KR102577765B1 - Curable resin composition, cured film prepared therefrom and electronic device comprising the cured film - Google Patents

Abstract

(A) Silicone-based polymer; (B) particles containing a functional group represented by the following formula (1) on the surface; and (C) a solvent, a cured resin composition containing the same, a cured film obtained by curing the same, and a device comprising the cured film.
[Formula 1]

(In Formula 1 above, each substituent is as defined in the specification)

Description

Curable resin composition, cured film thereof, and device comprising the cured film {CURABLE RESIN COMPOSITION, CURED FILM PREPARED THEREFROM AND ELECTRONIC DEVICE COMPRISING THE CURED FILM}

This description relates to a curable resin composition, a cured film obtained from the curable resin composition, and a device containing the cured film.

As the display field develops, various display devices using displays are diversifying, and the demand for technology to apply low-refraction materials to devices that handle light among various display devices is increasing. Using low refractive index characteristics, efficiency can be increased by reducing light loss inside the device through which light travels. In addition, because the low refractive index characteristic can also have the effect of low reflectance, it can be used in the low-reflection layer of a lens located outside a light sensor, or an anti-reflection film (AR) located on the outermost layer of a display or solar cell. The lower the refractive index of the low-refraction coating layer, the lower the thickness of the coating layer can be, which widens the margin of the coating film and increases the efficiency according to the device purpose.

If low-refractive silicon material is used between layers of the panel, the amount of light lost when light moves inside can be recycled to increase luminous efficiency. In particular, as it is difficult to increase the luminous efficiency of the Green QD emitter among QDPR (Quantum dot PhotoResist), the luminous efficiency of the Green QD emitter can be increased by introducing a low-refractive coating film on the upper and lower layers of the QD.

On the other hand, when the lower substrate has a pattern, a high level difference may occur between the patterns, and when a low refractive index layer is coated on top, a chemical solution may flow between the patterns and the low refractive index layer may accumulate thickly. Therefore, the low refractive index layer must have crack resistance so that cracks do not occur at high thicknesses, and at the same time must maintain high transparency.

The existing thermal curing method for obtaining low refractive index materials had limitations in that the thermosetting resin composition had to be cured at a high temperature of 350℃ or higher (at least 300℃ or higher). Considering that the recent curing process trend is low temperature curing, this is not desirable. In addition, existing deposition methods such as CVD have difficulty producing thick coatings and nanopores, making it difficult to obtain a low refractive index of about 1.20 to 1.30 based on a wavelength of 550 nm. Existing silicone low-refractive index materials had the problem that as the thickness of the cured film increases, the haze characteristics decrease and transparency decreases, and cracks often occur at thicknesses of 2.5㎛ or more. Therefore, there is a tendency to use, for example, epoxy polymers instead of silicone polymers. Although attempts have been made, it is difficult to obtain a low refractive index of about 1.20 to 1.30 based on a wavelength of 550 nm, and even if a low refractive index is achieved, there are problems such as cracks occurring at a thickness of 2 μm or more.

One embodiment provides a curable resin composition having a low refractive index with excellent crack resistance, adhesion, and transparency.

Another embodiment provides a cured film manufactured using the curable resin composition.

Another embodiment provides a device including the cured film.

One embodiment includes (A) a silicone-based polymer; (B) particles containing a functional group represented by the following formula (1) on the surface; and (C) a solvent.

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

L ² and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n is an integer greater than or equal to 1.

In Formula 1, L ² and L ³ may be the same.

In Formula 1, n may be an integer from 2 to 30.

The particles may have a hollow structure.

The particles may be fine particles of metal oxide including titanium oxide, silicon oxide, barium oxide, zinc oxide, zirconium oxide, or a combination thereof.

The particles may be hollow silica.

The average diameter (D ₅₀ ) of the particles may be 10 nm to 150 nm.

The silicone-based polymer may be a siloxane polymer.

The weight average molecular weight (Mw) of the silicone-based polymer converted to polystyrene may be 1,000 g/mol to 50,000 g/mol.

The curable resin composition includes 1 to 100 parts by weight of particles containing a functional group represented by Formula 1 on the surface of (B) based on 100 parts by weight of the silicone polymer (A), and the (C) ) It may contain 100 to 2,000 parts by weight of solvent.

Another embodiment may be a cured film obtained by curing the curable resin composition.

The cured film may have a refractive index of 1.35 or less at 500 nm to 550 nm.

Another embodiment may be a device including the cured film.

Details of other aspects of the invention are included in the detailed description below.

The cured film manufactured using the curable resin composition according to one embodiment has excellent crack resistance and adhesion, and also has high transparency and low refractive properties, so that it can be advantageously used in applications such as an antireflection film or a low refractive index layer.

Figure 1 is a schematic diagram showing surface-modified particles. (In Figure 1, R is a functional group represented by Chemical Formula 1.)

Hereinafter, embodiments of the present invention will be described in detail. 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 the claims to be described later.

Unless otherwise specified herein, “alkyl group” refers to a C1 to C30 alkyl group, “cycloalkyl group” refers to a C3 to C30 cycloalkyl group, “aryl group” refers to a C6 to C30 aryl group, and “aryl group” refers to a C1 to C30 alkyl group. “Alkyl group” means a C7 to C30 arylalkyl group, “heteroalkyl group” means a C1 to C30 heteroalkyl group, “heterocycloalkyl group” means a C2 to C30 heterocycloalkyl group, and “alkenyl group” means a C2 to C30 heterocycloalkyl group. means an alkenyl group, “alkynyl group” means a C2 to C30 alkynyl group, “alkylene group” means a C1 to C30 alkylene group, “cycloalkylene group” means a C3 to C30 cycloalkylene group, “Arylene group” means a C6 to C30 arylene group.

Unless otherwise specified herein, “substitution” means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an amino group, Amino group substituted with alkyl group, amino group substituted with aryl group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cyclo. As a substituent of an alkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof. It means replaced.

Also, unless otherwise specified herein, “hetero” means that at least one hetero atom of N, O, S, and P is included in the chemical formula.

Also, unless otherwise specified in the specification, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible, and “(meth)acryloyloxy group” means “acryloyloxy group”. This means that both "and "methacryloyloxy group" are possible.

Unless otherwise specified herein, “combination” means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, if a chemical bond is not connected at a position where a chemical bond should be connected, it means that a hydrogen atom is bonded at that position.

In this specification, when describing a numerical range, “X to Y” means “X to Y or less” (X ≤ and ≤ Y).

In this specification, in descriptions other than numerical ranges, “X to Y” means “X to Y.”

Additionally, unless otherwise specified in the specification, “*” refers to a portion connected to the same or different atom or chemical formula.

Hereinafter, a curable resin composition according to one embodiment will be described.

A curable resin composition according to an embodiment of the present invention includes (A) a silicone-based polymer; (B) particles containing a functional group represented by the following formula (1) on the surface; and (C) a solvent.

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

L ² and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n is an integer greater than or equal to 1.

The low refractive index layer located inside the QD-OLED panel causes the substrate to be uneven and have steps due to the color filter (red, green) layer pattern at the bottom. At this time, the step of the lower pattern is large, so there is a problem of cracks occurring when the composition that secures the existing low refractive index is coated and cured on the substrate with the step. Therefore, recently, crack resistance that can overcome steps of 3.6 ㎛ or more, specifically 4 ㎛ or more, is required for resin compositions with low refractive characteristics.

Additionally, in order to increase the luminous efficiency of the QD panel, the refractive index of the low-refractive material has a nebulizer characteristic. Accordingly, after long research, the inventors of the present invention introduced particles surface-treated with a specific compound, more specifically a specific oligomer, to achieve a crack margin of 3.6 ㎛ or more, specifically 4 ㎛ or more and a low refractive index, thereby improving crack resistance. Achievements (based on 550nm) We have developed a low-refractive index material (curable resin composition) with a refractive index of 1.35 or less, specifically 1.23 or less, and more specifically 1.22 or less.

In other words, all of the various technologies introduced to date (thermal curing, CVD deposition, use of existing silicon materials, use of non-silicon polymers, etc.) cannot be processed at low temperatures (below 250℃) or cracks occur when the thickness becomes thick, resulting in crack resistance. Low temperature processing, crack resistance, low refractive index, high adhesion, and high transparency (low haze) could not be achieved at the same time due to low temperature processing, high refractive index, low adhesion, and low transparency. Therefore, the above characteristics were not achieved. There is a very high demand for a low refractive index composition that can meet all requirements. The present inventors confirmed that all of the above characteristics can be satisfied by surface modifying the surface of the particle in the curable resin composition with a specific material (a functional group represented by Formula 1).

Below, each component is described in detail.

(B) Particles containing a functional group represented by Formula 1 on the surface

For example, in Formula 1, L ² and L ³ may be the same.

For example, in Formula 1, L ² and L ³ may each independently be a substituted C1 to C20 alkylene group.

For example, in Formula 1, n may be an integer of 2 or more, for example, an integer of 2 to 30.

When n is an integer of 2 or more, a lower refractive index can be secured and at the same time crack margin and adhesion can be further improved compared to when n is an integer of 1.

According to one embodiment, the surface modifier, which is an inducer of the functional group represented by Formula 1, can perform the role of a conventional pore-inducing material while vaporizing during the surface modification reaction of the particles, so the curable resin composition according to one embodiment is Even without the need to include a separate porogen (polymeric pore generator), it is possible to secure low refractive index characteristics at an equivalent level or higher compared to a conventional curable resin composition containing a pore-inducing material.

For example, the curable resin composition may be composed of the silicone polymer, particles containing the functional group represented by Formula 1 on the surface, and the solvent.

For example, the surface modifier, which is a derivative of the functional group represented by Formula 1, may be represented by the following Formula 1-1.

[Formula 1-1]

In Formula 1-1,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L ² and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

n is an integer greater than or equal to 1.

For example, the particles may have a hollow structure.

For example, the particles may be fine particles of metal oxide including titanium oxide, silicon oxide, barium oxide, zinc oxide, zirconium oxide, or a combination thereof, but are not necessarily limited thereto.

For example, the particles may be hollow silica (SiO ₂ ), but are not necessarily limited thereto.

The average diameter (D ₅₀ ) of the particles may be 10 nm to 150 nm, such as 10 nm to 130 nm, such as 10 nm to 110 nm, such as 20 nm to 110 nm, such as 40 nm to 110 nm, such as 60 nm to 110 nm, but is necessarily limited thereto. It doesn't work. When the average diameter of the particles satisfies the above range, the particles can be well dispersed in the silicone-based polymer and the low refractive index characteristics of the curable resin composition can be improved.

Additionally, when the particles comprise a hollow structure, the porosity is 40% to 90%, such as 40% to 80%, such as 40% to 70%, such as 40% to 60%, such as 40% to 50%. %, such as 50% to 90%, such as 60% to 90%, such as 70% to 90%, such as 80% to 90%, such as 50% to 70%, but is not necessarily limited thereto. no. If the porosity of the particle exceeds the above range, the size of the internal space of the particle increases and the outer thickness decreases, which may weaken the durability of the particle. If the porosity of the particle is less than the above range, the refractive index of the low refractive layer decreases. The effect may be minimal.

The particles are present in an amount of 1 part by weight to 100 parts by weight, such as 1 part by weight to 60 parts by weight, such as 3 parts by weight to 60 parts by weight, such as 5 parts by weight to 60 parts by weight, such as 5 parts by weight, based on 100 parts by weight of the silicone polymer. parts by weight to 50 parts by weight, such as 10 parts by weight to 50 parts by weight. When the particles are included in the above content range, it can be advantageous to improve crack margin and adhesion while maintaining an excellent low refractive index.

(A) Silicone-based polymer

In the present invention, the silicone-based polymer may be a siloxane polymer.

The siloxane polymer can be formed by hydrolyzing and condensing a compound represented by the following formula (2).

[Formula 2]

(R ² ) _a (R ³ ) _b (R ⁴ ) _c -Si-(OR ⁵ ) _4-abc

In Formula 2,

R ² to R ⁴ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 aryl group. C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, R '(C=O)-* (where R' is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group), (meth ) an acrylate group, a (meth)acryloyloxy group, or a combination thereof,

R ⁵ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or a substituted or unsubstituted C3 to C30 arylalkyl group thereof. It is a combination,

a, b, and c are each independently integers of 0 or 1, but 0 ≤ a+b+c < 4.

The siloxane polymer may be formed by hydrolyzing and condensing a compound represented by Formula 2 and a compound represented by Formula 3 below.

[Formula 3]

In Formula 3 above,

L ⁴ is a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

R ⁶ and R ⁷ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 aryl group. C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, or these A combination of, wherein at least one of R ⁶ and R ⁷ is a substituted or unsubstituted C6 to C30 aryl group,

R ⁸ is hydrogen, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, or these It is a combination of

m is an integer from 1 to 3.

When the siloxane polymer is formed by hydrolyzing and condensing the compounds represented by Formula 2 and Formula 3, the siloxane polymer contains an N-arylamino group as a substituent. In this case, the curable resin according to one embodiment The crack resistance and high transparency (low haze) characteristics of the composition can be further improved. In addition, the N-arylamino group can increase compatibility with the particles, thereby improving the transparency characteristics of a cured film manufactured using the curable resin composition.

The siloxane polymer is 50 to 85 mol% of the compound represented by Formula 2 and 15 to 50 mol% of the compound represented by Formula 3, for example, 55 to 80 mol% of the compound represented by Formula 2 and Formula 3. It may be formed by hydrolysis and condensation reaction, including 20 to 45 mol% of the compound, for example, 65 to 75 mol% of the compound represented by Formula 2 and 25 to 35 mol% of the compound represented by Formula 3. When included in the above range, the crack resistance and transparency characteristics of the curable resin composition prepared therefrom can be further improved.

The siloxane polymer may be formed by hydrolyzing and condensing the compounds represented by Formula 2 and Formula 3 together with a compound represented by Formula 4 below.

[Formula 4]

In Formula 4 above,

R ⁹ , R ¹⁰ , R ¹² and R ¹³ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C6 to C30 aryl group. or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, R'(C=O)-* (where R' is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group), (meth)acrylate group, (meth)acryloyloxy group, or a combination thereof,

R ¹¹ and R ¹⁴ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 aryl group. C30 arylalkyl group or a combination thereof,

Y ¹ is a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof, and the substituted or unsubstituted C6 to C30 arylene group. C30 arylene group consists of one aromatic ring, or two or more aromatic rings are formed by a single bond, *-O-*, *-S-*, *-(C=O)-*, *-(C=O) O-*, *-(C=O)NH-*, an aromatic ring connected by a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a combination thereof,

d, e, f and g are each independently integers of 0 or 1.

The siloxane polymer contains 5 mol% to 30 mol%, for example, 5 mol% to 25 mol%, for example, 5 mol% to 20 mol%, for example, of the compound represented by Formula 4 based on 100 mol% of the siloxane polymer. 5 mole% to 15 mole%, such as 5 mole% to 10 mole%, such as 10 mole% to 30 mole%, such as 15 mole% to 30 mole%, such as 25 mole% to 30 mole%. It may be formed through hydrolysis and condensation reactions, but is not necessarily limited thereto.

For example, in the present invention, better adhesion can be secured by using a mixture of two different types of siloxane polymers as the silicone polymer.

The weight average molecular weight (Mw) of the silicone-based polymer in terms of polystyrene is 1,000 to 50,000 g/mol, such as 2,000 to 50,000 g/mol, such as 3,000 to 50,000 g/mol, such as 5,000 to 50,000 g/mol, such as 7,000. to 50,000 g/mol, such as 9,000 to 50,000 g/mol, such as 10,000 to 50,000 g/mol, such as 15,000 to 50,000 g/mol, such as 20,000 to 50,000 g/mol, such as 25,000 to 50,000 g/mol , such as 1,000 to 45,000 g/mol, such as 1,000 to 40,000 g/mol, such as 1,000 to 35,000 g/mol, such as 1,000 to 30,000 g/mol, such as 1,000 to 25,000 g/mol, but must be It is not limited to this.

(C) Solvent

As the solvent, one or a mixture of two or more solvents that can be used at a process temperature of 200°C or higher can be used. For example, the solvent may be an alcohol-type solvent, such as butanol, isopropanol, etc., and a ketone-type solvent, such as PMEA, DIBK, etc., and other than these, any solvent known in the art that can be used above the process temperature One type of solvent or a mixture of two or more types can be used.

When two or more of the above solvents are mixed and used, a mixture of propylene glycol monomethyl ether acetate (PGMEA), gamma butyrolactone (GBL), and other types of solvents that can be used at a process temperature of 100°C to 230°C You can.

In one embodiment, the solvent is used in an amount of 100 to 2,000 parts by weight, for example, 100 to 1,000 parts by weight, for example, 100 to 500 parts by weight, for example, 100 to 400 parts by weight, for example, 100 to 100 parts by weight, based on 100 parts by weight of the silicone polymer. It may be included at 300 parts by weight, for example, 100 to 200 parts by weight, but is not necessarily limited thereto.

Other additives

The curable resin composition may further include a surfactant, such as a fluorine-based surfactant, to reduce the refractive index. In addition, by the resin composition further including the surfactant, coating properties can be improved and defects can be prevented when the resin composition is coated on a substrate.

The surfactant is present in an amount of 5 parts by weight or less, for example, 0.1 to 5 parts by weight, for example, 1 to 5 parts by weight, for example, 2 to 5 parts by weight, based on 100 parts by weight of the silicone polymer. It may be included in 3 to 5 parts by weight, but is not necessarily limited thereto.

The curable resin composition may further include a curing catalyst for promoting curing of unreacted silanol groups or epoxy groups at the terminals of the silicone polymer. This curing catalyst may be a thermal curing catalyst or a photocuring catalyst. Additionally, depending on the type of silicone polymer used, such curing catalyst may not be included. In one embodiment, an example of a curing catalyst for curing a silicone-based polymer may include one having an ammonium salt form such as tetrabutylammonium acetate (TBAA).

When using the curing catalyst, this catalyst is used in an amount of 0.1 to 1 part by weight, such as 0.3 to 1 part by weight, such as 0.5 to 1 part by weight, such as 0.7 to 1 part by weight, based on 100 parts by weight of the silicone polymer. It may be included in 0.8 to 1 part by weight, but is not necessarily limited thereto.

Another embodiment provides a cured film obtained by curing the curable resin composition.

The cured film obtained by curing the curable resin composition according to one embodiment not only has low refractive index characteristics, but also does not cause cracks in the cured film even when there is a step of 3.2 ㎛ or more, specifically 3.6 ㎛ or more, and more specifically 4 ㎛ or more. It has crack resistance and can also produce a coating film with excellent transparency even when forming a coating film of 2㎛ or more.

Specifically, the cured film obtained by curing the curable resin composition can have crack resistance up to a cured film thickness of 7㎛ at a low processing temperature of 230°C. In addition, it has high transparency with a Haze value of 0.5% or less at a wavelength of 650 nm, and a refractive index of 1.35 or less, for example, 1.23 or less, for example, 1.18 or less at a wavelength of 500 nm to 550 nm. In addition, the composition according to one embodiment was applied to a specimen measuring 1.5cm x 1.5cm, a pin was fixed thereto, cured at 180°C for 30 minutes, and then the adhesion between the pin and the specimen was measured (stud pin test) ), it may have an adhesive strength of 7 MPa or more, for example, 10 MPa or more, for example, 20 MPa or more.

Another embodiment provides a device including the cured film.

Hereinafter, preferred embodiments of the present invention will be described. However, the following example is only a preferred example of the present invention, and the present invention is not limited by the following example.

Example

Synthesis Example 1: Preparation of siloxane polymer (A-1)

Add 77.15 g of methyltrimethoxy silane (MTMS), 50.57 g of tetraethoxy orthosilicate (TEOS), and 215.56 g of PGMEA to a 500 ml three-necked flask, and add 45.43 g of water while stirring at room temperature. An aqueous hydrochloric acid solution in which 0.09 g of hydrochloric acid (36% aqueous solution) is dissolved in g is added over 10 minutes. Afterwards, the flask was immersed in an oil bath at 60°C and stirred for 4 hours, then reacted for 3 hours using a vacuum pump and Dean stark, and then the by-products of methanol, ethanol, aqueous hydrochloric acid solution, and water were evaporated to reduce the molecular weight. Obtain an adjusted siloxane polymer solution (A-1).

The solid content concentration of the obtained siloxane polymer solution (A-1) was 20.5% by weight, and the weight average molecular weight (Mw) of the obtained siloxane polymer (A-1) in terms of polystyrene was 2,600 g/mol.

Synthesis Example 2: Preparation of siloxane polymer (A-2)

In a 500 ml three-neck flask, 58.67 g of methyltrimethoxy silane (MTMS), 37.31 g of tetraethoxy orthosilicate (TEOS), and 36.59 g of n-phenylaminopropyltriethoxysilane (n-phenylaminopropyltriethoxysilane) g, and 221.94 g of PGMEA were added, and an aqueous hydrochloric acid solution prepared by dissolving 0.03 g of hydrochloric acid (36% aqueous solution) in 38.71 g of water was added over 10 minutes while stirring at room temperature. Afterwards, the flask was immersed in an oil bath at 60°C and stirred for 4.5 hours, then reacted for 3 hours using a vacuum pump and Dean stark, and then the by-products of methanol, ethanol, hydrochloric acid aqueous solution, and water were evaporated to reduce the molecular weight. Obtain an adjusted siloxane polymer solution (A-2).

The solid content concentration of the obtained siloxane polymer solution (A-2) was 20.2% by weight, and the weight average molecular weight (Mw) of the obtained siloxane polymer (A-2) in terms of polystyrene was 2,540 g/mol.

Manufacture of curable resin composition

The specifications of the ingredients used to manufacture the curable resin composition are as follows.

(A) Silicone-based polymer

(A-1) Siloxane polymer prepared in Synthesis Example 1

(A-2) Siloxane polymer prepared in Synthesis Example 2

(B) Particles containing a functional group represented by Formula 1 on the surface

(B-1) A hollow particle dispersion surface-treated with a functional group represented by the following formula E-1 (solid content 20%, average diameter 85 nm; Nano New Materials Co., Ltd.)

[Formula E-1]

(B-2) A hollow particle dispersion surface-treated with a functional group represented by the following formula E-2 (solid content 20%, average diameter 85 nm; Nano New Materials Co., Ltd.)

[Formula E-2]

(B-3) A hollow particle dispersion surface-treated with a functional group represented by the following formula E-3 (solid content 20%, average diameter 85 nm; Nano New Materials Co., Ltd.)

[Formula E-3]

(C) Solvent

Propylene glycol monomethyl ether acetate (PGMEA, SIGMA-ALDRICH)

(D) Other additives

(D-1) Fluorine-based surfactant (F-563, DIC Company)

(D-2) Pore inducing material (porogen; polypropylene glycol 4000, SIGMA-ALDRICH)

Examples 1 to 9, Comparative Example 1 and Comparative Example 2

According to the composition in Table 1 below, the polymer, surface-treated particles, solvent, and other additives are mixed and stirred for about 30 minutes to prepare a curable resin composition.

(Unit: g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 polymer (A-1) 32 30 28 16 15 14 30 30 32 30 32 (A-2) - - - 16 15 14 - - - - - particle
(dispersion) (B-1) - - - - - - 27 27 25 - - (B-2) 25 27 29 25 27 29 - - - - - (B-3) - - - - - - - - - - 25 menstruum 42 42 42 42 42 41 42 32 27 39 42 Other additives (D-1) One One One One One One One One One One One (D-2) - - - - - - - 10 15 30 -

Preparation and evaluation of cured films

(1) Refractive index evaluation

The curable resin compositions prepared in Examples 1 to 9, Comparative Examples 1 and 2 were spin-coated on a silicon wafer using a spin coater MS-A100 (Mikasa product) at 200 rpm for 5 seconds, then applied to a hot plate (hot plate). -plate) to obtain a 1.0㎛ thick coating cured film by baking at 100℃ for 2 minutes and then at 230℃ for 20 minutes.

The refractive index of the cured film was measured at a wavelength of 370 nm to 1,000 nm using an ellipsometer Base-160 (J.A. Woollam Co., Ltd.), of which the refractive index at 550 nm is shown in Table 2 below.

(2) Crack resistance (crack margin) evaluation

The curable resin compositions prepared in Examples 1 to 9, Comparative Examples 1 and 2 were spin-coated on a glass substrate at 200 rpm for 5 seconds using a spin coater MS-A100 (Mikasa Co., Ltd.), and then applied to a hot plate ( Using a hot-plate, bake at 100℃ for 2 minutes and then at 230℃ for 20 minutes to obtain a 5.0㎛ thick coating cured film.

When no cracks occurred in the cured film, part of the coating film was peeled off using a razor, and the thickness of the step was measured again using Tencor KLA P-6, and the results are shown in Table 2 below.

(3) Haze evaluation

The curable resin compositions prepared in Examples 1 to 9, Comparative Examples 1 and 2 were spin-coated on a glass substrate at 200 rpm for 5 seconds using a spin coater MS-A100 (Mikasa Co., Ltd.), and then applied to a hot plate ( Using a hot-plate, bake at 100°C for 2 minutes and then at 230°C for 20 minutes to obtain a 4.0㎛ thick coating cured film.

The degree of haze of the cured film was measured as a Haze value at a wavelength of 650 nm using a Hazemeter, and the results are shown in Table 2 below.

(4) Adhesion evaluation

The curable resin composition prepared in Examples 1 to 9, Comparative Example 1, and Comparative Example 2 was applied to a specimen measuring 1.5 cm x 1.5 cm, a pin was fixed there, and the specimen was cured at 180°C for 30 minutes. Afterwards, the adhesion between the pin and the specimen was measured through UTM (stud pin test), and the results are shown in Table 2 below.

refractive index Crack margin (㎛) Haze (%) at 4 ㎛ thickness Adhesion (MPa) Example 1 1.118 4.0 0.19 30 Example 2 1.126 5.0 0.22 33 Example 3 1.129 4.8 0.24 27 Example 4 1.206 5.7 0.37 40 Example 5 1.218 6.0 0.39 46 Example 6 1.192 5.8 0.36 38 Example 7 1.226 3.4 0.32 20 Example 8 1.213 3.5 0.50 12 Example 9 1.210 3.2 0.56 10 Comparative Example 1 1.184 1.8 0.59 4 Comparative Example 2 1.314 1.9 0.67 5

Referring to Table 2, it can be seen that particles containing the functional group represented by Formula 1 on the surface have low refractive index characteristics compared to particles that do not have the functional group, while having excellent crack margin, transparency, and adhesion. In particular, when using particles containing the functional group represented by Formula 1 on the surface, excellent effects (low refractive properties, excellent crack margin, high transparency and high adhesion) are achieved even without the use of a separate pore-inducing material (porogen). It can be confirmed that it has .

Although the preferred embodiments of the present invention have been described in detail above, it is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand the technical aspects of the present invention. It will be understood that it can be implemented in other specific forms without changing the idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.

Claims (13)

(A) Silicone-based polymer;
(B) particles containing a functional group represented by the following formula (1) on the surface; and
(C) Solvent
A curable resin composition comprising:
[Formula 1]

In Formula 1,
R ¹ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
L ¹ is a single bond or a substituted or unsubstituted C1 to C20 alkylene group,
L ² and L ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
n is an integer greater than or equal to 1.
According to paragraph 1,
A curable resin composition wherein L ² and L ³ are the same.
According to paragraph 1,
The curable resin composition wherein n is an integer of 2 to 30.
According to paragraph 1,
A curable resin composition in which the silicone-based polymer is a siloxane polymer.
According to paragraph 1,
The particles are a curable resin composition having a hollow structure.
According to paragraph 1,
A curable resin composition wherein the particles are fine particles of hollow metal oxide containing titanium oxide, silicon oxide, barium oxide, zinc oxide, zirconium oxide, or a combination thereof.
According to paragraph 1,
A curable resin composition in which the particles are hollow silica.
According to paragraph 1,
A curable resin composition wherein the particles have an average diameter (D ₅₀ ) of 10 nm to 150 nm.
According to paragraph 1,
A curable resin composition wherein the silicone polymer has a weight average molecular weight (Mw) converted to polystyrene of 1,000 g/mol to 50,000 g/mol.
According to paragraph 1,
The curable resin composition is,
For 100 parts by weight of the (A) silicone polymer,
(B) comprising 1 to 100 parts by weight of particles containing a functional group represented by Formula 1 on the surface,
A curable resin composition containing 100 to 2,000 parts by weight of the solvent (C).
A cured film obtained by curing the curable resin composition of any one of claims 1 to 10.
According to clause 11,
The cured film is a cured film having a refractive index of 1.35 or less at 500 nm to 550 nm.
A device comprising the cured film of claim 12.

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