having a refractive index in the visible spectral range that satisfies the following conditions: n _x = n _y ≠ n _z or n _x ≠ n _y = n _z or n _x = n _z ≠ n _y .

The term "AC-plate type optically anisotropic retardation layer" refers to an optical layer having refractive indices nx, ny, and nz that meet the following conditions in the visible spectral range: n _z <n _y <n _x .

The term "negative C-plate type optically anisotropic retardation layer" refers to an optical layer having refractive indices n _x , n _y and n _z in the visible spectral range that satisfy the following conditions: n _z <n _x = n _y .

For all types of anisotropic layers, the above definition does not vary with the rotation of the coordinate system (laboratory coordinate system) about the vertical z-axis.

The term "C-plate" refers to a birefringent optical element, for example, a plate or film having a major optical axis (generally referred to as "unusual optical axis") that is substantially perpendicular to the surface of the selected optical element. The primary optical axis means that the refractive index of the birefringent optical element along the axis is different from the substantially uniform refractive index along a direction normal to the main optical axis. For example, the C-plate system using the shafting shown in Fig. 1 is n _x = n _y ≠ n _z , where n _x , n _{y ,} and n _z are refractive indices along the x, y, and z axes, respectively. The optical anisotropy is defined as Δn _zx = n _{z -} n _x . For convenience, Δn _{zx is} referred to as its absolute value.

The term "A-plate" means a birefringent optical element, such as a plate or film having a major optical axis in the x-y plane of the optical element. The positive birefringent A-plate can be a uniaxially stretched film such as a polymer (for example, polyvinyl alcohol, polynorbornene or polycarbonate), or a nematic phase positive optical anisotropic liquid crystal polymer (LCP) material. A uniaxially oriented film is produced. The negative birefringent A-plate can be formed using a negative optical anisotropic nematic phase LCP material, including a uniaxially oriented film such as a discotic compound.

The term "biaxial phase difference plate" may refer to a birefringent optical element, for example, a plate or film having a different refractive index (i.e., n _x ≠n _y ≠n _z ) along all three axes. The biaxial phase difference plate can be manufactured by, for example, a biaxially oriented plastic film. The in-plane phase difference and the out-of-plane phase difference are parameters for describing the biaxial phase difference plate. Since the in-plane phase difference is close to zero, the biaxial phase difference plate element behaves more like a C-plate. Typically, the biaxial phase difference plate, as defined, has an in-plane phase difference of at least 3 nm for a 550 nm emission wavelength. A phase difference plate having a lower in-plane phase difference is considered to be a C-plate.

The term "polymer" should be understood to include polymers, copolymers (eg, polymers prepared using two or more different monomers), oligomers, and combinations thereof, and capable of passing in a miscible form. For example, a polymer, oligomer or copolymer formed by coextrusion or reaction, including transesterification. Unless otherwise specified, both block copolymers and random copolymers are included.

The term "polarization" refers to plane polarization, circular polarization, ellipsometry or any other non-random polarization state in which the electrical vector of the beam does not change direction randomly, but either maintains a constant orientation or changes systematically. In planar polarization, the electrical vector remains in a single plane, while in circular or elliptical polarization, the electrical vector of the beam rotates systematically.

The term "retardation or retardation" refers to the product of the difference between two perpendicular refractive indices and the thickness of the optical element.

The term "in-plane phase difference" refers to the product of the difference in refractive index between two perpendicular planes and the thickness of the optical element.

The term "out-of-plane phase difference" means the product of the difference in refractive index in the thickness direction (z direction) of the optical element minus the in-plane refractive index and the thickness of the optical element. Alternatively, the term refers to the product of the refractive index in the thickness direction (z direction) of the optical element minus the average of the refractive indices in the two perpendicular planes and the thickness of the optical element. Of course, the sign of the out-of-plane phase difference is positive or negative and is important to the user. However, for convenience, only the absolute value of the out-of-plane phase difference is given here. Of course, those skilled in the art will know when to use optical elements with positive or negative out-of-plane retardation. For example, it is generally considered that when the in-plane refractive index is substantially equal and the refractive index in the thickness direction is smaller than the above-described in-plane index, the alignment film containing triacetyl cellulose can produce a negative C-plate. However, in This describes the value of the out-of-plane phase difference as a positive value.

The term "substantially non-absorptive" refers to a level of transmission that is permeable to at least one optical state of visible light, permeable to at least 80% of the optical elements, where the percent transmittance is normalized by incident intensity, optionally polarized light.

The term "substantially non-scattering" refers to the level of parallel or nearly parallel incident light transmitted through the optical element, with at least one polarization state of visible light passing through at least 80% over an angle of less than 30°.

The term "j-phase difference plate" means a film or sheet that does not substantially absorb or scatter light at least one polarization state of visible light, wherein at least two of the three perpendicular refractive indices are unequal, and the in-plane phase difference does not exceed At 100 nm, the absolute value of the out-of-plane phase difference is at least 50 nm.

All values, whether or not stated, are assumed to be modified by the term "about." The term "about" is generally a range of index values, and those skilled in the art will recognize that the range of values is equivalent to the recited value (ie, having the same function or result). In most cases, the term "about" includes the value rounded to the nearest significant digit.

Weight percent, weight percent, wt%, etc. are synonymous with the weight of the material divided by the weight of the composition and multiplied by the concentration of the resulting material.

The range of values represented by the endpoints includes all values within the range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

As used in the specification and the appended claims, the s Thus, for example, reference to a composition containing "compound" also includes a mixture of two or more compounds. When used in the specification and the appended claims, the term "or" is used in its meaning unless otherwise specified. Including "and / or".

Example of water-soluble optical polymer

The water soluble optical polymer described herein comprises a chain of n subunits, each subunit having the following general structure: [-(Core(S) _m ) _k -G _l -] _n (I)

The number of subunits n can be between about 5 and 50,000, more specifically between 10 and 10,000. Those skilled in the art will appreciate that subunit numbers can define the physical properties of optical components based thereon. For example, when the number of subunits is relatively small, the corresponding polymer chain may be too short to achieve the desired orientation. On the other hand, when the number of subunits is relatively high, the corresponding polymer chain may be too long and cause the polymer to have high viscosity and low solubility. In this regard, the number of subunits and the corresponding chain length depend on the selected organic component (Core), linker (G), pendant group (S), desired orientation, and particular application.

In various embodiments, the above organic component Core provides linearity and rigidity of the macromolecule associated with the organic polymeric compound of formula (I). The hydrophilic side group (S _m ) and the number of organic units n can control the ratio between the mesogenic properties and the viscosity of the polymer solution. The choice of the organic component (Core), the hydrophilic side group (S) and the number of organic subunits n determines the type of optical film and double reflection.

In certain embodiments, most of the organic units in the polymer (eg, more than 90%, more than 95%, or more than 99%) are the same. However, in certain embodiments, at least one of the organic subunits is different to form a copolymer.

Each subunit may comprise at least four conjugated organic components Core capable of forming a rigid rod-shaped macromolecule. These conjugated components may be selected from the following structural formulae (II) to (VIII), respectively:

, where R1, R2=H, alkyl-C≡C- (X)

Wherein P is an integer equal to 1, 2, 3, 4, 5 or 6. It should be noted that the components (II) to (X) are capable of providing linearity and rigidity to the macromolecule when the structure is changed.

In a certain embodiment, the organic component (Core) in each subunit can be of the same type. In addition, each of the organic subunits may include a different type of Core that sequentially changes the optical characteristics of the optical element including the polymer compound. Those skilled in the art will appreciate that combining organic components into subunits can affect the optical properties of the optical component.

Further, each subunit may also include one or more linkers (G). Some examples of linkers include -C(O)-NR1-, =(C(O))2=N-, -O-NR1-, linear and branched (C1-C4) Alkyl, -CR1R2-OC(O)-CR1R2-, -C(O)-O-, -O-, -NR1-, wherein R1 and R2 are independently selected from the group consisting of H, alkyl, alkenyl, alkyne A list of bases and aryl groups.

Further, each subunit also contains one or more hydrophilic pendant groups (S), and the hydrophilic side groups include hydrophilic groups that provide solubility of the polymer or its salt in a suitable solvent. In certain embodiments, one or more of the pendant groups may be a hydrophilic group, such as -COOX, -SO3X, wherein X is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, alkali metal , NW4 (W is H or alkyl or any combination thereof), -SO2NP1P2 and -CONP1P2 (P1 and P2 are independently selected from the list comprising H, alkyl, alkenyl, alkynyl, aryl) . In the formula (I), the total number of the above side groups (m) is 0, 1, 2 or 3.

In various embodiments, the n organic units may include one or more terminal components connected to the n organic units as follows: T-[-(Core(S) _m ) _k -G _l -] _n -T

Wherein T comprises one or more of an alkenyl group, an alkynyl group, an acrylic acid or any other UV-curing group.

The number of side groups and the number of organic units n can control the ratio between the mesogenic properties of the polymer and the viscosity. The choice of the organic component (Core), the pendant group (S) and the number of organic units (i.e., the value of n) determines the type and dual reflection of the polymer and the corresponding optical element based on the above polymer. These polymers are capable of forming a solid optical retardation layer, such as a positive A-type retardation layer, a negative C-type retardation layer or an Ac-type retardation layer based on the orientation or de-orientation of the above-described polymer and its components. For example, the conjugated component having the above formula (II) is usually linear, but the conjugated component having the above formula (III) is usually disordered. Therefore, if the subunit contains only the conjugated component (II), the resulting polymer can have a negative C-type retardation layer. And once the conjugated components (II) and (III) are bonded to the subunit, the resulting polymer can It has an Ac-type retardation layer.

The molecules must be rigid and long enough to provide a sequence when dry. However, these two factors of the polymer in an aqueous solution may have a tendency to form LLC. This effect is not ideal when it is desired to manufacture a C-plate. In order to inhibit LLC formation, it is necessary to add a specific group that reduces the mesogenic properties, such as the following groups (but not limited to this):

(a) Introducing chain disordered (nonlinear) fragments or Or the following groups:

(b) Introducing large fragments that produce sterically trouble interactions:

(c) Introducing side groups that create interactions between interchain spaces:

In certain embodiments, the polymer can have a specific amount of organic compound and a linking group. In other words, the monomeric subunit forming the polymer can include, for example, two organic components, one of which has no pendant groups and the other of which has two pendant groups. The first organic component (Core) can be represented by any of the above formulas, that is, II (where p = 1), III (where p = 1), V, VII and VIII. The second organic component (Core) can be represented by the general formula II (where p = 2). The pendant group (S) may include sulfo-based SO ₃ H. The first linker (G) may comprise C(O)-NH- or =2(C(O))=N-, and the second linker (G) may comprise -C(O)-, -NH-C One of (O)-, -N=(C(O))2=. Examples of such subunits or polymers may include: poly(2,2'-disulfo-4,4'-benzidine-p-xylyleneamine), poly(2,2'-disulfo-4, 4'-benzidine m-xylamine, poly(2,2'-disulfo-4,4'-benzidine 1,3-dioxoisoindoline-5-carboxamide), Poly(2,2'-disulfo-4,4'-benzidine 1H-benzimidazole-2,5-dimethylguanamine), poly(2,2'-disulfo-4,4'- Benzidine 3,3',4,4'-biphenyltetracarboxylic acid diimine) and poly(2,2'-disulfo-4,4'-benzidine 1,4,5,8-naphthalene Diimine imine tetracarboxylate). The corresponding structural formulas (XI)-(XVI) of these subunits are as follows:

Wherein, the number of subunits n can be between about 5 and 500,000.

In other embodiments, the rigid rod macromolecule can be synthesized from n first type of organic subunits and k second type of organic subunits. In particular, the first type of organic subunits may include the following structural formula (XVII):

The second type of organic subunits may include the following structural formula (XVIII):

Among them, n can be in the range of 5 to 10,000, and k can be in the range of 5 to 10,000. R ₁ and R ₂ are independently selected from the group consisting of -H ⁺ , alkyl, -(CH ₂ ) _m SO ₃ M, -(CH ₂ ) _m Si(O-alkyl) ₃ , -CH ₂ -aryl The side group of the list of -(CH ₂ ) _m OH (m includes the number from 1 to 18). When one of the side groups is H ⁺ , the total number of H ⁺ does not exceed the side group in the macromolecule (R ₁ and R ₂ ) 50% of the total. The M system is selected from the group consisting of H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ba ²⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , Pb ²⁺ , Zn ²⁺ , La ³⁺ , Al ^a counterion of the list ³⁺ , Ce ³⁺ , Y ³⁺ , Yb ³⁺ , Gd ³⁺ , Zr ^{4+ ,} and NH _4-p Q _p ⁺ , wherein Q is selected from the group consisting of linear and branched (C1-C20) alkane A list of (C2-C20)alkenyl, (C2-C20)alkynyl and (C6-C20)arylalkyl groups, p is 0, 1, 2, 3 or 4. The first type of organic unit and the second type of organic unit are contained in a rigid rod-shaped macromolecule in any order, and at least one aromatic diamine monomer having, for example, the following structural formula (XIX) is polymerized:

Wherein R is a pendant group, and the pendant group is independently selected from the group consisting of -H ⁺ , alkyl, -(CH ₂ ) _m SO ₃ M, -(CH ₂ ) _m Si(O-alkyl) ₃ , -CH ₂ a different monomer of the list of -aryl and -(CH ₂ ) _m OH, wherein m is a number from 1 to 18, and at least one difunctional electrophilic monomer may have, for example, the following structural formula (XX):

The acid acceptor and at least two solvents, one of which is water and the other is water-immiscible organic solvent, and wherein the optimum pH of the polymerization step is between about 7 and 10.

In various embodiments, salts of one or more organic polymer solutions can be used, such as alkali metal salts, ammonium, alkyl substituted ammonium salts, alkenyl substituted ammonium salts, alkynyl substituted ammonium salts, aryl substituted ammonium salts.

In various embodiments, the polymer used for coating and/or the resulting polymer structure can include one or more inorganic compounds, such as hydroxides and alkali metal salts.

The solvent used to dissolve the polymer may include water, any organic solvent, or any combination thereof.

Example

Polymer synthesis example

The embodiments of the various embodiments of the present invention are described below, but the present invention is not limited thereto.

Example 1

This example describes the synthesis of poly(2,2'-disulfo-4,4'-benzidine m-xylyleneamine) sulfonium salt (ie, structure (XII)):

In detail, 1.377 g (0.004 mol) of 4,4'-diaminobiphenyl-2,2'-disulfonic acid was mixed with 1.2 g (0.008 mol) of cesium hydroxide monohydrate and 40 ml of water to disperse The stirrer was stirred until dissolved, and 0.672 g (0.008 mol) of sodium hydrogencarbonate was added to the above solution and stirred. While stirring the resulting solution at a high speed (2500 rpm), a solution obtained by dissolving 0.812 g (0.004 mol) of m-xylylene chloride (IPC) in dry toluene (15 ml) was gradually added over 5 minutes. Stirring was continued for more than 5 minutes to form a viscous white emulsion. The above emulsion was then diluted with 40 ml of water and the stirring speed was reduced to 100 rpm. After the reaction mass was homogenized, 250 ml of acetone was added to precipitate the polymer. The fibrous precipitate was filtered and dried.

The weight of the polymer sample was measured by gel permeation chromatography (GPC) average molecular weight, in the sample analyzed by a Hewlett-Packard system ^© (HP) 1050 Chromatography. The eluent was monitored using a diode array detector (DAD HP 1050 at 305 nm). GPC measurement was performed by connecting two columns TSKgel G5000PWXL and G6000PWXL in series (TOSOH Bioscience, Japan). The column is thermostated at 40 °C. The flow rate was 0.6 ml/min. Poly(4-styrenesulfonate sodium) was used as a GPC standard. The standard curve, weight average molecular weight Mw, number average molecular weight Mn, and polydispersity (D = Mw / Mn) were calculated using Varian GPC software Cirrus 3.2. The eluent was a mixture of 0.1 M phosphate buffer (pH = 7.0) and acetonitrile in a ratio of 80/20, respectively. The Mw, Mn and polydispersity (D) of the polymer were 720000, 80,000 and 9, respectively.

Example 2

Example 2 describes 2,2'-disulfo-4,4'-benzidine p-xylamine-m-xylyleneamine copolymer sulfonium salt (copolymer of structures (XI) and (XII)) Synthesis:

The same synthesis method as in Example 1 can be used to prepare copolymers of different molar ratios. In detail, in a 1 L beaker, 4.098 g (0.012 mol) of 4,4'-diaminobiphenyl-2,2'-disulfonic acid and 4.02 g (0.024 mol) of cesium hydroxide monohydrate in water ( Mix in 150 ml) and stir until the solid is completely dissolved. 3.91 g (0.012 mol) of sodium carbonate was added to the above solution, and stirred at room temperature until dissolved. Then, toluene (25 ml) was added. While stirring the resulting solution at 7000 rpm, a solution of 2.41 g (0.012 mol) of p-xylylene chloride (TPC) and 2.41 g (0.012 mol) of m-xylylene chloride (IPC) dissolved in toluene (25 ml) was added. . The resulting mixture thickened in about 3 minutes. The stirrer was stopped, 150 ml of ethanol was added, and the thickened mixture was pulverized with a stirrer to prepare a slurry suitable for filtration. The polymer was filtered and washed twice with 150 ml of 90% aqueous ethanol. The obtained polymer was dried at 75 °C. The GPC molecular weight of the samples was analyzed as described in Example 1.

Example 3

Example 3 describes poly(2,2'-disulfo-4,4'-benzidine 1,4,5,8-naphthalenetetramethyldiimide) triethylammonium salt (ie, the above structure (XVI) )) Synthesis:

4.023 g (0.015 mol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride, 5.165 g (0.015 mol) of 2,2'-disulfonic acid benzidine and 0.6 g of benzoic acid (catalyst) were placed in a stirred state. And a three-necked flask for the capillary for argon flushing. As the argon stream was started, 40 ml of molten phenol was added to the flask. Then, the flask was placed in a water bath of 80 ° C, and the above ingredients were stirred until a homogeneous mixture was obtained. 4.6 ml of triethylamine was added to the above mixture, and stirring was continued for 1 hour to obtain a solution. The temperature was then successively raised to 100 ° C, 120 ° C and 150 ° C. Stirring was continued for 1 hour at each temperature at 100 ° C and 120 ° C. During this process, the solution continues to thicken. The stirring time at 150 ° C is 4 to 6 hours.

The above thickening solution was diluted with liquid phenol (water/phenol (volume ratio) = 1/10 mixture) to obtain a target consistency at 100 ° C, and the resulting mixture was quenched with acetone. The weight average molecular weight of the polymer sample was determined by GPC. GPC analysis of the polymer samples was performed by a HP 1050 HPLC system and a diode array detector (λ = 380 nm). Chromatographic separation was performed using an OHpak SB-804 HQ column from Shodex. A mixture of dimethylammonium (DMSO) and dimethylformamide (DMF) having a fraction of 75:25 and 0.05 M lithium chloride (LiCl) were used as the mobile phase. Chromatographic data was collected and processed using ChemStation B10.03 (Agilent Technologies) and GPC software Cirrus 3.2 (Varian). Poly(styrenesulfonate) sodium salt was used as a GPC standard. Dissolve all polymer samples and standards to be analyzed at a concentration of approximately 1 mg/mL prior to GPC analysis DMSO.

Example 4

Example 4 describes poly(2,2'-disulfo-4,4'-benzidine 1,3-dioxoisoindoline-5-carboxamide) sulfonium salt (ie, the above structure (XIII) The synthesis of).

In particular, 2,5-diaminobenzene-1,4-disulfonic acid (0.688 g, 2.0 mmol), anhydrous N-methylpyrrolidone (10 ml), triethylamine (0.86 ml) and trimellitic anhydride Neodymium chloride (0.421 g, 2 mmol) was added to a two-necked flask equipped with a magnetic stirrer, a thermometer and an air condenser with an argon inlet. The reaction mixture was then heated to about 130-140 ° C and stirred for 24 hours. Then, the reaction mixture was cooled to room temperature, and the mixture was slowly added dropwise to isopropanol under stirring with a magnetic stirrer to coagulate the product. The precipitate was collected by vacuum filtration then suspended in methanol (50 mL) and filtered. The brown solid was air dried for several hours and then dried under vacuum at about 60 ° C for 2 hours under P ₂ O ₅ to a constant weight of 0.16 g.

The weight average molecular weight of the polymer sample was determined by GPC. GPC analysis of the polymer samples was performed by a HP 1050 HPLC system and a diode array detector (λ = 230 nm). Chromatography was performed using a TSKgel lyotropic G5000PWXL column (TOSOH Bioscience). A mixture of 0.1 M phosphate buffer (pH = 6.9-7.0) and acetonitrile was used as the mobile phase. Chromatographic data was collected and processed using ChemStation B10.03 (Agilent Technologies) and GPC software Cirrus 3.2 (Varian). Poly(styrenesulfonate) sodium salt was used as a GPC standard.

Example 5

This example describes the synthesis of rigid rod-shaped macromolecules of the general formula (XVII) (R ₁ is CH ₃ , M is Cs, k is equal to n).

In detail, 30 g of 4,4'-diaminobiphenyl-2,2'-disulfonic acid was mixed with 300 ml of pyridine. 60 ml of acetamidine chloride was added to the mixture with stirring, and the resulting reaction was stirred at 35-45 ° C for 2 hours. It was filtered again, and the filter cake was washed with 50 ml of pyridine and then with 1200 ml of ethanol. The resulting alcohol wet solid was dried at 60 °C. The yield of 4,4'-bis(ethylideneamino)biphenyl-2,2'-disulfonic acid pyridinium salt was 95%.

12.6 g of 4,4'-bis(ethylideneamino)biphenyl-2,2'-disulfonic acid pyridinium salt was mixed with 200 ml of DMF. 3.4 g of sodium hydride (60% dispersion in oil) was added. The reaction was stirred at room temperature for 16 hours. 7.6 ml of methyl iodide was added and the reaction was stirred at room temperature for 16 h. Then, the volatile components in the reaction mixture were distilled off, and the residue was washed with 800 ml of acetone and dried. The obtained 4,4'-bis[ethylmercapto(methyl)amino]biphenyl-2,2'-disulfonic acid was dissolved in 36 ml of 4 M sodium hydroxide. 2 g of activated carbon was added to the above solution, and stirred at 80 ° C for 2 hours. The liquid was clarified by filtration, neutralized to pH-1 with 35% HCl, and reduced to 30% by evaporation. Then, the precipitated material was separated and dried by refrigerating (5 ° C) overnight. The yield of 4,4'-bis[methylamino]biphenyl-2,2'-disulfonic acid was 80%.

2.0 g of 4,4'-bis[methylamino]biphenyl-2,2'-disulfonic acid and 4.2 g of cesium hydrogencarbonate were mixed with 6 ml of water. The solution was stirred with IKA UltraTurrax T25 at 5000 rpm for 1 minute. plus 2 ml of triethylene glycol dimethyl ether was added, then 4.0 ml of toluene was added, and the mixture was stirred at 20000 rpm for 1 minute. Then, a solution of 1.2 g of p-xylylene chloride in 2.0 ml of toluene was added to the mixture at 20,000 rpm. The polymer emulsion was stirred for 60 minutes and then poured into 150 ml of ethanol at 20000 rpm. After stirring for 20 minutes, the suspension of the polymer was filtered through a Buchner funnel with a fiber filter, and the obtained polymer was dissolved in 8 ml of water, poured into 50 ml of ethanol to precipitate, and dried at 70 ° C for 12 hours. The yield was 2.3 g.

Example 6

Example 6 describes the synthesis of UV-cured 2,2'-disulfo-4,4'-benzidine anti-butenediamine-m-xylylenediamine copolymer sodium salt.

Specifically, 15.0 g of 2,5-diaminobenzene-1,4-disulfonic acid and 9.7 g of sodium carbonate were mixed in 150 ml of water in a 2 L beaker, and stirred until the solid was completely dissolved. Further 350 ml of toluene was added. While stirring the resulting solution at 7000 rpm, a solution of 3.7 g of fumartal chloride and 4.9 g of m-xylylene chloride in toluene (350 ml) was added. The resulting mixture was stirred for 3 hours. The stirrer was stopped, 600 ml of acetone was added, and the thickened mixture was pulverized with a stirrer to form a slurry suitable for filtration. The polymer was filtered and washed twice with 350 ml portions of acetone. The obtained polymer was dried at 75 °C. GPC molecular weight analysis of the samples was performed as described in Example 1.

Optical film

The polymers listed above can be used to form optical components, such as optical phase differences Plates, light collimators, light diffusers, optical waveguides, optical fibers, lenses, LCD elements, optical security films, and various other components for optical films or optical components or components for optical devices. Optical properties, such as refractive index in each direction, depend on the type of polymer (eg, their length and stiffness), polymer orientation, and other factors. In particular, the optical properties can be controlled by selecting the organic component (Core), the pendant group (S) and the number of subunits (i.e., the value of n). As described above, by selecting these components and parameters, a positive A-plate, a negative C-plate, and an Ac-plate can be produced. In certain embodiments, the double reflection of the deposited film is at least about 0.05, more specifically between about 0.05 and 0.20.

In one embodiment, the polymer can be formed on a layer that forms a plane in the X and Y directions. The X direction can be the coating direction. The layer can have a thickness in the Z direction. In some embodiments, the refractive index in the X direction (ie, n _x ) can be greater than the refractive indices in the Y and Z directions (ie, n _y and n _z ). The refractive indices of the Y direction and the Z direction (i.e., n _y and n _z ) may be the same. This type of membrane can be referred to as a positive A-plate. The X direction (i.e., n _x ) has a refractive index of at least about 1.6, at least about 1.7, and even at least about 1.8. Very few existing polymers have such high refractive indices. The refractive indices in the Y and Z directions (i.e., n _y and n _z ) are at least about 1.4, and more specifically at least about 1.5. For example, the positive A-plate polymer has a refractive index of 1.85 in the X direction (i.e., n _x ), and a refractive index of 1.57 in the Y direction and the Z direction (i.e., n _y and n _z ).

In some embodiments, the refractive index of the X direction (ie, n _x ) is substantially the same as the refractive index of the Y direction (ie, n _y ) and greater than the refractive index of the Z direction (ie, n _z ). This type of membrane can be referred to as a negative C-plate. The X and Y directions (i.e., n _x and n _y ) have a refractive index of at least about 1.5, at least about 1.6, or even at least about 1.7, and the Z direction (i.e., n _z ) has a refractive index of at least about 1.5. More specifically, it is at least about 1.55. For example, the refractive index of the negative C-plate polymer in the X direction and the Y direction (i.e., n _x and n _y ) is 1.72, and the refractive index in the Z direction (i.e., n _z ) is 1.59.

In some embodiments, the refractive index in the X direction (ie, n _x ) is less than the refractive indices in the Y and Z directions (ie, n _y and n _z ). The refractive indices of the Y direction and the Z direction (i.e., n _y and n _z ) may also be different. For example, the refractive index of the Y direction (i.e., n _y ) is greater than the refractive index of the Z direction (i.e., n _z ). A membrane of this type can be referred to as a biaxial membrane. The refractive index in the X direction (i.e., n _x ) is at least about 1.5, and more specifically at least about 1.55.

In summary, some polymers can be formed into a uniaxial retardation layer of nz < nx = ny. Other polymers may be formed as a biaxial retardation layer of n _z <n _y <n _x .

Deposition method

2 is a high level diagram showing a substrate 202 having a surface covered by a polymer film 204. Polymer film 204 can be deposited on both sides of substrate 202 for those skilled in the art. Substrate 202 can include, for example, a polymeric substrate, a glass substrate, a TAC substrate, a polypropylene substrate, a polycarbonate substrate, an acrylic substrate, a PMMA substrate, and the like. Substrate 202 can have any suitable form and shape, such as a flat or arched panel, or other intricate form.

FIG. 3 shows a schematic diagram of a method 300 for depositing a polymer solution onto a substrate 202 in accordance with various embodiments of the present invention. The method 300 begins with a process 302 of providing a polymer solution. Various polymer examples are described above, and in general, water-soluble polymers may be included, although water-insoluble polymers may also be utilized. The soluble polymer described herein is soluble in water or other solvents. In various embodiments, the solvent may include water, a ketone, a diketone/alcohol mixture, a hydroxyketone, tetrahydrofuran (THF), methyl acetate (MA), MIBK. In various embodiments, the polymer solution can include one or more additives such as nonylphenoxy glycidyl ether, alcohols, acids, plasticizers, stabilizers, antioxidants, and hindered phenols. The choice of additives will depend on the particular polymer used, the type of substrate, and the particular purpose.

The polymer solution can be characterized by a solids content defined by the weight ratio of polymer and other non-solvent components, if any, to the total weight of the solution. The solid component can be varied to obtain the necessary viscosity and shrinkage between the wet coating and the dry coating. For the purposes of the present invention, the above shrinkage is defined by the thickness ratio of the two thicknesses, for example, the thickness of the polymer solution initially applied before any drying and the structure of the sufficiently dried polymer structure, that is, the structure having a solid content of 100%. In certain embodiments, shrinkage rates in certain intermediate states, such as shrinkage between a partially dry state and a sufficiently dry state, may be used. The above solutions can also be characterized by polymer type, polymer molecular weight, temperature, and other characteristics. Some of these characteristics are unique to a particular deposition technique.

In certain embodiments, substrate 202 can be pretreated in optional process 304 to increase the adhesion of the polymer to substrate 202, introduce crosslinkers, and other purposes. Some examples of pretreatment techniques may include cleaning the substrate 202, saponifying, eluting, oxidizing, or modifying surface relief (eg, by performing a corona discharge). Various examples of the pretreatment step are shown in the examples to be described later.

In process 306, a polymer solution is deposited onto one or more sides of substrate 202 to form a polymer solution layer. The wet thickness of the layer can be selected based at least in part on the desired dry thickness of the polymer. For example, the ratio of wet thickness to desired dry thickness of the polymeric film can be between about 5% and 20%. It should be noted that the above polymer solutions are identical before deposition.

In general, the polymer solution can be deposited using one or more of the following techniques: slot die technology, spray technique, molding technique, roll-to-roll coating technique, Meyer bar coating technique, roll coating technique, gravure coating technique , micro gravure coating technology, comma coating technology, blade coating technology, extrusion technology, printing technology, dip coating technology and so on. These techniques will be described in more detail later.

In process 308, the dissolution is removed from the polymer solution deposited onto the substrate 202. Agent. The solvent can be removed using one or more techniques, such as heating, drying, or performing UV or IR light illumination. Some examples of these techniques are described further below.

In optional process 310, one or more post deposition processing techniques may be employed. Post deposition processing techniques can include cross-linking organic units or shaped deposition polymer films. It should be understood that the order of process 308 and process 310 is arbitrary. In one embodiment, as shown in Figure 3, the first solvent should be removed and then subjected to a specific post deposition process. In some other embodiments, some post deposition processing is performed followed by solvent removal. In still other embodiments, process 308 and process 310 are performed simultaneously. Further, in still other embodiments, there may be a plurality of post deposition operations 310 performed prior to process 308 and just after process 308. Those skilled in the art will appreciate that other embodiments are equally feasible.

Examples related to the processes 304, 306, 308, and 310 are shown below.

Pre-deposited substrate processing technology example

In various embodiments of the present disclosure, the substrate 202 can be subjected to a pre-deposition treatment to enhance the wettability and adhesion of the subsequently deposited polymer film.

In one example of the pre-deposition treatment, the TAC substrate may be saponified by first rinsing the substrate with water, then impregnating or coating the substrate with an aqueous solution of sodium hydroxide, followed by additional rinsing, and finally drying. The above impregnation step can last between about 0.5 minutes and 5 minutes, more specifically between about 1 minute and 3 minutes, such as about 2 minutes. The aqueous solution may comprise from about 1% to about 20% by weight, more specifically from about 2% to about 10% by weight, for example about 6% by weight of sodium hydroxide. The above solution may be maintained at about 20 ° C to 90 ° C, more specifically about 40 ° C to 80 ° C, for example about 60 ° C. However, it should be noted that the above temperature may vary in the saponification process and is determined by a number of criteria.

In another example of the pre-deposition process, the glass substrate 202 can be ultrasonically cleaned using a moderately alkaline aqueous solution. For example, about 0.1 wt% to 10 wt% (e.g., about 1 wt%) of DECOX® 12-PA (available from Borer Chemie AG, Zuchwil, Switzerland) can be used for this purpose. The cleaning solution can be maintained at a temperature of from about 20 ° C to 40 ° C, for example, about 30 ° C. The duration of the ultrasonic cleaning stage can be from about 0.5 hours to about 24 hours, more specifically from 1 hour to 5 hours, for example about 2 hours. The glass substrate can then be soaked and rinsed with water prior to oxidation in an aqueous solution comprising about 1 wt% to 20 wt%, more specifically about 2 wt% to 15 wt%, for example about 15 wt% sodium hydroxide. The elution and oxidation can be carried out in an ultrasonic bath for about 5 minutes to 120 minutes, more specifically about 10 minutes to 60 minutes, for example about 30 minutes. The glass substrate can then be rinsed and dried.

In another example of a pre-deposition process, a thin layer of primer can be deposited onto the substrate 202 prior to deposition of the polymer solution layer. The dry thickness of the primer can be from about 10 nm to about 200 nm, more specifically from about 20 nm to about 100 nm, for example, about 50 nm. For example, decane or polyethyleneimine can be used as a primer. Aqueous polymer solutions containing less than 10% by weight, more specifically less than 2%, for example about 0.5% primer can be used for this purpose.

Other pre-deposited substrate processing techniques may include subjecting the surface of the substrate to corona discharge, coating a thin layer of surfactant solution, coating a thin layer of alcohol, applying an electron beam, applying an ion beam, applying a plasma discharge, and the like. In any event, pre-deposited substrate processing techniques will increase the adhesion and wettability characteristics of the substrate.

Deposition technique

Several examples of deposition techniques for applying a layer of polymer solution on substrate 202 are shown below. Those skilled in the art will appreciate that these characteristics are equally applicable to other deposition techniques.

Slot die extrusion

Slot die technology is generally suitable for solutions (or slurries) with a viscosity of 1 cP to 100,000 cP and maintained at temperatures up to 250 ° C, using a linear velocity of up to 500 m per minute, with a deposition thickness of approximately 1 μm to 2000 μm ( Uniform layer of wet). The viscosity of the coated polymer can be controlled by molecular weight, solid content, additives, and temperature. The viscosity affects the flow characteristics of the polymer solution, the shear stress applied to form the film, and the orientation of the resulting polymer molecules in the deposited layer and the optical properties of the resulting layer. The polymer solution temperature, also known as the feed temperature, is between about 10 ° C and 80 ° C. Below 10 ° C, water is close to its freezing point, and temperatures above 80 ° C will result in rapid evaporation and moisture loss, with the result that the system becomes difficult to control. Prior to deposition, it should be ensured that the polymer solution is homogeneous and can be achieved by warming and/or agitation. In this step, one or more additives may be added to the polymer solution depending on the application or a purpose.

The resulting solution is then deposited on a substrate to form a thin layer. As described above, according to one or more of the above embodiments, the polymer solution may be deposited onto the substrate or formed into an unsupported structure. The thickness of the deposited layer depends on one or more of the following: substrate feed rate, substrate width, polymer solution feed amount, and solid content. The substrate feed rate can range from 0.5 m/min to 500 m/min, more specifically from 2 m/min to 20 m/min. It is advantageous to consider faster speeds from processing capabilities, and the feed rate can be controlled to obtain specific shear forces for redistributing and aligning polymer molecules within the deposited layer. The polymer solution may be fed in an amount of from 1 g/min to 2500 g/min. In some embodiments, the deposited film thickness can range from 10 microns to 2000 microns, more specifically from 25 microns to 250 microns. The thickness is the wet coating thickness and will vary greatly upon drying. As mentioned above, the magnitude of the change, ie the shrinkage ratio, depends on the solid content and other factors.

When using slot die technology, the slit lip can be separated from 10 microns to 1000 microns. Meters, more specifically, distances from 25 microns to 250 microns. The lip spacing determines the pressure in the mold so that the film thickness is uniform. Additionally, the slot die is spaced apart from the substrate, allowing the polymer solution to flow onto the substrate and deposit into a uniform layer. In some embodiments, the gap between the slot die and the substrate is from 10 microns to 1000 microns, more specifically from 25 microns to 250 microns, which can be varied to control coating quality.

For a better understanding of some of the equipment based on parameters such as spacing thickness, substrate feed rate and solution feed rate, a detailed description of the slot die coating system may be helpful. The slot die coating system can include five main sections: a die, a die positioner, a roller, a liquid delivery system, and a substrate. The mold determines the amount of polymer solution dispensed onto the substrate. Liquid rheology (ie viscosity, surface tension) is the same factor as the design and location of the mold. Some polymer-based solutions have the specific rheological properties required for the particular design of the mold, ie the internal flow shape. The profile of the mold manifold is the flow shape machined onto the mold body. The function of the mold is to maintain the solution at the appropriate temperature required for the application, distribute it evenly to the desired coating width, and supply it to the substrate. The manifold distributes the coating liquid into the mold to a sufficient target width and is designed to produce a uniform laminar flow of material through the exit slit of the die. The mold positioner is an adjustable carriage that accurately positions the slot die at an optimum angle, snagging the roller and protecting the mold from vibrations that affect the coating application. The mold positioner stabilizes the interaction between the mold and the moving substrate, sets the angle of distribution between the mold and the substrate, and sets the distance between the mold and the substrate. The roller provides a surface that is accurately positioned relative to the mold position and is used to support the substrate. A liquid delivery system is used to meter the polymer solution into the mold. The delivery system is capable of determining the coating weight and thickness of the deposited layer.

Roll-to-roller deposition example

When using roll-to-roll technology (also known as roll operation or roll-to-roll operation), The polymer solution can be deposited onto a substrate that is presented in the form of a film. Any suitable technique can be used for the deposition. In one example, depositing can include using an applicator that can be adjusted on a moving substrate by a shear force (scraper). Deposition may be performed to apply further drying techniques, or to utilize UV crosslinking techniques as described below. Once the base film is coated, it is wound onto another roll, which can be cut to the desired size by a slitter or further extruded, pressed, applied at elevated temperature or impregnated into a barium chloride solution as detailed below. Processing (alone or in combination). Further, it should be noted that the base film can be fixed on the roll and discharged at a predetermined rate so that the above polymer solution can be delivered to the base film at a desired thickness.

As noted above, the uniformity of the polymer solution should be ensured prior to deposition. The web speed and/or coating solution flow rate should be set to control the desired shear stress and coating thickness. The solids concentration and feed temperature of the polymer solution should also be set.

In one example, the polymer solution is coated on a substrate to exhibit a negative C-plate behavior of the out-of-plane phase difference value (Rth) as defined below.

Rth=thickness × (nz-0.5(nx-ny))

The Rth value can be controlled by drying the coating thickness. Table 1 below shows 2,2'-disulfo-4,4'-benzidine p-xylamine-m-xylamine (also known as "P17") containing a known solid concentration (N). The various wet thicknesses obtained in the deposition technique of the polymer and at a flow rate of 15 ft/min through a 11-inch wide separator.

The dry thickness of the deposited polymer solution was determined to be linear at the set wet thickness (although not precise, but the polymer film shrinks by 4% due to drying). It can be predicted that the Rth measurement value is linear with the thickness of the P17 layer. Therefore, the phase difference can be controlled by deposition conditions and characteristics. Further shown in Fig. 4A and Fig. 4B, the dependence of the dry thickness on the wet thickness (Fig. 4A) and the dependence of the phase difference on the dry thickness (Fig. 4B) are shown.

As described above, the viscosity of the coating polymer solution can be controlled by various parameters such as molecular weight, solid content concentration, temperature, and the like. Viscosity also affects the flow and characteristics of the polymer solution, the shear stress applied to the film forming the polymer solution, and the orientation of the resulting polymer molecules in the deposited layer and the optical properties of the resulting optical layer. Figure 5 shows the dependence of viscosity (cP) as a function of shear rate (s ^-1 ) measured for different polymer concentrations (N).

Molding deposit

When molding techniques are used, the polymer solution can be delivered to a cast mold cavity having one or more surfaces that are permeable to air and water vapor but that are permeable to polymer molecules (i.e., because of their large size). The mold can be constructed to produce a shape of a lens or other optical element having specific physical optical properties such as refraction, aberration, curvature, and the like.

The molding operation sequence is schematically shown in Figures 6A-6C. In particular, FIG. 6A illustrates a mold 600 having a first surface 602 and a second surface 604. First surface 602 and second surface 604 forms a cavity 603 for receiving a polymer solution. The spacing between the first surface 602 and the second surface 604 is initially (e.g., when the polymer solution is contained) greater than the sides of the final polymer structure to accommodate shrinkage upon drying. In certain embodiments, the first surface 602 and the second surface 604 can be moved relative to one another to conform and control the drying (and shrinking) polymer profile.

Figure 6B shows a mold 600 in which a polymer solution 606 is placed in a cavity. The cavity is maintained in some initial closed configuration while the polymer solution 606 is injected into the cavity. The internal volume of the cavity determines the amount of polymer solution that can be placed in the mold 600. In another example, the cavity 603 can be opened first, and the polymer solution can be first supplied to one side of the mold 600 (i.e., the first surface 602) and then joined to the other surface (i.e., the second surface 604). Some polymer solution is drained from the chamber to ensure that the entire cavity is filled with polymer solution. Unlike conventional injection molding in which a thermoplastic polymer is melted and supplied to a mold in a molten state, the polymer solution 606 can be supplied at a relatively low temperature, that is, from about 40 ° C to 250 ° C to prevent polymer degradation. The viscosity of the polymer solution can be controlled by solid coating depending on the slit die coating as described above.

One or both of the surface 602 and the surface 604 are permeable to water vapor such that water vapor can escape the mold 600 as the polymer solution is dried. However, surface 602 and surface 604 still retain polymer molecules in the mold. For example, one or both of surface 602 and surface 604 have micropores. One or both of surface 602 and surface 604 can be heated to between about 100 ° C and 250 ° C to promote drying and evaporation of the solvent from the polymer solution.

As the solvent leaves the mold 600, the thickness of the polymer solution in the mold 600 decreases. In order to avoid the formation of a cavity in the mold 600, the surface 602 and the surface 604 may be formed in a shape that moves relative to each other in the direction shown in Fig. 6C. The location of surface 602 and surface 604 can be used to control the drying of the polymer solution, i.e., the heat supplied to surface 602 and surface 604, more particularly The temperature of face 602 and surface 604. This feedback can be used to prevent excessive drying or insufficient drying.

It should be noted that surface 602, surface 604 can have a particular shape, form, or design. For example, surface 602, surface 604 can be hemispherical to form a lens or similar device. Surface 602, surface 604 may also have a particular design to form, for example, a Fresnel lens type device.

Removable solvent technology example

Returning now to Figure 3, at step 308, the solvent is removed from the deposited polymer solution. The solvent can be removed by drying at a temperature of at least about 80 °C. The upper limit usually depends on the stability of the polymer used in the solution. These temperatures may represent the actual temperature of the material as it is dried or the temperature of the surrounding components, such as the temperature of the substrate, the temperature of the atmosphere on the surface of the material, and the like. Drying can also be carried out by blowing a dry gas at a specific temperature. For example, the drying gas can include nitrogen or heated air. Generally, higher temperatures help to promote the drying process. However, rapid removal of moisture can disrupt the alignment of the polymer molecules in the dry structure and distort the optical properties.

In an exemplary embodiment, the drying process can include multiple steps. For example, heat drying can also include subsequent cooling of the polymer solution. In various embodiments, one or more drying devices, such as a gas flow dryer, a rotary dryer, a spray dryer, a fluidized bed dryer, a vibrating fluidized bed dryer, a contact fluidized bed dryer, may be utilized. , hot plate dryers, etc.

Post deposition processing technique

forming

In various embodiments, post-deposition treatment process 310 forms a layer of polymer solution. For example, the polymer solution layer is pressed to form a groove, such as shown in Figures 7A and 7B. In particular, a substrate having a layer 202 of polymer solution deposited thereon is shown in Figure 7A. 7B The result of the grooving of the polymer solution layer 202, the so-called shaped polymer coating 702, is illustrated. The polymer solution layer formation can be carried out on a fully dried polymer structure (i.e., about 100% solids), a partially dried polymer structure, or any deposited polymer coating prior to drying. In the latter two cases, the forming device (i.e., the press roll) needs to accommodate subsequent thickness variations. As such, the tolerances of the forming apparatus used in these situations need not be as precise as the apparatus used to sufficiently dry the polymer structure.

The formation of the polymer structure (regardless of its dry state) can be carried out while maintaining the polymer structure at about 50 ° C to 200 ° C. The forming tool can also be heated to the temperature range. In certain embodiments, the forming tool is heated to between about 100 ° C and 200 ° C, while the polymer structure is maintained at the same temperature or lower prior to contact with the forming tool. Those skilled in the art will appreciate that if the polymer structure also contains a solvent, some drying can also be carried out under these conditions. In some embodiments, some drying can be performed after the polymer structure is formed. This post-forming drying can also be carried out in addition to preform drying.

In still other examples, the solid component in the dried polymer can be reduced by adding a solvent. This can be done sequentially to, for example, shape the polymer. Further, a sufficiently dried or partially dried polymer is extruded into the fibers and the hollow tube. Unlike conventional extrusion, which heats thermoplastic polymers to make them common, water can be added to the water soluble polymer prior to molding or extrusion.

Cross-linking

The post-deposition treatment process 310 can crosslink the polymer chains using UV light illumination, IR light illumination, or other types of activation energy sources, such as electron, ion, or gamma irradiation. Crosslinking can form a linkage between two or more adjacent polymer molecules and/or extended polymer molecules by a linker. As an example of the UV-inducing group involved in crosslinking, a carbon-carbon double bond and a carbon-carbon triple bond may be included. The groups may be introduced into some or all of the monomers in their synthesis. The groups can be relatively blunt in coating and in some or even the entire drying operation, but can be activated in some or all of the drying after coating, in certain embodiments. In various embodiments, the UV light illumination can have a wavelength of, for example, approximately 180 nanometers to 400 nanometers.

A UV cross-linking example will be described in detail below. The polymer shown below can be formed as a negative C-plate. When the deposited polymer film is irradiated with UV light, the irradiated polymer film becomes difficult to dissolve before any further post treatment, such as exposure to metal cations to crosslink it. Although there is no specific theoretical basis, it is believed that the double bonds present in each polymer molecule form intermolecular bonds with adjacent molecules under UV irradiation. Crosslinking examples of polymers having the structural formulae (XI) and (XII) are shown below.

The asterisk shown above indicates the elongation of the polymer chain. Although these asterisks indicate The 2D approach continues in both directions, but they can also continue in three directions in 3D.

The following formula shows another example. The polymer should use a chain stop to control the molecular weight. When these chain extenders are not used, the material will extend to a molecular weight of 220,000 units and become insoluble. When a chain terminator is used, the molecular weight will drop to about 20,000 units and have sufficient solubility. These chain terminators can be UV-curable groups (e.g., C=C double bonds) which can be readily activated to increase the molecular weight in the coated film, provide a 3D network and reduce solubility. This example is further illustrated in the following structural formula: The asterisk shown above indicates the elongation of the polymer chain.

Conversion of polymer membranes into water insoluble forms

In certain embodiments, method 300 uses a post-deposition treatment of a polymer layer with a water-soluble inorganic salt solution having one or more of the following cations: H ⁺ , Ba ²⁺ , Pb ²⁺ , Ca ²⁺ , Mg ^{2 +} , Sr ²⁺ , La ³⁺ , Zn ²⁺ , Zr ⁴⁺ , Ce ³⁺ , Y ³⁺ , Yb ³⁺ , Gd ³⁺ and any combination thereof. For example, the dried polymer layer may be contacted with one or more of the following materials, with or without impregnation: cerium chloride, cerium nitrate, cerium chloride, cerium nitrate, aluminum salts, and the like.

In one embodiment, the polymer layer may be dried without immersing or dipping it in contact with barium nitrate _{(Ba (NO 3) 2)} , barium chloride (BaCl ₂₎ or lanthanum (LaCl ₃₎ an aqueous solution of chloride. The concentration of cerium nitrate in water is about 2 wt% to 20 wt%, more specifically 5 wt% to 15 wt%, for example about 8.5 wt%. For example, 87.55 g of anhydrous cerium nitrate is dissolved in 942.45 g of water. The contact time of the dried polymer layer with the post-treatment solution is from about 0.1 second to about 10 seconds, more specifically from about 0.5 seconds to about 5 seconds, for example from about 1 second to about 2 seconds. After exposure to the salt solution, the polymer layer was rinsed with water and dried. In a roll-to-roll deposition process, the substrate can be passed through a bath containing a post-treatment solution and dried after passing through an aqueous bath. In certain embodiments, the post-treatment solution can be applied to the dried polymer layer as a coating using, for example, a slot die or spray technique to better control the dispensing of the post-treatment solution. The substrate can then be sprayed with water to rinse off the post-treatment solution and then dried. This method avoids exposing the back side of the substrate to any residual salts. In certain embodiments, one or more of the above operations are repeated one or more times using the same solution.

Optical component example

8 is a schematic cross-sectional view of an exemplary display system 800 including a light modulator 850 disposed on an optical compensator stack 801, the optical compensator stack 801 including a first liquid crystal layer 820. - phase difference plate 810. The j-phase difference plate 810 includes a polymer film layer that does not substantially absorb or scatter the at least one visible light polarization state. The j-phase difference plate 810 has x, y, and z vertical refractive indices, wherein at least two of the vertical refractive indexes are unequal, and the in-plane phase difference 100nm, the absolute value of the out-of-plane phase difference 50nm. The first liquid crystal layer 820 contains a liquid crystal material. The first liquid crystal layer 820 may be an o-plate, an a-plate, or the like. The optical compensator stack 801 may include a second liquid crystal layer 825 or a j-phase difference plate 810 disposed on the j-phase difference plate 810 to be disposed between the second liquid crystal layer 825 and the first liquid crystal layer 820. The second liquid crystal layer 825 may be a positive A-board or the like. The optical compensator stack 801 may further include a polarizing layer 830 disposed on the first liquid crystal layer 820 or the first liquid crystal layer 820 may be disposed between the polarizing layer 830 and the j-phase difference plate 810. Polarization layer 830 can be an absorbing polarizer or a reflective polarizer. The reflective polarizing layer 840 can be disposed on the polarizing layer 830 or the polarizing layer 830 can be disposed between the reflective polarizing layer 840 and the first liquid crystal layer 820.

9A-9B illustrate cross-sectional schematic views of various example display system stacks 900. Stack 900 is shown in FIG. 9A, which includes four substrates 905 (ie, TAC substrates) having a thickness of approximately 80 microns with a patterned vertical alignment (PVA) layer 910 disposed therebetween. The PVA layer 910 can have a thickness of approximately 20 microns. Adjacent to the substrate 905, a deposition region retardation layer 915 typified by a positive A-plate is produced by the technique described in the present specification, and a retardation layer 920 typified by a negative C-plate is produced by the technique described in the present specification. The thickness of the phase difference layers 915, 920 is approximately 3 microns or less. Stack 900 also includes a polymer stabilized orientation (PSA) layer 925 having a thickness of about 30 microns. A vertical alignment (VA) cell layer 930 is interposed between the substrates 905. A PET layer 935 and a protective film 940, which may have a thickness of about 25-30 microns, may also be used. The total thickness of stack 900 is approximately 200 microns.

Experimental result

An experiment was conducted to determine the effectiveness of post-treatment of barium chloride on the water solubility of the polymer. A polymer comprising 2,2'-disulfo-4,4'-benzidine-p-xylamine-m-xylyleneamine was deposited onto a TAC substrate to form a thick film of 350 nm. A set of samples was cut from the film, immersed in a 10 wt% aqueous solution of barium chloride for about 1-2 seconds, then rinsed with water and dried. Another set of samples was used as a reference without any post-treatment operations. Then, a portion of each group was exposed to 100% relative humidity for 3 days at room temperature, while the remainder of each group was exposed to 60% relative humidity at 60 ° C. Dew for 20 days. The adhesion of all samples to the polymer was then tested. The test results are shown in Table 2 below.

In detail, exposure to 90% relative humidity at 60 ° C for 20 days resulted in removal of 60% of the untreated film, effectively preventing the treated film from being removed. Exposure to 100% relative humidity at 25 ° C for 3 days resulted in 100% removal of the untreated film, while still effectively preventing the treated film from being removed. As such, post-deposition of 2,2'-disulfo-4,4'-benzidine-phthalimin-m-xylylenediamine with ruthenium chloride allows the treated layer to be treated with the untreated layer More resistant to moisture. Although there is no specific theoretical basis, it is believed that ruthenium chloride leads to the interlinking of 2,2'-disulfo-4,4'-benzidine p-xylamine-m-xylamine. Union. In summary, post-treatment makes water-soluble polymers that are easier to handle than other types of polymers to become waterproof polymers that are resistant to water commonly found in the operating environment.

In another experiment, evaluation of pretreatment techniques improved the wettability and adhesion of 2,2'-disulfo-4,4'-benzidine to phthalimin-m-xylamine to TAC substrate. The role of sex. One set of substrates was pretreated with polyethyleneimine and the other set was used as a reference without pretreatment. Both sets of substrates were coated with 2,2'-disulfo-4,4'-benzidine p-xylamine-m-xylamine to about 2.5 microns and dried. The adhesion of the samples was then determined using the ASTM 3359 standard. Some kind The product was tested immediately after coating, while the other samples were exposed to 60% relative humidity at 60 ° C for 40 days. The experimental results are shown in Table 3 below.

In particular, the pretreated substrate exhibited better adhesion than the untreated substrate after exposure to the above environmental conditions. Only 6% of the film was removed from the pretreated substrate, compared to nearly one-third of the film removed from the untreated substrate.

Figure 10 illustrates a slot die 1002 deposition technique that includes rolling the embossing roll 1004 in the coating direction 1003 on the substrate 1001 of the film. This technique results in a final structure 1005 imprinted on the film.

in conclusion

The above describes a method of forming various optical elements by depositing a polymer solution on a substrate. These methods may include one or more pre-deposition processes and/or one or more post-deposition processes. Although the foregoing concepts have been described in considerable detail, the embodiments of the invention may It should be noted that there are many alternative ways of implementing the processes, systems and devices disclosed in this specification. Therefore, the present embodiments are to be considered as illustrative and not restrictive.

300‧‧‧Process of depositing a polymer solution onto a substrate

302‧‧‧Providing polymer solution

304‧‧‧Predeposition substrate treatment

306‧‧‧Deposited polymer solution

308‧‧‧Remove solvent

Claims (29)

An optical element forming method, comprising: providing a polymer solution comprising a solvent and a polymer, wherein the polymer comprises n organic units having the following structural formula: [-(Core(S) _m ) _k -G _l -] _n in the formula, a conjugated organic unit comprising a rigid organic component Core, G is selected from the group comprising based -C (O) -NR1 -, = (C (O)) 2 = N -, - O-NR1 a linker of a list of linear and branched (C1-C4) alkylenes, -CR1R2-OC(O)-CR1R2-, -C(O)-O-, -O-, -NR1-, wherein R1 and R2 is independently selected from the list comprising H, alkyl, alkenyl, alkynyl, aryl; wherein S is a hydrophilic pendant group that provides solubility to the polymer in a solvent, the same or different and independently selected Self-contained list of one or more of the following: -COOX, -SO3X, NW4, -SO2NP1P2, and -CONP1P2, wherein X is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, base A list of metals, W is H or an alkyl group or any combination thereof, and P1 and P2 are independently selected from the list comprising H, alkyl, alkenyl, alkynyl, aryl; wherein m is 0, 1, 2 or 3, k is 1, 2 or 3, dissolve the polymer Layer is deposited onto the surface of the base structure, at least in part be selected polymer wherein the wet thickness of the solution layer was dried on the desired thickness; and drying the polymer layer is formed from a polymer solution the solvent was removed. The method of claim 1, wherein the polymer comprises a copolymer having two or more types of monomer units. The method of claim 1, wherein the n organic units further comprise one or more terminal components connected to the n organic units according to the following formula: T-[-(Core(S) _m ) _k -G _l -] _n -T, wherein T includes one or more alkenyl, alkynyl and acrylate groups. The method of claim 1, wherein the conjugated organic component Core comprises one or more of the following structural formulas: -C=C- -C≡C- wherein p is an integer equal to 1, 2, 3, 4, 5 or 6. The method of claim 1, wherein the method further comprises pretreating the matrix structure to provide wettability or adhesion of the reinforced polymer solution. The method of claim 5, wherein the pretreatment of the matrix structure comprises one or more of the following processes: saponification, elution and oxidation using a moderately alkaline aqueous solution, ultrasonic cleaning, deposition of at least one bottom The lacquer layer is subjected to corona discharge and plasma treatment to the substrate structure, wherein at least one of the primer layers comprises one or more of decane and polyethyleneimine. The method of claim 1, further comprising post-depositing the polymer solution with a post-deposition solution, wherein the post-deposition solution comprises one of the following onium salts, the following onium salts and aluminum salts. Or more: barium chloride, barium nitrate, barium chloride, barium nitrate. The method of claim 1, wherein the method further comprises crosslinking the n organic units. The method of claim 8, wherein the crosslinking is carried out by the crosslinking agent B according to the following formula: Among them, Core1 and Core2, S1 and S2, m1 and m2, k1 and k2, G1 and G2, n1 and n2 are the same or different. The method of claim 8, wherein the crosslinking is carried out by the crosslinking agent B according to the following formula: T-[(Core ₁ (S) _m1 ) _k1 -G ₁ -] _n1 -T+B +T-[(Core ₂ (S) _m2 ) _k2 -G ₂ -] _n2 -T→h v T-[(Core ₁ (S) _m1 ) _k1 -G ₁ -] _n1 -TBT-[(Core ₂ ( S) _m2 ) _k2 -G ₂ -] _n2 wherein Core 1 and Core ₂ , S 1 and S 2 , m 1 and m 2 , k 1 and k 2 , G 1 and G 2 , n 1 and n 2 are the same or different, and the T group is selected from an alkenyl group. One or more groups among the alkynyl groups and acrylic acid. The method of claim 8, wherein the crosslinking is carried out according to the following reaction: The method of claim 8, wherein the crosslinking is carried out according to the following reaction: The method of claim 1, wherein the crosslinking comprises one or more of the following: irradiating the polymer solution with ultraviolet (UV) light, and irradiating the polymer solution with infrared rays (IR). Light, the polymer solution is irradiated with an electron beam, the polymer solution is irradiated with an ion beam, and the polymer solution is irradiated with a gamma beam. The method of claim 1, wherein the removing the solvent from the polymer solution comprises one or more of the following: heating the polymer solution to at least 80 ° C, by applying a dry gas stream The polymer solution is irradiated with infrared light or ultraviolet light to dry the polymer solution. The method of claim 1, further comprising molding the polymer solution on the substrate structure to form at least one trench or selectively varying the thickness of the polymer solution layer. The method of claim 1, wherein the depositing of the polymer solution layer comprises one or more of the following techniques: slot die extrusion, Meyer bar coating, roll coating, concave Plate coating, micro gravure coating, comma coating, knife coating, extrusion, printing, spraying and dip coating. The method of claim 1, wherein the solvent comprises one or more of the following: a polar protic solvent, a polar aprotic solvent, and a non-polar solvent. The method of claim 17, wherein the solvent comprises one or more of the following solvents: water, ketone, alcohol, tetrahydrofuran, ester, alkaline aqueous solution, dimethyl hydrazine, Dimethylformamide, dimethylacetamide and dioxane. The method of claim 1, wherein the polymer solution further comprises one or more additives, wherein the additive is selected from the group consisting of surfactants, alcohols, acids, plasticizers, stabilizers, and anti-drugs. Group of oxidants. The method of claim 1, wherein the matrix structure comprises one or more of the following substrates: glass, triethyl fluorenyl cellulose, polyolefin, polycarbonate, polyamine, Polyimine, cycloolefin polymer, cyclic olefin copolymer, polyethylene terephthalate, polyacrylic acid, and polystyrene. The method of claim 1, wherein the polymer solution is each identical prior to depositing the layer. The method of claim 1, wherein the concentration of the polymer in the polymer solution is from about 0.1% by weight to about 30% by weight. The method of claim 1, wherein the dry polymer layer has a double reflection of about 0.03 to 0.2. The method of claim 1, wherein the dried polymer layer has a refractive index greater than about 1.6. The method of claim 1, wherein the dried polymer layer has refractive indices n _x , n _y and n _z , n _x , n _y and n _z correspond to the dry polymer layer The axis of the Cartesian coordinate system, wherein the x-axis and the y-axis substantially coincide with the surface of the base structure, n _{z is} less than n _x and n _y , and n _x and n _{y are} approximately the same value. The method of claim 1, wherein the dried polymer layer has refractive indices n _x , n _y and n _z , n _x , n _y and n _z correspond to the dry polymer layer The x, y, and z axes of the Cartesian coordinate system, wherein the x and y axes are substantially coincident with the surface of the base structure, n _{x is} greater than n _y , and n _{y is} greater than n _z . The method of claim 1, wherein the optical element comprises one or more of the following: an optical phase difference plate, a light collimator, a lens, an optical waveguide, a diffuser, an optical fiber, and an optical Safety film and liquid crystal display (LCD) components. An optical element forming method, the method comprising: providing a substrate; treating the substrate with one or more of the following techniques: cleaning, oxidizing, performing saponification, plasma treatment, corona discharge, and modifying the substrate a surface unevenness; depositing a polymer solution layer on at least one surface of the substrate, wherein the polymer comprises n organic units having the following structural formula: [-(Core(S)m)k-Gl-]n The organic unit comprises a rigid conjugated organic component Core, and the G system is selected from the group consisting of -C(O)-NR1-, =(C(O))2=N-, -O-NR1-, linear and branched (C1- C4) a linker of the alkylene, -CR1R2-OC(O)-CR1R2-, -C(O)-O-, -O-, -NR1-, wherein R1 and R2 are independently selected from the group consisting of H, a list of alkyl, alkenyl, alkynyl, aryl groups; S is a hydrophilic pendant group that provides solubility to the polymer in a solvent, the same or different and independently selected from the list comprising one or more of the following: -COOX, -SO3X, NW4, -SO2NP1P2, and a list of -CONP1P2, wherein X is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, alkali metal, W is H or alkyl or any combination thereof, and P1 and P2 are independently selected from a list comprising H, alkyl, alkenyl, alkynyl, aryl; wherein m is 0, 1, 2 or 3, k is 1, 2 or 3; and the solvent is evaporated from the polymer solution Solvent. An optical element forming method, the method comprising: providing a substrate; depositing a polymer solution layer on at least one surface of the substrate, wherein the polymer comprises n organic units having the following structural formula: [-(Core( S) m) k-Gl-]n wherein the organic unit comprises a rigid conjugated organic component Core, and the G system is selected from the group consisting of -C(O)-NR1-, =(C(O))2=N-,- a linking group of O-NR1-, linear and branched (C1-C4) alkylene, -CR1R2-OC(O)-CR1R2-, -C(O)-O-, -O-, -NR1-, wherein , R 1 and R 2 are independently selected from the list comprising H, alkyl, alkenyl, alkynyl, aryl; wherein S is a hydrophilic pendant group that provides solubility to the polymer in a solvent, the same or different and Independently selected from the list comprising one or more of the following: -COOX, -SO3X, NW4, -SO2NP1P2, and -CONP1P2, wherein X is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl List of bases, alkali metals, W is H or alkyl or any combination thereof, and P1 and P2 are independently selected from the list comprising H, alkyl, alkenyl, alkynyl, aryl; wherein m is 0 , 1, 2 or 3, k is 1, 2 or 3; The n organic units are crosslinked using one or more of the following techniques: UV light irradiation, IR light irradiation, electron beam irradiation, ion beam irradiation, γ beam irradiation; and evaporating from the polymer solution The solvent.