KR20120078459A - Anti-glare film composition and anti-glare film comprising the same - Google Patents

Abstract

PURPOSE: A composition for an anti-glare film is provided to impart higher haze even in case of using same content, and to able to provide an anti-glare film with excellent anti-glare, clearness of transmitted image, and reflection glossiness. CONSTITUTION: A composition for an anti-glare film comprises a particle of which radius is r, and surface area is larger than 4πr^2, and a binder resin. The particle is a porous particle. The porous particle comprises a pore of which diameter is 3-100 nm, has porous volume of 0.04-0.5 cm^3/g, and BET surface area is 20-400 m^2/g. The binder resin comprises hyperbranch (meth)acrylate oligomer.

Description

Anti-glare film composition and anti-glare film comprising the same {ANTI-GLARE FILM COMPOSITION AND ANTI-GLARE FILM COMPRISING THE SAME}

The present invention relates to an antiglare film comprising a composition for antiglare film, and a coating film coated with the composition for antiglare film. More specifically, the present invention is a composition for antiglare film having a radius r and particles having a surface area larger than 4πr ² ; And by including a binder resin, it is possible to achieve a higher haze even when used in the same content by increasing the degree of refraction and scattering of light by the large surface area of the particles, and eventually reduce the manufacturing cost due to the decrease in particle content It is related with the composition for anti-glare films which are excellent in transmission image clarity, total light transmittance, and an anti-glare function, and lower curl.

Recently, as a demand for high-quality products due to the high speed of information transmission, a large flat panel display has emerged. However, such a display causes problems such as fatigue of the user's eyes due to surface reflected light when the external light such as natural light is exposed, or an image generated inside the display is not recognized as a clear image.

In order to solve this problem, a method of adding a coating layer including a particle inducing internal / external light scattering to the display surface has been proposed. However, when the particles are included in the coating layer a lot, there may be restrictions such as coating layer thickness and manufacturing cost may be high. In particular, in displays used in mobile phones, small notebooks, and the like, as the demand for thin thickness increases, the demand for anti-glare films containing small particles is high.

In addition, curling occurs when the coating layer is formed by applying and curing the antiglare film composition including the particles and the binder resin. Curl is caused by thermal deformation and shrinkage of the film, and has been pointed out as a cause of defect of the film. Therefore, there is an urgent need for an anti-glare film having a low curl.

An object of the present invention is to provide a composition for an anti-glare film that can implement a higher haze even if the particles are included in the same amount.

Another object of the present invention is to provide a composition for an antiglare film which enables a coating having good anti-glare properties and transmission transparency.

Still another object of the present invention is to provide an antiglare film having a coating film coated with the antiglare film composition.

The present invention relates to a composition for antiglare film. The antiglare film composition includes particles having a radius r and a surface area larger than 4πr ² ; And binder resins.

The particles may be porous particles.

The particles can have a pore volume of 0.04 to 0.5 cm 3 / g.

The particles may have a BET surface area of 20 to 400 m ² / g.

The particles may include pores having a diameter of 3 to 100 nm.

The binder resin may include a hyperbranched (meth) acrylate oligomer.

The hyperbranched (meth) acrylate oligomer may be represented by the following formula (1).

[Formula 1]

  (In the above, core is an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom of C3-50 having a functional group which can be bonded to R1, and R1 and R2 are each independently C1-50 containing or not containing a hetero atom. Aliphatic or aromatic hydrocarbon, and E is an ester bond).

The composition may include 3 to 30% by weight of particles and 70 to 97% by weight of the binder resin.

Anti-glare film made of the composition may be 0 to 20 mm curling in the coating film thickness of 4 ~ 10㎛.

The composition is selected from the group consisting of photopolymerization initiators, solvents, photosensitizers, polymerization inhibitors, leveling agents, wettability modifiers, surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers and antifoaming agents. It may further comprise one or more.

The present invention relates to an antiglare film comprising a coating film coated with the composition for an antiglare film.

In an embodiment, the antiglare film may have a curling thickness of 0 to 20 mm at a coating film thickness of 4 to 10 μm.

The present invention can achieve higher haze values even when the particles are used in the same amount. In addition, the present invention can implement an anti-glare film having a good anti-glare, transmission clarity and 60 ° reflective gloss with low curling.

The composition for anti-glare film of the present invention

(a) particles of radius r and surface area larger than 4πr ² ; And

(b) may comprise a binder resin.

(a) particles

The particles may be used as long as the particle size is larger than 4πr ² when the radius is r. Although the kind is not specifically limited, For example, porous particle | grains can be used.

The particles can have a uniform or nonuniform pore distribution.

The particles may be at least one selected from the group consisting of particles having pores both on the surface and inside of the particles, particles having pores only on the surface of the particles, and particles having pores only inside the particles. Preferably, the particle surface area is 4πr ² Larger particles with pores on the particle surface can be used.

The particles may have one or more pores selected from the group consisting of macropore, mesopore and micropore. Preferably, the porous particles may have macropores.

In the present specification, the large pore means a pore having a pore diameter of 50 nm or more, the middle pore means a pore having a pore diameter of more than 2 nm and less than 50 nm, and the fine pore means a pore having a pore diameter of 2 nm or less.

The particles may have pores having a pore diameter of 3 to 100 nm. Within this range, there are many changes in the path of light and higher haze can be achieved even when used in the same amount.

The particles can have a pore volume of 0.04 to 0.5 cm 3 / g. Within this range, the larger the void volume, the higher the refraction of light at the interface between the binder resin and the particles, thereby increasing the haze with the same content.

The particles may have a BET surface area of 20 to 400 m ² / g. The larger the surface area within the above range, the more the interface with the inter-layer refractive index difference increases, and therefore, the haze can be increased even with the same content.

The particles are not particularly limited, but may preferably include all organic particles, inorganic particles, or a combination thereof.

The organic particles are polystyrene, polyacrylate-co-styrene, polymethylacrylate-co-styrene, polymethylmethacrylate-co-styrene, polycarbonate, polyvinylchloride, polybutylene terephthalate, polyethylene terephthalate, poly Amide system, polyimide system, polysulfone, polyphenylene oxide, polyacetal, epoxy resin, phenol resin, melamine resin, benzoguanamine, polydivinylbenzene, polydivinylbenzene-co-styrene, polydivinylbenzene- It may comprise one or more of one single or two or more copolymers selected from co-acrylates, polydiallylphthalates, and triallyl isocyanurate polymers.

The inorganic particles may include one or more of silica, amorphous titanium oxide, amorphous zirconium oxide, indium oxide, aluminum oxide, amorphous zinc oxide, amorphous cerium oxide, barium oxide, calcium carbonate, amorphous barium titanate and barium sulfate.

Particle size, pore diameter and content of particles in the antiglare film can be selected according to the desired haze of the antiglare film, computed radiography (CR), and the like. For example, the particles may be included in 3 to 30% by weight of the total anti-glare film composition on a solids basis. Preferably it may be included in 3-10% by weight.

The particles, in particular porous particles, can be prepared by conventional methods, for example by seeded polymerization or suspension polymerization. This can be readily accomplished by one of ordinary skill in the art or in the field of porous particles. For example, it may be prepared according to the method described in Korean Patent No. 10-0519661. Specifically, the long-chain crosslinking agent, the monomer, the oil-soluble initiator and the stabilizer are dissolved in a continuous phase to disperse-polymerize to prepare a powdered high-crosslinked seed particles, the crosslinked seed particles prepared by the above method is an aqueous phase in which the emulsifier is dissolved Redispersing, dispersing the secondary crosslinking monomer (DVB, PS_ in the aqueous phase in which the emulsifier is dissolved, introducing into the seed dispersion and swelling), and dispersing the swollen seed dispersion in a dispersion stabilizer. It may be prepared by the step of stabilizing and polymerizing by addition, followed by washing and drying.

Such particles, in particular porous particles, can be purchased commercially.

(b) binder resin

Curable binder resin can be used for the said binder resin. The kind is not specifically limited, The thing normally used in the technical field to which this invention belongs can be used.

In particular, the binder resin may include a hyperbranched (meth) acrylate oligomer. The hyperbranched (meth) acrylate oligomer may have a number of (meth) acrylate functional groups of 10 or more, preferably 10 to 30. It is possible to implement an anti-glare film having a low curl in the above range.

The hyperbranched (meth) acrylate oligomers may be represented by the following formula (1).

[Formula 1]

       (In the above, core is an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom of C3-50 having a functional group which can be bonded to R1, and R1 and R2 are each independently C1-50 containing or not containing a hetero atom. Aliphatic or aromatic hydrocarbon, and E is an ester bond).

In the present invention (meth) acrylate means that it may include both acrylate and methacrylate.

As an example, the hyperbranched (meth) acrylate oligomer has a structure in which cores, R1, R2, and E are hyperbranched, as shown in Chemical Formula 2 below, and reactive (meth) acrylate functional groups are formed in the core, R1, R2, and It has a structure surrounding the hyperbranched structure of E.

[Formula 2]

"는 core, R1, E 및 R2가 하이퍼브랜치화된 구조를 나타낸 것이다.)(In the above, "

"Represents the hyperbranched structure of core, R1, E and R2.)

The hyperbranched (meth) acrylate oligomers can be synthesized in a conventional manner by Diels-Alder reaction or esterification reaction, which is easy for those skilled in the art to which the present invention pertains. Can be implemented.

In one embodiment, the hyperbranched (meth) acrylate oligomer comprises a monomer having a tri- or six-functional hydroxy group as a core, and a high-functional polyester by ester condensation reaction with a monomer having a carboxylic acid group and two hydroxy groups simultaneously. Prepare a polyol. Then, it can be synthesized by introducing (meth) acrylic acid into the polyester polyol prepared above.

The monomer having a tri- or six-functional hydroxy group is preferably trimethyl propanol, pentaerythritol, dipentaerythritol, or the like. As a monomer which has the said carboxylic acid and two hydroxyl groups simultaneously, dimethyl propanoic acid, dimethyl butanoic acid, etc. are preferable. In addition, the (meth) acrylic acid may be acrylic acid or methacrylic acid.

The hyperbranched (meth) acrylate oligomers are commercially available. For example, UNDIC RC28-559 from DIC CORPORATION can be used.

The hyperbranched (meth) acrylate oligomer may be preferably applied having a weight average molecular weight of 5,000 ~ 10,000g / mol.

The viscosity of the Hiber branch (meth) acrylate oligomer may be 100 to 400 cps at 25 ℃.

The binder resin may further include a curable resin, for example, a conventional ultraviolet curable resin, in addition to the hyperbranched (meth) acrylate oligomer alone or the hyperbranched (meth) acrylate oligomer. Examples of the curable resin include relatively small molecular weights such as polyester resins of 100 to 1,000 Mw, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiro acetal resins, polybutadiene resins, and polythiols. (Meth) acrylate resin of polyfunctional compounds, such as a polyene resin and a polyhydric alcohol, etc. can be included.

The ultraviolet curable resin may be included in 0-85% by weight of the binder resin.

The binder resin is preferably included in 60-97% by weight of the total anti-glare film composition. Preferably it may contain 70 to 95% by weight, more preferably 80 to 90% by weight. The proper content can be selected according to the dispersibility of the particles and the coating thickness.

The binder resin may include 15 to 100% by weight of the hyperbranched (meth) acrylate oligomer in the binder resin. Within this range, curling does not occur and the hardness of the film does not decrease. Preferably it may include 20 to 50% by weight, more preferably 30 to 45% by weight.

Anti-glare  Composition for film

The composition for anti-glare film of this invention can contain the said particle | grain and binder resin.

The composition may include 3 to 30% by weight of the particles and 70 to 97% by weight of the binder resin on a solids basis. For example, the composition may include 3 to 10% by weight of the particles and 90 to 97% by weight of the hyperbranched (meth) acrylate oligomer based on solids.

The composition consists of a photopolymerization initiator, a solvent, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, a UV absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler and an antifoaming agent. It may further comprise one or more selected from the group.

The photopolymerization initiator can use a conventional photopolymerization initiator without limitation, and for example, a benzophenone-based compound such as 1-hydroxy cyclohexylphenylkenone can be used.

The solvent may be used by selecting a solvent having a solubility and swellability in the base film-> a solvent having a slight solubility and swellability, and a solvent having easy particle dispersibility. Specific examples include methyl ethyl ketone, cyclohexanone, acetone and diacetone alcohol, polyhydric alcohols and ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and cellosolve acetate, and methyl acetate acetate and acetic acid. Ethyl, halogenated hydrocarbons such as chloroform, methylene chloride, tetrachloroethane, nitrogen-containing compounds such as nitromethane, acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, and the like. It is not limited. One or more of these solvents may be used.

The composition for antiglare films of the present invention has a larger surface area of the particles than spherical particles having the same radius. Therefore, the same haze can be realized with a small particle content by increasing the degree of refraction and scattering of light. In addition, it is possible to use a small particle content in implementing the same haze, it can also reduce the cost of particle production.

The antiglare film prepared from the composition for an antiglare film of the present invention may have a curling thickness of 0 to 20 mm at a coating film thickness of 4 to 10 μm.

Anti-glare  film

The present invention relates to an antiglare film comprising a coating film coated using the composition for an antiglare film.

In an embodiment, the antiglare film may have a curling thickness of 0 to 20 mm or less at a thickness of 4 to 10 μm.

The thickness of the coating film may be 2 ~ 15㎛, preferably 4 ~ 10㎛. It is possible to adjust the transmission clarity while adjusting the particle protrusion in the above range thickness.

The formation method of an anti-glare film can be formed by a conventional method. In the specific example, the composition for anti-glare film is apply | coated to a base film, it is made to dry, and then ultraviolet-cured. The coating amount, drying conditions, and ultraviolet curing conditions of the composition for an antiglare film can be changed.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Each component used in the following Examples and Comparative Examples is as follows:

(a) particles

Porous particles: can be prepared directly using seed polymerization and suspension polymerization. Styrene monomer, 1.0 g of azobisisobutyronitrile as a fat-soluble initiator, 17.9 g of polyvinylpyrrolidone having a molecular weight of 40,000 g / mol as a dispersion stabilizer, and 877.7 g of a mixed solvent of ethanol and ultrapure water (8: 2 wt ㅂ) As the hydrophobic monomer, polydimethylsiloxane-based long chain monomer was added at 35% by weight based on the content of the styrene monomer. Polystyrene cross-linked seed particles were prepared by polymerizing with stirring at a stirring speed of 40 rpm for 24 hours at 70 ° C. under a nitrogen atmosphere. 1.0 g of the seed particles prepared above were ultrasonically irradiated to 100 g of 0.25% aqueous solution of lauryl chloride in 0.25% and redispersed in a glass reactor. Subsequently, the styrene / dibenylbenzene monomer mixture in which benzoyl peroxide initiator is dissolved in 200 g of the aqueous solution of lauryl chloride of the same concentration is emulsified simultaneously by ultrasonic irradiation and mechanical stirring of 20000 rpm or more, and is added dropwise to the seed particle dispersion to swell at room temperature. I was. After confirming that the swelling of the monomer mixture is finished, the total content was adjusted to 400 g using an aqueous solution in which 30 g of polyvinyl alcohol having a degree of saponification of 88% was dissolved. The temperature of the reactor was then raised to 80 degrees and polymerized for 10 hours. The unreacted material and the dispersion stabilizer were repeatedly removed from the polymer prepared by using a centrifuge, followed by drying in a vacuum oven for 24 hours to obtain porous particles in powder form.

-Spherical particles: MX-series / SX-series, Soken

(b) binder resin

Hyperbranched (meth) acrylate oligomer resin: UNDIC RC28-559 (DIC CORPORATION) was used.

Urethane acrylate resin: UNDIC RC27-947 (DIC CORPORATION) (not including hyperbranched structure) was used.

Example  1-2

Each component was added in the composition shown in Table 1 below (unit: g), and 3 g of BYK 306 (BYK Chemie) was added to the solids as a dispersant and dispersed by stirring at 25 ° C. for 20 minutes. Irgacure-184 (Ciba Co., Ltd.) as a photopolymerization initiator was added to the dispersion, 3 g of solids, and then stirred at 25 ° C. for 10 minutes to prepare a composition for a final anti-glare film.

The prepared composition was coated on a TAC (triacetyl cellulose) film (thickness 80㎛, Hyosung) using a # 8 or # 10 meyer bar coater to a thickness of 4 ~ 10㎛ and dried at 80 ℃ for 2 minutes. After drying, UV irradiation was performed at a light quantity of 350 mJ / cm ² using a high pressure mercury or the like to cure.

Comparative example  1-3

Except for changing each component to the composition of Table 1, it was carried out in the same manner as in Example 1.

Test Example

Haze, total light transmittance, anti-glare, transmission clarity, 60 ° reflection gloss, and curl of the TAC film having the coating layer formed by the above process were measured, and the results are shown in Table 1.

How to measure

(1) Haze (%): Measured using NDH 2000 (Nippon Denshoku) according to JIS K 7105/7361/13468.

(2) Total light transmittance (%): Measured using NDH 2000 (Nippon Denshoku) using JIS K 7105/7361/13468.

(3) Anti-glare: The anti-glare glossiness of 60 ° was measured using BYK Gardner according to JIS Z8741 and ISO 2813, and evaluated according to the following criteria according to the following criteria.

◎: 30 to 70

△: 70 to 100

×: 100 or more

(4) Curl (mm): A coating film sample of 100 mm x 100 mm size was prepared, and the height of the highest of four corners at the bottom was measured.

(5) 60 degree reflection glossiness: About the anti-glare film, it measured using BYK Gardner according to JISZ8741 and ISO 2813.

Example Comparative example One 2 One 2 3 Coating bar #8 #8 #8 #8 # 10 particle Porous particles 3 5 3 - - Spherical particles - - - 3 3 Binder Resin Resin 1 100 100 - 100 100 Resin 2 - - 100 - - Haze (%) 24.05 38.06 23.90 19.81 11.50 Total light transmittance (%) 90.53 90.64 90.21 90.10 90.45 Anti-glare ◎ ◎ ◎ △ X 60 ° reflectivity 58.7 42.3 57.2 74.3 143 Curling (mm) 0 0 40 0 0

* Resin 1: Hyperbranched (meth) acrylate oligomer resin

** Resin 2: Urethane Acrylate Resin

As shown in Table 1, the porous particles in the antiglare film coated with the antiglare film composition of the present invention was able to achieve a higher haze when included in the same content than the spherical particles (see Example 1 and Comparative Example 2). In addition, the hyperbranched (meth) acrylate oligomer resin in the antiglare film coated with the antiglare film composition of the present invention was able to implement a higher haze when included in the same content as when using a urethane acrylate resin (Example 1 And Comparative Example 1). In addition, it can be seen that the composition of the present invention has good total light transmittance and anti-glare property.

Claims (11)

(a) particles of radius r and surface area larger than 4πr ² ; And
(b) The composition for anti-glare films containing binder resin.
The composition for antiglare film of claim 1, wherein the particles are porous particles.
The composition for anti-glare film of claim 2, wherein the porous particles include pores having a pore diameter of 3 to 100 nm.
The composition of claim 2, wherein the porous particles have a pore volume of 0.04 to 0.5 cm 3 / g.
The composition of claim 2, wherein the porous particles have a BET surface area of 20 to 400 m ² / g.
The composition for antiglare film according to claim 1, wherein the binder resin comprises a hyperbranched (meth) acrylate oligomer.
The composition of claim 6, wherein the hyperbranched (meth) acrylate oligomer is represented by the following formula (1).
[Formula 1]

(In the above, core is an aliphatic or aromatic hydrocarbon containing or not containing a hetero atom of C3-C50 having a functional group which can be bonded to R1, and R1 and R2 are each independently C1-C50 containing or not including a hetero atom. Aliphatic or aromatic hydrocarbon of, E is an ester bond)
The composition for an antiglare film according to claim 1, wherein the composition comprises 3-30% by weight of the particles and 70-97% by weight of the binder resin on a solid content basis.
The composition of claim 1, wherein the composition is a photopolymerization initiator, a solvent, a photosensitizer, a photosensitizer, a polymerization inhibitor, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, a ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, The composition for an anti-glare film further comprising at least one selected from the group consisting of an inorganic filler and an antifoaming agent.
The composition for antiglare film according to claim 1, wherein the composition has a curl of 0 to 20 mm at a film thickness of 4 to 10 µm.
       An antiglare film comprising a coating film coated with the composition for antiglare film of claim 1.