KR20140046435A - Laminate, window sheet comprising the same and displaying apparatus comprising the same - Google Patents

Abstract

The present invention relates to a laminate, a window sheet comprising the same, and a display apparatus comprising the same, and more specifically, to a laminate which has high transparency and shock resistance, improved bending properties, weather resistance, surface hardness, and heat resistance; a window sheet comprising the laminate; and a display apparatus comprising the laminate.

Description

Laminate, window sheet comprising the same and a display device comprising the same {Laminate, window sheet comprising the same and displaying apparatus comprising the same}

The present invention relates to a laminate, a window sheet including the laminate, and a display device including the window sheet. More particularly, the present invention relates to a laminate having high transparency, high impact resistance, improved warpage characteristics, weather resistance, surface hardness and heat resistance, a window sheet including the laminate, and a display device including the same.

BACKGROUND ART [0002] Conventionally, a glass material has been widely used as a display material for an electrode substrate for a liquid crystal display panel, a plasma display panel, an electroluminescence fluorescent display tube, or a light emitting diode. However, glass is prone to breakage and has a large specific gravity, which has limits to pursuit of thinness and lightness.

Instead of glass materials, plastic materials with transparency attract attention. Plastic materials are lighter and less susceptible to breakage, which has the potential to replace conventional glass materials. Therefore, various researches have been carried out in order to improve transparency, surface hardness, durability and heat resistance of plastic materials.

Meanwhile, as display devices such as LCDs, PDPs, mobile phones, and projection televisions have greatly developed, attempts have been made to replace window sheets positioned at the outermost portions of these display devices with plastic materials. For example, Japanese Unexamined Patent Publication (Kokai) No. 2007-1766542 discloses a method of coating a transparent plastic film on a surface of a transparent plastic film by applying a high hardness material containing a silsesquioxane resin having photo-curability and photo-curing the same to obtain a film having transparency, high surface hardness, weather resistance, Or a material excellent in heat resistance. However, this material has a low impact resistance, which in itself has had a limitation in replacing the window sheet.

Related Prior Art Korean Unexamined Patent Publication No. 2009-0109927 (published on October 21, 2009, entitled "Removable Smart Window Sheet and Its Manufacturing Method") is available.

An object of the present invention is to provide a laminate excellent in both transparency, impact resistance, hardness and scratch resistance.

It is another object of the present invention to provide a laminate usable for window sheet applications.

Still another object of the present invention is to provide a window sheet and a display device including the laminate.

The laminate as one aspect of the present invention includes a plastic sheet, a pressure-sensitive adhesive layer, and a film containing silsesquioxane, and the pressure-sensitive adhesive layer may have a glass transition temperature of -50 ° C to -10 ° C.

Another aspect of the present invention is a laminate comprising a plastic sheet, a pressure-sensitive adhesive layer, and a film comprising silsesquioxane, wherein the pressure-sensitive adhesive layer has a modulus (G ') of 1 x 10 ⁴ - 1.5 x 10 ⁶ dyn / cm 2 .

Another aspect of the present invention is a laminate comprising a plastic sheet, a pressure-sensitive adhesive layer, and a film comprising silsesquioxane, and the plastic sheet may have an impact strength of at least 5J as measured by ASTM D4226.

Another aspect of the present invention is a laminate comprising a plastic sheet, a pressure-sensitive adhesive layer, and a film containing silsesquioxane, and the warp height may be less than 5 mm.

The window sheet, which is another aspect of the present invention, may include the above-described laminate.

A display device according to another aspect of the present invention may include the laminate or the window sheet.

The present invention provides a laminate which is excellent in transparency, impact resistance, hardness and scratch resistance and can be used as a window sheet, a window sheet including the same, and a display device.

1 is a cross-sectional view of a laminate according to one embodiment of the present invention.
2 is a cross-sectional view of a laminate according to another embodiment of the present invention.

The laminate as one aspect of the present invention may comprise a film comprising (A) a plastic sheet, (B) an adhesive layer, and (C) silsesquioxane.

In the laminate, the adhesive layer may be laminated between a plastic sheet and a film containing silsesquioxane.

The laminate may comprise one or more plastic sheets, an adhesive layer, and a film comprising silsesquioxane.

1 to 2 show a laminate according to an embodiment of the present invention. Referring to FIG. 1, a laminate 100 includes a plastic sheet 110 and an adhesive layer 120 and a film 130 containing silsesquioxane sequentially laminated on the plastic sheet 110. 2, the laminate 200 includes a plastic sheet 210, an adhesive layer 220a and a film 230a containing silsesquioxane are sequentially laminated on one side of the plastic sheet, On the other side of the sheet, an adhesive layer 220b and a film 230b containing silsesquioxane are successively laminated.

The laminate may be in the form of a sheet or a film, and may be laminated on a material including a touch panel such as a mobile phone, a polarizing plate, a glass substrate and the like. Further, the laminate has excellent impact resistance, hardness and transparency, and has low warpage, and can be used for a window sheet application.

Since the window sheet is located at the outermost part of various display devices, the laminate used for the window sheet should have good impact resistance, hardness and transparency, and have low warpage.

The laminate of the present invention may have a warp height of less than 5 mm. In the above range, it can be used as a window sheet, and the stability of the display device can be obtained. Preferably, it may be 0.1 mm to 3 mm.

The bending height can be measured by a conventional method. For example, the laminate is allowed to stand at 85 캜 and 85% relative humidity for 72 hours and then at 25 캜 for 4 hours. When the laminate is bent, the highest height at which the laminate is bent from the bottom surface is measured.

The thickness of the laminate may be 300 to 1100 占 퐉. The thickness of the plastic sheet in the laminate may be 100-1000 占 퐉, the thickness of the adhesive layer may be 5-50 占 퐉, and the thickness of the film containing silsesquioxane may be 50-500 占 퐉.

The laminate may have a transmittance of 87% or more in a wavelength range of 400-800 nm. Within this range, it can be used as a window sheet. Preferably 90-98%.

(A) The plastic sheet may have an impact resistance of 5J or more (Dupont drop tester), which is measured by a drop impact strength. Within the above range, sufficient impact resistance can be obtained when the adhesive layer and the plastic sheet are laminated, and high hardness of the surface and high impact resistance of the sheet can be obtained. Preferably, the impact strength may be 5-6J.

The impact resistance is not particularly limited, but can be measured by steel ball drop or Dupont drop tester. For example, Dupont Drop impact tester is analyzed and measured according to ASTM D 4226. Load of 500g and specimen size is measured by the thickness of the plastic sheet of 30mm * 70mm width * length.

The plastic sheet may have an impact resistance of 35 cm or more, preferably 35-90 cm, when measuring Dupont Drop Tester (500 g, pin 1/2 ", specimen 100 * 100 mm).

The plastic sheet may have a transmittance of 90% or more in a wavelength range of 400-800 nm. Within the above range, it can be used as the description of the window sheet.

The plastic sheet is not particularly limited. For example, the material of the plastic sheet is selected from the group consisting of polystyrene, (meth) acrylate-styrene copolymer, a mixture of polymethyl methacrylate and rubber, acrylonitrile-styrene copolymer, polycarbonate, polyvinyl alcohol, polyethylene terephthalate, Polyethylene naphthalate, polypropylene, polyethylene, cyclic olefin copolymer or a mixture thereof. Preferably, it may be a polycarbonate, a copolymer of polymethylmethacrylate and rubber.

The thickness of the plastic sheet may be 100-1000 占 퐉, preferably 100-900 占 퐉, more preferably 150-800 占 퐉. In the above range, a roll-to-roll process is possible, and a suitable thickness and impact resistance of the window sheet can be obtained.

(B) the adhesive layer may have a glass transition temperature of -50 to -10 占 폚. Within this range, a stable laminate can be realized by being laminated between a plastic sheet and a film containing silsesquioxane, and the laminate can have an adhesive strength not peeling off. Preferably, the glass transition temperature may be -40 to -10 占 폚, more preferably -25 to -10 占 폚.

The glass transition temperature of the adhesive layer can be measured by a usual method. For example, a pressure-sensitive adhesive and a curing agent were mixed and then coated on a release film, followed by drying and thermosetting. The glass transition temperature can then be measured by measuring the temperature up to 10 ° C per minute at -70 ° C with a DSC Q100 (TA Instrument) up to 50 ° C.

The adhesive layer may have a modulus (G ') of 1 x 10 ⁴ -1.5 x 10 ⁶ dyn / cm 2. Within this range, a stable laminate can be realized by being laminated between the substrate sheet and the plastic film, and durability can be obtained. Preferably, the modulus can be 1 x 10 ⁵ -1.45 x 10 ⁶ dyn / cm 2.

The modulus of the adhesive layer can be measured by a usual method. For example, the modulus measurement method of the pressure-sensitive adhesive composition is measured using ARES (ADVANCED RHEOMETRIC Expansion System, Rheometrics Scientific Co.) at a frequency of 10 rad / s, a strain of 5%, a temperature range of 25 to 70 ° C, And can take a value of 51.3 DEG C, but is not limited thereto.

The thickness of the adhesive layer may be 5-50 占 퐉, preferably 10-30 占 퐉.

The adhesive layer may have an adhesive strength of 2 to 15 N / inch. The adhesive strength of the pressure-sensitive adhesive and the curing agent was adjusted to 20 μm after drying on a PET film, followed by drying and thermal curing at 80 ° C. for 3 minutes. The film aged at 40 ° C for 48 hours is placed on a plain glass plate and allowed to stand for 4 hours and then evaluated by Shinto Scientific, Heidon.

The pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive composition comprising a (meth) acrylic copolymer and a curing agent. The pressure-sensitive adhesive composition may be thermally cured at 80 DEG C for 180 seconds to produce an adhesive layer.

The adhesive layer can be prepared by applying the pressure-sensitive adhesive composition between a plastic sheet and a film comprising silsesquioxane and then curing the adhesive layer, or by applying the pressure-sensitive adhesive film produced after application to the release film to plastic sheets and silsesquioxane- Laminating them between the films and curing them. The curing preferably includes a heat curing treatment and comprises treatment at 50-140 DEG C for 1 minute to 5 minutes. The adhesive film can be made into a film by a method such as a die coater, a gravure coater, a micro gravure coater, a reverse coater, a knife coater, a comma coater and the like.

(Meth) acrylic copolymer may have a glass transition temperature of -50 to -10 占 폚, preferably -40 to -20 占 폚.

(Meth) acrylic copolymer may be a copolymer of a mixture of at least one monomer selected from the group consisting of a vinyl-based monomer having a hydroxyl group, a vinyl-based monomer having an alkyl group, a vinyl-based monomer having a carboxyl group, have.

Preferably, it may be a copolymer of a monomer mixture containing a vinyl monomer having a hydroxyl group, a vinyl monomer having an alkyl group, and a vinyl monomer having a carboxyl group.

The vinyl-based monomer having a hydroxyl group may be a (meth) acrylic acid ester having a hydroxyl group. Preferably, the (meth) acrylic acid ester having a hydroxyl group may be a (meth) acrylic acid ester having at least one hydroxyl group and an alkyl group having 1 to 20 carbon atoms in the terminal or structure.

For example, the vinyl monomer having a hydroxyl group is preferably a vinyl monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- hydroxypropyl (meth) Cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentylglycolmono Acrylate, trimethylolpropane di (meth) acrylate, trimethylol ethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, and cyclohexanedimethanol mono From Which may comprise at least one member, but is not limited to these. The vinyl monomer having a hydroxyl group may be contained in the (meth) acrylic copolymer in an amount of 0.1 to 50% by weight, or 0.1 to 5% by weight.

The vinyl monomer having an alkyl group may include a non-cyclic (meth) acrylic acid ester having a linear or branched alkyl group having 1 to 20 carbon atoms. The vinyl monomer having an alkyl group may be included as the (meth) acrylic copolymer.

For example, the vinyl-based monomer having an alkyl group may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- butyl (meth) acrylate, (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl But are not limited to, at least one member selected from the group consisting of (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate and lauryl (meth) acrylate. The vinyl monomer having an alkyl group may be contained in the (meth) acrylic copolymer in an amount of 50 to 99% by weight, preferably 55 to 99% by weight.

The vinyl-based monomer having a carboxy (acid) group may be a (meth) acrylic acid ester having 1 to 10 carbon atoms or a carboxylic acid having a vinyl group at one end or in the structure and having at least one carboxyl group. The vinyl-based monomer having a carboxy (acid) group may be contained in an amount of 0 to 40% by weight of the (meth) acrylic copolymer. Within the above range, an effect of improving the adhesive property can be obtained. Preferably 0.1 to 40% by weight.

For example, the vinyl monomer having a carboxy (acid) group may include at least one member selected from the group consisting of (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and maleic anhydride, It is not limited.

The vinyl monomer having an aromatic ring may include a (meth) acrylate having an aromatic ring having the structure of Formula (1).

≪ Formula 1 >

(Wherein Y is hydrogen or an alkyl group of 1 to 5 carbon atoms, p is an integer of 0 to 10, X is a phenyl group, a methylphenyl group, a methylethylphenyl group, a methoxyphenyl group, a propylphenyl group, a cyclohexylphenyl group, A bromophenyl group, a phenylphenyl group, a benzyl group, and a benzylphenyl group.

Specifically, the vinyl monomer having the structure of Formula 1 may be at least one selected from the group consisting of phenyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, benzyl (Meth) acrylate, 3-phenylpropyl (meth) acrylate, 2-methylphenylethyl (meth) acrylate, (Meth) acrylate, 2- (4-methylphenyl) ethyl (meth) acrylate, 2- 2- (3-methoxyphenyl) ethyl (meth) acrylate, 2- (4-cyclohexylphenyl) ethyl (Meth) acrylate, 2- (4-chlorophenyl) ethyl (meth) acrylate, 2- (Meth) acrylate, benzyl (meth) acrylate and 2- (4-benzylphenyl) ethyl (meth) acrylate, but are not limited thereto no.

The vinyl monomer having an aromatic ring may be included as the (meth) acrylic copolymer. Within the above range, it is possible to obtain an effect of improving workability and suppressing stress at a high temperature.

The method for producing the (meth) acrylic copolymer is not particularly limited, and can be produced by a solution polymerization method, a photopolymerization method, a bulk polymerization method, an emulsion polymerization method, or an emulsion polymerization method. Preferably, the (meth) acrylic copolymer is produced by a solution polymerization method, and the polymerization temperature is preferably 50 ° C to 140 ° C. As the initiator that can be used at this time, an azo-based polymerization initiator such as azobisisobutyronitrile or azobiscyclohexanecarbonitrile; And / or peroxides such as benzoyl peroxide or acetyl peroxide, and the like.

The curing agent may be contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic copolymer. Within the above range, it is possible to realize the glass transition temperature of the pressure-sensitive adhesive layer, and to improve the durability and reworkability. Preferably 0.1 to 3 parts by weight.

The curing agent may be an isocyanate-based, epoxy-based, aziridine-based, melamine-based, amine-based, imide-based, carbodiimide-based, amide-based or mixture thereof, but is not limited thereto.

The pressure-sensitive adhesive composition may further optionally contain additives as required. The additive may be at least one selected from the group consisting of a coupling agent, a curing accelerator, a tackifier resin, a modified resin (polyol, phenol, acryl, polyester, polyolefin, epoxy, epoxylated polybutadiene resin, A heat stabilizer, a light stabilizer, an antistatic agent, or a mixture thereof.

The additive may be included in an amount of 0.05 to 15% by weight based on the pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition may further comprise a solvent. The solvent can be, but is not limited to, methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, cyclopentanone, dioxolane, dioxine, dimethoxyethane, toluene, xylene, ethyl acetate, Do not.

The pressure-sensitive adhesive composition can be prepared by mixing the above-mentioned (meth) acrylic copolymer, a curing agent, and an optional additive.

(C) The film containing silsesquioxane was extruded at a speed of 0.8 mm / sec under a load of 1 kg using a pencil hardness tester (Shinto Scientific, Heidon) with a Mitsubishi evaluation pencil (UNI) as a hardness plastic film , And the measured pencil hardness can be 9H-10H.

The thickness of the film may be from 50 탆 to 500 탆, preferably from 100 탆 to 300 탆.

The film may have a transmittance of 88% or more, preferably 90% or more, and more preferably 90-100% in the region of 200 m in thickness and 400-800 nm range.

The film includes a cured product of a photocurable resin composition containing a silsesquioxane resin, which is coated on the base film in one or both sides.

In addition, the film may be coated with a resin for a matrix containing a polyorganosiloxane or the like, such as a glass fiber, a glass fiber cloth, a glass fabric, a glass nonwoven fabric, a glass mesh, a glass bead, , Glass flakes, silica particles, colloidal silica, or mixtures thereof, and the like.

Specifically, the film is formed by laminating a resin layer (C1) having a light transmittance of 90% or more at a wavelength of 550 nm and a glass transition temperature of 250 DEG C or more and a transparent plastic film (C2) having a glass transition temperature of 70-220 It can become a sieve. The resin layer may be a cured product of a photocurable resin composition containing a cage silsesquioxane resin having photo-curable properties.

In one example, the cage-type silsesquioxane resin is represented by the following chemical formula 2

(2)

RSiX3

(In the above, R is a (meth) acryloyl group, a glycidyl group or a vinyl group, and X is a hydrolyzable group) in the presence of an organic polar solvent and a basic catalyst, And the resulting hydrolyzate is recondensed again in the presence of a non-polar solvent and a basic catalyst.

In another example, the cage type silsesquioxane resin may be represented by the following formula (3).

(3)

[RSiO3 / 2] n

(Wherein R is a (meth) acryloyl group, a glycidyl group or a vinyl group, and n is 8, 10, 12 or 14)

In another example, the cage-like silsesquioxane resin is represented by the following formula (4), (5), or (6)

(Wherein m is an integer of 1 to 3, and R < 1 > is hydrogen or a methyl group).

The base film may be at least one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene phthalate, cycloolefin polymer, cycloolefin copolymer, polycarbonate, acetate, acryl, vinyl chloride, polyamide, polyarylate, cellophane, polyether sulfone, Boron-based resin, and the like.

The ratio of the thickness of the resin layer (C1) to the thickness of the transparent plastic film (C2) may be 0.1-5.0.

The film containing silsesquioxane can be used by purchasing commercially available products such as Silplus J200 (Shinil Chemical Co., Ltd.), but the present invention is not limited thereto.

Further, the laminate may further include a hard coat layer for preventing scratches and pressing phenomenon during the process and for increasing the durability, impact resistance and hardness of the laminate. The hard coating layer may be formed on one side of the laminate, preferably one side of the base sheet in the laminate.

The hard coat layer can be measured with a pencil hardness meter (Shinto Scientific, Heidon) as a Mitsubishi evaluation pencil (UNI) at a rate of 0.8 mm / sec under a load of 1 kg, and then the measured pencil hardness can be 2H-3H. The thickness of the hard coat layer may be 0.5-10 mu m.

The hard coating layer may be formed of, but not limited to, a coating liquid containing a UV-curable material including a urethane-based material and a curing agent.

The window sheet, which is another aspect of the present invention, may be made of the above laminate. The laminate may be included in a display device such as a mobile phone as a window sheet.

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.

Manufacturing example  1: Preparation of pressure-sensitive adhesive composition

N-butyl acrylate (BA) and 1 part by weight of 4-hydroxybutyl acrylate (4-HBA) were added to a 1 L reactor equipped with a cooling device for regulating the temperature of the reflux of nitrogen gas. 120 parts by weight of ethyl acetate were added. After nitrogen was purged for 60 minutes to remove oxygen, the temperature was maintained at 60 占 폚 and 0.05 part by weight (based on 100 parts by weight of the acrylic copolymer) of 2,2'-azobisisobutyronitrile (AIBN) Respectively. Followed by reaction at 60 ° C for 8 hours to prepare an acrylic copolymer.

100 parts by weight (1986 g) of the acrylic copolymer, 3.02 parts by weight (60 g) of a curing agent (L-45R, Soken) and 45 parts by weight of methyl ethyl ketone (900 g) were stirred at room temperature for 45 minutes to prepare a pressure- .

Manufacturing example  2-5: Preparation of pressure-sensitive adhesive composition

A pressure-sensitive adhesive was prepared in the same manner as in Production Example 1, except that the content (unit: parts by weight) of the monomers of the copolymer and the kind and content (unit: parts by weight) of the curing agent were changed as shown in Table 1 below.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 (Meth) acrylic copolymer BA 99 55 99 50 99 4-HBA One 5 One 5 One MA - 40 - 35 - Vinyl resin - - - 10 - Hardener Hardener 1 1.9 - 1.9 - - Hardener 2 - 0.15 - 0.2 - Methyl ethyl ketone 40 45 40 40 40 additive - - 1.5 - - Glass transition temperature (캜) -24.81 -13.83 -24.81 -8.35 -56 Modulus (dyn / cm²) 1.43 * 106 1.12 * 106 1.43 * 106 1.85 * 106 7.07 * 105

* MA: Methacrylic acid

       * Curing agent 1: L-45R (Soken)

       * Hardener 2: DN 950 (Akegee)

       * Additives: Tinuvin 384 as UV absorber

* Vinyl resin: Hydroxyl-Modified Vinyl Chloride / Vinyl Acetate Copolymer (Dow chem)

Glass Transition Temperature: The glass transition temperature after curing the pressure-sensitive adhesive composition. The coating solution obtained by mixing the pressure-sensitive adhesive and the curing agent was coated on a release film (PET) and dried at 80 캜 for 3 minutes to be thermally cured. The temperature was raised from -70 ° C to 10 ° C per minute with a DSC Q100 (TA Instrument) and measured up to 50 ° C.

* Modulus: The modulus of the pressure sensitive adhesive composition was measured using ARES at a frequency of 10 rad / s, a strain of 5%, a temperature range of 25 to 70 ° C, a heating rate of 2 ° C / min and a G 'value of 51.3 ° C.

Specific specifications of the components used in the following examples and comparative examples are as follows.

(A) Film containing silsesquioxane: A film (Silplus J200, Nippon Steel Chemical Co., Ltd., thickness: 200 m) containing POS (polyhedral oligomeric silsesquioxane)

(B) Pressure-sensitive adhesive: The pressure-sensitive adhesive composition

(C) Plastic sheet: The plastic sheet shown in Table 2

division Impact resistance * (J) material thickness
(mm) Remarks Plastic Sheet 1 5.42 Polycarbonate 0.8 Cheil Industries Plastic Sheet 2 5.42 Polycarbonate 0.5 Cheil Industries Plastic sheet 3 16.27 Polymethyl methacrylate +
Rubber included 0.8 K-HI30-U25, KURARAY Plastic Sheet 4 3.25 Polymethyl methacrylate One Cheil Industries Plastic Sheet 5 3.25 Polycarbonate 0.2 Cheil Industries

* Impact resistance: Dupont drop impact tester analyzed and measured according to ASTM D 4226. 500g load, Specimen size Horizontal * Vertical 30mm * 70mm * Sample thickness mm,

Example  One

The pressure-sensitive adhesive composition prepared in Preparation Example 1 was coated on a polyethylene terephthalate film as a release film and dried to produce a pressure-sensitive adhesive film having a thickness of 20 탆. The produced adhesive film was aged at 40 DEG C for 48 hours. An adhesive film and a film containing silsesquioxane were sequentially laminated on the plastic sheet 1 and laminated at room temperature using a Pol attacher to produce a laminate having the structure of Fig.

Example  2-7

A laminate was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive composition and the plastic sheet were changed as shown in Table 3 below.

Example One 2 3 4 5 6 7 Pressure-sensitive adhesive composition Production Example 1 Production Example 2 Production Example 2 Production Example 2 Production Example 2 Production Example 3 Production Example 1 Plastic sheet Plastic Sheet 1 Plastic Sheet 1 Plastic Sheet 1 Plastic Sheet 1 Plastic Sheet 2 Plastic Sheet 1 Plastic sheet 3 Thickness of adhesive layer (占 퐉) 20 20 20 10 10 20 20 Laminate structure 1 1 1 1 2 1 1 Laminate thickness (mm) 1.02 1.02 1.02 1.01 0.92 1.02 1.02

Comparative Example  1-4

A laminate was produced in the same manner as in Example 1 except that the kinds of the pressure-sensitive adhesive and the plastic sheet were changed as shown in Table 4 below.

Comparative Example One 2 3 4 Pressure-sensitive adhesive composition Production Example 4 Production Example 5 Production Example 1 Production Example 2 Plastic sheet Plastic Sheet 1 Plastic Sheet 1 Plastic Sheet 4 Plastic Sheet 5 Thickness of adhesive layer (占 퐉) 20 20 10 10 Laminate structure 1 1 1 1 The laminate
Thickness (mm) 1.02 1.02 1.02 0.41

Experimental Example

The following properties of the laminate prepared in the above Examples and Comparative Examples were evaluated, and the results are shown in Table 5 below.

Property evaluation method

1. Impact resistance: A laminate (width x length, 5 cm x 6 cm) was fixed using a ball drop tester, and a 36 g steel ball was dropped at a height of 50 cm from the center point of the laminate. When the laminate was dropped three times repeatedly at each falling height, no crack was observed, and when it occurred, X was evaluated.

2. Warpage: laminate (width x length x thickness, 15 cm x 15 cm x The thickness of the laminate of Tables 3 and 4) was allowed to stand for 72 hours at 85 DEG C / 85% relative humidity and then left at 25 DEG C for 4 hours. The maximum height at which the laminate was bent from the bottom was measured using a clearance gauge.

3. Transmittance: Measured in the 400-800 nm region with a Lambda 950 (perkin elmer) instrument.

4. Peelability: The laminate was allowed to stand for 72 hours under the conditions of 85 ° C and 85% high temperature and high humidity chamber (New power ENG.), Left for 4 hours at room temperature, and peeled off from the plastic sheet and silsesquioxane film visually Respectively.

Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 Impact resistance (cm) ○ ○ ○ ○ ○ ○ ○ X ○ X X warp
(mm) 3 3 3 One 0.8 3 4 2 2 4 16 Transmittance
(%) 91.15 90.07 90.32 90.41 90.18 90.57 90.73 90.03 90.71 91.41 91.25 Whether or not peeling X X X X X X X ○ ○ X ○

As shown in Table 5, the laminate of the present invention can be used as a window sheet which is excellent in transparency, impact resistance, scratch resistance, low warpage, transparency, impact resistance, and the like. However, there was a problem that peeling occurred due to the low initial adhesion of Comparative Example 1, which was more than -10 degrees. Comparative Example 2 using a pressure-sensitive adhesive of less than -50 DEG C also exhibited excellent initial viscosity but deteriorated due to poor cohesion and durability. In addition, the laminated sheet of Comparative Example 3, in which the impact resistance is out of the range of the present invention, has a problem in that the laminated sheet fails to absorb the shock during the ball drop test and cracks or the thickness is not appropriate. The laminated sheet of Comparative Example 4 including a thin substrate sheet was not suitable for the present invention because of its strong warpage in the lamination with the structure of Fig.

Claims (19)

A film comprising a plastic sheet, an adhesive layer, and silsesquioxane,
The adhesive layer has a glass transition temperature is -50 ℃ ~ -10 ℃ laminated body.
A film comprising a plastic sheet, an adhesive layer, and silsesquioxane,
The laminated body 1.5 x 10 ⁶ dyn / cm² - the adhesive layer has a modulus (G ') is 1 x 10 ^4.
A film comprising a plastic sheet, an adhesive layer, and silsesquioxane,
The plastic sheet laminate according to ASTM D4226 characterized in that the falling impact strength of 5J or more.
A film comprising a plastic sheet, an adhesive layer, and silsesquioxane,
Laminates having a bending height of less than 5 mm.
The laminate according to any one of claims 1 to 4, wherein the film containing silsesquioxane has a pencil hardness of 9H-10H.
The laminate according to any one of claims 1 to 4, wherein the film containing silsesquioxane has a thickness of 50 µm to 500 µm and a transmittance of 88% or more.
The laminate according to any one of claims 1 to 4, wherein the plastic sheet has a shock resistance of 35 cm or more when measured by Dupont Drop Tester (500 g, pin 1/2 ", specimen 100 * 100 mm).
The plastic sheet according to any one of claims 1 to 4, wherein the plastic sheet is made of polystyrene, (meth) acrylate-styrene copolymer, a mixture of polymethylmethacrylate and rubber, acrylonitrile-styrene copolymer, and polycarbonate. , Polyvinyl alcohol, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cyclic olefin copolymer, or a mixture thereof.
The said adhesive layer is formed from the adhesive composition containing the (meth) acrylic-type copolymer and a hardening | curing agent, The laminated body of any one of Claims 1-4 characterized by the above-mentioned.
The method of claim 9, wherein the (meth) acrylic copolymer is at least one selected from the group consisting of a vinyl monomer having a hydroxyl group, a vinyl monomer having an alkyl group, a vinyl monomer having a carboxyl group, and a vinyl monomer having an aromatic ring. A laminate comprising a copolymer of a monomer mixture.
The laminate according to claim 9, wherein the curing agent is contained in an amount of 0.01-5 parts by weight based on 100 parts by weight of the (meth) acrylic copolymer.
The film containing silsesquioxane is a Mitsubishi evaluation pencil (UNI) using a pencil hardness tester (Shinto Scientific, Heidon) 1kg load, 0.8mm / After drawing at a speed of sec, the measured pencil hardness is 9H-10H, the laminate.
The said film containing silsesquioxane contains the hardened | cured material of the photocurable resin composition containing silsesquioxane resin, The laminated body of any one of Claims 1-4 characterized by the above-mentioned.
The film according to any one of claims 1 to 4, wherein the thickness of the plastic sheet is 100-1000 µm, the thickness of the adhesive layer is 5-50 µm, and the thickness of the film containing the silsesquioxane is 50 µm. It is -500 micrometers, The laminated body characterized by the above-mentioned.
The said laminated body is a laminated body of any one of Claims 1-4 in which the film containing the said adhesion layer and said silsesquioxane was sequentially laminated on the said plastic sheet.
The said laminated body is a film | membrane containing the said adhesion layer and the said silsesquioxane sequentially laminated on one surface of the said plastic sheet, The other surface of the said plastic sheet in any one of Claims 1-4. The laminated body characterized by laminated | stacking the film | membrane containing the said adhesion layer and said silsesquioxane sequentially.
The laminate according to any one of claims 1 to 4, wherein the laminate further comprises a hard coat layer.
The window sheet containing the laminated body of any one of Claims 1-4.
A display device comprising the window sheet of claim 18.

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