KR101332623B1 - Composition for hard-coating film having high hardness and hard-coating film prepared using the same - Google Patents

Abstract

상기 식에서,

이다.
본 발명에 따르면, 우수한 표면평활성, 경도, 내스크래치성, 밀착성 및 컬링 특성을 갖는 하드코팅 필름 제조용 조성물 및 이를 이용하여 제조된 고경도 하드코팅 필름을 제공할 수 있다.The present invention relates to a high hardness hard coating composition and a high hardness hard coating film prepared using the same, more specifically, a compound of Formula 1, a mixture of two or more polyfunctional urethane acrylate monomers having different functionalities, It relates to a composition for preparing a hard coat film comprising a photoinitiator and a solvent and a high hardness hard coat film prepared using the same:
≪ Formula 1 >

In this formula,

to be.
According to the present invention, it is possible to provide a composition for preparing a hard coat film having excellent surface smoothness, hardness, scratch resistance, adhesion and curling properties, and a high hardness hard coat film prepared using the same.

Description

Composition for preparing a high hardness hard coating film and a high hardness hard coating film manufactured using the same {Composition for hard-coating film having high hardness and hard-coating film prepared using the same}

The present invention relates to a high hardness hard coating composition and a high hardness hard coating film prepared using the same.

Conventionally used hard-coating film is a surface of a variety of display panels, such as liquid crystal display (LCD), plasma display (PDP), CRT (CRT), electroluminescent display (EL), etc. It is used for the purpose of protection. In addition, the hard coating film not only provides hard coating properties to the surface to be protected, but also imparts resistance to marks by fingerprints, markers, and the like, and contaminants can be easily removed during contamination of the surface. It also imparts anti-fouling properties.

As a material for forming the hard coating film, when organic materials such as UV-curable acrylic hard coating materials such as polyester, acrylate, urethane acrylate and epoxy acrylate are used, the organic material used alone is sufficient to have a hard coating film. There is a problem that it does not exhibit surface protection properties. Therefore, conventionally, various organic-inorganic coating liquids including colloidal silica particles, which are inorganic, have been used as hard coating film compositions to improve high hardness and wear resistance. However, the problem of precipitation of colloidal silica particles whose silica surface is modified with organic material or silane, the problem of stability due to gel generation, the degree of curing, optical transparency and adhesion still do not meet the requirements of the hard coating film for display device protection. have. In addition, in the conventional hard coating film, when the thickness is increased to improve the hardness, the hardness of the obtained hard coating film is improved. On the contrary, the hard coating layer is peeled off, and the end of the hard coating film is rolled due to curing shrinkage and hot / wet shrinkage. There is a problem that the rising curl becomes large and the handling aptitude is lowered.

For example, Korean Unexamined Patent Publication No. 2008-62355 discloses a hard coating solution and a high hardness hard coating film using the same, and more specifically, the surface hydroxyl group of the silica particles includes polyfunctional (meth) acrylate. Organic-inorganic silica particles chemically bonded to a multifunctional silane compound; Polyfunctional (meth) acrylates; Disclosed are a hard coating solution including an initiator and a solvent, and a high hardness hard coating film using the same. In addition, Korean Patent Laid-Open Publication No. 2009-7953 discloses a liquid crystal display device using an organic-inorganic hybrid photosensitive resin composition and a cured body thereof, more specifically, a colloidal inorganic sol; i) unsaturated carboxylic acids, unsaturated carboxylic anhydrides or mixtures thereof and ii) acrylic copolymers obtained by copolymerizing at least one acrylic unsaturated compound; Photoinitiators; Polyfunctional monomers having ethylenically unsaturated bonds; Silicone type compound containing an epoxy group or an amine group; And an organic-inorganic hybrid photosensitive resin composition comprising a solvent.

However, the above-described conventional techniques also have problems in that they do not exhibit excellent characteristics in surface smoothness, hardness, scratch resistance, adhesion, curling, and the like.

Accordingly, the present invention provides a composition for preparing a hard coating film having a superior surface smoothness, hardness, scratch resistance, adhesion and curling properties, and a high hardness hard coating film manufactured using the composition, compared to a conventional composition for preparing a hard coating film. I would like to.

In order to solve the first problem,

Provided is a composition for preparing a hard coat film comprising a compound of Formula 1, two or more types of polyfunctional urethane acrylate monomer mixtures having different functionalities, photoinitiators and solvents:

이다.In this formula,

to be.

According to an embodiment of the present invention, the composition is based on 100 parts by weight of the polyfunctional urethane acrylate monomer mixture, 400 to 600 parts by weight of the compound of Formula 1, 30 to 70 parts by weight of the photoinitiator and the solvent 15 to 25 It may include parts by weight.

According to another embodiment of the present invention, the multifunctional urethane acrylate monomer mixture may be a mixture of trifunctional urethane acrylate monomer and 10 functional urethane acrylate monomer.

According to another embodiment of the present invention, the mixture of the multifunctional urethane acrylate monomer may include 150 to 200 parts by weight of the trifunctional urethane acrylate monomer based on 100 parts by weight of the 10 functional urethane acrylate monomer.

According to another embodiment of the present invention, the photoinitiator may be a compound of Formula 2:

According to another embodiment of the present invention, the photoinitiator may be a compound of Formula 3:

According to another embodiment of the present invention, the photoinitiator may be a mixture of the compound of Formula 2 and the compound of Formula 3.

According to another embodiment of the present invention, the photoinitiator may include 100 to 200 parts by weight of the compound of Formula 2 with respect to 100 parts by weight of the compound of Formula 3.

According to another embodiment of the present invention, the solvent may be toluene.

In order to achieve the second object of the present invention,

It provides a hard coat film prepared by using the composition for producing a hard coat film.

According to the present invention, it is possible to provide a composition for preparing a hard coat film having excellent surface smoothness, hardness, scratch resistance, adhesion and curling properties, and a high hardness hard coat film prepared using the same.

The present invention provides a composition for preparing a hard coat film comprising a compound of Formula 1, two or more kinds of polyfunctional urethane acrylate monomer mixtures having different functionalities, a photoinitiator and a solvent:

≪ Formula 1 >

이다.In this formula,

to be.

In the composition according to the present invention, the content of each component, 400 to 600 parts by weight of the compound of Formula 1, 30 to 70 parts by weight of the photoinitiator and the solvent 15 with respect to 100 parts by weight of the polyfunctional urethane acrylate monomer mixture To 25 parts by weight. When the content of the polyfunctional urethane acrylate monomer mixture is less than the above range, there is a problem of curling, and when it exceeds the above range, there is a problem that desired scratch resistance cannot be achieved. In addition, when the content of the compound of Formula 1 is less than the above range, there is a problem that the hardness is not sufficient, and when it exceeds the above range, there is a problem of curling. In addition, when the content of the photoinitiator is less than the above range, there is a problem in UV curing, and when the content exceeds the above range, there is a problem that an overcuring phenomenon occurs. Finally, when the content of the solvent is less than the above range, there is a problem that a sufficient degree of polymerization cannot be achieved, and when it exceeds the above range, there is a problem of curing.

The compound of Formula 1 is acryl polyhedral oligomeric silsesquioxane (acryl POSS), and POSS is composed of a silica core and an organic functional group. POSS-based organic-inorganic nanocomposites have high thermal, mechanical and oxidative durability and offer new possibilities for the production of various types of hybrid materials. In particular, POSS is easily combined with conventional plastics by methods such as copolymerization or blending, and has a high solubility in various organic solvents, and thus does not require any modification in the synthesis process. In the present invention, by utilizing the excellent properties of the POSS it was intended to apply to the production of a composition for producing a hard coat film.

In addition, in the present invention, two or more kinds of polyfunctional urethane acrylate monomer mixtures having different functionalities are used as constituents of the composition for preparing a hard coat film, in order to achieve sufficient scratch resistance and at the same time prevent curling. .

For example, the multifunctional urethane acrylate monomer mixture may be a mixture of a trifunctional urethane acrylate monomer and a 10 functional urethane acrylate monomer, and specific examples of the trifunctional urethane acrylate monomer may include HR3940 manufactured by Miwon Co., Ltd. As a specific example of a urethane acrylate monomer, SC2153 of Unalike Corporation is mentioned.

The relative content of the tri- and 10-functional urethane acrylate monomers may be 150 to 200 parts by weight of the tri-functional urethane acrylate monomer with respect to 100 parts by weight of the 10-functional urethane acrylate monomer, 10-functional urethane acrylate If the content of the monomer is more than the above range there is a problem that can not achieve sufficient tensile strength, and if the content of the trifunctional urethane acrylate monomer is more than the above range there is a problem that sufficient hardness is not secured have.

In addition, the composition according to the present invention includes a photoinitiator, the photoinitiator may be used without limitation, initiators commonly used in the art to which the present invention belongs. Specific examples of such photoinitiators include 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketonebenzyldimethylketal, 2-hydroxy-2-methyl-1-phenyl -1-one, 4-hydroxycyclophenyl ketone, dimethoxy-2-phenylacetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4 -Dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone (Igacure-184) and 2,4,6-trimethylbenzoyl-diphenyl-diphenyl phosphine (Micure TPO) Can be mentioned.

However, the photoinitiator may be selected to prevent the yellowing phenomenon generated in the hard coat film produced by the composition, in consideration of this, the photoinitiator 1-hydroxycyclohexyl phenyl ketone represented by the following formula (2) or It is preferably 2,4,6-trimethylbenzoyl-diphenyl-diphenyl phosphine represented by the following formula (3), more preferably a mixture thereof:

(2)

<Formula 3>

When using a mixture of the compounds of Formulas 2 and 3 as a photoinitiator, 100 parts by weight of the compound of Formula 3, may include 100 to 200 parts by weight of the compound of Formula 2, when the content range is out of this There is a problem of occurrence of over-curing phenomenon.

Finally, the composition according to the invention may comprise a solvent as its component. The solvent may be used without limitation materials commonly used as a hard coating liquid solvent in the art, specific examples thereof include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; Or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy 3 Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate Ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2 Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-part Esters such as methyl oxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate, and the like can be used. In particular, in the present invention, toluene is preferably used as the solvent in consideration of the solubility and reactivity of each constituent component, the ease of forming a coating film of the composition, and the like.

However, the composition of the present invention is not limited to including only the above components, and, if necessary, antioxidants, UV absorbers, light stabilizers, thermal polymerisation inhibitors, levling agents, surfactants, lubricants, It may further include an antifouling agent.

On the other hand, the present invention also provides a hard coating film prepared using the composition for producing a hard coating film.

The high hardness hard coat film according to the present invention includes a crosslinked hard coat layer, and has a structure in which silica particles are chemically covalently bonded in the crosslinked network of the crosslinked hard coat layer. For example, the high hardness hard coating film may be a composition for preparing a hard coating film according to the present invention is applied to a transparent substrate, the silica particles in the acrylic POSS represented by the formula (1) is combined with the polyfunctional urethane acrylate monomer By crosslinking, the silica particles are chemically covalently bonded in the crosslinking network to provide high hardness, and the peeling, curling, and the like can be solved to increase the reliability.

Example

Manufacturing example  One

77% by weight of acrylic POSS (MA0736, Hybrid Plastics), 5% by weight of 10 functional urethane acrylate (SC2153, Miwon Corporation), 10% by weight of trifunctional urethane acrylate (HR3940, Miwon Corporation), 1-hydroxycyclohexyl as photoinitiator 3% by weight of phenylketone (Igacure-184, Ciba, Inc.) and 2% by weight of 2,4,6-trimethylbenzoyl-diphenyl-diphenyl phosphine (Micure TPO, Miwon Co., Ltd.), toluene (Sapphire Gold Co., Ltd.) 3 To prepare a composition for producing a hard coat film according to the invention by blending by weight.

Manufacturing example  2

Acrylic POSS (MA0736, Hybrid Plastics) 72 wt%, 10 functional urethane acrylate (SC2153, Miwon Corporation) 5 wt%, trifunctional urethane acrylate (HR3940, Miwon Corporation) 10 wt%, 1-hydroxycyclohexyl as photoinitiator 5% by weight of phenylketone (Igacure-184, Ciba, Inc.) and 5% by weight of 2,4,6-trimethylbenzoyl-diphenyl-diphenyl phosphine (Micure TPO, Miwon Co., Ltd.), toluene (Sapphire Gold Co., Ltd.) 3 To prepare a composition for producing a hard coat film according to the invention by blending by weight.

Manufacturing example  3

Acrylic POSS (MA0736, Hybrid Plastics) 72 wt%, 10 functional urethane acrylate (SC2153, Miwon Corporation) 5 wt%, trifunctional urethane acrylate (HR3940, Miwon Corporation) 10 wt%, 1-hydroxycyclohexyl as photoinitiator 6% by weight of phenylketone (Igacure-184, Ciba, Inc.) and 4% by weight of 2,4,6-trimethylbenzoyl-diphenyl-diphenyl phosphine (Micure TPO, Miwon Co., Ltd.), toluene (Sapphire Gold Co., Ltd.) 3 To prepare a composition for producing a hard coat film according to the invention by blending by weight.

Comparative Example  One

As a comparative example, 92% by weight of acrylic POSS (MA0736, Hybrid Plastics), 3% by weight of 1-hydroxycyclohexylphenylketone (Igacure-184, Ciba) as photoinitiator and 2,4,6-trimethylbenzoyl-diphenyl- 2 wt% of diphenyl phosphine (Micure TPO, Miwon Co., Ltd.) and 3 wt% of toluene (Great Gold Co., Ltd.) as a solvent were combined to prepare a composition for preparing a hard coat film.

Comparative Example  2

As a comparative example, 77% by weight of acrylic POSS (MA0736, Hybrid Plastics), 10% by weight of 1-hydroxycyclohexylphenylketone (Igacure-184, Ciba) as photoinitiator and 2,4,6-trimethylbenzoyl-diphenyl- 10 wt% of diphenyl phosphine (Micure TPO, Miwon Co., Ltd.), and 3 wt% of toluene (Great Gold Co., Ltd.) as a solvent were combined to prepare a composition for preparing a hard coat film.

Table 1 shows the constituent content ratios of the compositions according to Preparation Examples 1 to 3 and Comparative Examples 1 and 2 (unit: wt%).

ingredient Manufacturing example Comparative Example One 2 3 One 2 Acrylic POSS 77 72 72 92 77 Monomer (SC 2153) 5 5 5 - - Monomer (HR 3940) 10 10 10 - - Irgaqure 184 3 5 6 3 10 Micure TPO 2 5 4 2 10 Toluene 3 3 3 3 3

Experimental Example

Physical properties of the compositions prepared in Preparation Examples and Comparative Examples were measured as follows.

Surface smoothness

The coated surface of the film is illuminated by electric light and observed in the direction of inclination of 20 to 30 degrees to confirm the presence or absence of wrinkles or wrinkles which are thought to be due to the uniformity of the surface layer (microscopic) and the surface property of the hard coating layer. And the grade was evaluated as follows.

A: The surface layer is uniform without microscopic aggregation, and unevenness or wrinkles are not observed in the hard coat layer.

B: Although microscopic aggregation is seen in the surface layer, it is very mild and unevenness | corrugation and a wrinkle are not recognized by a hard coat layer.

C: Although micro aggregates are seen in the surface layer, irregularities and wrinkles are not observed in the hard coat layer.

D: Microscopic aggregation is remarkable in the surface layer, and irregularities and wrinkles are also seen in the hard coat layer.

The grading evaluation for each composition is shown in Table 2 below.

Pencil hardness

Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science Co., Ltd.) at 500 g. The pencil used Mitsubishi product, and was performed 5 times per one pencil hardness. If two or more scratches were found to be defective, the pencil hardness was indicated by the pencil before the defect occurred.

Scratch count 0: OK

Scratch number 1: OK

Scratches # 2 or above: No Good

Evaluations for each composition are shown in Table 2 below.

Scratch resistance

Scratch resistance was tested by reciprocating 10 times under 1 kg / (2 cm × 2 cm) using a steel wool tester (WT-LCM100, manufactured by Korea Protec Co., Ltd.). Steel wool used # 0000 and the grade was evaluated as follows.

A: 0 scratches

A ': 1 to 10 scratches

B: 11-20 scratches

C: 21-30 scratches

D: 31 or more scratches

The grading evaluation for each composition is shown in Table 2 below.

Adhesiveness

After eleven straight lines were formed on the coated surface of the film at intervals of 1 mm each to make 100 squares, three peel tests were conducted using a tape (CT-24, Nichi Nippon Co., Ltd.). The average value was recorded by testing three 100 squares, and the adhesion was evaluated as follows.

Adhesion = n / 100

n: the number of rectangles that are not to be peeled out of the entire rectangle

100: total number of squares

Therefore, when no peeling was performed, the adhesiveness was expressed as 100/100, and the results are shown in Table 2 below.

curling

The sample cut into square shape of A4 size (29.7X21.0cm) was placed on the flat glass plate with the coated surface of the film facing up, and the distance from the square glass plate was measured at 25 ° C. and 50% RH. Measured. Curling properties were evaluated as follows.

Very good: less than 15mm

Good: over 15mm ~ 30mm

Bad: more than 30mm ~ 50mm or less

Very bad: greater than 50 mm

Curling properties evaluation for each composition is shown in Table 2 below.

characteristic Manufacturing example Comparative Example One 2 3 One 2 Hard coating layer
Thickness (μm) 100 100 100 100 100 Surface smoothness A A A A - Pencil hardness 8H 8H 8H 2H - Scratch resistance A A A A - Adhesiveness 100/100 100/100 100/100 100/100 100/100 curling Very good Very good Very good Good Bad

As can be seen from the results of Table 2, when the hard coating layer of the same thickness is formed on the transparent substrate, the composition according to the present invention is very excellent in surface hardness and very good curling properties compared to the composition according to the comparative example It can be seen that.

Claims (10)

A composition for preparing a hard coat film comprising a compound of formula 1, two or more types of polyfunctional urethane acrylate monomer mixtures having different functionalities, a photoinitiator and a solvent:
&Lt; Formula 1 >

In this formula,

ego,
To about 100 parts by weight of the polyfunctional urethane acrylate monomer mixture, 400 to 600 parts by weight of the compound of Formula 1, 30 to 70 parts by weight of the photoinitiator and 15 to 25 parts by weight of the solvent composition for producing a composition. delete The method of claim 1, wherein the polyfunctional urethane acrylate monomer mixture is a composition for producing a hard coat film, characterized in that the mixture of trifunctional urethane acrylate monomers and 10 functional urethane acrylate monomers. The hard coating film according to claim 3, wherein the mixture of the polyfunctional urethane acrylate monomers comprises 150 to 200 parts by weight of the trifunctional urethane acrylate monomer based on 100 parts by weight of the 10 functional urethane acrylate monomer. Composition for preparation. The method of claim 1, wherein the photoinitiator is a composition for producing a hard coat film, characterized in that the compound of formula (2):
(2)

The composition of claim 1, wherein the photoinitiator is a compound of Formula 3:
(3)

The composition of claim 1, wherein the photoinitiator is a mixture of a compound of Formula 2 and a compound of Formula 3:
(2)

(3)

The composition of claim 7, wherein the photoinitiator comprises 100 to 200 parts by weight of the compound of Formula 2 with respect to 100 parts by weight of the compound of Formula 3. 9. The composition of claim 1, wherein the solvent is toluene. A hard coat film prepared using the composition for producing a hard coat film according to any one of claims 1 and 3 to 9.