KR101625266B1 - Composite sheet and displaying apparatus comprising the same - Google Patents

Abstract

The present invention relates to a composite sheet having a silicone-based matrix and a reinforcing material impregnated in the silicone matrix and having a compression elongation of 30% or more, and a display device comprising the composite sheet.

Description

Technical Field [0001] The present invention relates to a composite sheet and a display device including the composite sheet.

The present invention relates to a composite sheet and a display device including the composite sheet.

As substrate materials for display devices, miniaturization, thinness, light weight, impact resistance, flexibility and the like are required. As a material for replacing the glass substrate of the conventional display device, a substrate for a flexible display has been spotlighted.

A matrix impregnated with a woven form of glass fiber or glass fiber can be used as a flexible substrate. However, the matrix of silicone material has a high thermal expansion coefficient compared to glass fiber, and cracks may occur or break in the substrate when the flexible substrate is processed at a high temperature.

In this regard, Korean Patent Laid-Open Publication No. 2010-0014391 discloses a method for fabricating a nanosubstrate comprising the steps of: impregnating a fiber reinforcement into a nanosource-filled silicone composition comprising a hydrosilylation-curable silicone composition and a carbon nanomaterial; And curing the silicone resin of the impregnated fiber reinforcement. ≪ Desc / Clms Page number 2 >

A problem to be solved by the present invention is to provide a composite sheet free from cracking or cracking at the interface between a matrix and a reinforcing material even when left at a high temperature of 250 占 폚 or more.

Another object of the present invention is to provide a composite sheet having high flexibility and heat resistance.

Another object of the present invention is to provide a composite sheet having a predetermined range of modulus so that a part or a layer is not separated or broken from a composite sheet when a predetermined part or a layer is laminated on the upper surface of the composite sheet.

The composite sheet, which is one aspect of the present invention, includes a silicon-based matrix and a reinforcing material impregnated into the silicon-based matrix, and the compression elongation can be 30% or more.

The composite sheet, which is another aspect of the present invention, comprises a silicon-based matrix and a reinforcing material impregnated into the silicon-based matrix. The composite sheet has a transmittance of 80% measured at 25 ° C and a wavelength of 550 nm, Or more.

A display device, which is another aspect of the present invention, includes a substrate, and a member for an apparatus formed on the substrate, and the substrate may include the composite sheet.

The present invention provides a composite sheet free from cracking or cracking at the interface between a matrix and a reinforcing material even when left at a high temperature of 250 占 폚 or more.

The present invention provides a composite sheet having high flexibility and heat resistance.

The present invention provides a composite sheet having a certain range of modulus to prevent the component or layer from being separated or broken from a composite sheet upon lamination of certain parts or layers on the top surface of the composite sheet.

1 is a cross-sectional view of a composite sheet according to an embodiment of the present invention.
2 is a cross-sectional view of a composite sheet according to another embodiment of the present invention.
3 is a cross-sectional view of a display device according to an embodiment of the present invention.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

In the present specification, the term "compressive elongation" refers to the elongation measured after compressive deformation of the composite sheet, as a matrix-only portion of the composite sheet (for example, a window portion of a composite sheet (when a glass cloth is used as a reinforcing material, The micro indentor was inserted at a rate of 0.01 mm / sec at a microindentor per unit area (1 mm ² ) at a rate of 0.01 mm / sec. (S / tx 100) of the measured length (s) with respect to the total thickness (t, unit: 占 퐉) of the composite sheet.

As used herein, the term "modulus" for a composite sheet refers to a portion of a composite sheet that consists only of a matrix (e.g., a window portion of a composite sheet (a portion where a glass cloth and a warp do not intersect with each other, Means a value calculated by applying a force of 10 mN with a micro indentor (Vicker indenter) per unit area (1 mm ² ) for 10 seconds, creeping for 3 seconds, and relaxation for 10 seconds.

Hereinafter, a composite sheet according to an embodiment of the present invention will be described with reference to FIG. 1 is a cross-sectional view of a composite sheet according to an embodiment of the present invention. Referring to FIG. 1, a composite sheet 100 according to an embodiment of the present invention may include a matrix 1 and a reinforcing material 5 impregnated into the matrix 1.

The composite sheet 100 may have a compression elongation of 30% or more, for example, 30 to 60%. If the compression elongation is less than 30%, the difference in thermal expansion coefficient between the matrix and the reinforcing material can not be compensated for when used in a TFT (thin film transistor) process including repeatedly treating the composite sheet at a high temperature of 250 캜 or more, May occur, and cracks may occur at the matrix and reinforcement interface.

Accordingly, the composite sheet 100 may have a transmittance of 80% or more, for example, 80 to 99% measured at 25 캜 and a wavelength of 550 nm after being left at 250 캜 for 1 hour for a thickness of 100 탆. When used in a TFT process for repeatedly treating a composite sheet at a high temperature of 250 캜 or more, cracks are generated in the composite sheet, and when the transmittance is less than 80%, the composite sheet can not be used for a substrate.

Further, the composite sheet 100 may have a modulus of 5 to 20 MPa, for example, 5 to 15 MPa. When the modulus is within the above range, separation from the composite sheet can be prevented even if a part or layer of a predetermined material is laminated on the upper surface of the composite sheet. Generally, as the modulus of the composite sheet increases, the compressive elongation of the composite sheet decreases. However, the composite sheet of the present invention increases the compressive elongation and secures the modulus within a predetermined range, thereby securing the thermal stability and the modulus of the composite sheet. can do.

The composite sheet 100 may have a surface roughness Ra of 100 nm or less, specifically 50 nm or less, more specifically 5 nm to 50 nm, and the composite sheet may have a thermal expansion coefficient of 0 ppm / ° C to 400 ppm / To 10 ppm / ° C, more specifically from 3 ppm / ° C to 7 ppm / ° C. Within this range, thermal deformation can be suppressed during production of the flexible substrate. The thermal expansion coefficient is measured by a thermo-mechanical analyzer (expansion mode, force 0.05N) according to ASTM E 831 method and measured from the curve of the sample length according to the temperature (30 to 250 ° C) can do. The composite sheet may have a thickness of 15 탆 to 200 탆. Within this range, it can be used as a composite sheet for a flexible substrate. The composite sheet may be transparent in the visible light region.

The matrix (1) may have a tensile elongation of 15% or more, for example, 15 to 40%. In the above range, the composite sheet has good thermal stability and heat resistance and cracks may not be generated even at high temperature treatment, flexibility is good, cracks do not occur at the interface between the matrix and the reinforcing material, The separation from the composite sheet can be prevented. The term "tensile elongation" means a value measured at a speed of 50 mm / min with TA.XT.plus (TA instrument) for a matrix specimen (Width 5 mm, Length 20 mm).

The matrix 1 is a silicone-based matrix, and may specifically include a cured product of a linear silicone rubber. The linear silicone rubber has a structure in which siloxane units are connected in a predetermined length to increase the tensile elongation of the matrix so that thermal expansion of the matrix and thermal expansion difference between the reinforcement can be alleviated even at high temperature treatment of the composite sheet.

Specifically, the linear silicone rubber may be a siloxane having a curable functional group, and may be, for example, a copolymer comprising a first repeating unit having a curable functional group and at least one second repeating unit having no curable functional group have. The siloxane having a curable functional group may be formed by a polymerization reaction of a first monomer containing a curable functional group and at least one second monomer containing a curable functional group, wherein the first monomer containing a curable functional group is a total monomer By weight, for example, 0.01 to 1.0% by weight, based on the total weight of the composition. Within the above range, the curable functional group, which is a crosslinking site, is added in a specific range, thereby increasing the tensile elongation of the matrix and improving the thermal stability of the composite sheet. The above-mentioned "curable functional group" is a functional group capable of curing the matrix composition and performing a cross-linking reaction with the cross-linking agent and / or the non-rubbery silicone compound, and includes an unsaturated hydrocarbon group having 2 to 12 carbon atoms having an unsaturated bond at the terminal, For example, a vinyl group or an allyl group.

For example, the linear silicone rubber may be a vinyl group-containing polydimethylsiloxane (PDMS). In embodiments, the vinyl group-containing polydimethylsiloxane may be a composition for preparing a silicone-based rubber comprising phenylmethyldimethoxysilane (PMDMS), dimethyldimethoxysilane (DMDMS), and vinylmethyldimethoxysilane (VMDMS) , Specifically by hydrolysis, polymerization and end-capping reactions of PMDMS, DMDMS, VMDMS. At this time, the VMDMS may be contained in an amount of 1.0% by weight or less, for example, 0.01 to 1.0% by weight based on the sum of PMDMS, DMDMS and VMDMS. Within the above range, the vinyl group as the crosslinking site is included in a specific range to maximize the tensile elongation of the matrix, increase the compression elongation of the composite sheet, and prevent cracking of the composite sheet at high temperatures. In this case, the PMDMS may be included in an amount of 10 to 80% by weight and the DMDMS may be included in an amount of 10 to 90% by weight, specifically 19 to 85% by weight, depending on the target refractive index in the sum of PMDMS, DMDMS and VMDMS. Within the above range, the refractive index of the target composite sheet can be ensured.

In one embodiment, the linear silicone-based rubber may be a linear siloxane oligomer or polymer having a curable functional group and an aliphatic hydrocarbon group, and / or an aromatic hydrocarbon group, and the like. The aliphatic hydrocarbon group, the aromatic hydrocarbon group and the like are for supporting the matrix and for bonding between the matrix and the reinforcing material. In particular, the aromatic hydrocarbon group can increase the permeability of the composite sheet by matching the refractive index between the reinforcing material and the matrix. Specifically, the linear silicone-based rubber may comprise the following Formula 1, Formula 2, and Formula 3:

≪ Formula 1 >

(2)

(3)

Wherein R _a , R _b , R _c , R _d , R _e , R _f , R _g and R _h are each independently selected from the group consisting of hydrogen, alkyl group, having 6 to 20 carbon atoms of the aryl group, C7 to C20 arylalkyl group, or terminal carbon atoms, an unsaturated hydrocarbon group of 2 to 12 having a double bond in the a, R _a, R _b, R _c, R _d, R _e, At least one of R _f , R _g and R _h is an unsaturated hydrocarbon group having 2 to 12 carbon atoms and having a double bond at the terminal). More specifically, the linear silicone rubber may include the repeating units of the formula (1) and the repeating units (2) and (3) at the terminal.

Specifically, the linear silicone-based rubber may comprise repeating units of the following formula:

≪ Formula 4 >

(In the formula (4), * is a connecting site of the element, 0 <x <1, 0 <y <1, 0? Z? 1, and Me is a methyl group).

For example, a linear silicone-based rubber may be represented by the following formula 5 or 6:

&Lt; Formula 5 >

(In the formula 5, 10? X? 400, 10? Y? 700, 0? Z? 700, and Me is a methyl group).

(6)

(In the formula 6, 10? X? 400, 10? Y? 700, 0 <z? 700, and Me is a methyl group).

The linear silicone rubber may have a number average molecular weight (Mn) of 2000 to 50,000 g / mol. Within the above range, the matrix can be supported and the compression elongation of the composite sheet can be increased.

In one embodiment, the matrix 1 may be formed by curing a composition for a matrix comprising a linear silicone-based rubber and a cross-linker. The crosslinking agent is a monomolecular or oligomer having two or more -Si-H groups so that it can undergo hydrosilylation with a curing functional group of a linear silicone rubber, and can be activated by heat or UV to perform a hydrosilyl reaction . Further, the cross-linking agent has a siloxane unit, so that it is possible to realize a high heat resistance effect as well as compatibility with a resin. In the composition for a matrix, the linear silicone rubber may be contained in an amount of 80 to 99% by weight and the crosslinking agent may be contained in an amount of 1 to 20% by weight based on the solid content. Within the above range, the compression elongation of the composite sheet can be ensured and the thermal stability of the composite sheet can be enhanced.

For example, the crosslinking agent may comprise the following structural formulas (7), (8), and (9)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

(In the formula 7 to 9, and * in a joint of the elements, R _i, R _j, R _k, R _l, R _m, R _n, R _o, R _p is independently hydrogen, C 1 -C 10 alkyl group, an aryl group, or a silyl oxy group having 6 to 20, R _i, R _j, R _k, R _l, R _m, R _n, R _o, R _p Lt; / RTI &gt; is hydrogen). The "silyloxy group" means an -Si-O- group having an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. That is, the crosslinking agent may include the repeating unit represented by the formula (7), while the terminals may include the following formulas (8) and (9).

Specifically, the crosslinking agent may be a single compound selected from the group consisting of compounds represented by any one of the following formulas (10) to (14), and oligomers of the following formula (15)

&Lt; Formula 10 >

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

(In the formula (15), 0? X? 30, 0? Y? 40, 0? Z? 40, and Me is a methyl group. The number average molecular weight (Mn) of the crosslinking agent of Formula 15 may be 200 to 3000 g / mol. Within this range, excellent compatibility with a resin such as a linear silicone rubber or the like can be obtained and the curing efficiency can be increased.

The ratio of the number of moles of the silicon-curing functional group (e.g., Si-vinyl group) in the linear silicone rubber to the weight average molecular weight of the linear silicone rubber is defined as A, A: B may be from 1: 1 to 1: 3, for example, from 1: 1 to 1: 2, where B is the ratio of the number of moles of Si- Within the above range, the compression elongation of the composite sheet can be ensured and the thermal stability of the composite sheet can be enhanced.

The composition for a matrix may further comprise at least one of a catalyst and an inhibitor.

The catalyst is used for increasing the crosslinking reaction rate, and a catalyst commonly used in the production of a composite sheet for a flexible substrate can be used. For example, the catalyst may be a platinum-based or rhodium-based catalyst, a complex of platinum and an organic compound, a platinum-vinylated organosiloxane complex, a rhodium-olefin complex, or the like. Specifically, the catalyst may be a vinylalkylsilane platinum complex, a platinum black, a chloroplatinic acid, a chloroplatinic acid-olefin complex, a chloroplatinic acid-olefin complex, A chloroplatinic acid-alcohol complex, or a mixture thereof may be used. The catalyst may comprise from 2 ppm to 2000 ppm, for example from 5 ppm to 500 ppm, based on the weight of the metal, for the linear silicone rubber. Within the above range, the crosslinking reaction rate can be sufficiently increased, and unnecessary use of the catalyst can be avoided.

The inhibitor suppresses the action of the catalyst at room temperature and does not inhibit the catalyst in the curing process at high temperature, so that the composition for matrix can be cured at a high temperature and an inhibitor commonly used in the production of a composite sheet for a flexible substrate can be used. For example, the inhibitor may be selected from the group consisting of acetylenic alcohols, pyridine, and the like, including 3,5-dimethyl-1-hexyn- Phosphine, organic phosphite, unsaturated amide, dialkyl carboxylate, dialkyl acetylene dicarboxylate, alkylated malateate (also referred to as &quot; alkylated maleate, diallyl maleate, or mixtures thereof. The inhibitor may be included at from 100 ppm to 2500 ppm for the linear silicone rubber. Within this range, it is possible to control the suppression of the catalyst depending on the temperature, and the high temperature curing.

The matrix of the composite sheet may comprise 30 to 70% by weight, for example 40 to 60% by weight. Within the above-mentioned range, the high heat resistance and mechanical properties of the flexible substrate can be secured, transparency, flexibility and light weight can be improved, and flexibility of the composite sheet can be provided.

The stiffener 5 is embeddable within the matrix 1, and may be specifically included in the matrix in a dispersed, single layer or multilayer structure. 1 shows only the structure in which the reinforcing material 5 is impregnated in the matrix 1 in layers, but the present invention is not limited thereto. The reinforcing materials may be dispersed in a matrix, impregnated in a woven form, or arranged in a uni direction And may be impregnated. Further, the reinforcing material may be formed as a single layer or a plurality of layers. The reinforcing material in the composite sheet may be contained in an amount of 40 to 70% by weight, for example, 45 to 65% by weight. Within the above-mentioned range, the high heat resistance and mechanical properties of the flexible substrate can be secured, transparency, flexibility and light weight can be improved, and flexibility of the composite sheet can be provided.

The stiffener 5 may have a refractive index difference with respect to the matrix 1 (refractive index of the stiffener - absolute value of the refractive index of the matrix) of 0.01 or less. Within this range, it can have excellent transparency and translucency. For example, the refractive index difference may be from 0 to 0.005, for example from 0.0001 to 0.005. Specifically, the reinforcing material may have a refractive index of 1.5 or less, specifically 1.45 to 1.49. The reinforcing material having a refractive index of 1.5 or less has a small difference in refractive index from the silicone matrix, so that the composite sheet can secure transparency. The reinforcing material may have a coefficient of thermal expansion of 10 ppm / ° C or less, specifically 3 to 5 ppm / ° C. When such a reinforcing material is used, the thermal expansion coefficient of the entire composite sheet can be lowered, have. The thermal expansion coefficient is measured by a thermo-mechanical analyzer (expansion mode, force 0.05N) according to ASTM E 831 method and measured from the curve of the sample length according to the temperature (30 to 250 ° C) can do. Specifically, the reinforcing material may include at least one selected from the group consisting of glass fiber, glass fiber cloth, glass fabric, glass nonwoven fabric, glass mesh, Do not.

Hereinafter, a matrix of another embodiment of the present invention will be described. The matrix of another embodiment of the present invention may comprise a cured product of said linear silicone-based rubber, said crosslinking agent, and a composition for a matrix comprising a non-rubbery silicone compound. By further including the non-rubbery silicone compound, modulus control of the composite sheet can be facilitated by controlling the molar ratio between the linear silicone rubber and the non-rubbery silicone compound. Is substantially the same as the matrix of the embodiment of the present invention except that it includes a non-rubbery silicone compound.

The non-rubbery silicone compound may be, for example, a cyclic siloxane compound. The cyclic siloxane compound has a structure in which siloxane units are linked in the form of a ring to increase the modulus of the composite sheet. The cyclic siloxane compound may include a curing functional group and an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group, and the curable functional group may be an unsaturated hydrocarbon group having 2 to 12 carbon atoms having a double bond at the terminal, for example, a vinyl group, .

In embodiments, the cyclic siloxane compound is a cyclic siloxane compound having from 3 to 10 identical or different siloxane units linked together, such as cyclotrisiloxane, cyclotetrasiloxane, cyclopentasiloxane, A cyclohexasiloxane, a cycloheptasiloxane, or a cyclooctasiloxane, or a compound having a curing functional group as described above bonded to at least one of the silicones. For example, cyclic siloxane compounds can include tetravinyltetramethylcyclotetrasiloxane, derivatives prepared from tetravinyltetramethylcyclotetrasiloxane, derivatives prepared from tetramethylcyclotetrasiloxane, and the like .

In one embodiment, the cyclic siloxane compound can be represented by the formula:

&Lt; Formula 16 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6 ,} R _{7 and} R ₈ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An allyl group, an allyloxy group, a vinyloxy group, or a group represented by the following formula (17)

&Lt; Formula 17 >

(In the above formula (17), * is a connecting site to Si in the above formula (16)

R ₉ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms and R ₁₀ , R ₁₁ and R ₁₂ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An allyl group, an allyloxy group, or a vinyloxy group, X ₁ and X ₂ each independently represent a single bond, O, S, or NR (R is hydrogen or an alkyl group having 1 to 10 carbon atoms)

_{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R one or more of the ₈ is a vinyl group, an allyl group, an allyloxy group, a vinyloxy group, R _10, R _11, R ₁₂ of the one or more vinyl group formula 17, R _10, R _11, R ₁₂ is one or more of allyl group of the formula 17, R _10, R _11, R one or more of ₁₂ the allyloxy group formula 17, or R _10, R _11, R &lt; ₁₂ &gt; is a vinyloxy group.

The derivative can be prepared by a conventional method. For example, it can be prepared by converting an alkyl group in a tetravinyl tetraalkylcyclotetrasiloxane to a halogenated alkyl group and reacting a curable functional group-containing compound such as allyl alcohol, vinyl alcohol or the like under a Karstedt platinum catalyst.

Specifically, the cyclic siloxane compound may be represented by any one of the following formulas (18) to (43), but is not limited thereto:

&Lt; Formula 18 >

(19)

(20)

&Lt; Formula 21 >

(22)

&Lt; Formula 23 >

&Lt; EMI ID =

&Lt; Formula 25 >

(26)

&Lt; Formula 27 >

(28)

(29)

(30)

(31)

(32)

&Lt; Formula 33 >

(34)

&Lt; Formula 35 >

&Lt; EMI ID =

(37)

&Lt; Formula 38 >

&Lt; EMI ID =

&Lt; EMI ID =

&Lt; EMI ID =

(42)

&Lt; Formula 43 >

(In the above Chemical Formulas 18 to 43, Me is a methyl group and Ph is a phenyl group).

The ratio of the number of moles of the silicon-curing functional group (e.g., Si-vinyl group) in the non-rubbery silicone compound to the molecular weight of the non-rubbery silicone compound is represented by C, A may be 1: 1 to 6: 1, for example, 3: 1 to 6: 1, where A is the ratio of the number of moles of silicon-curing functional groups (e.g., Si- Within the above range, the compression stability of the composite sheet can be ensured and the modulus can be kept within a specific range and the thermal stability can be improved. When the ratio of the number of moles of silicon-H (Si-H) in the cross-linking agent to the (weight) average molecular weight of the cross-linking agent is B, the ratio of (A + C): B is 1: 1 to 1: 3, 1: 1 to 1: 2. Within the above range, the compression stability of the composite sheet can be ensured and the modulus can be kept within a specific range and the thermal stability can be improved.

In the composition for a matrix, the linear silicone rubber, the non-rubber silicone compound and the crosslinking agent may be contained in an amount of 60 to 80% by weight, 1 to 30% by weight, and 1 to 20% by weight, respectively. Within the above range, the crosslinking site in an appropriate range reacts to increase the compression elongation of the composite sheet and to prevent the permeability of the composite sheet from being hindered by the unreacted material.

The method for producing a composite sheet according to an embodiment of the present invention can be produced by impregnating a matrix composition with a reinforcement and curing the composition, and the curing may include at least one of heat curing and light curing. The thermal curing may be performed at 30 to 100 캜 for 1 to 3 hours, but is not limited thereto. Photocuring can be carried out by irradiation with a light quantity of 10 to 500 mJ at the UV wavelength, but is not limited thereto.

Hereinafter, a composite sheet according to another embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of a composite sheet according to another embodiment of the present invention. 2, a composite sheet 200 according to another embodiment of the present invention includes a matrix 1, a stiffener 5 impregnated into the matrix 1, and a barrier layer (not shown) formed on the upper surface of the matrix 1 20). Is the same as the composite sheet of the embodiment of the present invention except that the barrier layer 20 is further included. In addition, although only one barrier layer is formed on the upper surface of the matrix in FIG. 2, the barrier layer may be formed in two or more layers, or may be formed on the bottom surface as well as the top surface of the matrix.

The barrier layer 20 may be formed on one side of the matrix 1 to realize the effect of maximizing gas barrier property, moisture permeability, mechanical properties, or smoothness of the composite sheet 200. In one embodiment, the barrier layer 20 may comprise at least one of silicon nitride, silicon oxide, silicon carbide, aluminum nitride, indium tin oxide (ITO), indium zinc oxide (IZO). The modulus of the barrier layer 20 may be 5 to 20 GPa, specifically 10 to 20 GPa, and the thickness may be 5 to 300 nm. Within this range, there can be excellent surface flatness and effective moisture permeability control effect without affecting the permeability of the matrix impregnated with the reinforcement.

The barrier layer 20 may be formed on the surface of the matrix 1 by physical vapor deposition, chemical vapor deposition, coating, sputtering, evaporation, ion plating, wet coating, or organic inorganic multilayer coating.

The display device of the present invention may include the composite sheet of the present invention. The display device may be, for example, a flexible liquid crystal display device, a flexible organic light emitting diode display device or the like, but is not limited thereto. The display device includes a substrate and a member for an apparatus formed on the substrate, and the member for the apparatus may include an organic light emitting element, a liquid crystal, or the like.

Hereinafter, a display device according to an embodiment of the present invention will be described with reference to FIG. 3 is a cross-sectional view of a display device according to an embodiment of the present invention. 3, a display device according to an embodiment of the present invention includes a substrate 110, a buffer layer 25 formed on the substrate 110, a gate electrode 41 formed on the buffer layer 25, And a gate insulating film 40 formed between the electrode 41 and the buffer layer 25. In the gate insulating film 40, an active layer 35 including source and drain regions 31, 32, and 33 is formed. An interlayer insulating film 51 having source and drain electrodes 52 and 53 is formed on the gate insulating film 40. A passivation layer 61 including a contact hole 62 is formed on the interlayer insulating film 51, A first electrode 70, and a pixel defining layer 80 are formed. The organic emission layer 71 and the second electrode 72 are formed on the pixel defining layer 80 and the substrate 110 may include the composite sheet of the present invention.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Manufacturing example  1: Linear silicon system Rubber  Produce

Was synthesized by using phenylmethyldimethoxysilane (PMDMS), dimethyldimethoxysilane (DMDMS), and vinylmethyldimethoxysilane (VMDMS). After PMDMS, DMDMS and VMDMS were weighed (PMDMS: DMDMS = 3: 2 by weight and 0.5% by weight in VMDMS + PMDMS + DMDMS + VMDMS), 1 hour at 70 ° C under DIW (deionized water) / KOH Followed by hydrolysis. The polymerization reaction was carried out at 90 ° C, Toluene and H ₂ O were added, the temperature was lowered to 25 ° C, and the reaction solution was washed with H ₂ O. After that, 1,3-divinyltetramethyldisiloxane (Vi-MM) was added and the end capping was performed at 50 ° C for 5 hours. The reaction mixture was washed with H ₂ O at room temperature, And the final linear silicone rubber was synthesized. The number average molecular weight (Mn) of the synthesized linear silicone rubber was 7,000 g / mol.

Manufacturing example  2: Linear silicon system Rubber  Produce

A linear silicone rubber was prepared in the same manner as in Production Example 1 except that the addition equivalent of VMDMS was changed to 1.0 wt% of PMDMS + DMDMS + VMDMS.

Manufacturing example  3: Linear silicon system Rubber  Produce

A linear silicone rubber was prepared in the same manner as in Production Example 1, except that the addition equivalent of VMDMS was changed to 2.0 wt% in PMDMS + DMDMS + VMDMS.

Manufacturing example  4: Linear silicon system Rubber  Produce

A linear silicone rubber was prepared in the same manner as in Production Example 1 except that the addition equivalent of VMDMS was changed to 3.0 wt% of PMDMS + DMDMS + VMDMS.

Manufacturing example  5: Linear silicon system Rubber  Produce

A linear silicone rubber was prepared in the same manner as in Production Example 1, except that the addition equivalent of VMDMS was changed to 5.0 wt% in PMDMS + DMDMS + VMDMS.

Example  One

The linear silicone rubber of Production Example 1 and a crosslinking agent (tris (dimethylsiloxy) phenylsilane, purity: 98% or more, JJ Chem) were blended so as to have a functional group molar ratio of A: B = 1: Karstedt catalyst (Umicore), and inhibitor (Surfynol) were added to prepare a matrix composition. The content of the linear silicone rubber in the matrix composition was 96% by weight. The composition for a matrix was impregnated with a glass fiber cloth (refractive index: 1.48, thermal expansion coefficient: 3 ppm / 占 폚, D-glass cloth, Owens Corning) so as to contain 60% by weight in the composite sheet and thermally cured at 50 占 폚 for 2 hours Sheet. In the functional group molar ratio, A is the number of moles of Si-vinyl groups relative to the weight average molecular weight of the linear silicone rubber, and B is the number of moles of Si-H groups with respect to the molecular weight of the crosslinking agent.

Example  2

(Tris (dimethylsiloxy) phenylsilane, tris (dimethylsiloxy) phenylsilane, purity: 98% or more, JJ Chem), and a non-rubbery silicone compound, tetravinyltetramethylcyclotetrasiloxane (Tetravinyl tetramethyl cyclotetrasiloxane, D4vinyl, purity: 95% or more, JJ Chem) was blended so that the functional group molar ratios were C: A = 5.5: 1 and (C + A): B = , and inhibitor (Surfynol) were added to prepare a matrix composition. The content of the linear silicone rubber of Production Example 1 in the composition for the matrix was 68% by weight. The composition for a matrix was impregnated with a glass fiber cloth (refractive index: 1.48, thermal expansion coefficient: 3 ppm / 占 폚, D-glass cloth, Owens Corning) and thermally cured at 50 占 폚 for 2 hours to prepare a composite sheet. A is the mole number of the Si-vinyl group relative to the weight average molecular weight of the linear silicone rubber, B is the number of Si-H groups relative to the molecular weight of the crosslinking agent, C is the Si- Means the number of moles of vinyl groups.

Example  3

C: A = 4.1: 1 A composite sheet was prepared in the same manner as in Example 2, except that the content of the linear silicone rubber in the matrix composition was changed to 73% by weight.

Example  4

A composite sheet was prepared in the same manner as in Example 2 except that C: A = 3.3: 1, and the content of the linear silicone rubber in the matrix composition was changed to 76 wt%.

Example  5

A composite sheet was produced in the same manner as in Example 1, except that the linear silicone rubber of Production Example 2 was used in place of the linear silicone rubber of Production Example 1.

Example 6

A composite sheet was produced in the same manner as in Example 2, except that the linear silicone rubber of Production Example 2 was used in place of the linear silicone rubber of Production Example 1.

Comparative Example  One

A composite sheet was produced in the same manner as in Example 1, except that the linear silicone rubber of Production Example 3 was used in place of the linear silicone rubber of Production Example 1.

Comparative Example  2

A composite sheet was produced in the same manner as in Example 1, except that the linear silicone rubber of Production Example 4 was used instead of the linear silicone rubber of Production Example 1.

Comparative Example  3

A composite sheet was produced in the same manner as in Example 1, except that the linear silicone rubber of Production Example 5 was used instead of the linear silicone rubber of Production Example 1.

The following properties (1) to (4) were measured on the composite sheet prepared in Examples 1 to 6 and Comparative Examples 1 to 3, and are shown in Table 1 below.

(1) Relaxation modulus: Relaxation modulus: The window part (the portion where the glass fiber and the warp do not intersect but the resin only) is pressed against the composite sheet by a micro indentor (HM2000, Fisher) 10 mN force for 10 s, creep for 3 s, and relaxation for 10 s.

(2) Compression elongation: The window portion (the portion where the glass fiber and the warp do not cross each other but the resin only) of the composite sheet was pressed with a micro indentor using a micro indentation device (HM2000, Fisher) sec, the length (s, unit: 탆) in which the micro indentor is inserted to the point at which the window portion is broken is measured. (S / t x 100) of the length (s) to the total thickness (t, unit: 탆) of the composite sheet.

(3) Transmittance: The initial state permeability of the composite sheet (thickness: 100 mu m) was measured at 25 DEG C and a wavelength of 550 nm. The composite sheet was allowed to stand at 250 DEG C for 1 hour, and then the transmittance of the composite sheet was measured at 25 DEG C and a wavelength of 550 nm. The transmittance was measured using a UV-Vis spectrometer (Lambda 35, PerkinElmer).

(4) Creation of cracks: The occurrence of cracks in the composite sheet at an initial state at 25 ° C was measured by an optical microscope in a reflection mode. The composite sheet was allowed to stand at 250 DEG C for 1 hour and cracked at 25 DEG C in the same manner. When there was no crack on the surface of the composite sheet, it was evaluated as X, when the crack was only partially, and when it was mostly cracked.

In Examples 1 to 6 and Comparative Examples 1 to 3, a matrix was prepared by curing the matrix composition without impregnating the glass fiber cloth, and the tensile elongation of the matrix was measured. The tensile elongation of the matrix was determined by stretching the matrix at a rate of 50 mm / min using an Instron (TA.XT.plus, TA instrument) with respect to the total length of the matrix specimen (Width 5 mm, Length 20 mm) The percentages are calculated as shown in Table 1 below.

* VMDMS content
(weight%) ** Silicone rubber content
(weight%) Modulus (Mpa) Compression elongation (%) Tensile elongation (%) of matrix Initial state After standing at 250 DEG C for 1 hour Permeability (%) Crack occurrence Permeability (%) Crack occurrence Example 1 0.5 96 5 48 25 88.0 × 88.2 × Example 2 0.5 68 10 38 18 88.4 × 88.2 × Example 3 0.5 73 7 38 20 87.5 × 88.1 × Example 4 0.5 76 6 43 24 87.8 × 86.9 × Example 5 1.0 96 5 40 21 86.9 × 87.0 × Example 6 1.0 68 5 45 20 88.0 × 88.1 × Comparative Example 1 2.0 96 7 28 14 87.5 × 77.4 △ Comparative Example 2 3.0 96 8 21 11 81.0 △ 53.0 ○ Comparative Example 3 5.0 96 8 15 8 74.1 ○ 49.2 ○

*: The content of VMDMS in the linear silicon-based rubber manufacturing process of Production Examples 1 to 5

**: Content of linear silicone rubber in solid matrix composition

As shown in Table 1, the composite sheet of the present invention was found to have a compressive elongation of 30% or more, and cracking did not occur even after being left at 250 ° C for 1 hour. As a result, it was confirmed that the permeability was maintained at 80% or more.

However, in Comparative Examples 1 to 3, in which the addition equivalent of VMDMS was out of the range of the present invention, the compressive elongation was less than 30% and cracks were slightly generated at 250 DEG C for 1 hour, %, And the effect of the present invention can not be obtained.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (17)

A silicon-based matrix, and
And a reinforcing material impregnated in the silicone matrix,
A composite sheet having a compression elongation of 30% or more,
Wherein the silicone-based matrix comprises a cured product of a linear silicone-based rubber-containing composition,
Wherein said linear silicone rubber is made from a composition for the preparation of a silicone-based rubber comprising phenylmethyldimethoxysilane, dimethyldimethoxysilane and vinylmethyldimethoxysilane. A silicon-based matrix, and a reinforcing material impregnated in the silicon-based matrix, wherein the sheet is a composite sheet having a transmittance of 80% or more measured at 25 DEG C and a wavelength of 550 nm after being left at 250 DEG C for 1 hour for a thickness of 100 mu m,
Wherein the silicone-based matrix comprises a cured product of a linear silicone-based rubber-containing composition,
Wherein said linear silicone rubber is made from a composition for the preparation of a silicone-based rubber comprising phenylmethyldimethoxysilane, dimethyldimethoxysilane and vinylmethyldimethoxysilane. The composite sheet according to claim 1 or 2, wherein the silicone matrix has a tensile elongation of 15% or more. delete delete The composite sheet according to claim 1 or 2, wherein the vinyl methyl dimethoxysilane is contained in an amount of more than 0 wt% to 1.0 wt% or less in the silicone rubber composition. The composite sheet according to claim 1 or 2, wherein the linear silicone rubber comprises a repeating unit represented by the following formula (4)
&Lt; Formula 4 >

(Wherein x is a linking site of the element, 0 <x <1, 0 <y <1, 0 <z <1, and Me is a methyl group). The composite sheet according to claim 1 or 2, wherein the composite sheet has a modulus of 5 to 20 MPa. The composite sheet according to claim 1 or 2, wherein the matrix composition further comprises a non-rubbery silicone compound. The composite sheet according to claim 9, wherein the non-rubbery silicone compound is a cyclic siloxane compound. The composite sheet according to claim 10, wherein the cyclic siloxane compound is represented by the following formula (16)
&Lt; Formula 16 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6 ,} R _{7 and} R ₈ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An allyl group, an allyloxy group, a vinyloxy group, or a group represented by the following formula (17)
&Lt; Formula 17 >

(In the above formula (17), * is a connecting site to Si in the above formula (16)
R ₉ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms and R ₁₀ , R ₁₁ and R ₁₂ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, , An allyl group, an allyloxy group, and a vinyloxy group; X ₁ and X ₂ each independently represent a single bond, O, S, or NR (R is hydrogen or an alkyl group having 1 to 10 carbon atoms)
_{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R one or more of the ₈ is a vinyl group, an allyl group, an allyloxy group, a vinyloxy group, R _10, R _11, R ₁₂ of the one or more vinyl group formula 17, R _10, R _11, R ₁₂ is one or more of allyl group of the formula 17, R _10, R _11, R one or more of ₁₂ the allyloxy group represented by general formula [16], or R _10, R _11, R &lt; ₁₂ &gt; is a vinyloxy group.       The composite sheet according to claim 9, wherein the linear silicone rubber is contained in an amount of 60 to 80% by weight based on a solid content of the matrix composition, and the non-rubbery silicone compound is contained in an amount of 1 to 30% by weight. The composite sheet according to claim 1 or 2, wherein the reinforcing material has a refractive index of 1.5 or less. The reinforcing member according to claim 1 or 2, wherein the reinforcing material is at least one selected from the group consisting of glass fiber, glass fiber cloth, glass fabric, glass nonwoven fabric, and glass mesh Including a composite sheet. The composite sheet according to claim 1 or 2, wherein the silicone matrix further comprises a barrier layer on one side or both sides. 16. The composite sheet according to claim 15, wherein the barrier layer comprises at least one of silicon nitride, silicon oxide, silicon carbide, aluminum nitride, indium tin oxide (ITO), and indium zinc oxide (IZO). A substrate, and a member for an apparatus formed on the substrate,
Wherein the substrate comprises the composite sheet according to claim 1 or 2.

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