KR101816660B1 - Polyimide film with Self-healing characteristic - Google Patents
Polyimide film with Self-healing characteristic Download PDFInfo
- Publication number
- KR101816660B1 KR101816660B1 KR1020150179795A KR20150179795A KR101816660B1 KR 101816660 B1 KR101816660 B1 KR 101816660B1 KR 1020150179795 A KR1020150179795 A KR 1020150179795A KR 20150179795 A KR20150179795 A KR 20150179795A KR 101816660 B1 KR101816660 B1 KR 101816660B1
- Authority
- KR
- South Korea
- Prior art keywords
- healing
- polyimide film
- self
- solvent
- acid
- Prior art date
Links
Images
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a polyimide film; And a nanocapsule dispersed in the polyimide film, wherein when the self-healing polyimide film is damaged, the nanocapsules of the damaged part are broken and the healing material flows out, and after the healing material fills the damaged part, the viscoelastic material The present invention relates to a self-healing polyimide film. The polyimide film according to the present invention includes a nanocapsule containing a healing substance. The polyimide film has an effect of self-healing when a damage occurs. It can prevent secondary damage or damage propagation, can be used for flexible displays, and can also exhibit performance without self-healing, such as catalyst or light irradiation.
Description
The present invention relates to self-healing polyimide films.
Recently, research and development of various high-tech materials are being carried out due to the growth of high-tech industries. Among these materials, high heat-resistant polymer materials are essential materials for miniaturization, high performance and high reliability of products in accordance with the development of advanced technology, and they are widely used in the fields of space, air, electric / electronic , Automobiles and precision instruments.
On the other hand, the polyimide in the polymer material has excellent mechanical strength, chemical resistance, weather resistance, and heat resistance based on the chemical stability of the imide ring. In addition, it has an advantage that it is easy to synthesize, can form a thin film, and does not require a crosslinking agent for curing. In addition, due to its excellent electrical properties, it is widely regarded as a high-functional polymer material ranging from microelectronics and optical fields. In particular, polyimide films based on polyimide are expected to be used for display in the future.
Conventionally, when such a polyimide film is damaged such as cracks or scratches, there is a problem in that it is costly in the process of repairing or replacing, and the repairing or replacing process is troublesome.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a polyimide film including a nanocapsule containing a healing substance.
According to an embodiment of the present invention, there is provided a polyimide film comprising: a polyimide film; And a nanocapsule dispersed in the polyimide film, wherein when the self-healing polyimide film is damaged, the nanocapsules of the damaged portion are broken and a healing substance flows out, A self-healing polyimide film is provided which is converted into a viscoelastic material.
The self-healing polyimide film according to the present invention includes a nanocapsule containing a healing substance, and has an effect of self-healing when cracks, scratches, or the like are damaged.
Further, the self-healing polyimide film according to the present invention can exhibit performance without any additional conditions such as catalyst or light irradiation in self-healing.
1 shows a schematic structure of a nanocapsule according to the present invention.
FIG. 2 is a schematic view illustrating a process of self-healing by forming a viscoelastic organic gel by flowing a healing material from a damaged nanocapsule when a self-healing polyimide film according to the present invention is damaged.
FIG. 3 illustrates the conversion of the healing material and the healing material into an organic gel having viscoelasticity according to an embodiment of the present invention.
FIG. 4 is a graph showing the results of a self-healing polyimide film according to Example 3 of the present invention after damaging the surface thereof with a razor blade and observing the surface of the resultant with a scanning electron microscope (SEM) It is a SEM photograph showing the result of confirming that healing has occurred.
The present invention relates to a polyimide film; And a nanocapsule dispersed in the polyimide film, wherein when the self-healing polyimide film is damaged, the nanocapsules of the damaged portion are broken and a healing substance flows out, Healing polyimide film which is converted into a viscoelastic material.
The self-healing polyimide film according to the present invention includes nanocapsules containing a healing substance and has an effect of self-healing upon occurrence of damage such as cracks or scratches, and has a performance Can be expressed.
In the meantime, the term self-healing used throughout the specification and claims of the present invention means that when a damage such as cracks or scratches occurs in a polyimide film containing a nanocapsule containing a healing substance, And means to restore the original function of the material by filling the damaged portion.
Hereinafter, the present invention will be described in more detail.
A self-healing polyimide film according to one embodiment for achieving the object of the present invention comprises a polyimide film; And nanocapsules dispersed in the polyimide film. When the self-healing polyimide film is damaged, the nanocapsules of the damaged portion are broken and the healing substance flows out, and the healing substance is converted into the viscoelastic substance after filling the damaged portion.
1 is a cross-sectional view of a nanocapsule according to an embodiment of the present invention. Referring to FIG. 1, a
On the other hand, if the polyimide film is a film produced using polyimide as a main material, the production method thereof is not particularly limited.
In one embodiment of the present invention, the polyimide film may be a polyimide film prepared by stirring a dianhydride monomer and a diamine monomer in a solvent.
In one embodiment of the present invention, the dianhydride may be a dianhydride of formula (1).
≪ Formula 1 >
(R 1 in the formula 1 is the chemical structure:
. ≪ / RTI >
Meanwhile, in one embodiment of the present invention, the diamine may be a dianhydride of the following formula (2).
(2)
(R 2 is the chemical structure of the following in formula (2)
≪ / RTI > X is an integer satisfying 1? X? 50, n is a natural number in the range of 1 to 20, W, X and Y are each an alkyl or aryl group having 1 to 30 carbon atoms, and Z is an ester group , An amide group, an imide group and an ether group.
In the case where the self-healing polyimide film is damaged such as cracks or scratches, the nanocapsules disposed in the damaged portion of the
The healing material according to one embodiment of the present invention includes an organo-gelator, a high boiling solvent, and a low boiling solvent.
The organo-gelator serves to gel the high boiling point solvent after evaporating the low boiling point solvent from the healing material filled with the cracked portion.
In one embodiment of the present invention, the organic gelator is one or more kinds selected from the group consisting of an anthracene derivative, a pyrene derivative, an anthraquinone derivative, a naturally alkane, a steroid compound, a terpenoid compound and a sugar compound It may be a gelator. In particular, as the organic gelator, the n-alkane may have 20 to 40 carbon atoms.
Meanwhile, in the present invention, the high-boiling solvent means a solvent having a boiling point of 200 ° C or higher, and forms a residual organic gel without evaporating the healing substance filled in the cracked portion.
In one embodiment of the present invention, the high boiling point solvent is selected from the group consisting of normal propyl bromide, silicone oil, tol oil, castor oil, linseed oil, isophorone, trimethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Tricresyl phosphate, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, ortho-phenylenediamine, 3-aminopropyltriethoxysilane, isononanoic acid, neodecanoic acid , Cyclohexyl methacrylate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2-aminoethoxyethanol, triethanolamine, glyceryl monostearate, triethylene glycol monobutyl Diethylene glycol diethyl ether, triethylene glycol dimethyl ether, dioctyl maleate, hexamolydine, triclosan, dodecyl succinic anhydride, nicotine, tetraethylene glycol, diethanolamine, hexamethylene diisocyanate, (2-butoxyethyl) phosphate, pentaethylene hexamine, n-butyl diethanolamine, 2-ethylhexyl anthrylamine, 2-ethylhexyl methacrylate, , Cinnamic aldehyde, tributyl phosphate, hexahydrophthalic anhydride, dibutyl tin dilaurate, tributyl amine, triacetin, tri-isobutyl phosphate, tetraethylenepentamine, disodium laureth sulfosuccinate , Diethylene glycol monoethyl ether acetate, dimethyl adipate, propylene carbonate, normal methyl diethanolamine, dimethylaminoethyl methacrylate, mononitrobenzene, isopropyl palmitate, tripropylene glycol methyl ether, furfuryl alcohol, 2- Hydroxyethyl acrylate, isopropyl myristate, phenoxyethanol, oleic acid, caprylic acid, capric acid, Malic acid, citric acid, octylic acid, dodecane, and glycerol.
In the present invention, the low boiling point solvent refers to a solvent having a boiling point of 130 ° C or lower, and serves to evaporate the healing material filled with the cracked portion to form an organic gel.
In one embodiment of the present invention, the low boiling point solvent is selected from the group consisting of methyl ethyl ketone, methyl propyl ketone, cyclohexane, glyoxal, dimethylacetoacetamide, esthazole, ethyl lactate, cyclopentyl methyl ether, butyl lactate, Propylene glycol monomethyl ether, methyl formate, chlorobenzene, octane, toluene, distearyl dimethyl ammonium chloride, dioxane, vinyl pyrrolidone, ethyl acetate, Polybutene, epichlorohydrin, acetone, ethanol, dimethylcarbonate, tridecyl alcohol, dibutyl maleate, thiolactic acid, 1,2-dichloroethane, 1-butanol, 1,3-dioxolane, Acetate, 1,2-dimethoxyethane, piperidine, acrolein, ammonium thioglycolate, acrylonitrile, acetaldehyde, isobutylaldehyde, propylene oxide, Ethylamine, diethylhydroxylamine, aminoethylethanolamine, ethylene dichloride, pyridine, n-propanol, n-hexane, dichlorofluoroethane, dichloropropane, dichloromethane, propargyl alcohol, , 4-trimethylpentane, 1,1,1-trichloroethane, acetic acid, 3-methoxypropylamine, tert-butanol, methyl alcohol, methyl methacrylate, isopropyl alcohol, methanol, At least one solvent selected from the group consisting of methanol, ethanol, methyl cellosolve, trichlorethylene, and tetrachlorethylene.
In the meantime, as the healing substance located in the core portion of the nanocapsule, 0.1 to 5 parts by weight of the organic gelator, 10 to 90 parts by weight of the high boiling solvent and 10 to 90 parts by weight of the low boiling solvent may be included in the healing substance . More specifically, the healing material may include 0.1 to 3 parts by weight of the organogelator, 30 to 70 parts by weight of the high boiling solvent, and 30 to 70 parts by weight of the low boiling point solvent.
When the organic gelator is contained in an amount of less than 0.1 part by weight, gelation may not occur. When the organic gelator is more than 5 parts by weight, gelation may proceed during encapsulation.
On the other hand, when the high-boiling solvent is contained in an amount of less than 10 parts by weight, the amount of the healing material that fills the cracks during the formation of cracks may be too small to self-heal, and gelation may not occur if the solvent contains more than 90 parts by weight There is a problem.
On the other hand, when the low-boiling solvent is contained in an amount of less than 10 parts by weight, gelation may not occur. If the solvent contains more than 90 parts by weight of the low boiling point solvent, the amount of the healing substance is too small to self-heal.
As a result, in the damaged self-healing polyimide film, when the healing material has the above-described kind, composition, and content ratio according to the present invention, in the damaged part of the
Meanwhile, the nanocapsule according to the present invention comprises a polymer capsule membrane S surrounding the core portion C (see FIG. 1). The capsule membrane shields and protects the healing material contained in the core part from the external environment, and is also capable of breaking the healing material when the damage occurs. Therefore, it is preferable that the capsule membrane has proper mechanical properties that can be broken easily when the capsule membrane is damaged while being handled. In addition, the capsule film prevents the internal healing material from leaking out over a long period of time, effectively prevents external moisture or the like from entering the core, and is excellent in thermal stability and adhesion to the matrix material.
In one embodiment of the present invention, the polymer as the material of the encapsulating membrane is a urea-formaldehyde polymer, a polyurethane, a melamine-formaldehyde polymer, a urea-melamine-formaldehyde polymer, silica, a polyurea resin, a polyamide resin, Gelatin, gum arabic, acrylic acid resin, polymethyl methacrylate resin, polyvinyl alcohol resin, and cellulose.
Meanwhile, the thickness of the capsule membrane S of the nanocapsule may be 10 to 500 nm, more specifically 30 to 300 nm. If the thickness of the capsule membrane is within the above range, the capsule membrane is not easily broken during the handling process, and when the capsule membrane is damaged, the capsule membrane can be broken well so that the damaged portion can be effectively healed. Meanwhile, the shape of the nanocapsule 10 described above is not particularly limited, and may be, for example, a spherical shape including a circular shape and an elliptical shape.
Meanwhile, the diameter of the nanocapsules may be 100 nm to 5 μm, more specifically 200 nm to 1 μm. If the diameter of the nanocapsules is within the above range, the healing material can be sufficiently contained, and the dispersion in the polyimide film becomes effective, so that the self-healing effect can be maximized.
Meanwhile, the nanocapsules described above are dispersed in the polyimide film. On the other hand, the content of the nanocapsules contained in the self-healing polyimide film is such that the content of the polyimide May be contained in an amount of 5 to 200% by weight, more specifically 10 to 100% by weight. Wherein the content of the nanocapsules is less than that of the polyimide If it is less than 5% by weight, there is a problem that the damaged portion is not sufficiently cured, If it is more than 200% by weight based on the weight, it may be difficult to formulate and the mechanical properties of the self-healing polyimide film may deteriorate .
In one embodiment of the present invention for producing such a self-healing polyimide film, the method for producing a self-healing polyimide film comprises the steps of: (a) preparing a mixture comprising an organic gelator, a high boiling solvent and a low boiling solvent; (b) nanocapsulating the mixture to prepare a nanocapsule; (c) introducing the polyimide and the nanocapsule into a solvent and dispersing the polyimide uniformly; And (d) filming the polyimide composition; .
On the other hand, the solvent of the step (c) is not particularly limited as long as it can dissolve the polyimide. For example, Amide solvents such as N, N -dimethylformamide, N, N -dimethylacetamide and N -methyl-2-pyrrolidone can be used. These organic solvents are usually used alone, but two or more of them may be suitably used in combination.
As described above, the polyimide film according to the present invention includes a nanocapsule containing a healing substance. The polyimide film according to the present invention has an effect of self-healing upon occurrence of damage such as cracks or scratches, The performance can be expressed without.
Particularly, the polyimide film according to the present invention can prevent secondary damage or damage from being propagated to the viscoelastic organic gel after the healing material is filled in the damaged part at the time of damage, so that the polyimide film is suitable for flexible display applications .
The polyimide film according to an embodiment of the present invention has a yellow index of 5 or less and a light transmittance of 80% or more with respect to light having a wavelength of 450 nm at a thickness of 20 탆.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. It should be understood, however, that the following examples and experimental examples are provided to aid understanding of the present invention and are not intended to limit the scope of the present invention thereto.
Example
Example 1: Preparation of healing material
To 9.95 g of cyclohexane, 0.05 g of hexatriacontain was added to dissolve and dissolved in 9.9 g of silicone oil by adding 0.1 g of hexatriacontaine. The two substances were mixed in a 25 ml vial at a weight ratio of 1: 1 to obtain a composition for a healing material.
The healing material composition was confirmed to be a fluid having a flowability by dropping a drop of the composition on a slide glass and tilting the slide glass (Fig. 3 (a)). On the other hand, the drop of the composition was dropped on a slide glass, left at room temperature for 5 minutes, and then tilted on a slide glass. As a result, it was confirmed that the composition did not flow down and was converted into an organic gel having viscoelasticity (FIG.
Example 2: Nanocapsulation
5 mL of an aqueous 2.5 wt% ethylene-maleic anhydride copolymer solution and 20 mL of distilled water were added to a 100 mL beaker and mixed at 25 ° C. Thereafter, the beaker was placed in a thermostatic chamber and stirred at 300 rpm using a digital mixer.
0.50 g of urea, 0.050 g of ammonium chloride and 0.050 g of resorcinol were dissolved in the beaker. NaOH aqueous solution and HCl aqueous solution were then added to the beaker to adjust the pH of the beaker contents to 3.5. To remove the bubbles in the beaker contents, 2 to 3 drops of 1-octanol as a defoaming agent was added to remove the bubbles.
10 ml of the healing material composition prepared in Example 1 as the core material was slowly added to the beaker and stirred to form an emulsion. An ultrasonic device tip was inserted into the emulsion, and after the ultrasonic wave was applied, the beaker contents were allowed to stand for about 15 minutes in order to stabilize the emulsion. Then, 1.456 g of 37% by weight formaldehyde aqueous solution was added to the beaker so that the molar ratio of formaldehyde to urea was 1: 1.8. Subsequently, the temperature of the beaker contents was slowly raised to 60 ° C. over about 30 minutes, and the mixture was stirred at the temperature. The capsule film formation reaction was performed for a total of 4.5 hours from the start of the temperature rise. Thereafter, the beaker contents were cooled to 25 DEG C, filtered, and washed with water and acetone to obtain capsules. Then, the capsules were lyophilized for 12 hours or longer to obtain nanocapsules.
The nanocapsule may include a core portion containing an organic gelator (hexa tricaine con- tainer), a high boiling point solvent (silicone oil) and a low boiling point solvent (cyclohexane) as a healing material, and a urea- And a capsule membrane containing formaldehyde resin.
Example 3: Preparation and evaluation of a pre-aliphatic self-healing polyimide film
136 mL of dimethylsulfoxide (DMSO) was added to a 500-mL 2-neck round bottom flask substituted with nitrogen gas, and 10.507 g (0.05 mol) of 1,2,3,4-cyclopentane tetracarboxylic dianhydride and 1 , And 5.709 g (0.05 mol) of 4-diaminocyclohexane were added thereto, and the mixture was reacted at 25 ° C for 24 hours to synthesize polyamic acid.
Next, 10.209 g (0.1 mol) of acetic anhydride and 7.91 g (0.1 mol) of pyridine were added to the synthesized polyamic acid solution, and the mixture was refluxed at 160 ° C. for 12 hours, Lt; / RTI > and then re-precipitated with excess ice water. After filtration, the filtrate was washed with 100 mL of water and 100 mL of methanol, followed by vacuum drying to synthesize all aliphatic polyimide.
The nanocapsules prepared in Example 2 were mixed in a weight ratio of 9: 1 to a solution of the synthesized polyimide in N -methyl-2-pyrrolidone (NMP), uniformly dispersed, Stabilized, and then heated in an oven or on a hot plate at 40 DEG C for 6 hours to prepare a polyimide film having all-aliphatic self-healing properties.
On the other hand, the self-healing polyimide film was damaged with a razor blade, and the surface of the polyimide film was observed with a scanning electron microscope (SEM). As a result, it was confirmed that the healing substance flowed to fill the damaged area and self-healing occurred ).
Comparative Example 1: Preparation and evaluation of self-healing polyimide film with different composition of healing material
0.0099 g of hexatriacontain was dissolved in 9.995 g of silicone oil and 0.005 g of hexatriacontain was dissolved in 9.995 g of cyclohexane. The two substances were mixed in a 25 ml vial at a weight ratio of 1: 1 to obtain a composition for a healing material.
The self-healing coating material was prepared and evaluated in the same manner as in Example 2 and Example 3 using the above-mentioned healing material composition. As a result, the healing material composition flowing from the broken capsule at the damaged area did not form an organic gel, I could confirm that it did not happen.
Comparative Example 2: Preparation and evaluation of self-healing polyimide film with different composition of healing material
To 9.95 g of cyclohexane, 0.05 g of hexatriacontain was added to dissolve and dissolved in 9.9 g of silicone oil by adding 0.1 g of hexatriacontaine. These two substances were mixed in a 25 ml vial at a weight ratio of 1: 19 to obtain a composition for a healing material.
The self-healing coating material was prepared and evaluated in the same manner as in Example 2 and Example 3 using the above-mentioned healing material composition. As a result, the healing material composition flowing from the broken capsule at the damaged area did not form an organic gel, I could confirm that it did not happen.
Comparative Example 3: Preparation and evaluation of self-healing polyimide film with different composition of healing material
To 9.95 g of cyclohexane, 0.05 g of hexatriacontain was dissolved and dissolved in 9.9 g of silicone oil by adding 0.1 g of hexatriacontaine. The two substances were mixed in a 25 ml vial at a weight ratio of 19: 1 to obtain a composition for a healing material.
The self-healing coating materials were prepared and evaluated in the same manner as in Example 2 and Example 3 using the above-mentioned healing material composition, and as a result, a large amount of cyclohexane was evaporated from the healing material composition flowing from the broken capsule at the damaged portion It was confirmed that the healing substance did not sufficiently fill the damaged area and self-healing did not occur.
Unit (g)
Unit (g)
Unit (g)
Unit (g)
(Mixture B)
Unit (g)
Unit (g)
Unit (g)
Unit (g)
That is, a healing substance was prepared according to Example 1 of the present invention, a nanocapsule containing the healing substance was prepared according to Example 2, and a self-healing polyimide film containing nanocapsules according to Example 3 As a result of evaluation, when the film was damaged, the healing material in the nanocapsule flowed out to fill the damaged area, and self-healing was observed.
On the other hand, as shown in Table 1, it was confirmed that the self-healing did not occur in the polyimide film in the case of the healing material composition prepared according to Comparative Examples 1 to 3.
10: Nano capsules
20: polyimide film
30: Healing substance
40: Viscoelastic organic gel (organo-gel)
S: capsule membrane C: core part
Claims (13)
When the self-healing polyimide film is damaged, the nanocapsules of the damaged portion are broken and the healing material flows out, the healing material is converted into a viscoelastic material after filling the damaged portion,
Wherein the healing substance comprises an organo-gelator, a high boiling point solvent having a boiling point of 200 DEG C or higher and a low boiling point solvent having a boiling point of 130 DEG C or lower,
Wherein the nanocapsule self-healing material comprises 0.1 to 5 parts by weight of an organic gelator, 10 to 90 parts by weight of a high boiling solvent, and 10 to 90 parts by weight of a low boiling solvent.
Wherein the viscoelastic material is an organo-gel.
0.1 to 3 parts by weight of an organic gelator as a healing material in the nanocapsule, 30 to 70 parts by weight of a high boiling solvent, and 30 to 70 parts by weight of a low boiling solvent.
Wherein the organic gelator is at least one gelator selected from the group consisting of an anthracene derivative, a pyrene derivative, an anthraquinone derivative, a normal alkane having 20 to 40 carbon atoms, a steroid compound, a terpenoid compound and a sugar compound Self-healing polyimide film.
The high boiling point solvent is at least one solvent selected from the group consisting of normal propyl bromide, silicone oil, toole oil, castor oil, linseed oil, isophorone, trimethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Butanediol, 1,2-pentanediol, ortho-phenylenediamine, 3-aminopropyltriethoxysilane, isononanoic acid, neodecanoic acid, Cyclohexyl methacrylate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2-aminoethoxyethanol, triethanolamine, glyceryl monostearate, triethylene glycol monobutyl ether , Triethylene glycol dimethyl ether, dioctyl maleate, hexamolyndine, triclosan, dodecyl succinic anhydride, nicotine, tetraethylene glycol, diethanolamine, hexamethylene diisocyanate, 2- , Acetophenone, butyl carbitol, dipropylene glycol, 2-hydroxyethyl methacrylate, tris (2-butoxyethyl) phosphate, pentaethylene hexamine, n-butyl diethanolamine, But are not limited to, aldehyde, aldehyde, acid, cinnamic aldehyde, tributyl phosphate, hexahydrophthalic anhydride, dibutyl tin dilaurate, tributyl amine, triacetin, triisobutyl phosphate, tetraethylenepentamine, disodium laureth sulfosuccinate Diethylene glycol monoethyl ether acetate, dimethyl adipate, propylene carbonate, n-methyl diethanolamine, dimethylaminoethyl methacrylate, mononitrobenzene, isopropyl palmitate, tripropylene glycol methyl ether, furfuryl alcohol, 2-hydroxyethyl acrylate, isopropyl myristate, phenoxyethanol, oleic acid, caprylic acid, Acid, octylic acid, dodecane and the self-healing glycerol least one solvent selected from the group consisting of a polyimide film.
The low boiling point solvent is a solvent having a boiling point of 130 占 폚 or less and may be a solvent selected from the group consisting of methyl ethyl ketone, methyl propyl ketone, cyclohexane, glyoxal, dimethylacetoacetamide, esthazole, ethyl lactate, cyclopentyl methyl ether, butyl lactate, Propylene glycol monomethyl ether, methyl formate, chlorobenzene, octane, toluene, distearyl dimethyl ammonium chloride, dioxane, vinyl pyrrolidone, ethyl acetate, Polybutene, epichlorohydrin, acetone, ethanol, dimethylcarbonate, tridecyl alcohol, dibutyl maleate, thiolactic acid, 1,2-dichloroethane, 1-butanol, 1,3-dioxolane, Acetate, 1,2-dimethoxyethane, piperidine, acrolein, ammonium thioglycolate, acrylonitrile, acetaldehyde, isobutylaldehyde, propylene oxide , Diethylamine, diethylhydroxylamine, aminoethylethanolamine, ethylene dichloride, pyridine, n-propanol, n-hexane, dichlorofluoroethane, dichloropropane, dichloromethane, propargyl alcohol, 1,4-dioxane 2 , 2,4-trimethylpentane, 1,1,1-trichloroethane, acetic acid, 3-methoxypropylamine, tert-butanol, methyl alcohol, methyl methacrylate, isopropyl alcohol, methanol, - self-healing polyimide film which is at least one solvent selected from the group consisting of pentanone, methylcellosolve, trichlorethylene and tetrachlorethylene.
The polymer as a capsule membrane material of the nanocapsule may be selected from the group consisting of urea-formaldehyde polymer, polyurethane, melamine-formaldehyde polymer, urea-melamine-formaldehyde polymer, silica, polyurea resin, polyamide resin, alginic acid, gelatin, An acrylic acid resin, a polymethyl methacrylate resin, a polyvinyl alcohol resin, and a cellulose.
Wherein the content of the nanocapsules in the polyimide film is 5 to 200% by weight based on the weight of the polyimide.
The self-healing polyimide film has a yellow index of 5 or less and a light transmittance of 80% or more with respect to light having a wavelength of 450 nm at a thickness of 20 탆.
The polyimide film is used for a flexible display.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150179795A KR101816660B1 (en) | 2015-12-16 | 2015-12-16 | Polyimide film with Self-healing characteristic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150179795A KR101816660B1 (en) | 2015-12-16 | 2015-12-16 | Polyimide film with Self-healing characteristic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170071748A KR20170071748A (en) | 2017-06-26 |
| KR101816660B1 true KR101816660B1 (en) | 2018-01-09 |
Family
ID=59282388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150179795A KR101816660B1 (en) | 2015-12-16 | 2015-12-16 | Polyimide film with Self-healing characteristic |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101816660B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200046859A (en) | 2018-10-26 | 2020-05-07 | 한국전기연구원 | Self-healable crosslinked polyimide-urea copolymer and method of manufacturing the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019117330A1 (en) * | 2017-12-12 | 2019-06-20 | 한국생산기술연구원 | Scratch self-healing clearcoat composition for automobiles using charge transfer complex, clearcoat comprising same, and method for producing same |
| CN111534096B (en) * | 2020-06-12 | 2022-09-13 | 湖北洋田塑料制品有限公司 | Self-repairing thermoplastic elastomer sheath material and preparation method thereof |
| CN113717622A (en) * | 2021-10-13 | 2021-11-30 | 深圳市深赛尔股份有限公司 | Asparagus resin-containing water-based self-repairing industrial coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101168038B1 (en) | 2011-12-15 | 2012-07-27 | 한국건설생활환경시험연구원 | Microcapsule, self-healing coating material forming composition, capsule dispersion type self-healing coating material and manufacturing method of the coating material |
| US20120321828A1 (en) | 2011-06-16 | 2012-12-20 | United States Of America As Represented By The Administrator Of The National Aeronautics And Spac | Self-Healing Polymer Materials for Wire Insulation, Polyimides, Flat Surfaces, and Inflatable Structures |
-
2015
- 2015-12-16 KR KR1020150179795A patent/KR101816660B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120321828A1 (en) | 2011-06-16 | 2012-12-20 | United States Of America As Represented By The Administrator Of The National Aeronautics And Spac | Self-Healing Polymer Materials for Wire Insulation, Polyimides, Flat Surfaces, and Inflatable Structures |
| KR101168038B1 (en) | 2011-12-15 | 2012-07-27 | 한국건설생활환경시험연구원 | Microcapsule, self-healing coating material forming composition, capsule dispersion type self-healing coating material and manufacturing method of the coating material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200046859A (en) | 2018-10-26 | 2020-05-07 | 한국전기연구원 | Self-healable crosslinked polyimide-urea copolymer and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170071748A (en) | 2017-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101816660B1 (en) | Polyimide film with Self-healing characteristic | |
| KR101780451B1 (en) | Self-healing coating formulation, and Self-healing coating material using the same | |
| Liu et al. | Glycerol induced catalyst‐free curing of epoxy and vitrimer preparation | |
| JP6489494B2 (en) | Aluminum chelate-based latent curing agent, method for producing the same, and thermosetting epoxy resin composition | |
| JP5707662B2 (en) | Thermosetting epoxy resin composition | |
| TWI709586B (en) | Manufacturing method of aluminum chelate latent hardener and thermosetting epoxy resin composition | |
| EP3134456B1 (en) | Use of a composition of a vitrimer-type thermosetting resin for the production of electrical insulating parts | |
| JP5374343B2 (en) | Core-shell particle and method for producing core-shell particle | |
| CN101362836B (en) | Method for preparing microencapsulated ammonium polyphosphate | |
| Liang et al. | Microcrack self‐healing capability of waterborne polyurethane/polyacrylate composites with dynamic disulfide bond | |
| FR2789070A1 (en) | Composition useful for making silica glass by a sol-gel process, e.g. an optical fiber overcladding, comprises silica, a binder polymer obtained from an aqueous premix of N-methylol(meth)acrylamide and a crosslinker, and a solvent | |
| TWI676631B (en) | Aluminum chelate latent curing agent and preparation method thereof | |
| CN109096472A (en) | A kind of application of novel P-N-Si cooperative resistance combustion epoxy curing agent in epoxy-resin systems | |
| KR20190017818A (en) | A latent curing agent, a preparation method thereof, and a thermosetting epoxy resin composition | |
| JP2008156570A (en) | Method of manufacturing latent hardening agent particle, method of manufacturing adhesive, and method of manufacturing adhesive film | |
| US7935738B2 (en) | Transparent flexible film and fabrication method thereof | |
| JP5354192B2 (en) | Thermosetting conductive paste composition | |
| KR102164845B1 (en) | Polyhedral Oligomeric Silsesquioxane Having Epoxy Functional Group and Method Of Manufacturing | |
| EP3906278A1 (en) | Electrical insulation material and manufacturing process | |
| KR20230078387A (en) | Method for producing latent curing agent for epoxy resin, latent curing agent for epoxy resin obtained by the method | |
| EP2817361B1 (en) | Process for in-situ synthesis of silica nanoparticules | |
| Ni et al. | Self-Repairing Mechanism of MUF/Epoxy Microcapsules for Epoxy Material | |
| CN110305117B (en) | Preparation method of completely water-soluble epoxy resin | |
| JPH0786465A (en) | Epoxy resin composition for sealing semiconductor | |
| KR101390155B1 (en) | Acetal epoxy resin composition for low temperature and method for manufacturing thereof |
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 | ||
| GRNT | Written decision to grant |