KR102119009B1 - Method of preparing the stretchable substrate and method of preparing the flexible electronic device comprising the same - Google Patents

Abstract

The present invention comprises the steps of: (a) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate; (b) a first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution Forming a second portion comprising; And (c) curing the first portion and the second portion to produce a stretchable substrate including a first cured polymer portion and a second cured polymer portion on the substrate. . In the present invention, when a stretchable substrate including a hard pattern portion formed by curing the substrate is inserted by inserting a curing agent into a specific region of a polymer solution to form a stretchable substrate, separation between the substrate and the device does not occur even after repeated stretching. The efficiency of the device can be maintained. In addition, the flexible substrate can be applied to various flexible electronic devices.

Description

Manufacturing method of stretchable substrate and manufacturing method of stretchable electronic device including the same{METHOD OF PREPARING THE STRETCHABLE SUBSTRATE AND METHOD OF PREPARING THE FLEXIBLE ELECTRONIC DEVICE COMPRISING THE SAME}

The present invention relates to a method of manufacturing a stretchable substrate and a method of manufacturing a stretchable electronic device comprising the same, and more specifically, by inserting a curing agent in a specific region of a polymer solution to form a stretchable substrate, the substrate is cured to be hardly formed. It relates to a method of manufacturing a stretchable substrate including a pattern portion and a method of manufacturing a stretchable electronic device comprising the same.

Stretchable electronic devices are devices that can maintain their function even under new construction, and have been spotlighted as a promising solution to resolve mechanical mismatch between existing rigid electronic devices and soft curved systems. In order to develop stretchable electronic devices, intensive research has been conducted from academia and industry to develop new materials that are mechanically durable, deformable conductors and circuits, new processing methods, and elastic materials for stretchable substrates. have. Among them, the stretchable substrate constitutes an element that withstands the applied strain, thereby giving the device elasticity, thereby giving important properties to the overall performance of the stretchable electronic device.

To date, studies have used silicon-based elastomers as a stretchable substrate material to implement stretchable devices. However, since substrates made of existing elastomeric materials have a problem of being separated from each other due to imbalance of mechanical properties between the rigid element portion and the soft substrate portion in the element fabrication process, it is essential to develop a technique for manufacturing a new flexible substrate. . In addition, since the process using the existing substrate material is complicated and requires a multi-step process, the development of manufacturing technology through a simple and short process is required for commercialization of stretchable electronic devices.

An object of the present invention is to solve the above problems, and by inserting a curing agent into a specific region of a polymer solution to form a stretchable substrate, to provide a method for manufacturing a stretchable substrate including a hardly formed pattern portion by curing the substrate. have.

In addition, it is to provide a method for manufacturing a stretchable electronic device in which the performance of the device is maintained because separation between the substrate and the device does not occur even after the stretchable substrate is repeatedly stretched.

Also, by using a cover during curing, there is no difference in height between a portion of the boundary between the stretchable region and the non-stretchable region, thereby providing a stretchable substrate having high flatness.

According to an aspect of the present invention, (a) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate; (b) a first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution Forming a second portion comprising; And (c) curing the first portion and the second portion to produce a stretchable substrate including a first cured polymer portion and a second cured polymer portion on the substrate. .

The first curing agent and the second curing agent may be controlled to control the elastic modulus of the first curing polymer part and the second curing polymer part by adjusting the input amounts of the first curing agent and the second curing agent, respectively.

The injection of the second curing agent may be performed by one or more methods selected from a scanning probe method, an inkjet printing method, an imprinting method, a 3D printing method, a slot-die coating method, and a spray coating method.

The second curing agent may be introduced at 50 to 500 μm intervals to the predetermined portion.

(B') between the steps (b) and (c), placing the cover on the first part and the second part so as to abut the surface of some or all of the first part and the second part; It can contain as.

The cover may include at least one selected from the group consisting of glass, polymer, metal, ceramic and mixtures thereof.

The crosslinking density of the second cured polymer portion may be greater than the crosslinking density of the first cured polymer portion.

The modulus of the second cured polymer portion may be greater than the modulus of the first cured polymer portion.

The elastic modulus (Ms) of the first cured polymer portion may be 0.8 to 3.0 MPa, and the elastic modulus (Mp) of the second cured polymer portion may be 15 to 110 Mpa.

The ratio (Mp/Ms) of the elastic modulus (Mp) of the second cured polymer portion to the elastic modulus (Ms) of the first cured polymer portion may be 5.0 to 137.5.

When stretching the stretchable substrate, the ratio of the strain of the second cured polymer portion to the strain of the first cured polymer portion may be 0 to 1%.

The substrate may include any one selected from glass, ceramic, and polymer.

The oligomer includes a functional group covalently bonded to the main chain and the main chain, and the functional group includes at least one selected from a vinyl group, an epoxy group, an isocyanate group, a hydroxyl group, a thiol group, and a carboxyl group, and the main chain is silicone, Polydimethylsiloxane, polytetrafluoroethylene, polyurethane, polystyrene, polyacrylate, polyarylate, polyester, polyethylene, polypropylene, polycarbonate, polyimide, polyamide, acrylic resin, epoxy resin, amino It may include one or more selected from resins and phenolic resins, and the oligomer may be a plurality of functional groups covalently attached to the main chain.

The first curing agent and the second curing agent may be the same or different from each other, each independently orthosilicic acid, tetravinylsilane, Si(OH) _n (OR) _{4 -n} (n is an integer from 1 to 4, R is a C1-C10 alkyl group ), 3-(Triethoxysilyl)propyl isocyanate, Bis(2-methacryloyl)oxyethyl disulfide, 1,4-Bis(4-vinylphenoxy)butane, Divinylbenzene, p-Divinylbenzene, Glycerol ethoxylate, Glycerol ethoxylate-co-propoxylate triol, Hexa( ethylene glycol) dithiol, 2-[8-(3-Hexyl-2,6-dioctylcyclohexyl)octyl]pyromellitic diimide oligomer(maleimide terminated), 2-[8-(3-Hexyl-2,6-dioctylcyclohexyl)octyl]pyromellitic diimide oligomer (maleimide terminated), 11-Maleimidoundecanoic acid, Pentaerythritol ethoxylate, Pentaerythritol ethoxylate, Pentaerythritol propoxylate, 1,4-Phenylenediacryloyl chloride, Poly(ethylene glycol) bisazide, Ethylene glycol diacrylate, Poly(ethylene glycol) diacrylate, 2,4, 6,8-Tetramethyl-2,4,6,8-tetrakis(propyl glycidyl ether)cyclotetrasiloxane, 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione, Di(ethylene glycol) diacrylate, Ethylene glycol dimethacrylate, Di( ethylene glycol) dimethacrylate, Triethylene glycol dimethacrylate, Tetra(ethylene glycol) diacrylate, monomethyl ether hydroquinone, Trimethylolpropane ethoxylate, Trimethylolpropane ethoxylate, Trimethylolpropane ethoxylate, 4-Vinylbenzocyclobutene, 3-Aminophenyl sulfone, 4-Aminophenyl sulfone, 5-Amino-1,3 ,3-trimethylcyclohexanemethylamine, 1,2,4-Benzenetricarboxylic anhydride, Bisphenol A acetate propionate technical grade, Bisphenol A diglycidyl ether, Bisphenol A propoxylate diglycidyl ether, Bisphenol F, Castor oil glycidyl ether, 1,2-Cyclohexanedicarboxylic anhydride, 2,2 ′-Diallyl bisphenol A diacetate 1,4,5,6,7,7-Hexachloro-5-norbornene-2,3-dicarboxylic anhydride, 6-Maleimidohexanoic acid,cis-1,2,3,6-Tetrahydrophthalic anhydride, Trimethylolpropane triglycidyl ether, Trimethylolpropane tris[poly(propylene glycol), N,N′-Methylenebisacrylamide, N,N′-Methylenebisacrylamide, N,N′-(1,2-Dihydroxyethylene)bisacrylamide, N-(1-Hydroxy-2,2 -dimethoxyethyl)acrylamide, 1,4-Cyclohexanedimetha nol divinyl ether, N,N′-(1,2-Dihydroxyethylene)bisacrylamide, 1,6-Hexanediol diacrylate, 4,4′-Methylenebis(cyclohexyl isocyanate), Poly(ethylene glycol) dimethacrylate, Tetraethylene glycol dimethyl ether, Bromoacetic acid N-hydroxysuccinimide 3-Maleimidobenzoic acid N-hydroxysuccinimide 4-(N-Maleimidomethyl)cyclohexanecarboxylic acid N-hydroxysuccinimide 3-(2-Pyridyldithio)propionic acid N-hydroxysuccinimide Dimethyl pimelimidate dihydrochloride, 3,3′-Dithiodipropionic acid ester), and Suberic acid bis (3-sulfo-N-hydroxysuccinimide ester).

The first curing agent and the second curing agent may be the same as or different from each other, and each independently may be a compound represented by Structural Formula 1.

[Structural Formula 1]

In the structural formula 1,

A is a carbon atom or a silicon atom,

R ¹ to R ⁴ may be the same or different from each other, and each independently a hydrogen atom, a hydroxyl group, a vinyl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, an epoxy group, or a glycidyl group,

R ¹ to R ⁴ are not hydrogen atoms at the same time.

R ¹ to R ⁴ may be the same or different from each other, and each independently a hydrogen atom, a hydroxyl group, a vinyl group, a C1-C10 alkyl group, or a C1-C10 alkoxy group.

After step (c), the step (d) of separating the stretchable substrate from the substrate may be further included.

According to another aspect of the invention, (1) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate; (2) A first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution. Forming a second portion comprising; (3) curing the first portion and the second portion to produce a stretchable substrate comprising a first cured polymer portion and a second cured polymer portion on the substrate; And (4) positioning an electronic device or an electrode on the second cured polymer part. A method of manufacturing a stretchable electronic device is provided.

The method for manufacturing the stretchable electronic device may further include a step (3') of placing an adhesive layer on the second cured polymer portion between steps (3) and (4).

The electronic device may include at least one selected from a thin film transistor, a solar cell, an organic light emitting diode, and a display.

In the method of manufacturing the stretchable substrate of the present invention, when a stretchable substrate including a hardly formed pattern portion is cured by inserting a curing agent into a specific region of a polymer solution to form a stretchable substrate, separation between the substrate and the device occurs There is an effect that does not.

In addition, the method of manufacturing a stretchable electronic device including the method of manufacturing the stretchable substrate has an effect that the performance of the device is maintained even after repeated stretching.

In addition, the method of manufacturing the stretchable substrate has an effect that the stretchable substrate has a high flatness because there is no difference in height between the boundary between the stretchable region and the non-stretchable region by using a cover during curing.

1 is a flow chart for explaining a method of manufacturing a stretchable substrate according to the present invention.
2A and 2B are structural views of the stretchable substrate according to Example 2 and Example 1.
3 is a view for explaining a change in the elastic modulus depending on the position in the stretchable substrate according to the first embodiment.
4 is a graph comparing the durability of the stretchable substrate prepared according to Example 1 and Comparative Example 4.
5 is a view showing strain rates of stretchable and non-stretchable regions in the stretchable substrate according to the first embodiment.
6 is a stress-strain curve of a stretchable substrate according to thickness.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted. .

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, or combination thereof described in the specification exists, or that one or more other features or It should be understood that the existence or addition possibilities of numbers, steps, actions, elements, or combinations thereof are not excluded in advance.

Also, when a component is referred to as being “formed” or “stacked” on another component, it may be formed or stacked directly attached to the front or one side of the surface of the other component, but may be intermediate. It should be understood that there may be other components in the.

1 is a flow chart for explaining a method of manufacturing a stretchable substrate according to the present invention.

Hereinafter, a method for manufacturing the stretchable substrate of the present invention will be described in detail with reference to FIG. 1. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of claims to be described later.

The present invention comprises the steps of: (a) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate; (b) a first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution Forming a second portion comprising; And (c) curing the first portion and the second portion to produce a stretchable substrate including a first cured polymer portion and a second cured polymer portion on the substrate. .

The first curing agent and the second curing agent may be controlled to control the elastic modulus of the first curing polymer part and the second curing polymer part by adjusting the input amounts of the first curing agent and the second curing agent, respectively.

The injection of the second curing agent may be performed by one or more methods selected from a scanning probe method, an inkjet printing method, an imprinting method, a 3D printing method, a slot-die coating method, and a spray coating method.

The second curing agent may be introduced at 50 to 500 μm intervals to the predetermined portion.

(B') between the steps (b) and (c), placing the cover on the first part and the second part so as to abut the surface of some or all of the first part and the second part; It can contain as.

The cover may include at least one selected from the group consisting of glass, polymer, metal, ceramic and mixtures thereof.

The crosslinking density of the second cured polymer portion may be greater than the crosslinking density of the first cured polymer portion.

The modulus of the second cured polymer portion may be greater than the modulus of the first cured polymer portion.

The elastic modulus (Ms) of the first cured polymer part may be 0.8 to 3.0 MPa, and the elastic modulus (Mp) of the second cured polymer part may be 15 to 110 MPa.

The ratio (Mp/Ms) of the elastic modulus (Mp) of the second cured polymer portion to the elastic modulus (Ms) of the first cured polymer portion may be 5.0 to 137.5.

When stretching the stretchable substrate, the ratio of the strain of the second cured polymer portion to the strain of the first cured polymer portion may be 0 to 1%.

The substrate may include any one selected from glass, ceramic, and polymer.

The oligomer includes a functional group covalently bonded to the main chain and the main chain, and the functional group includes at least one selected from a vinyl group, an epoxy group, an isocyanate group, a hydroxyl group, a thiol group, and a carboxyl group, and the main chain is silicone, Polydimethylsiloxane, polytetrafluoroethylene, polyurethane, polystyrene, polyacrylate, polyarylate, polyester, polyethylene, polypropylene, polycarbonate, polyimide, polyamide, acrylic resin, epoxy resin, amino It may include one or more selected from resins and phenolic resins, and the oligomer may be a covalent bond of a plurality of the functional groups to the main chain.

Here, the oligomer is an oligomer and has a molecular weight of 200 to 10,000 or less. The oligomer is not a dendritic material such as a polymer compound having a high degree of polymerization, and can be distilled and separated and can be present as a solution like ordinary organic materials. In addition, one or several types of atoms or atomic groups (structural units) are molecules formed by repeatedly connecting dozens to dozens of each other, and their physical properties may change according to the increase or decrease of 1 to several structural units.

The first curing agent and the second curing agent may be the same or different from each other, each independently orthosilicic acid, tetravinylsilane, Si(OH) _n (OR) _{4 -n} (n is an integer from 1 to 4, R is a C1-C10 alkyl group ), 3-(Triethoxysilyl)propyl isocyanate, Bis(2-methacryloyl)oxyethyl disulfide, 1,4-Bis(4-vinylphenoxy)butane, Divinylbenzene, p-Divinylbenzene, Glycerol ethoxylate, Glycerol ethoxylate-co-propoxylate triol, Hexa( ethylene glycol) dithiol, 2-[8-(3-Hexyl-2,6-dioctylcyclohexyl)octyl]pyromellitic diimide oligomer(maleimide terminated), 2-[8-(3-Hexyl-2,6-dioctylcyclohexyl)octyl]pyromellitic diimide oligomer (maleimide terminated), 11-Maleimidoundecanoic acid, Pentaerythritol ethoxylate, Pentaerythritol ethoxylate, Pentaerythritol propoxylate, 1,4-Phenylenediacryloyl chloride, Poly(ethylene glycol) bisazide, Ethylene glycol diacrylate, Poly(ethylene glycol) diacrylate, 2,4, 6,8-Tetramethyl-2,4,6,8-tetrakis(propyl glycidyl ether)cyclotetrasiloxane, 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione, Di(ethylene glycol) diacrylate, Ethylene glycol dimethacrylate, Di( ethylene glycol) dimethacrylate, Triethylene glycol dimethacrylate, Tetra(ethylene glycol) diacrylate, monomethyl ether hydroquinone, Trimethylolpropane ethoxylate, Trimethylolpropane ethoxylate, Trimethylolpropane ethoxylate, 4-Vinylbenzocyclobutene, 3-Aminophenyl sulfone, 4-Aminophenyl sulfone, 5-Amino-1,3 ,3-trimethylcyclohexanemethylamine, 1,2,4-Benzenetricarboxylic anhydride, Bisphenol A acetate propionate technical grade, Bisphenol A diglycidyl ether, Bisphenol A propoxylate diglycidyl ether, Bisphenol F, Castor oil glycidyl ether, 1,2-Cyclohexanedicarboxylic anhydride, 2,2 ′-Diallyl bisphenol A diacetate 1,4,5,6,7,7-Hexachloro-5-norbornene-2,3-dicarboxylic anhydride, 6-Maleimidohexanoic acid,cis-1,2,3,6-Tetrahydrophthalic anhydride, Trimethylolpropane triglycidyl ether, Trimethylolpropane tris[poly(propylene glycol), N,N′-Methylenebisacrylamide, N,N′-Methylenebisacrylamide, N,N′-(1,2-Dihydroxyethylene)bisacrylamide, N-(1-Hydroxy-2,2 -dimethoxyethyl)acrylamide, 1,4-Cyclohexanedimetha nol divinyl ether, N,N′-(1,2-Dihydroxyethylene)bisacrylamide, 1,6-Hexanediol diacrylate, 4,4′-Methylenebis(cyclohexyl isocyanate), Poly(ethylene glycol) dimethacrylate, Tetraethylene glycol dimethyl ether, Bromoacetic acid N-hydroxysuccinimide ester, 3-Maleimidobenzoic acid N-hydroxysuccinimide ester, 4-(N-Maleimidomethyl)cyclohexanecarboxylic acid N-hydroxysuccinimide ester, 3-(2-Pyridyldithio)propionic acid N-hydroxysuccinimide ester, Dimethyl pimelimidate dihydrochloride, 3,3′ -Dithiodipropionic acid ester), and Suberic acid bis (3-sulfo-N-hydroxysuccinimide ester).

The first curing agent and the second curing agent may be the same as or different from each other, and each independently may be a compound represented by Structural Formula 1.

[Structural Formula 1]

In the structural formula 1,

A is a carbon atom or a silicon atom,

R ¹ to R ⁴ may be the same or different from each other, and each independently a hydrogen atom, a hydroxyl group, a vinyl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, an epoxy group, or a glycidyl group,

R ¹ to R ⁴ are not hydrogen atoms at the same time.

R ¹ to R ⁴ may be the same or different from each other, and each independently a hydrogen atom, a hydroxyl group, a vinyl group, a C1-C10 alkyl group, or a C1-C10 alkoxy group.

After step (c), the step (d) of separating the stretchable substrate from the substrate may be further included.

According to another aspect of the invention, (1) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate; (2) A first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution. Forming a second portion comprising; (3) curing the first portion and the second portion to produce a stretchable substrate comprising a first cured polymer portion and a second cured polymer portion on the substrate; And (4) positioning an electronic device or an electrode on the second cured polymer part. A method of manufacturing a stretchable electronic device is provided.

The method for manufacturing the stretchable electronic device may further include a step (3') of placing an adhesive layer on the second cured polymer portion between steps (3) and (4).

The electronic device may include at least one selected from a thin film transistor, a solar cell, an organic light emitting diode, and a display.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes, and the scope of the present invention is not limited thereby.

Example 1: Stretchable substrate 1 prepared through a curing agent injection method

In this embodiment, a silicone rubber PDMS (Sylgard184, Dow corning) was used to construct a stretchable substrate, which was initially composed of two solutions. The first solution is a basic PDMS oligomer consisting of a small amount of an organo-platinum catalyst dissolved in a silicone resin having a vinyl function, that is, a Karstedt catalyst, and the second solution has a PDMS polymer having a vinyl function at the end and a trimethylsiloxy function end as a curing agent. It is composed of poly(methylhydrosiloxane) polymer. When the two solutions are mixed with each other, in the presence of a platinum catalyst, hydrogen of the vinyl functional group and hydrosilane is crosslinked through a hydrogenation reaction to form a stretchable substrate.

The two solutions were mixed at a weight ratio of 20:1 and stirred for 5 minutes to mix thoroughly. Then, after vacuuming for 5 minutes to remove air bubbles in the PDMS mixed solution, the mixed solution was poured at a constant rate on a flat plastic or glass container. After the PDMS mixed solution was completely spread on the container surface, orthosilicic acid solution as an additional curing agent was precisely injected into a circular shape using a scanning probe in an area corresponding to 20% to 30% of the total substrate area before curing. The orthosilicic acid used as the additional curing agent may undergo a hydrosilylation reaction with the PDMS polymer main chain to induce higher density crosslinking, thereby forming a non-stretchable region (hard) in the stretchable substrate. Thereafter, in order to control the height difference between the boundary between the soft region and the soft region (hard), the mixture solution layer was covered with a flat plastic or glass container and cured in an oven at 70° C. for 2 hours. Thereafter, the entire stretchable substrate layer was separated from the two containers located at the top (the container covering the mixed solution layer) and the bottom (the container where the mixed solution was poured) to produce a stretchable substrate having a hard pattern portion (non-stretched area).

Example 2: Stretchable substrate 2 prepared through curing agent injection method

It was prepared in the same manner as in Example 1, except that instead of covering and curing the mixed solution layer with a flat plastic or glass container in Example 1, without curing the mixed solution layer with a flat plastic or glass container.

Comparative Example 1: PDMS substrate using Sylgard 184

PDMS, which is a silicone rubber, was used to fabricate a stretchable substrate used as a comparative example, and it is composed of the same solution as the two solutions used in Example 1.

The two solutions were mixed at a weight ratio of 20:1 and stirred for 5 minutes to mix thoroughly. Then, after vacuuming for 5 minutes to remove air bubbles in the PDMS mixed solution, the mixed solution was poured at a constant rate on a flat plastic or glass container. After the PDMS mixed solution was completely spread on the surface of the container, it was cured in an oven at 70° C. for 2 hours. Thereafter, the formed transparent film layer was removed from the container to produce a stretchable substrate.

Comparative Example 2: Silicon rubber substrate using Ecoflex 00-30

As a silicone rubber through platinum catalytic reaction, Ecoflex 00-30 (Smooth-On) is composed of two liquids: 1A (containing silicone resin and platinum catalyst) and 1B (curing agent). Mix and stir for 5 minutes to mix thoroughly. It was then vacuumed for 5 minutes to remove air bubbles in the mixed solution. The mixed solution was then poured on a flat plastic or glass container at a constant rate. After the mixture solution was completely spread on the surface of the container, it was cured in an oven at 70° C. for 2 hours. Thereafter, the formed translucent film layer was removed to produce a stretchable substrate.

Comparative example 3: Polystyrene-block- poly (ethylene-ran- butylene )-block-polystyrene (SEBS) substrate Tuftec H1062

SEBS is an elastic block copolymer. Tuftec H1062 has a poly(ethylene-co-butylene) volume fraction of 82%, and a pellet-type product is dissolved in toluene at a concentration of 200mg/ml to produce a substrate. . The SEBS solution was then poured on a plastic container at a constant rate. After the mixture solution was completely spread on the surface of the container, it was stored in an oven at 70° C. for 2 hours to evaporate the toluene solvent. Thereafter, the formed transparent film layer was removed to produce a stretchable substrate.

Comparative Example 4: Stretchable substrate prepared by injecting a curing agent after complete curing of PDMS

In Example 1, instead of injecting the orthosilicic acid solution as an additional curing agent before curing after the PDMS mixed solution was completely spread on the container surface, the PDMS mixed solution was completely spread on the container surface and completely cured orthosilicic acid solution as an additional curing agent It was prepared in the same manner as in Example 1, except that 20% to 30% of the substrate area was injected into a circular shape using a scanning probe.

[Test Example]

Test Example 1: Comparison of the hardness of the stretchable substrate

Table 1 shows the hardness test results obtained by measuring and comparing the hardness of the hard pattern portion (non-stretch region) and the hardness of the stretchable substrate prepared according to Comparative Examples 1 to 3 in the stretchable substrate prepared according to Example 1. Hardness was measured through Shore durometer type A, which is mainly used to measure the hardness of polymers or elastomers. When a load is applied to a specific part of the sample surface with the indentor of the Durometer device, the hardness value of the sample can be obtained by estimating according to the depth of the indentation. In addition, this value can be converted into an elastic modulus value and compared.

Board Shore Hardness Modulus Example 1 98 109.9 Comparative Example 1 41 1.8 Comparative Example 2 22 0.8 Comparative Example 3 57 3.2

Referring to Table 1, in the stretchable substrate prepared according to Example 1, the elastic modulus of the pattern portion was the highest at 109.9 MPa, and the elastic modulus of the stretchable substrate prepared according to Comparative Example 2 was the lowest at 0.8 MPa. Therefore, it was found that the hardness of the hard pattern portion formed by injecting the curing agent into a specific region of the stretchable substrate increased by 5 to 137.5 times than the hardness of the expansion region where the curing agent was not injected.

Test Example 2: Comparison of the overall elongation of the stretchable substrate

Table 2 shows the results of comparing the overall elongation of the stretchable substrates prepared according to Example 1 and Comparative Examples 1 to 3.

Board Elongation at break (%) Example 1 70 Comparative Example 1 142 Comparative Example 2 680 Comparative Example 3 420

Referring to Table 2, it was found that the additional elongation proceeded in part because the overall elongation of the stretchable substrate on which the hard pattern portion (non-stretched region) was formed by inserting a curing agent was decreased.

Test Example 3: Adjusting the height difference between the stretched and non-stretched areas of the stretchable substrate

2A and 2B are structural views of the stretchable substrate according to Example 2 and Example 1.

2A and 2B, the structure of Example 2 (FIG. 2A) fabricated without covering with a container and Example 1 (FIG. 2B) fabricated with a container in a process of manufacturing a stretchable substrate having a non-stretchable region is compared. As a result, it can be seen that Example 2 produced without covering with a container has a difference in height between the boundary between the stretched region and the non-stretched region, and Example 1 produced by covering with a container has a flat substrate formed without a difference in height between the boundary between the two regions. .

This indicates that the substrate may be formed differently according to the manufacturing process of the substrate, and the substrate having no difference in height between the two regions can be easily connected to other hard devices because it is applied to the stretchable electronic device and may occur when driving the device. It seems to reduce defects.

Test Example 4: Elastic modulus change according to the position on the stretchable substrate

In order to compare the elastic modulus according to the position of the stretched region and the non-stretched region in the stretchable substrate prepared according to Example 1, the hardness was measured and the elasticity was measured while moving the measurement region of the substrate sample through the durometer instrument used in Test Example 1 It was converted into a coefficient value. 3 is a view for explaining a change in the elastic modulus depending on the position in the stretchable substrate according to the first embodiment.

Referring to FIG. 3, in the stretchable substrate manufactured according to Example 1, the elastic region shows a low elastic modulus, whereas the elastic modulus increases rapidly from the portion where the non-stretch region is formed, so that the two regions having the elastic modulus of a large difference It was found that it was formed in one substrate.

Test Example 5: Durability test of stretchable substrate

4 is a graph comparing the durability of the stretchable substrate prepared according to Example 1 and Comparative Example 4. Under the strains of 20%, 30%, 40%, 50%, and 60%, respectively, compared to the initial length of the substrate sample through an automatic stretching and repeating apparatus having the stretched substrate prepared according to Example 1 and the substrate prepared according to Comparative Example 4 It is an experiment comparing the durability of the non-stretch region of each stretchable substrate after applying a repetition stretch cycle.

Referring to FIG. 4, a stretchable substrate including a non-stretchable region prepared by injecting an additional curing agent prior to PDMS curing according to Example 1 under various stretching conditions is prepared by completely curing PDMS according to Comparative Example 4 and then injecting an additional curing agent It was confirmed that the durability against cracks occurring in the non-stretch region is better than the stretchable substrate including the non-stretch region. It appears that the stretchable substrate prepared according to Example 1 exhibits high stretch durability and is more suitable for application to stretchable electronic devices.

Test Example 6: Comparison of the strain rate of the soft and hard parts of the stretchable substrate

5 is a view showing the strain rate of the stretchable region and the hard region in the stretchable substrate according to the first embodiment. In FIG. 6, the soft part is the strain measured in the stretch region of the stretchable substrate according to Example 1, and the hard part is the strain measured in the non-stretch region.

Referring to FIG. 5, it is possible to know the strain rate generated in the stretched and non-stretched regions according to the deformation applied from the outside. It can be seen that as the strain applied from the outside increases, the strain generated in the stretch region continues to increase, but the strain generated in the non-stretch region has little change. That is, since the non-stretchable region of the stretchable substrate according to Example 1 is made of a non-stretchable material, deformation hardly occurs because the mechanical strength is greater than that of the stretchable substrate according to Example 1.

Test Example 8: Comparison of physical property change according to the thickness of the stretchable substrate

6 is a graph comparing the physical properties of the stretchable substrate prepared by varying the thickness by the method according to Example 1. Table 3 below shows the elongation and modulus values according to the thickness.

Substrate thickness (um) Elongation (%) Modulus (MPa) 100 35 0.21 200 44 0.28 300 52 0.39 400 59 0.66 500 63 0.82 600 70 1.12 700 73 1.2 800 82 1.42 900 88 1.62 1000 93 1.78

Referring to FIG. 6 and Table 3, as the thickness of the stretchable substrate increased from 100 um to 1000 um, the elongation modulus continued to increase. Therefore, the elongation modulus was adjusted according to the thickness to have desired properties. It seems that a flexible hybrid substrate can be produced.

Test example 9: Comparison of stretch properties according to the increase in the proportion of additional curing agent in the stretchable substrate

Table 4 shows the results of comparing the elastic properties by varying the proportions of the additional curing agent by the method according to Example 1.

Ratio of total substrate area of additional curing agent (vol%) Elongation (%) Modulus (MPa) 20 76 0.78 22 74 0.88 24 73 1.00 26 73 1.10 28 72 1.42 30 72 1.66

According to Table 4, as the proportion of the total substrate area of the additional curing agent increases, it can be seen that the modulus continues to increase and the elongation does not change significantly. Therefore, it seems that it is possible to manufacture a stretchable hybrid substrate having a desired modulus by adjusting the ratio of the total substrate area of the additional curing agent as described above.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and it should be interpreted that all changes or modified forms derived from the meaning and scope of the claims and equivalent concepts thereof are included in the scope of the present invention. do.

Claims (20)

(a) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate;
(b) a first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution Forming a second portion comprising;
(b') placing a cover on the first portion and the second portion so as to abut some or all surfaces of the first portion and the second portion; And
(c) curing the first portion and the second portion to produce a stretchable substrate comprising a first cured polymer portion and a second cured polymer portion on the substrate;
Method for manufacturing a stretchable substrate containing. According to claim 1,
Method of manufacturing a stretchable substrate, characterized in that to control the elastic modulus of the first cured polymer portion and the second cured polymer portion by adjusting the input amount of the first curing agent and the second curing agent, respectively. According to claim 1,
Method for manufacturing a stretchable substrate, characterized in that the second curing agent is introduced by at least one method selected from a scanning probe method, an inkjet printing method, an imprinting method, a 3D printing method, a slot-die coating method, and a spray coating method. . According to claim 1,
The method of manufacturing a stretchable substrate, characterized in that the second curing agent is introduced at 50 to 500 μm intervals to the predetermined portion. delete According to claim 1,
Method of manufacturing a stretchable substrate, characterized in that the cover comprises at least one selected from the group consisting of glass, polymer, metal, ceramic and mixtures thereof. According to claim 1,
A method of manufacturing a stretchable substrate, wherein the crosslinking density of the second cured polymer portion is greater than the crosslinking density of the first cured polymer portion. According to claim 1,
A method of manufacturing a stretchable substrate, wherein the modulus of the second cured polymer portion is greater than the modulus of the first cured polymer portion. According to claim 1,
Method of manufacturing a stretchable substrate, characterized in that the elastic modulus (Ms) of the first cured polymer portion is 0.8 to 3.0 MPa, and the elastic modulus (Mp) of the second cured polymer portion is 15 to 110 MPa. According to claim 1,
A method of manufacturing a stretchable substrate, wherein the ratio (Mp/Ms) of the elastic modulus (Mp) of the second cured polymer portion to the elastic modulus (Ms) of the first cured polymer portion is 5.0 to 137.5. According to claim 1,
A method for manufacturing a stretchable substrate, wherein the ratio of the strain of the second cured polymer portion to the strain of the first cured polymer portion is 0 to 1% when the strain of the stretchable substrate is stretched. According to claim 1,
Method of manufacturing a stretchable substrate, characterized in that the substrate comprises any one selected from glass, ceramic, and polymer. According to claim 1,
The oligomer includes a main chain and a functional group covalently attached to the main chain,
The functional group includes at least one selected from vinyl group, epoxy group, isocyanate group, hydroxy group, thiol group, carboxyl group,
The main chain is silicone, polydimethylsiloxane, polytetrafluoroethylene, polyurethane, polystyrene, polyacrylate, polyarylate, polyester, polyethylene, polypropylene, polycarbonate, polyimide, polyamide, acrylic Contains at least one selected from resins, epoxy resins, amino resins, and phenol resins,
The oligomer is a method of manufacturing a stretchable substrate, characterized in that a plurality of functional groups are covalently bonded to the main chain. According to claim 1,
The first curing agent and the second curing agent may be the same or different from each other, each independently orthosilicic acid, tetravinylsilane, Si(OH) _n (OR) _{4 -n} (n is an integer from 1 to 4, R is a C1-C10 alkyl group ), 3-(Triethoxysilyl)propyl isocyanate, Bis(2-methacryloyl)oxyethyl disulfide, 1,4-Bis(4-vinylphenoxy)butane, Divinylbenzene, p-Divinylbenzene, Glycerol ethoxylate, Glycerol ethoxylate-co-propoxylate triol, Hexa( ethylene glycol) dithiol, 2-[8-(3-Hexyl-2,6-dioctylcyclohexyl)octyl]pyromellitic diimide oligomer(maleimide terminated), 2-[8-(3-Hexyl-2,6-dioctylcyclohexyl)octyl]pyromellitic diimide oligomer (maleimide terminated), 11-Maleimidoundecanoic acid, Pentaerythritol ethoxylate, Pentaerythritol ethoxylate, Pentaerythritol propoxylate, 1,4-Phenylenediacryloyl chloride, Poly(ethylene glycol) bisazide, Ethylene glycol diacrylate, Poly(ethylene glycol) diacrylate, 2,4, 6,8-Tetramethyl-2,4,6,8-tetrakis(propyl glycidyl ether)cyclotetrasiloxane, 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione, Di(ethylene glycol) diacrylate, Ethylene glycol dimethacrylate, Di(e thylene glycol) dimethacrylate, Triethylene glycol dimethacrylate, Tetra(ethylene glycol) diacrylate, monomethyl ether hydroquinone, Trimethylolpropane ethoxylate, Trimethylolpropane ethoxylate, Trimethylolpropane ethoxylate, 4-Vinylbenzocyclobutene, 3-Aminophenyl sulfone, 4-Aminophenyl sulfone, 5-Amino-1,3 ,3-trimethylcyclohexanemethylamine, 1,2,4-Benzenetricarboxylic anhydride, Bisphenol A acetate propionate technical grade, Bisphenol A diglycidyl ether, Bisphenol A propoxylate diglycidyl ether, Bisphenol F, Castor oil glycidyl ether, 1,2-Cyclohexanedicarboxylic anhydride, 2,2 ′-Diallyl bisphenol A diacetate 1,4,5,6,7,7-Hexachloro-5-norbornene-2,3-dicarboxylic anhydride, 6-Maleimidohexanoic acid,cis-1,2,3,6-Tetrahydrophthalic anhydride, Trimethylolpropane triglycidyl ether, Trimethylolpropane tris[poly(propylene glycol), N,N′-Methylenebisacrylamide, N,N′-Methylenebisacrylamide, N,N′-(1,2-Dihydroxyethylene)bisacrylamide, N-(1-Hydroxy-2,2 -dimethoxyethyl)acrylamide, 1,4-Cyclohexanedimethan ol divinyl ether, N,N′-(1,2-Dihydroxyethylene)bisacrylamide, 1,6-Hexanediol diacrylate, 4,4′-Methylenebis(cyclohexyl isocyanate), Poly(ethylene glycol) dimethacrylate, Tetraethylene glycol dimethyl ether, Bromoacetic acid N-hydroxysuccinimide 3-Maleimidobenzoic acid N-hydroxysuccinimide 4-(N-Maleimidomethyl)cyclohexanecarboxylic acid N-hydroxysuccinimide 3-(2-Pyridyldithio)propionic acid N-hydroxysuccinimide Dimethyl pimelimidate dihydrochloride, 3,3′-Dithiodipropionic acid di(N-hydroxysuccinimide ester), and Suberic acid bis (3-sulfo-N-hydroxysuccinimide ester). According to claim 1,
The first curing agent and the second curing agent may be the same as or different from each other, and each independently, a method for producing a stretchable substrate, characterized in that the compound represented by structural formula 1:
[Structural Formula 1]

In the structural formula 1,
A is a carbon atom or a silicon atom,
R ¹ to R ⁴ may be the same or different from each other, and each independently a hydrogen atom, a hydroxyl group, a vinyl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, an epoxy group, or a glycidyl group,
R ¹ to R ⁴ are not hydrogen atoms at the same time. The method of claim 15,
The R ¹ to R ⁴ may be the same as or different from each other, and each independently a hydrogen atom, a hydroxyl group, a vinyl group, a C1-C10 alkyl group, or a C1-C10 alkoxy group. According to claim 1,
And (c) separating the stretchable substrate from the substrate after step (c). (1) placing a first mixed solution comprising an oligomer and a first curing agent on a substrate;
(2) A first portion comprising the oligomer and the first curing agent on the substrate, and the oligomer, the first curing agent and the second curing agent by adding a second curing agent to a predetermined portion of the first mixed solution. Forming a second portion comprising;
(2') placing a cover on the first part and the second part so as to contact the surface of some or all of the first part and the second part;
(3) curing the first portion and the second portion to produce a stretchable substrate comprising a first cured polymer portion and a second cured polymer portion on the substrate; And
(4) placing an electronic device or an electrode on the second cured polymer portion;
Method for manufacturing a stretchable electronic device comprising a. The method of claim 18,
Between the steps (3) and (4) of the manufacturing method of the stretchable electronic device,
A method of manufacturing a stretchable electronic device further comprising the step of placing an adhesive layer on the second cured polymer portion (3'). The method of claim 18,
Method for manufacturing a flexible electronic device, characterized in that the electronic device comprises at least one selected from a thin film transistor, a solar cell, an organic light emitting diode and a display.

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