KR20190106808A - Method of preparing the stretchable substrate and method of preparing the flexible electronic device comprising the same - Google Patents

Abstract

The present invention relates to a method for manufacturing a stretchable substrate, which comprises the steps of: (a) positioning a first mixed solution including oligomer and a first curing agent on a substrate; (b) forming a first part including the oligomer and the first curing agent and a second part including the oligomer, the first curing agent, and a second curing agent on the substrate by injecting the second curing agent into a predetermined portion of the first mixed solution; and (c) preparing a stretchable substrate including first and second cured polymer parts on the substrate by curing the first and second parts. Accordingly, the efficiency of a device can be maintained since separation between a substrate and the device is not generated even after repeated stretching when using the stretchable substrate including a hard pattern part formed by curing the substrate by inserting a curing agent into a specific region of a polymer solution for forming the stretchable substrate. In addition, the flexible substrate may be applied to various flexible electronic devices.

Description

Method for manufacturing stretchable substrate, and method for manufacturing stretchable electronic device including 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 for manufacturing a stretchable substrate and a method for manufacturing a stretchable electronic device including the same, and more particularly, by hardening the substrate by inserting a curing agent into a specific region of a polymer solution to form the stretchable substrate. The present invention relates to a method of manufacturing a stretchable substrate including a pattern portion and a method of manufacturing a stretchable electronic device including the same.

Stretchable electronics are devices that can maintain their function even in stretch, and are emerging as a promising solution for eliminating mechanical incompatibility between existing rigid electronics and smooth curved systems. Intensive research is undertaken by academics and industry on the development of new mechanically durable materials, deformable conductors and circuits, new processing methods, and elastic materials for stretchable substrates for the development of stretchable electronics. have. Among other things, the flexible substrate constitutes an element that withstands the strain applied, thereby providing flexibility to the device, thereby imparting important characteristics to the overall performance of the stretchable electronic device.

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

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a stretchable substrate including a pattern portion formed by hardening the substrate by inserting a curing agent into a specific region of the polymer solution to form the stretchable substrate. have.

Another object of the present invention is to provide a method of manufacturing a stretchable electronic device in which the separation between the substrate and the device does not occur even after the stretchable substrate is repeatedly stretched.

In addition, the use of the cover during curing provides a stretchable substrate having a high flatness because there is no difference in height between portions of the boundary between the stretched and non-stretched regions.

According to one aspect of the invention, (a) positioning 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, the oligomer, the first curing agent and the second curing agent by injecting a second curing agent into a predetermined portion of the first mixed solution; Forming a second portion comprising a; And (c) manufacturing the stretchable substrate including a first cured polymer portion and a second cured polymer portion on the substrate by curing the first portion and the second portion. .

An elastic modulus of the first cured polymer part and the second cured polymer part may be controlled by adjusting the doses of the first and second hardeners, 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 added to the predetermined portion at 50 to 500μm intervals.

(B ') positioning a cover between the steps (b) and (c) to abut the surface of some or all of the first and second portions on the first and second portions; It can be included as.

The cover may include one or more selected from the group consisting of glass, polymers, metals, ceramics, and mixtures thereof.

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

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

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 modulus of elasticity (Mp) of the second cured polymer part to the modulus of elasticity (Ms) of the first cured polymer part may be 5.0 to 137.5.

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

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

The oligomer comprises a main chain and a functional group covalently bonded 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, and the main chain is silicon, Polydimethylsiloxane, polytetrafluoroethylene, polyurethane, polystyrene, polyacrylate, polyarylate, polyester, polyethylene, polypropylene, polycarbonate, polyimide, polyamide, acrylic resin, epoxy resin, amino At least one selected from a resin and a phenol resin, and the oligomer may be one in which a plurality of functional groups are covalently bonded 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 of 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, 5 H) -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-Dihydroxyethy lene) bisacrylamide, N- (1-Hydroxy-2,2-dimethoxyethyl) acrylamide, 1,4-Cyclohexanedimethanol 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) may include one or more selected.

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

[Formula 1]

In the above formula 1,

A is a carbon atom or a silicon atom,

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

After step (c), the method may further comprise a step (d) of separating the stretchable substrate from the substrate.

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

The method of manufacturing the stretchable electronic device may further include a step (3 ') of placing the adhesive layer on the second cured polymer portion between the 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 for manufacturing a stretchable substrate of the present invention, when a stretchable substrate including a pattern portion formed by hardening the substrate by hardening the substrate by inserting a curing agent into a specific region of the polymer solution to form the stretchable substrate, separation between the substrate and the device occurs. There is no effect.

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

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

1 is a flowchart illustrating a method of manufacturing a stretchable substrate according to the present invention.
2A and 2B are structural diagrams of the stretchable substrate according to the second embodiment and the first embodiment.
3 is a view for explaining the change in elastic modulus according to the position in the stretchable substrate according to the first embodiment.
4 is a graph comparing durability of the stretchable substrates prepared according to Example 1 and Comparative Example 4. FIG.
FIG. 5 is a diagram illustrating strain rates of stretched and non-stretched regions in the stretchable substrate according to Example 1. FIG.
6 is a stress-strain curve of a stretchable substrate with thickness.

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

However, the following descriptions are not intended to limit the present invention to specific embodiments, and detailed descriptions of well-known techniques related to the present invention will be omitted when it is determined that the present invention may obscure the gist of the present invention. .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, operation, component, or combination thereof described in the specification, and one or more other features or It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, operations, components, or combinations thereof.

In addition, when a component is referred to as being "formed" or "laminated" on another component, it may be directly attached to, or laminated to, the front or one side on the surface of the other component, It will be understood that other components may exist in the.

1 is a flowchart illustrating a method of manufacturing a stretchable substrate according to the present invention.

Hereinafter, a method of 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, by which the present invention is not limited and the present invention is defined only by the scope of the 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 the substrate; (b) a first portion comprising the oligomer and the first curing agent on the substrate, the oligomer, the first curing agent and the second curing agent by injecting a second curing agent into a predetermined portion of the first mixed solution; Forming a second portion comprising a; And (c) manufacturing the stretchable substrate including the first cured polymer portion and the second cured polymer portion on the substrate by curing the first portion and the second portion. .

An elastic modulus of the first cured polymer part and the second cured polymer part may be controlled by adjusting the doses of the first and second hardeners, 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 added to the predetermined portion at 50 to 500μm intervals.

(B ') positioning a cover between the steps (b) and (c) to abut the surface of some or all of the first and second portions on the first and second portions; It can be included as.

The cover may include one or more selected from the group consisting of glass, polymers, metals, ceramics, and mixtures thereof.

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

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

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 modulus of elasticity (Mp) of the second cured polymer part to the modulus of elasticity (Ms) of the first cured polymer part may be 5.0 to 137.5.

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

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

The oligomer comprises a main chain and a functional group covalently bonded 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, and the main chain is silicon, Polydimethylsiloxane, polytetrafluoroethylene, polyurethane, polystyrene, polyacrylate, polyarylate, polyester, polyethylene, polypropylene, polycarbonate, polyimide, polyamide, acrylic resin, epoxy resin, amino At least one selected from a resin and a phenol resin, and the oligomer may be one in which a plurality of functional groups are covalently bonded to the main chain.

The oligomer is here an oligomer and refers to a molecular weight of 200 to 10,000 or less. The oligomer is not a dendritic substance such as a polymer compound having a high degree of polymerization, and can be distilled and separated and exist as a solution like ordinary organic substances. In addition, a molecule formed by repeating one or several atoms or groups of atoms (structural units) from several to several tens of each other, and its physical properties may change depending on the increase and decrease of one 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 of 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, 5 H) -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-Dihydroxyethy lene) bisacrylamide, N- (1-Hydroxy-2,2-dimethoxyethyl) acrylamide, 1,4-Cyclohexanedimethanol 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 , At least one selected from 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) can do.

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

[Formula 1]

In the above formula 1,

A is a carbon atom or a silicon atom,

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

After step (c), the method may further comprise a step (d) of separating the stretchable substrate from the substrate.

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

The method of manufacturing the stretchable electronic device may further include a step (3 ') of placing the adhesive layer on the second cured polymer portion between the 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 Flexible Substrate 1 Prepared Through Curing Agent Injection Method 1

In this embodiment, a silicon rubber PDMS (Sylgard184, Dow corning) was used to construct a flexible substrate, which initially consists of two solutions. The first solution consists of a small amount of organic-platinum catalyst, or Karstedt catalyst, dissolved in a silicone resin with vinyl functional group as the basic PDMS oligomer. It is composed of poly (methylhydrosiloxane) polymer. When the two solutions are mixed with each other, the vinyl functional group and the hydrogen of the hydrosilane are cross-linked through hydrosilylation in the presence of a platinum catalyst to form a flexible substrate.

The two solutions were mixed at a weight ratio of 20: 1 and stirred for 5 minutes to mix thoroughly. The vacuum solution was then vacuumed for 5 minutes to remove bubbles in the PDMS mixed solution, followed by pouring the mixed solution at a constant rate on a flat plastic or glass container. The 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 after the PDMS mixed solution was completely spread on the container surface. 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. Then, in order to control the height difference of the boundary between the soft and the non-stretch hard (hard) to cover the mixed solution layer in a flat plastic or glass container and cured for 2 hours in a 70 ℃ oven. Thereafter, the entire flexible substrate layer was separated from the two containers positioned at the upper side (the container covering the mixed solution layer) and the lower side (the container in which the mixed solution was poured) to prepare a flexible substrate having a hard pattern portion (non-stretched area).

Example 2 Flexible Substrates 2 Prepared Through a Curing Agent Injection Method

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

Comparative Example 1: PDMS Substrate Using Sylgard 184

PDMS, a silicone rubber, was used to fabricate the flexible substrate used as a comparative example, which 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. The vacuum solution was then vacuumed for 5 minutes to remove bubbles in the PDMS mixed solution, followed by pouring the mixed solution 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. The formed transparent film layer was then removed from the container to produce a stretchable substrate.

Comparative Example 2: Silicon Rubber Substrate Using Ecoflex 00-30

Ecoflex 00-30 (Smooth-On) consists 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 bubbles in the mixed solution. The mixed solution was then poured at a constant rate on a flat plastic or glass container. After the 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 translucent film layer was removed to prepare a stretchable substrate.

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

SEBS is a block copolymer showing elasticity. Tuftec H1062 has a volume fraction of poly (ethylene-co-butylene) of 82%. The substrate is prepared by dissolving pellet-type products in toluene at a concentration of 200 mg / ml. . The SEBS solution was then poured on a plastic container at a constant rate. After the mixed solution was completely spread on the surface of the vessel, the mixture was stored for 2 hours in an oven at 70 ° C. to evaporate the toluene solvent. Then, the formed transparent film layer was removed to prepare a stretchable substrate.

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

Instead of injecting the orthosilicic acid solution as an additional hardener before curing after the PDMS mixed solution has completely spread on the container surface in Example 1, the orthosilicic acid solution as an additional hardener is completely spread after the PDMS mixed solution is completely spread and completely cured on the container surface. 20% to 30% of the substrate area was prepared in the same manner as in Example 1 except that the injection probe was used in a circular shape.

[Test Example]

Test Example 1: Comparison of Hardness of Flexible Substrate

Table 1 shows the hardness test results obtained by measuring the hardness of the hard pattern portion (non-stretched region) of the stretchable substrate manufactured according to Example 1 and the hardness of the stretchable substrate prepared according to Comparative Examples 1 to 3. Hardness was measured by 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 by the indentor of the Durometer instrument, the hardness value of the sample can be obtained by estimating according to the depth of 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, the elastic modulus of the pattern portion in the stretchable substrate manufactured according to Example 1 was the highest as 109.9 MPa, and the elastic modulus of the stretchable substrate prepared according to Comparative Example 2 was the lowest as 0.8 MPa. Therefore, it was found that the hardness of the hard pattern portion formed by injecting the curing agent into the specific region of the stretchable substrate increased by 5 to 137.5 times than the hardness of the stretching region where the curing agent was not injected.

Test Example 2: Comparison of the total elongation of the flexible substrate

Table 2 shows the results of comparing the total 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, the overall elongation of the stretchable substrate on which the hard pattern portion (non-stretched region) was formed by inserting the curing agent was reduced, indicating that additional curing was partially performed.

Test Example 3: Control of the difference in boundary height between stretched and unstretched regions of the stretchable substrate

2A and 2B are structural diagrams of the stretchable substrate according to the second embodiment and the first embodiment.

Referring to FIGS. 2A and 2B, the structure of Example 2 (FIG. 2A), which is manufactured without covering the container and manufactured by covering the container, is compared with the structure of Example 1 (FIG. 2B) which is manufactured without covering the container in the manufacturing process of the stretchable substrate having the non-stretchable region As a result, Example 2 manufactured without covering the container has a height difference between the boundaries between the stretched and non- stretched regions, and Example 1, covered with the container, showed that the substrate was formed flat without the height difference between the two regions. .

This indicates that the substrate may be formed differently according to the fabrication process of the substrate. In the case where the substrate having no height difference between the two regions is applied to the flexible electronic device, it is easy to connect with other rigid devices, and may occur when driving the device. It seems that defects can be reduced.

Test Example 4 Change in Elastic Modulus According to Position on a Flexible 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 manufactured according to Example 1, the hardness was measured while moving the measuring portion of the substrate sample through the durometer device used in Test Example 1 It was converted into count values. 3 is a view for explaining the change in elastic modulus according to 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 rapidly increases from the portion where the non-stretched region is formed, so that two regions having a large difference in elastic modulus are formed. It was found that it was formed in one substrate.

Test Example 5: Durability Test of Flexible Substrate

4 is a graph comparing durability of the stretchable substrates prepared according to Example 1 and Comparative Example 4. FIG. With a stretchable substrate prepared according to Example 1 and a prepared substrate according to Comparative Example 4, an automatic stretchable repeater was used at a strain rate of 20%, 30%, 40%, 50% and 60% of the initial length of the substrate sample, respectively. After applying the repeated stretching cycle, it is an experiment comparing the durability of the non-stretched region of each stretchable substrate.

Referring to FIG. 4, a stretchable substrate including a non-stretched region prepared by injecting an additional curing agent before curing of PDMS according to Example 1 under various stretching conditions is prepared by injecting an additional curing agent after completely curing PDMS according to Comparative Example 4. It was confirmed that the durability against cracks occurring in the non-stretched region is better than that of the stretchable substrate including the stretched non-stretched region. This shows 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 Soft and Hard Strains of a Flexible Substrate

FIG. 5 is a diagram illustrating a strain of a stretched region and a hard region in the stretchable substrate according to Example 1. FIG. In FIG. 6, the soft part is a strain measured in the stretch region of the stretchable substrate according to Example 1, and the hard part is a strain measured in the non stretch region.

Referring to FIG. 5, the strain generated in the stretched and non-stretched regions according to the deformation applied from the outside can be seen. As the external strain increases, the strain generated in the stretched region continues to increase, but the strain generated in the non-stretched region shows little change. That is, since the non-stretchable region of the stretchable substrate according to Example 1 is made of a non-stretch material, deformation is hardly caused because the mechanical strength is larger than that of the stretchable substrate according to Example 1.

Test Example 8 Comparison of Property Changes According to Thickness of Flexible Substrate

Figure 6 is a graph comparing the physical properties of the flexible substrate prepared by varying the thickness by the method according to Example 1. Table 3 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

6 and Table 3, as the thickness of the stretchable substrate increases from 100 μm to 1000 μm, the elongation modulus continuously increases. Accordingly, the elongation modulus is adjusted according to the thickness to have desired properties. Flexible hybrid substrates could be fabricated.

Test Example  9: Comparison of stretching properties with increasing proportion of additional hardener in flexible substrate

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

Percentage 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, it can be seen that the modulus (moudulus) continues to increase as the ratio of the total substrate area of the additional curing agent increases, and the elongation does not change significantly. Therefore, it is possible to manufacture a flexible 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 shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being 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, the oligomer, the first curing agent and the second curing agent by injecting a second curing agent into a predetermined portion of the first mixed solution; Forming a second portion comprising a; And
(c) curing the first portion and the second portion to prepare a stretchable substrate including a first cured polymer portion and a second cured polymer portion on the substrate;
Method for producing a stretchable substrate comprising. The method of claim 1,
And adjusting the amounts of the first curing agent and the second curing agent, respectively, to control the elastic modulus of the first cured polymer part and the second cured polymer part. The method of claim 1,
Method of producing a flexible substrate, characterized in that the injection of the second curing agent is carried out 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. . The method of claim 1,
The second curing agent is injected into the predetermined portion 50 to 500μm manufacturing method of a stretchable substrate, characterized in that. The process of claim 1 wherein between steps (b) and (c)
(b ') positioning a cover on the first portion and the second portion to abut the surface of the portion or the entirety of the first portion and the second portion. Way. The method of claim 4, wherein
The cover of claim 1, wherein the cover comprises at least one member selected from the group consisting of glass, polymers, metals, ceramics and mixtures thereof. The method of claim 1,
The crosslinking density of the second cured polymer portion is greater than the crosslinking density of the first cured polymer portion. The method of claim 1,
The modulus of elasticity of the second cured polymer part is greater than the modulus of elasticity of the first cured polymer part. The method of claim 1,
The elastic modulus Ms of the first cured polymer part is 0.8 to 3.0 MPa, and the elastic modulus Mp of the second cured polymer part is 15 to 110 MPa. The method of claim 1,
The elastic substrate (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. The method of claim 1,
And a stretch ratio of the strain of the second cured polymer part to the strain of the first cured polymer part upon extension deformation of the stretchable substrate. The method of claim 1,
The substrate is flexible, characterized in that it comprises any one selected from glass, ceramic, and polymer. The method of claim 1,
The oligomer comprises a main chain and a functional group covalently bonded 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 1 or more types selected from resin, epoxy resin, amino resin, and phenol resin,
The oligomer is a stretchable substrate, characterized in that a plurality of the functional groups are covalently bonded to the main chain. The method of 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 of 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-Dihydroxyethyl ene) bisacrylamide, N- (1-Hydroxy-2,2-dimethoxyethyl) acrylamide, 1,4-Cyclohexanedimethanol 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) The manufacturing method of an elastic board | substrate made into. The method of claim 1,
The first curing agent and the second curing agent may be the same or different from each other, each independently a method of producing a flexible substrate, characterized in that the compound represented by the formula (1):
[Formula 1]

In the above formula 1,
A is a carbon atom or a silicon atom,
R ¹ to R ⁴ may be the same as or different from each other, and are 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. The method of claim 1,
And (d) 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, the oligomer, the first curing agent and the second curing agent by introducing a second curing agent into a predetermined portion of the first mixed solution Forming a second portion comprising a;
(3) 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; And
(4) placing an electronic device or an electrode on the second cured polymer part;
Method for manufacturing a stretchable electronic device comprising. The method of claim 18,
Between the steps (3) and (4) of the method for manufacturing the stretchable electronic device,
The method of manufacturing a stretchable electronic device further comprises the step (3 ') of placing an adhesive layer on the second cured polymer portion. The method of claim 18,
The electronic device is a method for manufacturing a stretchable electronic device, characterized in that it 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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