KR20100023126A - Ultra-violet curable composition - Google Patents

Abstract

PURPOSE: A UV curable resin composition is provided to realize scratch resistance and antistatic effects and to form excellent optical patterns with good elastic restoring force. CONSTITUTION: A UV curable resin composition comprises an acrylic resin, a photoinitiator and an antistatic agent. The liquid refractive index is 1.47~1.58. The acrylic resin comprises a high reflective acrylic resin 10~70 weight%, an aliphatic acryl monomer resin 2~30 weight%, an acryl monomer resin and oligomer resin 20~70 weight%, and silicone-modified polyacrylate resin 0.02~5 weight%. The high reflective acrylic resin is any one of bisphenylphenol monoacrylate or bisfluorene diacrylate or their mixture.

Description

UV curable resin composition {Ultra-violet curable Composition}

TECHNICAL FIELD The present invention relates to an ultraviolet curable resin composition, and more particularly, to an ultraviolet curable resin composition capable of antistatic and having excellent scratch resistance and suitable for optical film production, and an optical film produced using the resin composition. .

Conventionally, it is composed of polyethylene terephthalate (Poly Ethylene Terephthalate), polymethyl methacrylate (PMMA), and polycarbonate (PC) polymer resin, which is a base film used in the optical film of LCD. do. The generation of static electricity causes static electricity when the diffusion film or prism sheet is stacked, which causes problems such as deterioration of LCD brightness, assembly failure during LCD production, and reduction of production yield.

In particular, in the case of optical films such as diffusion films and prism films used in LCD backlight devices, dust or fine particles in the air generated by the electrostatic phenomena of the film may be mixed on the film surface during the BLU assembly process. Incorporation of such foreign matters can result in optical loss, increasing the incidence of defects.

In addition, in the case of an optical film having a specific shape, such as a prism acid, an optical loss is caused due to acid collapse or fine scratches.

Conventionally, quaternary ammonium is added to acrylic resin to prevent the generation of static electricity, but when UV curing, quaternary ammonium is a non-reactive type, dissolution of salt under high temperature and high humidity (60 ℃, 75% relative humidity) and interlayer between substrate and coating There was a problem of causing a decrease in adhesion.

On the other hand, the prism film that forms the prism acid used in the BLU optical film of LCD is applied to the prism film (including composite film: mixed prism acid and lenticular film or prism deformation film) and scratching phenomenon of the prism film generated during the BLU assembly process Due to this, the upper portion of the prism acid is broken or worn, resulting in a problem of lowering luminance.

Therefore, various studies have been conducted to improve the scratch resistance, among which, scratches generated on the surface of the cured product by self-healing force containing UV-curable urethane (meth) acrylate oligomer and photoinitiator in Japanese Patent Application Laid-Open No. 2001-2744. Although it has been proposed to prevent the scratch, the scratch resistance has been significantly improved, but there is a problem that it is insufficient to be applied to various applications because the scratch resistance is insufficient to be used without being limited to the use.

The technical problem to be solved by the present invention is to form a network in the form of a ladder (ladder) of the molecular structure of the ultraviolet curable material by adjusting the content of the ultraviolet curable acrylic resin while adding an antistatic agent to the ultraviolet curable resin composition and linear structure of both The present invention provides an ultraviolet curable resin composition and an optical film produced using the resin composition which simultaneously introduce an alkyl chain containing an alkyl or oxygen atom and an aromatic group, and an aromatic group to simultaneously realize excellent scratch resistance and antistatic effects.

The ultraviolet curable resin composition according to the present invention for solving the above problems includes an acrylic resin, a photoinitiator and an antistatic agent, characterized in that the liquid refractive index is 1. 47 ~ 1. 58.

The acrylic resin in the present invention, high refractive acrylic resin 10 to 70% by weight, aliphatic acrylic monomer resin 2 to 30% by weight, aromatic acrylic monomer resin and oligomer resin 20 to 70% by weight, silicone modified polyacrylate resin 0.02 to 5% by weight It is characterized by including the%.

On the other hand, the optical film which concerns on this invention forms the optical pattern, such as a specific pattern, for example, a lens, a prism, or its mixed form, using the ultraviolet curable resin composition mentioned above to the base film.

Optical film according to the invention is characterized in that the surface resistance value of 1010 ~ 1012 Ω / cm2.

And the optical film of the present invention is characterized in that the load acid strength is 120 ~ 250g.

According to the present invention, by adding an antistatic agent to the UV-curable resin composition and at the same time the molecular structure of the UV-cured product by adjusting the content of the UV-curable acrylic resin to form a network in the form of a ladder (ladder) and alkyl or oxygen atoms on both linear structures By introducing an alkyl chain containing an aromatic and an aromatic to realize the effect of the expression of the excellent scratch resistance and antistatic at the same time, in particular, there is an advantage that can form an optical pattern excellent in elastic resilience in the optical film.

The present invention forms a network in the form of a ladder (Ladder) the molecular structure of the ultraviolet curable through the addition of an ultraviolet curable antistatic agent and the content adjustment of the ultraviolet curable acrylic resin and an alkyl chain containing alkyl or oxygen atoms in both linear structures and By introducing an aromatic to simultaneously realize the effect of the expression of excellent scratch resistance and antistatic, the ultraviolet curable resin composition of the present invention is as follows.

(A) 10 to 70% of high refractive acrylic resin for controlling refractive index of UV curable composition

(B) 2 to 30% of aliphatic acrylic monomer resin

(C) 20-70% of aromatic acrylic monomers and oligomer resins

(D) silicone modified polyacrylate resin 0.02 to 5%

(E) 2-6% photoinitiator

(F) other functional additives (antistatic agent) 0.1-30%

Bisphenyl phenol monoacrylate which is (A) component which comprises the resin composition of this invention, and bisflorene diacrylate are necessary components which maintain a refractive index high and adjust the viscosity distribution of a composition. 10-70 weight% is preferable with respect to resin composition, Especially preferably, it is 25-60 weight%.

The resin composition (B) and (C) components of the present invention contain aliphatic and aromatic acrylates with or without ethylene oxide. The aliphatic acrylic monomers include vinyl monomers and lauryl (meth) acrylates. , Stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, meth A methoxy difluoro ethylene glycol (meth) acrylate and cyclohexyl (meth) acrylate are mentioned.

Meanwhile, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and tetramethylene glycol Di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethoxylated dimethylol propane tri (meth) acrylate, propoxylated trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, gglyceryl tri (meth) acrylate, propoxylated gglyceryl tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Triacrylate, pentaerythritol tetra (meth) acrylate, ditrimetholol propane tetra (meth) acrylate, etc. are mentioned.

As a component of an aromatic monomer and an oligomer, phenyloxyethylene acrylate, benzoyl acrylate, and phenyloxy phenyl ethyl acrylate are the main components which are necessary for the adjustment of the refractive index which falls with aliphatic monofunctional acrylate as a main component. Examples of the aromatic monomers and oligomers include ethoxybisphenol A di (meth) acrylate containing ethylene oxide, and a component containing 2 to 30 repeating units of ethoxy. A oxy bisphenol A epoxy diacrylate component is also included.

Component (D) of the resin composition of the present invention is BYK-307, BYK-323, BYK-331, BYK-333, BYK-356, BYK-371 manufactured by BYK-Chemie as the silicone and silicone-modified polymer. , BYK-377 BYK-UV3510, BYK-3500, BYK-UV3530, BYK-UV3570, DC-57 from Dow Chem., DC-190, Tego glide 100 from Tegussa, Tego glide 410, Tego glide 432, Tego glide 435, Tego glide 440, Tego glide 440, Tego glide 455, Tego glide, Tego glide A 115, Tego glide B 1484, Tego glide ZG 400, Tego rad 2100, Tego rad 2200N, Tego rad 2250, Tego rad 2300, Tego rad 2500, Tego rad 2600, Tego rad 700, and EEKA company EFKA-3232, EFKA-3236, EFKA-3239, EFKA-3288, and EFKA-3299. Here, the names of the silicone-modified polymers are all commercially available, and thus the specific chemical composition is not mentioned. And the appropriate content of this component (D) is 0.02 to 5% by weight, more preferably 0.02 to 2.0% by weight.

As for content of the photoinitiator which is the resin composition (E) of this invention with respect to the whole resin composition, 1.0-10 weight% is preferable. More preferably, it is 2-5 weight%.

If it is less than 1.0% by weight, the photocurability is not achieved, so it exists as a tacky component that does not have a pattern shape.The photocuring of the resin composition proceeds more than 10% by weight, but a resin component having a low molecular weight is generated as a by-product. It will adversely affect the physical properties of the water. Examples of the component (E) include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- [4- (2-hydroxy Oxyethoxy) phenyl] -2-methyl-1-propanone, methylbenzoylformate, oxy-phenyl-acetic acid 2- [2-oxo-2phenyl-acetoxy-ethoxy] -ethylester / oxy-phenyl -Acetic2- [2-hydroxy-ethoxy] -ethylester mixture, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl-1-butanone, 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylpostin oxide, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] Propaneone], oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / tripropylene glycol diacrylate mixture, oligo [2-hydroxy-2-methyl- 1- [4 (1-methylvinyl) phenyl] propanone] / Trimethylolpropanetriacrylate mixture containing methylene oxide or prepropylene oxide, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / glycerylpropoxide tree Acrylate mixture, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / 2-hydroxy-2-methyl-1-phenyl-1-propanone mixture, Esacure ONE (Lamberti), 2,4,6-trimethylbenzophenone / 4-methylbenzophenone mixture, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / 2,4,6-trimethylbenzophenone / 4-methylbenzophenone mixture, etc. are mentioned. The photoinitiator may be used alone or in a mixed form.

Resin composition group (F) of the present invention is quaternary ammonium salt, ELECON-700DA, 500DA, 100ED, Pri-HR-SS, PRIZOL-600DA (NanoCamtech Co., Ltd.) and SY-ICA-P212B, SY-ICA-P211 , SY-ICA-P226A (Sooyang Chemtech) AS-66 (Nischem) AS1021 (Miwon Corporation) and KOEI's IL-A2, ILA2-7, IL-AP1, IL-M8, ILA21-9, IL- A5, IL-AP3, IL-P14, etc. are mentioned. The names given herein as examples of antistatic agents are all commercially available and do not mention their specific chemical composition.

As content with respect to the whole ultraviolet curable resin composition, 0.1-30 weight% is preferable. More preferably, it is 0.1-20 weight%. If the excess is more than 30%, the dissolution of the antistatic agent occurs and causes the poor adhesion to the optical film substrate.

The surface resistance of the patterned film of the ultraviolet curable resin composition by applying the antistatic agent is characterized in that it has a range of 10 ¹⁰ ~ 10 ¹² Ω / cm ² .

Curing conditions

The UV curable resin composition was subjected to UV irradiation process (H-bulb, 500-600 mJ / cm 2) using a nickel mold of a prism acid shape [25 μm (prism acid height) × 15 μm (pitch)] on a 250 μm PET film. A prismatic acid patterned film was prepared.

(Assessment Methods)

In order to evaluate the properties of the UV cured coated prism sheet, refractive index, viscosity, adhesion, antistatic agent dissolution phenomenon, surface resistance value, and load acid strength were measured. The analysis method for each item was performed as follows.

Refractive index

Refractive index was measured at 25 ℃, ABBE Refractometer @ 589.3nm.

Viscosity

It was measured at BrookFild LV DVIII +, Spindle # 18, 7rpm, 25 ℃.

Adhesion

The room temperature adhesion to the optical film substrate and the adhesion after high temperature and high humidity were subjected to strict lattice adhesion test according to ASTM D3359. The coated film was cut in gold using a cross hatch cutter (Elcometer 107) to form 100 square grids, and the Japanese Nitto Denko Tape 31B was attached on a gold plated grid and quickly peeled off. The remaining number of square grids remaining on the film indicates the relative adhesion rate. Initial adhesion was measured immediately after forming the film from the pattern molder, and after high humidity, the adhesion was left in a constant temperature and humidity chamber at 65 ° C./75%RH/24hrs.

Coating surface dissolution phenomenon

After leaving for 20 minutes in 100 ° C water, the dissolution of the pattern surface was observed.

Surface resistance

The surface resistance was measured for 30 seconds under a voltage of 1000V by using URS PROBE with MITSUBISHI CHEMICAL's MCP-HT450.

weight Mountain river  ( Scratch resistance )

The steel wool # 0000 tester manufactured by Daesung Precision Co., Ltd. was used to measure the conical shape of the steel wool. Place the pointed part of the cone on the polarizing film and place the film with the pattern to be measured under the polarizing film. Perform 5 round trips of the cone at a constant speed while sequentially increasing the constant weight (g). The surface scratch degree of the patterned film (prism) laminated under the polarizing film was evaluated in g according to the weight of the weight. The extent of repair of the scratched surface was evaluated after 30 seconds in appearance.

Example 1

In order to realize the antistatic property and the restoring force of the cured product, Example 1 of the composition (A) is not added (B) component, 17 weight%, (C) component, 62 weight%, (D) component, 1 weight It prepared by mix | blending%, (E) component, 5 weight%, (F) component, and 15 weight%.

The refractive index was 1.50, the viscosity was 320 cP., The load acid strength was 180 g, and the surface resistance was 5.0 × 10 ¹² Pa / cm ² . In addition, the scratch of the surface was visually confirmed to be completely restored after 30 seconds.

Examples 2, 3, 4, and 5 were blended by adjusting the content of ingredients under the same conditions as in Example 1, as shown in Table 1. The physical property results of the examples are shown in Table 2.

   Table 1. Example Composition Ratio

(A) ingredient (B) ingredient (C) component (D) component (E) component (F) ingredient One - 17 62 One 5 15 100 2 20 20 45 0.7 4.3 10 100 3 55 10 17 One 5 12 100 4 57 6 19 One 2 15 100 5 55 4.8 18 0.2 5 17 100

       Table 2. Example Test Results

Liquid refractive index Viscosity Load acid strength Surface resistance Substrate adhesion Pattern Restoration One 1.50 320 180 g 5.0 × 10 ¹² Great restore 2 1.53 380 250 g 4.0 × 10 ¹¹ Great restore 3 1.54 380 250 g 7.0 × 10 ¹⁰ Great restore 4 1.55 560 160 g 5.0 × 10 ¹² Great restore 5 1.56 400 120 g 4.0 × 10 ¹¹ Great restore

     1) Evaluation method of optical substrate adhesion: 100/100 (excellent), 99/100 to 95/100 (good), 95/100 or less (bad)

Claims (15)

An ultraviolet curable resin composition comprising an acrylic resin, a photoinitiator and an antistatic agent, and having a liquid refractive index of from 1.47 to 1.58. The method of claim 1, The acrylic resin, High refractive acrylic resin 10 to 70% by weight Aliphatic acrylic monomer resin 2 to 30% by weight 20 to 70% by weight of aromatic acrylic monomer resin and oligomer resin An ultraviolet curable resin composition comprising 0.02 to 5% by weight of a silicone-modified polyacrylate resin. The method of claim 2, The said high refractive acrylic resin is any one or a mixture of bisphenyl phenol monoacrylate or bisfluorene diacrylate, The ultraviolet curable resin composition characterized by the above-mentioned. The method of claim 2, The aliphatic acrylic monomer resins include vinyl monomers, lauryl (meth) acrylates, stearyl (meth) acrylates, butoxyethyl (meth) acrylates, ethoxydiethylene glycol (meth) acrylates, and methoxytrees. UV light, characterized in that any one or a mixture selected from ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy difluoro propylene glycol (meth) acrylate, cyclohexyl (meth) acrylate Curable resin composition. The method of claim 2, The aliphatic acrylic monomer resins include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and tetramethylene glycol Di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, ethoxylated dimethylol propane tri (meth) acrylate, propoxylated trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, gglyceryl tri (meth) acrylate, propoxylated gglyceryl tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Triacrylate, pentaerythritol tetra (meth) acrylate, ditrimetholpropane tetra (meth) acrylate, or any one or a mixture thereof. UV-curable resin composition. The method of claim 2, The aromatic monomer and the oligomer resin is any one or a mixture thereof selected from ethoxy bisphenol A di (meth) acrylate containing ethylene oxide, bisphenol F urethane diacrylate, and ethoxy bisphenol A epoxy diacrylate. UV curable resin composition. The method of claim 2, The photopolymerization initiator has a ratio of 1.0 to 10% by weight of the total resin composition, UV curable resin composition. The method of claim 7, wherein The photoinitiator is 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- [4- (2-hydroxyethoxy ) Phenyl] -2-methyl-1-propanone, methylbenzoylformate, oxy-phenyl-acetic acid 2- [2-oxo-2phenyl-acetoxy-ethoxy] -ethylester / oxy-phenyl-acetic 2- [2-hydroxy-ethoxy] -ethylester mixture, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl-1-butanone, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylpostin oxide, 2-hydroxy-1- {4- [4- (2-hydroxy-2- Methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone], oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / tripropylene glycol diacrylate mixture, oligo [2-hydroxy-2-methyl-1- [4 ( 1-methylvinyl) phenyl] propane ] / Trimethylolpropanetriacrylate mixture containing ethylene oxide or prepropylene oxide, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / glycerylpropoxide Cittriacrylate mixture, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone] / 2-hydroxy-2-methyl-1-phenyl-1-propanone Mixture, Esacure ONE (Lamberti), 2,4,6-trimethylbenzophenone / 4-methylbenzophenone mixture, oligo [2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propane Non] / 2,4,6-trimethylbenzophenone / 4-methylbenzophenone mixture, or an ultraviolet curable resin composition characterized by the above-mentioned. The method of claim 2, The antistatic agent has an ultraviolet curable resin composition, characterized in that the ratio of 0.1 to 30% by weight of the total resin composition. The method of claim 9, The antistatic agent is ELECON-700DA, 500DA, 100ED, Pri-HR-SS, PRIZOL-600DA, SY-ICA-P212B, SY-ICA which coordinates to the acrylic resin matrix containing quaternary ammonium salts and alkali metal salts. Any selected from -P211, SY-ICA-P226A, AS-66, AS1021, IL-A2, ILA2-7, IL-AP1, IL-M8, ILA21-9, IL-A5, IL-AP3, IL-P14 Ultraviolet curable resin composition, characterized in that one or a mixture thereof. The optical film in which the optical pattern was formed in the base film using the ultraviolet curable resin composition of Claims 1-11. The method of claim 11, The optical film is an optical film, characterized in that the surface resistance value of 1010 ~ 1012 Ω / cm2. The method of claim 11, The optical film is any one of a diffusion film, a prism film, a composite film or a polarizing film. The method of claim 11, The optical film is an optical film, characterized in that the load acid strength is 120 ~ 250 g. The method of claim 11, The base film is any one selected from polyethylene terephthalate (Polyethylenterephthalate), polymethyl methacrylate (PMMA: Polymethylmetacrylate), polycarbonate (PC: Polycarbonate), polyethersulfone (PES: Polyethersulfone) .