KR102033747B1 - A composition for forming a film having a wrinkle structure and a method of forming the film - Google Patents
A composition for forming a film having a wrinkle structure and a method of forming the film Download PDFInfo
- Publication number
- KR102033747B1 KR102033747B1 KR1020150086837A KR20150086837A KR102033747B1 KR 102033747 B1 KR102033747 B1 KR 102033747B1 KR 1020150086837 A KR1020150086837 A KR 1020150086837A KR 20150086837 A KR20150086837 A KR 20150086837A KR 102033747 B1 KR102033747 B1 KR 102033747B1
- Authority
- KR
- South Korea
- Prior art keywords
- film
- photocuring agent
- photoinitiator
- composition
- photocuring
- Prior art date
Links
- QQVRKQNCCBKPGH-UHFFFAOYSA-N C=Cc(c(F)c(c(OCCO)c1F)F)c1F Chemical compound C=Cc(c(F)c(c(OCCO)c1F)F)c1F QQVRKQNCCBKPGH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The present invention relates to a film-forming composition having a wrinkled structure, and a method for producing a film having a wrinkled structure. More specifically, the composition according to the present invention may include a photocuring agent and a photoinitiator dissolved in the photocuring agent. At this time, the cutoff light transmission wavelength of the photocuring agent is larger than the cutoff absorption wavelength of the photoinitiator. As a result, the composition according to the present invention may induce the formation of a photocurable thin film on the composition film during initial photocuring. Subsequently, due to the shrinkage of the film due to subsequent photocuring, the upper photocurable thin film formed first may form a wrinkle so that a film having a wrinkled structure may be formed. The wrinkle structure of the film can be controlled by the relationship between the cutoff light transmission wavelength of the photocuring agent constituting the composition and the cutoff absorption wavelength of the photoinitiator, the photocuring rate of the composition, and the film thickness constructed from the composition before photocuring. . The film having a corrugated structure can increase the luminous efficiency of LED and OLED by light scattering effect, and can increase the sensing efficiency of the sensor by increasing the surface area of the film.
Description
The present invention relates to a film-forming composition having a wrinkled structure, and a method for producing a film having a wrinkled structure.
Wrinkles are a common phenomenon in nature. Wrinkle structures can occur in the process of eliminating the stress acting on the film when the double layer of strong, thin skin and a soft, thick formation layer shrinks. A thick layer can impart shrinkage here. For example, the skin of an apple can be seen as a thin film, and the pulp of the apple can be seen as a thick layer. When the apple is dried, the pulp shrinks and wrinkles form the skin of the apple.
On the other hand, the size of the wrinkle structure of the film and its control are important techniques in OLED. Light extraction of OLEDs requires wrinkle cycles and depths of several microns to several hundred nm. In addition, since the surface area varies according to the wrinkle structure of the film, it is important to control the wrinkle structure as a material of the sensor. The film having a wrinkle structure having a period and depth of several hundreds of nm to several hundred nm has a large difference in modulus of elasticity between the film and the thick layer, and can be obtained only from a metal film on PDMS capable of forming a film of several tens of nm thick.
Meanwhile, the present inventors have studied a compound (prepolymer) capable of forming a wrinkle structure in relation to a film having an irregular wrinkle structure (Korean Patent Publication No. 10-2014-0016125). However, prior studies only disclose curable compounds to form wrinkled films, and there is no disclosure of combinations with photoinitiators suitable for these compounds and the principles of effective wrinkle structure film formation using these combinations. Furthermore, there are no disclosures of various factors that can control the size of the wrinkle structure as well as the formation of the wrinkle structure film (solution composition, concentration of photocuring agent and photoinitiator, photocuring rate, light intensity, and thickness of the coated film). .
The problem to be solved by the present invention is to provide a composition that can form a film having a wrinkle structure spontaneously only by UV irradiation.
Another object of the present invention is to provide a method for producing a film having a wrinkled structure using the composition.
According to the inventive concept, the composition for forming a wrinkle structure film may include a first photocuring agent and a first photoinitiator dissolved in the first photocuring agent. In this case, the first cut-off light transmission wavelength of the first photocuring agent is larger than the first cut-off light absorption wavelength of the first photoinitiator, and the first cut-off light transmission wavelength is irradiated with light to the first photocuring agent having a thickness of 1 mm. When the light transmittance is the largest light wavelength of 1.0% or less, the first cut-off absorption wavelength is the light wavelength of 0.05 or less when the light absorbance of 10ⅹmm 1.0ⅹ10 -4 mol% of the first photoinitiator lean solution is less than 0.05. It can be a small light wavelength.
The first cut-off light transmission wavelength of the first photocuring agent and the first cut-off absorption wavelength of the first photoinitiator may be 250 nm to 350 nm.
The first photocuring agent may be a liquid having a viscosity of 1 cP to 10 7 cP at 25 ° C.
The concentration of the first photoinitiator may be 0.01 wt% to 10 wt% with respect to the total weight of the composition.
The first photocuring agent may include two or more substituted or unsubstituted styrene groups in its molecule.
The composition may further include a second photocuring agent. In this case, the second photocuring agent has a second cut-off light transmission wavelength smaller than the first cut-off absorption wavelength of the first photoinitiator, the second photocuring agent is 1% to 70% by weight based on the total photocuring agent weight May be%.
The second photocuring agent may include two or more substituted or unsubstituted acrylic groups in its molecule.
The composition may further include a third photocuring agent. In this case, the third photocuring agent may have a solid phase, and the third photocuring agent may be 1 wt% to 70 wt% with respect to the total photocuring agent weight.
The first photoinitiator may include at least one selected from the group consisting of Irgacure 184, Irgacure 651, Irgacure 754, Irgacure 2959, Darocur 1173, and Darocur MBF.
The composition may further include a second photoinitiator dissolved in the first photocuring agent. In this case, the second photoinitiator has a second cut-off absorption wavelength greater than the first cut-off light transmission wavelength of the first photocuring agent, the second photoinitiator is 0.1% to 50% by weight relative to the total photoinitiator weight Can be.
The second photoinitiator in the group consisting of Darocur TPO, Irgacure 369, Irgacure 907, Irgacure 819, Irgacure 2100, Irgacure 784, Irgacure 250, Irgacure 250, Irgacure 184, Irgacure 651, Irgacure 754, Irgacure 2959, Darocur 1173 and Darocur MBF It may include at least one selected.
The composition may further include a photopolymerization monomer. In this case, the photopolymerization monomer is 2,3,4,5,6-pentafluoro styrene, methyl methacrylate, methyl acrylate, trifluoroacetic acid allyl ester, trifluoroacetic acid vinyl ester, 2,2,2- Trifluoroethyl methacrylate,
The composition may further include a solvent for diluting the first photocuring agent. The solvent is cyclopentanone, cyclohexanone, gamma-butyrolactone, toluene, methanol, ethanol, ethyl ether, N, N-dimethyl acetamide ), N-methyl pyrrodinone, tetrahydrofuran, tetrahydrofuran, ethyl acetate, and at least one selected from the group consisting of hexane.
According to another concept of the present invention, a method for producing a film includes providing a composition comprising a photocuring agent and a photoinitiator dissolved in the photocuring agent on a substrate to form a photocuring film; And curing the photocured film to form a film having an irregular wrinkled structure on its surface. In this case, the photoinitiator has a cut-off absorption wavelength of 310 nm or less, and the cut-off absorption wavelength is the smallest light wavelength of the optical wavelengths having an absorbance of 0.05 or less when irradiated with light of 1.0 × 10 -4 mol% photoinitiator lean solution having a thickness of 10 mm. Can be.
Curing the photocured film may include irradiating ultraviolet light to the photocured film.
The photoinitiator may include at least one selected from the group consisting of Irgacure 184, Irgacure 651, Irgacure 754, Irgacure 2959, Darocur 1173, and Darocur MBF.
When curing the photocured film, the photocuring rate constant ( k a pp ) may be 0.08 to 0.86 min −1 .
The thickness of the photocurable film may further include adjusting the size of the wrinkle structure by adjusting the thickness of 0.1μm to 1000μm.
The wavelength range of the ultraviolet light may be 200nm to 500nm.
Irradiating the ultraviolet light may be performed under an inert gas atmosphere or vacuum for 1 to 30 minutes.
The composition according to the present invention can form a film having a wrinkle structure having a size of several μm only by ultraviolet irradiation only by combining the characteristics between the light transmission wavelength of the photocuring agent and the absorption wavelength of the photoinitiator. In addition, the photocuring rate of the photocuring agent, that is, the concentration of the photoinitiator, the light intensity, the concentration of the photofunctional group of the photocuring agent, etc. It can be used to adjust the size of the wrinkle structure. Furthermore, since the film produced using the composition includes an irregular wrinkled structure, it may be suitable for a light scattering film for display or a light extraction film for illumination.
1 is a graph showing the light transmission spectrum and the light absorption spectrum of the photoinitiator of the photocuring agent according to embodiments of the present invention.
2A to 2C are cross-sectional views schematically illustrating a method of manufacturing a film having a wrinkled structure according to an embodiment of the present invention.
3 is a light transmission spectrum of ethylbenzene as a model compound of styrene and polystyrene.
4 is a graph showing the light transmission spectrum and the light absorption spectrum of the photoinitiator of the photocuring agent according to a comparative example of the present invention.
5A to 5C are cross-sectional views schematically illustrating a method of manufacturing a film having no wrinkle structure according to a comparative example of the present invention.
FIG. 6 is a graph showing ultraviolet (UV) light transmission spectra of acrylic photopolymer monomers and styrene photopolymer monomers.
7 is a cross-sectional view schematically showing a UV exposure machine for forming a photocured film according to the experimental examples of the present invention.
8 is a graph comparing absorption spectra and light transmission spectra of various photoinitiators and photocuring agents.
9 is a planar and cross-sectional electron scanning microscope (SEM) photograph of photocured films formed from compositions of TEGDMA / Irgacure 184 and UV5 / Darocur TPO.
FIG. 10 is a planar and cross-sectional electron scanning microscope (SEM) photograph of photocurable films formed from various photocuring agents having styrene crosslinking groups and a
FIG. 11 is a photograph and planar and cross-sectional SEM photographs of photocurable films prepared according to changes in photoinitiator concentration in a UV5 / Irgacure 184 composition.
12 is a planar and cross-sectional SEM photograph of photocured films prepared by varying light irradiation time and light intensity in a composition of photoinitiator of UV5 / Irgacure 184 (0.5% by weight photoinitiator).
13 is a graph showing the apparent photocuring rate constant ( k app ) by measuring the consumption rate of vinyl groups while varying the content of the photoinitiator from the UV5 / Irgacure 184 composition.
FIG. 14 is a planar and cross-sectional SEM photograph of photocured films prepared by varying the mixing ratio of acrylic crosslinker-containing and styrene crosslinker-containing photocuring agents of the UV5 / TEGDA / Irgacure 184 composition.
FIG. 15 is a planar and cross-sectional SEM photograph of photocured films prepared by varying the mixing ratio of styrene crosslinker-containing liquid and solid photocuring agents of the UV5 / UV33 /
FIG. 16 is a planar and cross-sectional SEM photograph of photocured films obtained by varying the rotational coating speed from the UV3 /
Objects, other objects, features and advantages of the present invention will be readily understood through the following preferred embodiments associated with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and to fully convey the spirit of the invention to those skilled in the art.
In the present specification, when it is mentioned that a film (or layer) is on another film (or layer) or substrate, it may be formed directly on another film (or layer) or substrate or a third film between them. In addition, in the drawings, sizes, thicknesses, etc. of components are exaggerated for clarity. In addition, in various embodiments herein, the terms first, second, third, etc. are used to describe various regions, films (or layers), etc., but these regions, films are defined by these terms. It should not be. These terms are only used to distinguish any given region or film (or layer) from other regions or films (or layers). Therefore, the film quality referred to as the first film quality in one embodiment may be referred to as the second film quality in other embodiments. Each embodiment described and illustrated herein also includes its complementary embodiment. The expression 'and / or' is used herein to include at least one of the components listed before and after. Portions denoted by like reference numerals denote like elements throughout the specification.
Hereinafter, a film forming composition having a wrinkle structure according to the present invention, a manufacturing method of a film using the composition and a manufacturing method of an organic electronic device will be described in detail with reference to the accompanying drawings.
1 is a graph showing the light transmission spectrum and the light absorption spectrum of the photoinitiator of the photocuring agent according to embodiments of the present invention. 2A to 2C are cross-sectional views schematically illustrating a method of manufacturing a film having a wrinkled structure according to an embodiment of the present invention.
Referring to FIG. 1, the composition for forming a film having a wrinkle structure according to embodiments of the present invention may include a first photocuring agent (PP1) and a first photoinitiator (PI1). The first photoinitiator PI1 may form radicals by absorbing irradiated light. The radical may react with the photocurable group (eg, vinyl group) of the first photocuring agent (PP1), so that the first photocuring agent (PP1) may be photocured.
The first photocuring agent (PP1) may include two or more vinyl groups in a molecule as a prepolymer. The first photocuring agent (PP1) may be a liquid at room temperature. More specifically, the first photocuring agent may have a viscosity of 1 cP to 10 7 cP at 25 ℃.
The first photocuring agent PP1 may have a first cut-off light transmission wavelength W1. The first cut-off light transmission wavelength W1 may be the largest light wavelength among light wavelengths in which the light transmittance of the first photocuring agent PP1 is 1.0% or less. The light transmittance may be based on when light is irradiated to the first photocuring agent applied to a thickness of 1 mm. That is, as shown in Figure 1, the first photocuring agent (PP1) may have a high transmittance for light having a long wavelength (B), but for light having a short wavelength gradually transmittance gradually decreases to 0% Can be reached close to. In this case, the wavelength of the light at which the light transmittance of the first photocuring agent PP1 reaches 1.0% may be referred to as the first cut-off light transmission wavelength W1. For example, the light transmittance of the first photocuring agent PP1 may be 1.0% or less with respect to the light wavelength between A and W1. However, the cutoff light transmission wavelength of the present invention may be defined as W1, which is the largest light wavelength at which the light transmittance becomes 1.0% or less.
The first cut-off light transmission wavelength W1 may be included in a wavelength range of 270 nm to 350 nm. Preferably, the first cut-off light transmission wavelength W1 may be 300 nm or more.
The vinyl group of the first photocuring agent (PP1) may include a substituted or unsubstituted styrene group. The first cut-off light transmission wavelength W1 may be greatly affected by the vinyl group of the first photocuring agent PP1. In this case, when the vinyl group includes a styrene group, the first cut-off light transmission wavelength W1 may indicate a larger wavelength. That is, the first cutoff light transmission wavelength W1 may be red-shifted on the spectrum. More specifically, the first photocuring agent (PP1) may include a compound of
[Formula 1]
[Formula 2]
[Formula 3]
[Formula 4]
In
For example, the compound of
[Formula 5]
[Formula 6]
[Formula 7]
[Formula 8]
[Formula 9]
For example, the compound of
[Formula 10]
For example, the compound of
[Formula 11]
For example, the compound having two or more substituted or unsubstituted styrene groups may be a compound of Formula 12.
[Formula 12]
The composition according to the embodiments may further include a second photocuring agent. The second photocuring agent may have a second cut-off light transmission wavelength (not shown). The second cut-off light transmission wavelength may be the largest light transmission wavelength at which light transmittance of the second photocuring agent is 1.0% or less. The second cutoff light transmission wavelength may be smaller than the first cutoff light transmission wavelength W1, and may be smaller than the first cutoff light absorption wavelength W2 which will be described later. The second cut-off light transmission wavelength of the second photocuring agent may be included in the wavelength range of 250nm to 320nm. The second photocuring agent may include a substituted or unsubstituted acrylic group. More specifically, the second photocuring agent may include a compound of Formula 13 below.
[Formula 13]
In Formula 13, R 1 are each independently hydrogen or a halogen element, R 6 and R 7 are each independently hydrogen or a methyl group, and p may be an integer of 0 to 100.
In this case, the concentration of the second photocuring agent may be 1% by weight to 70% by weight based on the total weight of the first photocuring agent (PP1) and the second photocuring agent. If the concentration of the second photocuring agent exceeds 70% by weight, the photocurable film L2 to be described later may be formed so thick that a film having a wrinkled structure may not be formed (see FIG. 13). At this time, by adjusting the concentration of the second photoinitiator within the range of 0.1% by weight to 50% by weight, it is possible to change the size of the wrinkle structure of the film surface to be described later.
The composition according to the embodiments of the present invention may further include a third photocuring agent. The third photocuring agent may be a solid independent of the cutoff light transmission wavelength. The third photocuring agent may include a substituted or unsubstituted styrene group or an acryl group.
Here, the concentration of the third photocuring agent may be 1% by weight to 70% by weight based on the total weight of the first photocuring agent (PP1) and the third photocuring agent. If the concentration of the third photocuring agent exceeds 70% by weight, the photocurable film L2 to be described later may be formed so thick that a film having a wrinkled structure may not be formed (see FIG. 15). At this time, by adjusting the concentration of the third photoinitiator within the range of 0.1% by weight to 50% by weight, the size of the wrinkle structure of the film surface to be described later can be changed.
The first photoinitiator PI1 may have a first cut-off absorption wavelength W2. The first cutoff absorption wavelength W2 may be smaller than the first cutoff light transmission wavelength W1. The first cut-off absorption wavelength W2 may be the smallest wavelength among optical wavelengths in which the absorbance of the lean solution in which the first photoinitiator PI1 is dissolved is 0.05 or less. The absorbance may be based on when light is irradiated to 6.010 -5 to 3.010 -4 mol% of the photoinitiator lean solution applied to a thickness of 10 mm. That is, as shown in Figure 1, the first photoinitiator (PI1) may have a high absorbance for light having a short wavelength (A), but the absorbance for light having a long wavelength gradually decreases close to zero Can be reached. In this case, the wavelength of the light at which the absorbance of the first photoinitiator PI1 reaches 0.05 may be referred to as the first cut-off absorption wavelength W2. For example, the absorbance of the first photoinitiator PI1 may be 0.05 or less with respect to the light wavelength between W2 and B. However, the cutoff absorption wavelength of the present invention can be defined as W2, which is the smallest light wavelength at which the absorbance is 0.05 or less.
The first cut-off absorption wavelength W2 may be included in a wavelength range of 250 nm to 350 nm. Preferably, the first cut-off absorption wavelength W2 may be 310 nm or less. The photoinitiator may include materials having the first cut-off absorption wavelength (W2) blue-shifted in the spectrum, for example,
The concentration of the first photoinitiator (PI1) may be 0.01 wt% to 10 wt% with respect to the total weight of the composition. As the concentration of the first photoinitiator PI1 is higher, the photocuring rate of the first photocuring agent PP1 may be increased. Therefore, if the concentration of the first photoinitiator (PI1) is lower than 0.1% by weight, the photocuring rate may be too slow to form a film having a wrinkled structure. If the concentration of the first photoinitiator (PI1) is higher than 10% by weight, the photocurable group of the first photocuring agent (PP1) may be rapidly reduced to shorten the first cut-off light transmission wavelength (W1). . As a result, the photocured film L2 to be described later may be formed so thick that a film having a wrinkled structure may not be formed (see FIG. 11). That is, within the range in which the wrinkle structure is formed on the film, the size of the wrinkle structure can be changed by changing the concentration range of the first photoinitiator.
In the composition according to the embodiments, the first cut-off light transmission wavelength W1 of the first photocuring agent (PP1) than the first cut-off absorption wavelength (W2) of the first photoinitiator (PI1) It can be equal or greater. Therefore, when light having a wavelength longer than the first cut-off light transmission wavelength W1 is irradiated to the composition, the first photoinitiator PI1 does not react and photocuring of the first photocuring agent PP1 occurs. You can't. Furthermore, when light having a wavelength shorter than the first cut-off absorption wavelength W2 is irradiated to the composition, the first photoinitiator PI1 present on the surface of the composition may generate radicals. As a result, photocuring may occur only at the surface of the composition.
The composition may further include a photopolymerization monomer. The photopolymerization monomer may be a low molecular vinyl monomer, and acts as a chain extender to further increase molecular weight after crosslinking of the first photocuring agent (PP1).
The photopolymerization monomer may be 1% to 70% by weight based on the total weight of the composition. The photopolymerization monomer is 2,3,4,5,6-pentafluoro styrene (2,3,4,5,6-pentafluoro styrene), methyl methacrylate, methyl acrylate, trifluoroacetic acid allyl ester (trifluoroacetic) acid allyl ester, trifluoroacetic acid vinyl ester, 2,2,2-trifluoroethyl methacrylate,
The composition may further include a solvent for diluting the first photocuring agent (PP1) or a solvent capable of dissolving the third photocuring agent. The solvent may be 1 wt% to 99 wt% with respect to the total weight of the composition. The solvent is cyclopentanone, cyclohexanone, gamma-butyrolactone, toluene, methanol, ethanol, propanol, ethyl ether, N, N-dimethyl acetamide (N, N- It may be at least one selected from the group consisting of dimethyl acetamide, N-methyl pyrrodinone, tetrahydrofuran, ethyl acetate and hexane.
The composition according to the embodiments may further include a second photoinitiator. The second photoinitiator may have a second cutoff absorption wavelength (not shown) that is greater than the first cutoff light transmission wavelength W1. The concentration of the second photoinitiator may be 0.1 wt% to 50 wt% with respect to the total weight of the first photoinitiator (PI1) and the second photoinitiator. By adjusting the concentration of the second photoinitiator, it is possible to change the size of the wrinkle structure of the film surface to be described later. A detailed description of the second photoinitiator will be described later.
1 and 2A, the composition film L1 may be formed on the
The composition film L1 may be formed to a thickness of 0.1 μm to 1000 μm. For example, when the composition film L1 is formed by using a rotation coating method, the thickness of the composition film L1 may be adjusted by adjusting the rotational coating speed of the
1 and 2B, light 200 may be irradiated onto the composition film L1 to form a photocurable film L2 on the composition film L1. The light 200 may include a wavelength range capable of activating a photoinitiator. For example, the light 200 may be ultraviolet rays. The light 200 may have a wide wavelength range. The wavelength range of the light 200 may include a range of the short wavelength A to the long wavelength B of FIG. 1. That is, the first cutoff light transmission wavelength W1 and the first cutoff absorption wavelength W2 may be included in the wavelength range of the light 200. More specifically, the light 200 may be irradiated in a wavelength range of 200nm to 500nm.
As described above, the range of the light transmission wavelength of the first photocuring agent PP1 (for example, W1 to B) and the absorption wavelength of the first photoinitiator PI1 (for example, A to W2). Since the light does not overlap with the composition film L1, the photocuring reaction of the first photocuring agent PP1 may occur only at the surface of the composition film L1 at the initial stage of irradiation. Therefore, in the present embodiment, the photocurable film L2 may be a thin film formed on the surface of the composition film L1. The composition film L1 under the photocurable film L2 may not be photocured, and thus may be a liquid film as shown in FIG. 2A. Furthermore, the photocurable film L2 may be a solid film having high strength due to the photocuring of the first photocuring agent PP1.
When the photocurable film L2 is formed, the primary photocuring rate constant k a pp may be 0.08 to 0.86 min −1 . If the photocuring rate constant k a pp is less than 0.08 min −1 or more than 0.86 min −1 , the photocuring rate may be too slow or too fast so that no wrinkle structure is formed on the film. Furthermore, when the photocuring speed is changed within the above range, the size of the wrinkle structure formed may also be changed. The photocuring rate constant ( k a pp ) may be proportional to the concentration of the photoinitiator, the intensity of the light, the concentration of the vinyl group, and the like. Therefore, by adjusting such factors (concentration of photoinitiator, etc.) to adjust the photocuring rate constant ( k a pp ) to an appropriate range, it is possible to control the formation and size of the wrinkle structure on the film.
1 and 2C, the light 200 may be continuously irradiated onto the photocurable film L2 to form a photocurable film WF on the substrate. The photocurable film WF may be a film having a wrinkled structure WS.
Figure 3 is a light curing group, the light transmission spectrum of ethylbenzene as a model compound of styrene and polystyrene. Referring to FIG. 3, in the case of the compound having ethylbenzene having a small double bond, the light transmission spectrum is blue-shifted compared to the compound having styrene as the photocurable group (for example, the first photocuring agent (PP1)). Shows. This is because ethylbenzene is not bound to a vinyl group.
The liquid composition film L1 may be cured due to the photocuring reaction continuously performed after the photocuring film L2 is formed. When the photocurable layer (L2) is formed, the double bond of the photocurable group is reduced, so that the transmission spectrum of the photocurable layer (L2) may be blue-shifted. Thereby, the composition film L1 can also be cured because the light transmittance increases (see FIG. 3). At this time, the composition film (L1) may be shrinkage while curing. At the same time, the photocurable film L2 having a high strength is deformed to solve the stress acting on it, and thus can form the corrugated structure WS. Herein, the size of the wrinkle structure that is generated in the future may vary according to the thickness of the composition film L1 that is liquid.
Irradiation of the light 200 described above with reference to FIGS. 2B and 2C may be performed under an atmosphere of inert gas such as nitrogen or under vacuum for 1 to 30 minutes. After irradiating the light 200, heat treatment may be further performed on the photocurable film (WF) at 100 ° C. to 300 ° C. FIG. At this time, it may be performed under an atmosphere of an inert gas such as nitrogen or under vacuum.
The photocurable film (WF) manufactured as described above can be applied to the light scattering layer of the organic light emitting diode, as well as to the light extraction film and the light sensor of various displays and lighting.
4 is a graph showing the light transmission spectrum and the light absorption spectrum of the photoinitiator of the photocuring agent according to a comparative example of the present invention. 5A to 5C are cross-sectional views schematically illustrating a method of manufacturing a film having no wrinkle structure according to a comparative example of the present invention. Detailed descriptions of technical features overlapping with those described with reference to FIGS. 1 and 2A through 2C will be omitted, and differences will be described in detail. The same reference numerals may be provided for the same configuration as the method for manufacturing a film having a wrinkled structure for explaining the concept of the present invention.
Referring to FIG. 4, the film forming composition according to the comparative example of the present invention may include a second photocuring agent (PP2) and a photoinitiator. The photoinitiator may be a first photoinitiator (PI1) or a second photoinitiator (PI2). The second photocuring agent PP2 may have a second cut-off light transmission wavelength W3. The second cut-off light transmission wavelength W3 of the second photocuring agent PP2 may be included in a wavelength range of 250 nm to 320 nm. The second photocuring agent (PP2) may include a substituted or unsubstituted acrylic group. More specifically, the second photocuring agent (PP2) may include the compound of Formula 13.
The second photoinitiator PI2 may have a second cutoff absorption wavelength W4. The second cutoff absorption wavelength W4 may be the same as the first cutoff absorption wavelength W2 of the first photoinitiator PI1 described above with reference to FIG. 1. In addition, the second cutoff absorption wavelength W4 may be greater than the second cutoff light transmission wavelength W3. For example, the second photoinitiator (PI2) is Darocur TPO, Darocur 1173, Darocur MBF,
Under the wavelength range (C) of W3 to W4, the second photocuring agent (PP2) has a transmittance of 0 or more and at the same time the second photoinitiator (PI2) may have a absorbance of 0 or more. Therefore, when the light of the wavelength range (C) is irradiated to the composition, since the light transmits the composition to a predetermined depth, a photocuring reaction may occur in the composition of the predetermined depth.
4 and 5A, the composition film L1 may be formed on the
4 and 5B, light 200 may be irradiated onto the composition film L1 to form a photocurable film L2 on the composition film L1. The photocurable film L2 may have a first thickness D1.
In the case of FIG. 2B, the range of the light transmission wavelength of the first photocuring agent PP1 (for example, W1 to B) and the absorption wavelength of the first photoinitiator PI1 (for example, A to W2). Since do not overlap, the photocured film L2 may be formed into a thin thin film. On the other hand, according to this comparative example, the range of the light transmission wavelength of the second photocuring agent (PP2) (for example, W3 ~ B) and the absorption wavelength of the second photoinitiator (PI2) (for example, A ~ W4) may overlap in the wavelength range C of W3 to W4. Therefore, in the case of FIG. 5B, since the light 200 is transmitted at the initial irradiation time by the first thickness D1 corresponding to the transmittance T1, the photocuring reaction is generated. It may have a first thickness D1 that is thicker than the thickness of the layer L2. As the value of the wavelength range C increases, the thickness of the photocured film L2 at the initial stage of irradiation may increase.
4 and 5C, the light 200 may be continuously irradiated onto the photocurable film L2 to form a photocurable film TF on the substrate. However, the photocurable film TF may not have a wrinkle structure, as described above with reference to FIG. 2C. Since the photocurable film L2 is a film having a relatively thick first thickness D1 rather than a thin film, the composition film L1 may not form a wrinkled structure even when the remaining composition film L1 is cured and shrunk.
As described above, the present invention may include a composition combining a photocuring agent having a red-shifted cut-off light transmission wavelength and a photoinitiator having a blue-shifted cut-off absorption wavelength. That is, since the light transmission wavelength range of the photocuring agent and the absorption wavelength range of the photoinitiator do not overlap each other, a film having a wrinkled structure can be easily formed only by simple ultraviolet irradiation. For example, the film having the wrinkle structure may be applied to the light scattering layer of the organic light emitting diode.
Experimental Example 1: styrene Photopolymerization Monomer and Acrylic Photopolymerization Monomeric Light transmission spectrum
Methyl methacrylate (MMA) and methyl acrylate (MA) were prepared as acrylic photopolymerization monomers. Styrene (St) and 2,3,4,5,6-pentafluorostyrene (PFSt) were prepared as styrene photopolymerization monomers. Ultraviolet (UV) light transmission spectra of the acrylic photopolymerization monomers and the styrene photopolymerization monomers are shown in FIG. 6.
As shown in FIG. 6, the cutoff light transmission wavelength of the styrene-based photopolymerization monomers St and PFSt is greater than 300 nm, but the cutoff light transmission wavelength of the acrylic photopolymerization monomers MMA and MA is smaller than 300 nm. can confirm. That is, the styrene-based photopolymerization monomers St and PFSt are conjugated with a vinyl group as a photocuring group, thereby confirming that the cut-off light transmission wavelength is more red-shifted than the acrylic photopolymerization monomers MMA and MA. Can be.
Experimental Example 2: 1 , 2,4,5- Tetrafluoro -3- (2- {2- [2- (2- {2,3,5,6- tetrafluoro Synthesis of -4-vinyl-phenoxy} -ethoxy) -ethoxy] -ethoxy} -ethoxy) -6-vinyl-benzene [UV5]
UV5 was synthesized according to
Referring to
Experimental Example 3: 1 , 2,4,5- Tetrafluoro -3- (2- {2- [2,3,5,6- tetrafluoro Synthesis of -4-vinyl-phenoxy] -ethoxy} -ethoxy) -6-vinyl-benzene [UV3]
UV3 was synthesized according to
Referring to
Experimental Example 4: 1 , 2,4,5- Tetrafluoro -3- [2- (2,3,5,6,- tetrafluoro Synthesis of -4-vinyl-phenoxy) -ethoxy] -6-vinyl-benzene [UV2]
UV2 was synthesized according to
Referring to
Experimental Example 5: 1- (2- {2- [2- (1,1-Difluoro-2- {2,3,5,6-tetrafluoro-4-vinyl-phenoxy} -ethoxy) -1,1,2,2 -tetrafluoro-ethoxy] -1,1,2,2-tetrafluoro-ethoxy} -2,2-difluoro-ethoxy) -2,3,5,6-tetrafluoro-4-vinyl-benzene [UVF5]
UVF5 was synthesized according to
Referring to
Experimental Example 6: 1- (2- {2- [1,1-Difluoro-2- (2,3,5,6-tetrafluoro-4-vinyl-phenoxy) -ethoxy] -1,1,2,2-tetrafluoro- ethoxy} -2,2-difluoro-ethoxy) -2,3,5,6-tetrafluoro-4-vinyl-benzene [UVF4]
UVF4 was synthesized according to
Referring to
Experimental Example 7: 2- (2- {2- [1,1-Difluoro-2- (2,3,5,6-tetrafluoro-4-vinyl-phenoxy) -ethoxy] -1,1,2,2-tetrafluoro- ethoxy} -1,1,2,2-tetrafluoro-ethoxy) -2,2-difluoro-ethanol [7]
Photocuring agent intermediate 7 according to embodiments of the present invention was synthesized according to Scheme 6 below.
Scheme 6
Referring to Scheme 6, in a 250 mL two-necked flask, 20.0 g of fluorinated tetraethylene glycol and 2,3,4,5,6-pentafluorostyrene (1, 2,3, 11.4 g of 4,5,6-pentafluoro styrene) was dissolved under a stream of nitrogen using 40 mL of anhydrous dimethyl acetmide (DMAc). 10.2 g of potassium carbonate was added as a reaction catalyst. The reaction proceeded for about 24 hours at 60 ° C. under a nitrogen atmosphere. After the reaction was completed, potassium carbonate was removed and the reaction solution was dipped in distilled water. The reactant was extracted with ethyl acetate and ethyl acetate was evaporated to give a brown reactant. The brown reactant was purified by column with ethyl acetate / hexane (1/5, v / v) as a developing agent to obtain a colorless transparent liquid reactant (7) and vacuum dried at 35 ° C. for 48 hours. Yield: 12.8 g (45%). IR ｖ max (Liquid, NaCl) / cm - 1 : 3377 m (OH str., Hydroxyl); 3038w (= CH str., Vinyl); 2965w (CH str., Methylene); 1647 m (C = C str., Vinyl, and aromatic); 1203, 1092 s (CO str., Ether). 1 H NMR δ H (CDCl 3 , 300 MHz): 6.70-6.60 (1H, m, vinyl); 6.11-5.68 (2H, m, vinyl); 4.54 (2H, t, methylene); 3.95 (2H, t, methylene); 2.65 (1H, s, hydroxyl). 19 F NMR δ F (CDCl 3 , 300 MHz): −78.67 (2F, m); -80.91 (2F, m); -88.92 (4F, m); -89.09 (4F, s); -144.39 (2F, m); -158.19 (2F, m). MS ( m / z ): calcd. 584.21; found 584.
Experimental Example 8: 2,3,5,6,2 ', 3', 5 ', 6'-Octafluoro-4,4'-bis- [2- (2- {2- [1,1-Difluoro-2- ( 2,3,5,6-tetrafluoro-4-vinyl-phenoxy) -ethoxy] -1,1,2,2-tetrafluoro-ethoxy} -1,1,2,2-tetrafluoro-ethoxy) -2,2- difluoro-ethoxy] -biphenyl [ UVDF5 Synthesis of
UVDF5 was synthesized according to Scheme 7 as a photocuring agent according to embodiments of the present invention.
Scheme 7
Referring to Scheme 7, in a 50 mL two-necked flask, 5.3 g of intermediate (7) and 1.5 g of decafluorobiphenyl (8) obtained in Experiment 7 were dissolved under nitrogen stream using 15 mL of anhydrous dimethyl acetmide (DMAc). 0.1 g of cesium fluoride and 0.6 g of calcium hydride were added as a reaction catalyst. The reaction proceeded for about 48 hours at 60 ° C. under a nitrogen atmosphere. After the reaction was completed, the catalysts were removed and the reaction solution was immersed in distilled water. The reactant was extracted with ethyl acetate and ethyl acetate was evaporated to give a brown reactant. The brown reactant was purified by column with ethyl acetate / hexane (1/5, v / v) as a developing agent to give a colorless transparent liquid reactant (UVDF5) which was vacuum dried at 35 ° C. for 48 hours. Yield: 4.0 g (61%). IR ｖ max (Liquid, NaCl) / cm - 1 : 3038 w (= CH str., Vinyl); 2971w (CH str., Methylene); 1649 w (C = C str., Vinyl, and aromatic); 1210, 1115 s (CO str., Ether); 939 m (= CH oop ben., Vinyl). 1 H NMR δ H (CDCl 3 , 300 MHz): 6.69-6.59 (2H, m, vinyl); 6.11-5.68 (4H, m, vinyl); 4.64 (4H, t, methylene); 4.54 (4H, t, methylene). 19 F NMR δ F (CDCl 3 , 300 MHz): −78.70 (8F, m); -88.89 (8F, m); -89.07 (8F, m); -138.67 (4F, m); -144.39 (4F, m); -155.90 (4F, m); -158.21 (4F, m). MS ( m / z ): calcd. 1462.51; found 1462.
Experimental Example 9: Synthesis of 2- (2,3,5,6-Tetrafluoro-4-vinyl-phenoxy) -ethanol [9]
Photocuring agent intermediate 9 according to embodiments of the present invention was synthesized according to Scheme 8 below.
Scheme 8
Referring to Scheme 8, in a 100 mL two-necked flask, 8.4 g of ethylene glycol and 2,3,4,5,6-pentafluorostyrene (2,3,4,5,6-pentafluoro 17.9 g of styrene) was dissolved under a nitrogen stream using 25 mL of anhydrous dimethyl acetmide (DMAc). 13.0 g of potassium carbonate was added as a reaction catalyst. The reaction proceeded for about 24 hours at room temperature under a nitrogen atmosphere. After the reaction was completed, potassium carbonate was removed and the reaction solution was dipped in distilled water. The reactant was extracted with ethyl acetate and ethyl acetate was evaporated to give a brown reactant. The brown reactant was purified by column with ethyl acetate / hexane (1/5, v / v) as a developing agent to obtain a colorless transparent liquid reactant (9) and vacuum dried at 35 ° C. for 48 hours. Yield: 7.5 g (35%). 1 H NMR δ H (CDCl 3 , 300 MHz): 6.69-6.56 (1H, m, vinyl); 5.60-5.56 (2H, m, vinyl); 4.30 (2H, t, methylene); 4.14 (2H, t, methylene); 2.15 (1H, s, hydroxyl). 19 F NMR δ F (CDCl 3 , 300 MHz): −145.81 (2F, m); -158.98 (2F, m). MS ( m / z ): calcd. 236.16; found 236.
Experimental Example 10: 2 -Methyl-acrylic acid 2- (2,3,5,6- tetrafluoro Synthesis of -4-vinyl-phenoxy) -ethyl ester [UVA2]
UVA2 was synthesized according to Scheme 9 as a photocuring agent according to embodiments of the present invention.
Scheme 9
Referring to Scheme 9 above, in a 50 mL two-necked flask, 3.1 g of intermediate (9) and 2.5 g of metharylic anhydride (10) obtained in Experiment 9 were dissolved under nitrogen stream using 10 mL of anhydrous dimethyl acetmide (DMAc). As reaction catalyst, 2.8 mL of triethyl amine (Et 3 N) and 0.1 g of 4-dimethyl aminopyridine (DMAP) were added. The reaction proceeded for about 24 hours at room temperature under a nitrogen atmosphere. After the reaction was completed, the reaction solution was immersed in distilled water. The reactant was extracted with ethyl acetate and ethyl acetate was evaporated to give a brown reactant. The brown reactant was purified by column with ethyl acetate / hexane (1/20, v / v) as a developing agent to obtain a colorless transparent liquid reactant (UVA2) and vacuum dried at 35 ° C. for 48 hours. Yield: 1.8 g (44%). 1 H NMR δ H (CDCl 3 , 300 MHz): 6.63-6.53 (1H, m, vinyl); 6.06-5.96 (2H, m, vinyl); 5.62-5.55 (2H, m, vinyl); 4.44 (4H, s, methylene); 1.90 (3H, s, methyl). 19 F NMR δ F (CDCl 3 , 300 MHz): −145.22 (2F, m); -158.68 (2F, m). MS ( m / z ): calcd. 304.24; found 304.
Experimental Example 11: 1 -[2,3- di -(2,3,5,6,- tetrafluoro -4-vinyl- phenoxy )- propoxy ] -2,3,5,6-tetrafluoro-4-vinyl-benzene [UV33] Synthesis
UV33 was synthesized according to
Referring to
Experimental Example 12: Tetraethyleneglycol dimethacrylate ( TEGDMA ) And purification of tetraethyleneglycol diacrylate (TEGDA)
TEGDMA and TEGDA were prepared as photocuring agents according to comparative examples of the present invention as follows. TEGDMA and TEGDA were each purified by column with ethyl acetate / hexane (1/1, v / v) as a developing agent to obtain a colorless transparent liquid reaction product and vacuum dried at 35 ° C. for 48 hours. TEGDMA is a compound of formula 14, TEGDA is a compound of
[Formula 14]
[Formula 15]
Experimental Example
13:
TEGDMA
Of
0.0285 g of
Experimental Example 14 Preparation of UV5 /
0.1278 g of
Experimental Example 15 Measurement of Photocuring Rate of UV5 /
Each of the compositions having different concentrations of photoinitiators prepared in Experimental Example 14 (Examples 7-1 to 7-6) were spun onto NaCl window and measured the conversion of styrene vinyl groups with time to determine the apparent photocuring rate from
[Equation 1]
ln ( [M] 0 / [M] t ) = k app t
Where [M] = I 1632 / I 1455 , [M] 0 is the initial styrene concentration, [M] t is the styrene concentration after t hours, and k app is the apparent primary photocuring rate constant.
Experimental Example 16: Preparation of UV5 /
UV5 prepared in Experimental Example 2 and TEGDA prepared in Experimental Example 12 were mixed as shown in Table 2 at different ratios.
Experimental Example 17 Preparation of UV5 / UV33 /
UV5 prepared in Experimental Example 2 and UV33 prepared in Experimental Example 11 were mixed as shown in Table 3 at different ratios.
Experimental Example 18 Preparation of UV Photocurable Film
7 is a cross-sectional view schematically showing a UV exposure machine for forming a photocured film according to the experimental examples of the present invention.
The photocurable compositions prepared in Comparative Example 1, Comparative Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, and Example 9 were applied to a glass substrate coated with SiO 2 . The coating was spun at 30 rpm at 3000 rpm (30 seconds at 550 rpm for Example 1). The solution of Example 2 varied the application speed of rotation of 3000rpm / 30sec to 5000rpm / 30sec and 5000rpm / 50sec to determine the effect of membrane thickness on the size of the corrugation structure. In the UV exposure machine shown in FIG. 7, UV light was irradiated to the photocurable composition coated on the glass substrate for 10 minutes under a nitrogen stream. Specifically, the glass substrate sample coated with the photocurable composition was placed in a glass container, and the nitrogen stream was passed at a flow rate of 10 L / min. The UV lamps used Mercury UVH lamps and the power was 1 kW. UV light irradiated to the photocurable film was used in the form A or B shown in Table 4. Unless otherwise specified, it means a type A investigation.
UVV: 395-445 nm; UVA: 320-390 nm; UVB: 280-320 nm; UVC: 250-260 nm.
Experimental Example 19: Light transmission spectrum of photocuring agent and photoinitiator
UV-vis spectroscopy was performed using a
Experimental Example 20: Analysis
Infrared spectroscopy was performed using a Nicolet 6700 FT-IR spectrometer. Hydrogen and fluorine nuclear magnetic resonance spectroscopy were performed using a
The spectra of the photocuring agent and photoinitiator used and prepared in the above experimental examples were examined and shown in FIG. 8. 8 is a graph comparing absorption spectra and light transmission spectra of various photocuring agents and photoinitiators.
Referring to FIG. 8, first,
As a photocuring agent, UV5 and DVB, which are styrene photocuring agents, have a cutoff light transmission wavelength greater than 300 nm, whereas acrylic light curing agents TEGDMA and TEGDA have a cutoff light transmission wavelength smaller than 280 nm. That is, UV5 and DVB, which are styrene-based photocuring agents, may be advantageous in obtaining a film having a wrinkle structure in combination with a photoinitiator than TEGDMA and TEGDA, which are acrylic photocuring agents.
The light transmission wavelength ranges of the styrene-based light curing agents UV5 and DVB do not overlap the absorption wavelength range of the
On the other hand, the combination of TEGDMA and TEGDA, an acrylic photocuring agent, and
Furthermore, the combination of styrene-based photocuring agents UV5 and DVB or acrylic photocuring agents TEGDMA and TEGDA and photoinitiator Darocur TPO may overlap the light transmission wavelength range of the photocuring agent and the absorption wavelength range of the photoinitiator (eg, comparison Example 2). Therefore, as described with reference to FIGS. 4 and 5A-5C, the use of Darocur TPO as a photoinitiator is difficult to form a film having a wrinkled structure.
In conclusion, when TEGDMA and TEGDA, which are acrylic photocuring agents, are used as the photocuring agent, it is difficult to form a film having a wrinkled structure using any photoinitiator. In the case of using Darocur TPO as a photoinitiator, it is difficult to form a film having a wrinkled structure by using any photocuring agent. As shown in FIG. 9, these results can be confirmed from SEM images of photocured films prepared from the compositions of Comparative Examples 1 and 2. However, if ultraviolet rays of 270 nm to 280 nm or less are irradiated to the composition film, wrinkles may be formed on the photocured film irrespective of the photocuring agent or photoinitiator.
On the other hand, the combination of styrene-based photocuring agents UV5 and DVB with
Using the composition solution of Examples 7-1 to 7-6 prepared above to prepare a film having a wrinkle structure. Planar and cross-sectional electron scanning microscope (SEM) photographs of the prepared films are shown in FIG. 11.
FIG. 11 is an electron scanning microscope (SEM) photograph of a photocurable film prepared according to the change of the photoinitiator concentration. FIG.
Referring to FIG. 11, Examples 7-2 (1.0 wt%), Examples 7-3 (2.0 wt%), Examples 7-4 (3.0 wt%) and Examples 7-5 (5.0 wt%) of When using the composition solution, it can be seen that a film having a wrinkled structure is formed. That is, when the concentration of the photoinitiator in the composition is 1.0% by weight to 5.0% by weight, a film having a wrinkled structure may be formed. The wrinkled structure of the formed film can be confirmed that both the length of the wrinkles and the depth of the wrinkles depending on the concentration of the photoinitiator.
12 is a SEM photograph of a film photocured by increasing the irradiation time and the light intensity of the film of the composition of Example 7-1 (0.5% by weight) having a small amount of photoinitiator.
Since the rate of photocuring reaction is proportional to 1/2 power of photoinitiator concentration as shown in
[Equation 2]
Where k p and k t are propagation rate constant and termination rate constant, respectively. Φ is the quantum yield for initiation, I 0 is the incident light intensity, ε is the extinction coefficient, [ I ] is the concentration of the initiator, b is the film thickness, and k app is the apparent primary photocuring rate constant defined by
[Equation 3]
13 is a graph showing the apparent photocuring rate constant ( k app ) by measuring the photocuring group consumption rate from the compositions of Examples 7-1 to 7-6. That is, when the content of the photoinitiator is changed through FIG. 13, the change of the photocuring rate constant ( k app ) may be confirmed.
Referring to FIG. 13, it can be seen that the apparent photocuring rate constant ( k app ) of the composition forming the corrugation structure is in the range of 0.08 to 0.86 min −1 .
If the concentration of the photoinitiator is higher than 5% by weight, the styrene group of the photocuring agent may be rapidly reduced to shorten the cutoff light transmission wavelength. As a result, the initial photocuring film may be formed too thick so that a film having a wrinkled structure may not be formed (FIG. 3).
Through the present experimental example, it can be seen that the wrinkle structure of the film can be variously changed by adjusting the concentration of the photoinitiator. That is, the wrinkle structure can be changed by adjusting the photocuring reaction rate.
The film having a wrinkled structure was prepared using the composition solution of Examples 8-1 to 8-4 prepared in Experimental Example 16 above. Planar and cross-sectional electron scanning microscope (SEM) photographs of the prepared films are shown in FIG. 14.
14 is an electron scanning microscope (SEM) photograph of a photocurable film prepared according to a change in the combination ratio of photocuring agents.
Referring to FIG. 14, Example 8-1 (UV5: TEGDA = 10: 0, a), Example 8-2 (UV5: TEGDA = 7: 3, b), Example 8-3 (UV5: TEGDA = The photocured film was prepared using the composition solution of 6: 4, c), and Example 8-4 (UV5: TEGDA = 5: 5, d). In this case, in Examples 8-1, 8-2 and 8-3 it can be confirmed that the film having a wrinkled structure is formed. That is, when the acrylic photocuring agent is mixed with the styrene photocuring agent at 50 wt% or less, a wrinkle structure may be formed. At this time, the wrinkle structure of the formed film can be confirmed that the length of the wrinkles and the depth of the wrinkles are all different according to the ratio of the acrylic photocuring agent. In conclusion, by adjusting the mixing ratio of the styrenic photocuring agent and the acrylic photocuring agent in the composition solution, it is possible to vary the wrinkle structure. Similarly, when the acrylic photocurable group and the styrene photocurable group are chemically present in the photocuring agent, a wrinkled structure film can be obtained during photocuring (Example 6, FIG. 10F).
FIG. 15 is an SEM image of photocurable films prepared by changing a mixing ratio of a liquid photocuring agent UV5 and a solid photocuring agent UV33.
Referring to Figure 15, Example 8-1 (UV5: UV33 = 10: 0, a), Example 9-1 (UV5: UV33 = 7: 3, b), Example 9-2 (UV5: UV33 = 5: 5, c), and the composition solution of Example 9-3 (UV5: UV33 = 3: 7, d) were used to prepare a photocured film. At this time, in the case of Examples 8-1, 9-1 and 9-2 it can be confirmed that the film having a wrinkle structure is formed. That is, when the solid styrene-containing photocuring agent is mixed with the liquid styrene-containing photocuring agent at 70 wt% or less, a wrinkle structure may be formed. In this case, the wrinkled structure of the formed film can be confirmed that the length of the wrinkles and the depth of the wrinkles are all different according to the ratio of the solid styrene-containing photocuring agent and the liquid styrene-containing photocuring agent. In conclusion, by adjusting the mixing ratio of the solid styrene-containing photocuring agent and the liquid styrene-containing photocuring agent in the composition solution, it is possible to vary the wrinkle structure.
In addition, even if the composition of the same composition, it can be seen through Figure 16 that the size of the wrinkle structure changes under certain conditions depending on the thickness of the film produced.
FIG. 16 is a SEM photograph of a photocured film obtained by varying the rotational application rate from the UV3 /
Claims (20)
The first cut-off light transmission wavelength of the first photocuring agent is greater than the first cut-off absorption wavelength of the first photoinitiator,
The first cut-off light transmission wavelength is the largest light wavelength among light wavelengths of 1.0% or less when light is irradiated to the first photocuring agent having a thickness of 1 mm,
The first cut-off absorption wavelength is the smallest light wavelength among optical wavelengths having an absorbance of 0.05 or less when irradiated with light at 1.0ⅹ10 -4 mol% of the first photoinitiator lean solution having a thickness of 10 mm,
The second photocuring agent has a second cutoff light transmission wavelength smaller than the first cutoff absorption wavelength of the first photoinitiator,
The second photocuring agent is a composition for forming a wrinkle structure film is 1% to 70% by weight based on the total photocuring agent weight.
The first cut-off light transmission wavelength of the first photocuring agent, and the first cut-off absorption wavelength of the first photoinitiator are 250nm to 350nm.
The first photocuring agent is a liquid composition having a viscosity of 1 cP to 10 7 cP at 25 ℃.
The concentration of the first photoinitiator is 0.01 to 10% by weight relative to the total weight of the composition.
The first photocuring agent is a composition comprising two or more substituted or unsubstituted styrene groups in the molecule thereof.
The second photocuring agent is a composition comprising two or more substituted or unsubstituted acrylic groups in the molecule thereof.
Further comprising a third photocuring agent,
The third photocuring agent has a solid phase,
The third photocuring agent is 1% to 70% by weight relative to the total photocuring agent weight.
The first photoinitiator comprises at least one selected from the group consisting of Irgacure 184, Irgacure 651, Irgacure 754, Irgacure 2959, Darocur 1173 and Darocur MBF.
Further comprising a second photoinitiator dissolved in the first photocuring agent and the second photocuring agent,
The second photoinitiator has a second cutoff absorption wavelength greater than the first cutoff light transmission wavelength of the first photocuring agent,
The second photoinitiator is 0.1 wt% to 50 wt% with respect to the total photoinitiator weight.
The second photoinitiator is at least selected from the group consisting of Darocur TPO, Irgacure 369, Irgacure 907, Irgacure 819, Irgacure 2100, Irgacure 784, Irgacure 250, Irgacure 184, Irgacure 651, Irgacure 754, Irgacure 2959, Darocur 1173, and Darocur MBF A composition comprising one.
It further comprises a photopolymerization monomer,
The photopolymerization monomer is 2,3,4,5,6-pentafluoro styrene, methyl methacrylate, methyl acrylate, trifluoroacetic acid allyl ester, trifluoroacetic acid vinyl ester, 2,2,2-trifluoro Roethyl methacrylate, acrylic acid 1,1,1,3,3,3-hexafluoroisopropyl ester, methacrylic acid 1,1,1,3,3,3, -hexafluoroisopropyl ester, 1 -Pentafluorophenyl-pyrrole-2,5-dione, N -methyl maleimide, N -ethyl maleimide, N -propyl maleimide, N -butyl maleimide, N -tertiary-butyl maleimide, N -pentyl A composition comprising at least one selected from the group consisting of maleimide and N-hexyl maleimide.
Further comprising a solvent for diluting the first photocuring agent,
The solvent is cyclopentanone, cyclohexanone, gamma-butyrolactone, toluene, methanol, ethanol, propanol, ethyl ether, N, N-dimethyl acetamide (N, N -dimethyl acetamide), N-methyl pyrrodinone, N-methyl pyrrodinone, tetrahydrofuran, tetrahydrofuran, ethyl acetate, and at least one selected from the group consisting of hexane (hexane).
Curing the composition film, including forming a film having an irregular wrinkle structure on the surface,
The first photocuring agent has a first cutoff light transmitting wavelength, the second photocuring agent has a second cutoff light transmitting wavelength smaller than the first cutoff light transmitting wavelength,
The photoinitiator has a cutoff absorption wavelength of 310 nm or less,
The cut-off absorption wavelength is the smallest light wavelength among optical wavelengths having an absorbance of 0.05 or less when irradiated with light to a 1.0 × 10 -4 mol% photoinitiator lean solution having a thickness of 10 mm,
Wherein the second photocuring agent is from 1% to 70% by weight based on the total photocuring agent weight.
Curing the composition film comprises irradiating the composition film with ultraviolet light.
Wherein the photoinitiator comprises at least one selected from the group consisting of Irgacure 184, Irgacure 651, Irgacure 754, Irgacure 2959, Darocur 1173, and Darocur MBF.
The method of producing a film having a photocuring rate constant ( k a pp ) of 0.08 to 0.86 min −1 when curing the composition film.
Adjusting the thickness of the composition film to 0.1μm to 1000μm manufacturing method of the film further comprising adjusting the size of the wrinkle structure.
The wavelength range of the ultraviolet ray is a manufacturing method of the film 200nm to 400nm.
Irradiating the ultraviolet light is carried out under an inert gas atmosphere or vacuum for 1 to 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/822,417 US10472276B2 (en) | 2014-12-04 | 2015-08-10 | Composition for forming film having wrinkle structure and method of forming the film |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140172626 | 2014-12-04 | ||
| KR20140172626 | 2014-12-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160068634A KR20160068634A (en) | 2016-06-15 |
| KR102033747B1 true KR102033747B1 (en) | 2019-10-18 |
Family
ID=56135269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150086837A KR102033747B1 (en) | 2014-12-04 | 2015-06-18 | A composition for forming a film having a wrinkle structure and a method of forming the film |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102033747B1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140017454A1 (en) | 2012-07-13 | 2014-01-16 | Massachusetts Institute Of Technology | Thin Films with Micro-Topologies Prepared by Sequential Wrinkling |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100067037A (en) * | 2008-12-10 | 2010-06-18 | 한국전자통신연구원 | Compounds containing crosslinkable moieties, prepolymers, compositions and polymer sheets obtained therefrom, and waveguides for optical interconnection |
| KR20130066271A (en) * | 2011-12-12 | 2013-06-20 | 한국전자통신연구원 | Method of fabricating organic light emitting diode |
| KR101639200B1 (en) * | 2012-07-25 | 2016-07-14 | 한국전자통신연구원 | Chemical compound being used for forming a random wrinkle structure, composition containing the compound, film having the structure, method of forming the film, and OLED comprising the film |
-
2015
- 2015-06-18 KR KR1020150086837A patent/KR102033747B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140017454A1 (en) | 2012-07-13 | 2014-01-16 | Massachusetts Institute Of Technology | Thin Films with Micro-Topologies Prepared by Sequential Wrinkling |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160068634A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6206413B2 (en) | Polymerizable compound, polymerizable composition, polymer, and optical anisotropic body | |
| TWI491982B (en) | Coloring the photosensitive resin composition | |
| US9012127B2 (en) | Thermoreversible network scaffolds and methods of preparing same | |
| CN104995219A (en) | Polymerizable compound, polymerizable composition, polymer, and optically anisotropic body | |
| TW201205642A (en) | Formation method of pattern and fabricating method of pattered substrate | |
| EP2560033A1 (en) | Process for production of liquid crystal element, and liquid crystal element | |
| JPWO2018186503A1 (en) | Anisotropic light absorbing film and laminate | |
| US10472276B2 (en) | Composition for forming film having wrinkle structure and method of forming the film | |
| KR101251778B1 (en) | Novel fluorinated compounds, composition comprising the same and method for preparing of film using the same | |
| Taki et al. | Oxygen concentration and conversion distributions in a layer-by-layer UV-cured film used as a simplified model of a 3D UV inkjet printing system | |
| TW200424292A (en) | Liquid crystal film, optical film comprising the liquid crystal film, and liquid crystal display device equipped with the optical film | |
| KR102033747B1 (en) | A composition for forming a film having a wrinkle structure and a method of forming the film | |
| TWI638214B (en) | Composition for forming alignment film | |
| JP2009271444A (en) | Photosensitive composition | |
| WO2014038260A1 (en) | Process for producing aligned liquid crystal film | |
| JP6071533B2 (en) | Photocurable composition | |
| KR101737668B1 (en) | Method for preparing polarized light splitter and polarized light splitter | |
| TWI786074B (en) | Polymerizable liquid crystal compound, retardation film, polarizing plate and optical display including the retardation film | |
| KR101639200B1 (en) | Chemical compound being used for forming a random wrinkle structure, composition containing the compound, film having the structure, method of forming the film, and OLED comprising the film | |
| WO2015029596A1 (en) | Method for producing polarizing film | |
| Kang et al. | Photopatternable and refractive-index-tunable sol–gel-derived silica–titania nanohybrid materials | |
| Daschiel et al. | Selected polymers that contain aromatic ester units: synthesis, photoreactions, and refractive index modulation | |
| Huh et al. | Synthesis of a photo‐patternable cross‐linked epoxy system containing photodegradable carbonate units for deep UV lithography | |
| Wang et al. | Preparation, photoisomerization, and microfabrication with two‐photon polymerization of crosslinked azo‐polymers | |
| KR101627167B1 (en) | Azide-functionalized polysilsesquioxane, preparation method of the same and high-strength film using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right |