KR20160042505A - Curable composition - Google Patents

Abstract

The present invention relates to a curable composition and a use thereof. The curable composition of the present invention does not need a separate additional process for curing during production by enabling additional heat curing after partially polymerization reaction of a monomer mixture, can prevent adhesive omission or durability reduction due to excellent transparency and storage modulus when being applied to the adhesive, and can be helpfully applied to an optical member due to excellent embeddability and stepped overcoming properties.

Description

{CURABLE COMPOSITION}

The present application relates to a curable composition and its use.

The curable composition is useful as a protective film, a commercial film, a cleaning sheet, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, And the like.

In the case of producing an optical adhesive film containing the curable composition, drying with ultraviolet rays is performed in consideration of coating property and processability.

However, when an optical adhesive film is produced through drying with ultraviolet rays, there is a problem in that it is difficult to dispose the pressure-sensitive adhesive agent or to secure durability properties.

Patent Document 1 proposes a transparent pressure-sensitive adhesive sheet as the optical adhesive product.

Patent Document 1: Korean Patent Publication No. 2011-0079711

The present application provides curable compositions and uses thereof.

The present application relates to a curable composition.

The curable composition of the present application may be of the non-solvent type. As used herein, the term "non-solvent type curable composition" means that the curable composition does not contain a solvent such as an organic solvent or an aqueous solvent, and may be referred to as a "non-solvent type curable composition". Since the solventless curable composition does not contain a solvent, it is possible to increase the process efficiency of production of an adhesive product such as an adhesive film, and to produce an adhesive product such as a uniform adhesive film substantially free from variation in thickness. Further, by eliminating the solvent, generation of bubbles and lowering of leveling caused by the volatilization process of the solvent and the like can be prevented, and a uniform thick adhesive film can be effectively produced. In addition, no solvent volatilization process is required, so that contamination is not caused during the process.

Exemplary curable compositions of the present application may include syrups. The term " syrup " used in the present invention means, for example, a state in which an oligomer or a part of the oligomer contained in an oligomer or mixture of monomers, which is a mixture of polymerizable oligomers or monomers, can do.

The syrup comprises a radical reactive oligomer and a radical reactive monomer, and the oligomer or monomer may comprise a thermosetting functional group. The term " radical reactive oligomer " as used herein means a compound in which two or more compounds are polymerized or bonded, and may be collectively referred to as a compound having a reactive group capable of participating in a crosslinking or polymerization reaction, The polymerization reaction can be induced by applying appropriate heat or moisture, or by irradiating electromagnetic waves.

The radical-reactive oligomer-forming monomer or the radical-reactive monomer may be a compound containing at least one functional group capable of participating in a radical reaction, without any particular limitation. For example, a (meth) acrylic ester compound , An epoxy acrylate compound or a urethane acrylate compound can be exemplified, but the above (meth) acrylic acid ester compound can be preferably used.

The (meth) acrylic acid ester compound is not particularly limited. For example, the first (meth) acrylic acid ester compound and the homopolymer having a glass transition temperature of 10 占 폚 or lower of the homopolymer may have a second Methacrylate ester compound. As used herein, the term " glass transition temperature of a polymer " may mean a glass transition temperature measured or calculated from a homopolymer formed solely of the compounds contained in the polymer.

The kind of the first (meth) acrylic acid ester compound and / or the second (meth) acrylic acid ester compound is not particularly limited as long as the glass transition temperature of the homopolymer formed from each of the above compounds satisfies the above-mentioned range.

The glass transition temperature of the homopolymer of the first (meth) acrylic acid ester compound may be, for example, 10 占 폚 or lower, 0 占 폚 or lower, -10 占 폚 or lower or -20 占 폚 or lower. The lower limit of the glass transition temperature of the homopolymer of the first (meth) acrylic acid ester compound is not particularly limited and may be, for example, about -50 ° C, -40 ° C, or -30 ° C.

As the first (meth) acrylic acid ester compound, for example, alkyl (meth) acrylate can be used. Specifically, from the viewpoints of controlling haze and storage modulus of a cured product to be described later, the compound having a carbon number of 1 to 14 or a carbon number of 1 (Meth) acrylate having an alkyl group of 1 to 12 carbon atoms can be used. Examples of such compounds include ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t- (Meth) acrylate, 2-ethylhexyl (meth) acrylate and 2-ethylbutyl (meth) acrylate. Of these, one kind or more kinds of them may be used.

The glass transition temperature of the homopolymer of the second (meth) acrylic acid ester compound may be, for example, 50 占 폚 or higher, 60 占 폚 or higher, or 70 占 폚 or higher. The upper limit of the glass transition temperature of the homopolymer of the second (meth) acrylic acid ester compound is not particularly limited and may be, for example, about 110 캜, 100 캜 or 95 캜.

As the second (meth) acrylic acid ester compound, for example, alkyl (meth) acrylate can be used. Specifically, from the viewpoints of controlling haze and storage modulus of a cured product to be described later, the compound having a carbon number of 1 to 14 or a carbon number of 1 (Meth) acrylate having an alkyl group of 1 to 12 carbon atoms can be used. Examples of such compounds include methyl (meth) acrylate, isopropyl (meth) acrylate or isobonyl (meth) acrylate, and one or more of the above compounds may be used.

The (meth) acrylic acid ester compound is used in an amount of 50 to 80 parts by weight, 55 to 80 parts by weight or 55 to 75 parts by weight and a second (meth) acrylic acid ester compound 10 to 100 parts by weight, 30 to 30 parts by weight, 15 to 30 parts by weight or 15 to 25 parts by weight. The content ratio between the components contained in the (meth) acrylic acid ester compound is adjusted to the above-mentioned range so that additional curing can be performed even after the curing, thereby improving the durability of the cured product as described later, When the cargo is applied as the pressure sensitive adhesive, it is possible to exhibit the effect of improving the pressure drop of the pressure sensitive adhesive.

In one example, the thermosetting functional group is not particularly limited, but may be any one selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an amine group, an epoxy group, an isocyanate group and a nitrile group, Epoxy group. The curable composition of the present application can include a radical reactive oligomer containing the epoxy group and a radical reactive monomer to enable more efficient radical reaction.

In one example, the syrup may be a partial polymeric mixture of a monomer mixture comprising a reactive monomer comprising a (meth) acrylic acid ester compound and an epoxy group. The term " partial polymerizate " used in the present invention means a state in which oligomers or a part of monomers contained in an oligomer or monomer mixture are polymerized to constitute a polymer, and such a polymer is mixed with an unreacted oligomer or monomer. When the oligomer or monomer mixture is partially polymerized, the degree of partial polymerization is not particularly limited and may be adjusted according to the purpose. For example, the degree of the partial polymerization can be controlled within a range in which the composition can satisfy the viscosity range described later.

In one example, the curable composition of the present application further comprises a radical reactive oligomer and a radical reactive monomer in addition to the syrup (hereinafter referred to as " first syrup "), and the oligomer or monomer is a thermosetting functional group (Hereinafter referred to as " second syrup ") containing another thermosetting functional group (hereinafter referred to as " second thermosetting functional group ") having reactivity with a thermosetting functional group (hereinafter referred to as a first thermosetting functional group).

The content of the reactive oligomer and the radical reactive monomer which can be contained in the second syrup is the same as that of the first syrup.

In one example, the second thermosetting functional group is selected from any one selected to be capable of reacting with a first thermosetting functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an amine group, an epoxy group, an isocyanate group and a nitrile group, , But it may preferably be a carboxyl group as an acid functional group.

The second syrup may contain from 0.01 to 2 equivalents, from 0.025 to 1 equivalent, or from 0.05 to 0.5 equivalent of the second thermosetting functional group per equivalent of the first thermosetting functional group. The curable composition of the present application is prepared by adjusting the equivalent amount of the second thermosetting functional group of the second syrup capable of reacting with the first thermosetting functional group contained in the first syrup to the above range so as to enable further curing after curing, As well as improving the durability of the cured product, it is possible to exhibit an effect of improving contamination problems that may occur at the time of cutting, and detachment of the pressure sensitive adhesive when the cured product is applied as a pressure sensitive adhesive.

As the reactive monomer, for example, a compound having a site capable of being polymerized with other monomers contained in the monomer mixture such as glycidyl (meth) acrylate and having the reactive functional group can be used. In the production of pressure-sensitive adhesives, reactive monomers having reactive functional groups as described above are variously known. All of these monomers can be used in the polymer. Examples of the reactive monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate such as 2-hydroxyethyleneglycol (meth) acrylate or 8-hydroxyoctyl (Meth) acrylate such as (meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyl or the like can be used as the reactive monomer having a carboxyl group. (Meth) acryloyloxybutyric acid, acrylic acid dimer, itaconic acid, maleic acid, maleic anhydride, and the like can be used, but the present invention is not limited thereto.

As the reactive monomer having an epoxy group, glycidyl (meth) acrylate, allyl glycidyl ether or the like can be used, but it is not limited thereto.

In one example, the monomer mixture comprises 70 to 100 parts by weight, 75 to 95 parts by weight or 80 to 90 parts by weight of the aforementioned (meth) acrylic acid ester compound and 5 to 30 parts by weight of a reactive monomer , 5 parts by weight to 25 parts by weight, or 5 parts by weight to 20 parts by weight. By controlling the content of the components in the monomer mixture in the above range, the haze and the storage elastic modulus of the cured product can be appropriately controlled as described later to improve the durability of the cured product, It is possible to exhibit an effect of improving the detachment of the pressure-sensitive adhesive.

The viscosity of the partial polymer at 25 DEG C may be in the range of 100 cp to 5000 cp, 200 cp to 4000 cp, or 300 cp to 3000 cp. The partial polymerization of the partial polymer with the unreacted monomer contained in the polymer may be controlled by controlling the viscosity at 25 ° C in the above range so that additional thermal curing as described below is possible so that an additional process is required for curing It is possible to provide a cured product which can be effectively applied to an optical member because it can prevent dropout and deterioration in durability when applied with a cured product and has excellent transparency as well as filling property and step difference overcoming property.

In the present application, the monomer mixture may further comprise any comonomer. Examples of such a comonomer include a compound having a copolymerizable functional group and a compound having a glass transition temperature of -130 ° C to 50 ° C in a non-crosslinked state when being polymerized with a homopolymer. In one example of the present application, the comonomer as described above may be a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ to R ₃ each independently represents hydrogen or alkyl; R ₄ represents cyano; Phenyl unsubstituted or substituted with alkyl; Acetyloxy; Or COR < _{5 &} gt ;, wherein R < ₅ > represents amino or glycidyloxy substituted or unsubstituted with alkyl or alkoxyalkyl.

In the definition of R ₁ to R _{5 in} the above formula, alkyl or alkoxy may mean straight-chain, branched-chain or cyclic alkyl or alkoxy having 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, Methyl, ethyl, methoxy, ethoxy, propoxy or butoxy.

Specific examples of the compound of Formula 1 that can be used in the present application include nitrogen-containing monomers such as (meth) acrylonitrile, N-methyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide; Styrene-based monomers such as styrene or methylstyrene; Or a vinyl ester of a carboxylic acid such as vinyl acetate, and the like, but is not limited thereto.

The monomer mixture of the present application may contain up to 20 parts by weight of the compound of formula (1). If the proportion of the compound of the formula (1) is excessively high, there is a problem that the flexibility of the pressure-sensitive adhesive decreases when the cured product is applied as a pressure-sensitive adhesive.

The method of polymerizing the monomer mixture is not particularly limited, but general polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization may be used And if necessary in this process, a suitable polymerization initiator or molecular weight regulator, a chain transfer agent and the like may be used together, and among these polymerization methods, bulk polymerization is preferably used, but is not limited thereto.

The curable composition of the present application may further include a radical reactive multi-functional crosslinking agent having two or more functional groups capable of reacting with the radically polymerizable group and / or the thermosetting functional group, in addition to the above components.

The multifunctional crosslinking agent may further react with the thermosetting functional group of the polymer after the reaction of the radical polymerizable group at the time of forming the cured product to form a crosslinked structure. The type of the polyfunctional crosslinking agent in the present application is not particularly limited as long as it contains a functional group capable of reacting with an epoxy group. For example, a conventional crosslinking agent such as a resin having an acidic property, an amine compound or an imidazole compound may be used .

The resin having the acidic property may be a resin having a polar functional group, and a resin containing the polar functional group may be used without particular limitation. For example, the polar functional group may be a hydroxyl group or a carboxyl group.

The amine compound or the imidazole compound is not particularly limited and includes, for example, tetramethylguanidine, imidazole or a derivative thereof, a carboxylic acid hydrazide, a tertiary amine, an aromatic amine, an aliphatic amine, And derivatives thereof. Examples of imidazole derivatives include 2-methylimidazole, 1-benzyl-2-methylimidazole and 2-ethyl-4-methylimidazole. Examples of the carboxylic acid hydrazide derivative include adipic acid hydrazide and naphthalenecarboxylic acid hydrazide. Examples of the tertiary amine include N, N-dimethylaniline, N, N-dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol and the like. Examples of the aromatic amine include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m- Diethyltoluenediamine, and the like. Examples of the aliphatic amine include diethylenetriamine, triethylenetetramine, isophoronediamine, bis (aminomethyl) norbornane, bis (4-aminocyclohexyl) methane, dimeric acid ester of polyethyleneimine and the like. Also included are modified amines obtained by reacting an amine having an active hydrogen, such as an aromatic amine and an aliphatic amine, with a compound such as an epoxy compound, acrylonitrile, phenol, formaldehyde or thiourea.

As the amine compound, a latent curing agent can also be used in that the storage stability of the resin composition is excellent. The latent curing agent is a curing agent that exhibits activity by causing a phase change or a chemical change by a constant stimulus such as heat or light. Examples of latent curing agents include amine adduct type latent curing agents, microcapsulated latent curing agents, dicyandiamide or derivatives thereof, and the like. The amine adduct type latent curing agent means a compound having a primary, secondary or tertiary amino group or an active ingredient such as various imidazole derivatives reacted with a compound capable of reacting with these compounds, Insoluble at storage temperature. The microcapsulated latent curing agent refers to a coating of a high molecular material such as an epoxy resin, a polyurethane resin, a polystyrene, or a polyimide or a cyclodextrin as a shell with a hardener as a nucleus to reduce the contact between the epoxy resin and the curing agent It says. A derivative of dicyandiamide is obtained by binding various compounds to dicyandiamide and includes a reaction product with an epoxy resin and a reaction product with a vinyl compound or an acrylic compound.

Examples of commercially available amine-duct type latent curing agents include "Amicure (registered trademark)" PN-23, PN-H, PN-40, PN-50, PN-F, MY- EH-3615S, EH-4070S (manufactured by ADEKA Corporation), and the like can be given. As a commercially available product of the microcapsule type latent curing agent, "Novacure (registered trademark)" HX-3721, HX-3722 (manufactured by Asahi Kasei Chemicals Co., Ltd.) can be used. Commercially available products of dicyandiamide include DICY-7 and DICY-15 (manufactured by Japan Epoxy Resins Co., Ltd.). These amine compounds or imidazole compounds may be used alone or in combination of two or more.

The multifunctional crosslinking agent may be contained in an amount of 0.01 to 10 parts by weight, 0.1 to 10 parts by weight or 1 to 7.5 parts by weight based on 100 parts by weight of the total of the first and second syrups. The content of the polyfunctional crosslinking agent can be controlled within the above-mentioned range to appropriately indicate the physical properties of the cured product to a desired level.

The curable composition of the present application may further comprise a radical initiator such as a photopolymerization initiator to induce an efficient reaction of the radical polymerizable group.

As the radical initiator, for example, a radical initiator such as benzoin-based initiator, a hydroxyketone-based initiator, an amino ketone-based initiator, or a phosphine oxide-based initiator may be used which generates radicals by irradiation with ultraviolet light or the like to initiate photopolymerization Initiators may be used without limitation.

More specifically, examples of the photopolymerization initiator include? -Hydroxyketone compounds (e.g., IRGACURE 184, IRGACURE 500, IRGACURE 2959, DAROCUR 1173, Ciba Specialty Chemicals); Phenylglyoxylate-based compounds (ex IRGACURE 754, DAROCUR MBF; Ciba Specialty Chemicals); Benzyldimethylketal compounds (ex IRGACURE 651; Ciba Specialty Chemicals); α-aminoketone-based compounds (ex IRGACURE 369, IRGACURE 907, IRGACURE 1300, Ciba Specialty Chemicals); Monoacylphosphine based compounds (MAPO) (ex. DAROCUR TPO; Ciba Specialty Chemicals); Bisacylphosphine compounds (BAPO) (ex IRGACURE 819, IRGACURE 819DW; Ciba Specialty Chemicals); Phosphine oxide-based compounds (ex IRGACURE 2100; Ciba Specialty Chemicals); Metallocene compounds (ex IRGACURE 784; Ciba Specialty Chemicals); Iodonium salt (ex.IRGACURE 250 from Ciba Specialty Chemicals); And mixtures of at least one of the foregoing, and the like, but are not limited thereto.

The radical initiator may be contained in an amount of 0.01 to 10 parts by weight, 0.05 to 5 parts by weight or 0.1 to 1 part by weight based on 100 parts by weight of the total of the first and second syrups. If the content of the radical initiator is too small, the effect due to the addition may be insignificant. If the radical initiator is too large, the physical properties such as durability and transparency may be adversely affected. .

The curable composition of the present application can be added with a tackifier if necessary. Useful tackifiers include, for example, rosin ester resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and terpene resins. In general, a bright tackifier selected from hydrogenated rosin esters, terpenes or aromatic hydrocarbon resins may be used. In addition, other materials, such as oils, plasticizers, antioxidants, UV stabilizers, pigments, curing agents, polymer additives and other additives, may be added for special purposes if they do not reduce the optical transparency of the cured product of the curable composition .

In one example, the curable composition of the present application can satisfy Equation 1 below.

[Equation 1]

(Y-X) / X 占 100? 30

X is the storage modulus immediately after the radical reaction of the curable composition (measurement conditions: 30 ° C and 1 rad / sec), Y is the storage elastic modulus after maintaining the curable composition at 80 ° C for 24 hours after the radical reaction Measurement conditions: 30 占 폚 and 1 rad / sec).

X represents the storage modulus immediately after the radical reaction of the curable composition (measurement conditions: 30 ° C and 1 rad / sec) and the storage elastic modulus after the radical reaction at 80 ° C for 24 hours : 30 ° C and 1 rad / sec), the larger the Y difference is, the more excellent the filling property and the step difference overcome when applied as a pressure sensitive adhesive, so that the X is 0.05 MPa to 0.15 MPa, 0.06 MPa to 0.14 MPa, 0.07 MPa to 0.13 MPa, 0.08 MPa to 0.12 MPa, or 0.09 MPa to 0.11 MPa.

In the above formula (1), Y is not particularly limited as far as the formula (1) is satisfied in relation to X, but Y may be in the range of 0.15 MPa to 1 MPa, 0.16 MPa to 0.5 MPa, or 0.17 MPa to 0.25 MPa, for example .

By controlling the storage elastic modulus of the curable composition of the present application to satisfy the above-mentioned formula 1, it is possible to perform additional thermal curing described later, so that no additional process is required for curing, and when the cured product is applied as an adhesive, It is possible to provide a cured product which can be effectively applied to optical members as well as being capable of preventing degradation as well as being excellent in the filling property and step difference overcoming property as well as transparency.

In one example, the curable composition of the present application is cured to produce a cured product having a haze of less than 1%, less than 0.7%, or less than 0.4%.

It is possible to control the haze of the curable composition after curing within the above-mentioned range so that the transparency is more excellent, so that the composition can be effectively applied to optical members.

The present application also relates to a laminate.

Exemplary such laminates may be laminates that may be applied to optically clear pressure sensitive adhesives. As used herein, the term " optically transparent " means that in the wavelength range of 400 nm to 700 nm, i.e. in the visible light range, luminous transmission is greater than about 90%, turbidity is less than about 2% Or less than about 1%. Both luminous transmittance and turbidity can be determined, for example, using an ASTM-D 1003-95 instrument, and optically transparent laminates may refer to laminates that are visually free of bubbles.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagrammatic representation of an optically transparent laminate of the present application. In one example, the optically transparent laminate comprises a first substrate 20 and a second substrate 40, and between the first (20) and second (40) substrates a light- And a cargo 30.

The first substrate, the second substrate, or both the first substrate and the second substrate may be an optically transparent substrate. The first base material, the second base material, or both the first base material and the second base material may be selected from a display panel, a touch panel, an optical film, a cover lens or a window glass so long as the base material is optically transparent. .

The display panel may be selected from, for example, a liquid crystal display, a plasma display, an OLED display, an electrowetting display, and a cathode ray tube display, but is not limited thereto.

The optical film may be selected from, for example, a reflector, a polarizer, a mirror, an anti-glare or anti-reflection film, a anti-shatter film, a diffuser, or an electromagnetic interference filter.

Representative examples of optically transparent substrates include glass substrates, and glass substrates and substrates made of polycarbonates, polyesters (e.g., polyethylene terephthalate and polyethylene naphthalate), polyurethanes, poly (meth) acrylates Polyvinyl alcohols, polyolefins, such as those containing polyethylene, polypropylene, and cellulose triacetate. Typically, the cover lens can be made of glass, polymethyl methacrylate, or polycarbonate.

In another example, the substrate, i.e., the first substrate, the second substrate, or both the first substrate and the second substrate may be a release liner. Any suitable release liner may be used. Exemplary release liners include those made from paper (e.g., kraft paper) or polymeric materials (such as polyolefins such as polyethylene or polypropylene, ethylene vinyl acetate, polyurethanes, polyesters such as polyethylene terephthalate, . At least some of the release liner is coated with a layer of release agent, such as a silicon-containing material or a fluorocarbon-containing material. Exemplary release liners include liners commercially available under the trade designations "T-30" and "T-10" from CP Film (Martinsville, VA) having a silicone release coating on a polyethylene terephthalate film But is not limited to.

The release liner may be removed to attach the optical film to another substrate. (I.e., the release liner can be removed to expose the surface of the adhesive layer and subsequently bond it to another substrate surface). Often, the adhesive layer is permanently bonded to these other substrates, although in some cases adhesion may be limited in view of reworking of the display.

The thickness of the above-described substrates is not particularly limited and may be suitably set as long as it can function as an optical film. For example, the thicknesses of the substrates, e.g., the first substrate and the second substrate, may be the same or different, respectively, and the thickness ranges from about 5 탆 to 2000 탆, from about 10 탆 to 1000 탆, To about 500 mu m.

The above substrates are not particularly limited, but if necessary, appropriate bonding treatment such as corona discharge treatment, ultraviolet ray irradiation treatment, plasma treatment or sputter etching treatment may be performed.

The manner of producing the optically transparent laminate of the present application is not particularly limited. For example, a coating solution may be formed from the curable composition of the present application and coated or laminated on a separately prepared substrate.

The curable composition of the present application is capable of further thermal curing after the partial polymerization of the monomer mixture, so that no additional process is required for curing in the production, and when applied as a pressure sensitive adhesive, transparency and storage elastic modulus are excellent, It is possible to provide a cured product which can prevent deterioration in durability and is excellent in the filling property and the step difference overcoming property and can be applied to optical members.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram schematically showing the structure of a laminate according to one example of the present application. Fig.

Hereinafter, the present application will be described in more detail by way of examples according to the present application and comparative examples not complying with the present application, but the scope of the present application is not limited by the following examples.

The physical properties in the following examples and comparative examples were evaluated in the following manner.

One. Hayes  evaluation

The coated cured product of the curable composition (thickness: 150 mu m) prepared in Examples and Comparative Examples was irradiated with ultraviolet rays to prepare a pressure sensitive adhesive layer. The haze of the pressure sensitive adhesive layer thus prepared was measured with a haze meter (COH-400, Nippon Denshoku) Was measured immediately after aging at 80 ° C. for 24 hours in accordance with JIS K 7105-1 standard, and is shown in Table 3.

2. Evaluation of storage modulus

The storage moduli of the curable compositions prepared in Examples and Comparative Examples were measured using a Rheometric Expansion System (TA). The curable composition was cut into a specimen having a thickness of 1 mm and a diameter of 8 mm, and then a parallel plate fixture having the same diameter was cut at a temperature of 30 [deg.] C through a frequency sweep at a strain rate of 10% (Storage elastic modulus (1)) of the curable composition, and aging at 80 캜 for 24 hours after irradiating the ultraviolet (storage) Elastic modulus (2)) were measured and shown in Table 3.

Manufacturing example  1. Preparation of syrup (A)

65 parts by weight of 2-ethylhexyl acrylate (EHA), 20 parts by weight of isobornyl acrylate (IBOA) and 20 parts by weight of glycidyl (metha) acrylate were added to a 2 L reactor equipped with a cooling device for refluxing nitrogen gas, ) Acrylate acrylic acid (GMA) (15 parts by weight). Nitrogen gas was purged for 60 minutes to remove oxygen, and then 0.2 parts by weight of azobisisobutyronitrile (AIBN) as a reaction initiator and 0.2 part by weight of 2,4-diphenyl-4 -Methyl-1-pentane was added to initiate the reaction. Thereafter, oxygen was injected into the reaction mixture reacted for about 2 hours while 50% of the initial monomer loading ratio was added to the initial injection amount, and polymerization was completed to prepare syrup (A).

Manufacturing example  2. Preparation of syrup (B)

Syrup (B) was prepared in the same manner as in Preparation Example 1, except that the kinds and / or ratios of raw materials and additives used in the production of syrup (A) of Preparation Example 1 were adjusted as shown in Table 1 .

Raw material V-65 DMP EHA IBOA GMA AA syrup A 65 20 15 - 0.02 0.02 B 65 20 - 15 0.02 0.02 Content Unit: g
EHA: 2-ethylhexyl acrylate
IBOA: isobornyl acrylate
GMA: glycidyl (meth) acrylate
AA: acryl acid
V-65: 2,2'-azobis (2,4-dimethyl valeronitrile)
DMP: 2,4-diphenyl-4-methyl-1-pentene

Example  One

Preparation of Curable Composition

100 parts by weight of a mixture obtained by mixing 50 parts by weight of the syrup (B) prepared in Preparation Example 2 with 100 parts by weight of the syrup (A) prepared in Preparation Example 1 was mixed with 100 parts by weight of pentaerythritol triacrylate (M340, 1 part by weight) and 0.5 part by weight of photo-initiator Irgacure 184 (BASF) were uniformly mixed to prepare a curable composition.

Manufacture of laminate

The curable composition prepared above was coated on a RF12N film (SKC-Haas) as a carrier film with a blade coat to a thickness of 150 mu m, and an RF02N film (SKC-Haas) was laminated on the coating layer. Thereafter, the coating layer was irradiated with ultraviolet ray (ultraviolet ray, A region-based 5 mW for 3 minutes) with a black light ultraviolet lamp (UV irradiation apparatus, manufactured by Kanetec Corp.) in order to cut off oxygen supply, After that, the film on the upper and lower portions of the coating layer was removed to prepare a laminate.

Example  2

2 parts by weight of triethylenetetramine curing agent per 100 parts by weight of the syrup (A), 2 parts by weight of pentaerythritol triacrylate (M340, manufactured by MIWON CORPORATION) as a photo-crosslinking agent, And 0.5 parts by weight of a photoinitiator Irgacure 184 (BASF) were added to the curable composition and the laminate.

Example  3

A curable composition and a laminate were prepared in the same manner as in Example 2 except that 2 parts by weight of 2-ethyl-4-methylimidazole was used instead of trimethylolpropane triethylenetetramine curing agent as a curing agent.

Comparative Example  One

A curable composition and a laminate were prepared in the same manner as in Example 2, except that the triethylene tetramine curing agent was not used.

The types and / or ratios of raw materials and additives used in the preparation of the curable compositions used in the above Examples and Comparative Examples are shown in Table 2. The properties and evaluation of the curable compositions measured in the respective Examples and Comparative Examples The results are shown in Table 3 below.

division syrup Cross-linking agent PETA Ir A B TET EMI Example 1 100 50 - - One 0.5 Example 2 100 - 2 - 2 0.5 Example 3 100 - - 5 2 0.5 Comparative Example 1 100 - - - 2 0.5 Content Unit: g
TET: triethylene tetramine
EMI: 2-ethyl-4-imidazole
PETA: pentaerythritol triacrylate
Ir: Irgacure 184 (BASF)

division Example Comparative Example One 2 3 One Haze (Unit:%) 0.2 0.3 0.3 0.1 Storage elasticity (1)
(Unit: MPa) 0.11 0.11 0.09 0.06 Storage elasticity (2)
(Unit: MPa) 0.22 0.20 0.17 0.07 Storage elasticity (1): Storage elasticity measured immediately after UV irradiation
Storage modulus (2): The storage modulus measured after UV irradiation and aging

As can be seen from the above Table 3, in the case of the curable composition and the laminate of the present application, transparency and storage elastic modulus are within a desired range due to additional thermosetting rather than immediately after mixing of the monomer mixture, Can be prevented from detaching the pressure-sensitive adhesive and decreasing the durability, and is excellent in the filling property and the step difference overcoming property, so that it can be effectively applied to the optical member.

20: First substrate
30: Hardened cargo
40: second substrate

Claims (19)

A radical reactive oligomer and a radical reactive monomer, wherein the oligomer or monomer comprises a syrup containing an epoxy group,
A curable composition which satisfies the following formula (1):
[Equation 1]
(YX) / X 占 100? 30
X is the storage modulus immediately after the radical reaction of the curable composition (measurement conditions: 30 ° C and 1 rad / sec), Y is the storage elastic modulus after maintaining the curable composition at 80 ° C for 24 hours after the radical reaction Measurement conditions: 30 占 폚 and 1 rad / sec). The curable composition according to claim 1, wherein X in the formula (1) is in the range of 0.05 MPa to 0.15 MPa. The curable composition according to claim 1, wherein Y in the formula (1) is in the range of 0.15 MPa to 1 MPa. The curable composition of claim 1, wherein the syrup comprises a radical reactive oligomer and a radical reactive monomer, wherein the oligomer or monomer comprises an epoxy group. The curable composition according to claim 1, wherein the syrup is a partial polymer of a monomer mixture comprising a reactive monomer containing a (meth) acrylic acid ester compound and an epoxy group as polymerized units. The composition according to claim 5, wherein the (meth) acrylic acid ester compound is a first (meth) acrylic acid ester compound having a glass transition temperature of not higher than 10 ° C and a second (meth) acrylic acid ester compound having a glass transition temperature of not lower than 50 ° C of the homopolymer ≪ / RTI > The curable composition according to claim 6, wherein the (meth) acrylic acid ester compound comprises 50 to 80 parts by weight of the first (meth) acrylic acid ester compound and 10 to 30 parts by weight of the second (meth) acrylic acid ester compound. 6. The curable composition according to claim 5, wherein the viscosity of the partial polymer at 25 DEG C is in the range of 100 cp to 5000 cp. The curable composition of claim 1, further comprising a syrup containing a radical reactive oligomer and a radical reactive monomer, wherein the oligomer or monomer comprises an acid functional group. 10. The curable composition of claim 9, wherein the acid functionality is a carboxyl group. The curable composition of claim 1, further comprising a radically reactive multifunctional crosslinker. 12. The curable composition of claim 11, wherein the multifunctional crosslinking agent is present in a proportion of from 0.01 to 10 parts by weight relative to 100 parts by weight of the syrup. The curable composition of claim 1, further comprising a radical initiator. 14. The curable composition of claim 13, wherein the radical initiator is present in a proportion of from 0.01 to 10 parts by weight relative to 100 parts by weight of the syrup. The curable composition according to claim 1, which is cured to produce a cured product having a haze of 1% or less. A first substrate and a second substrate,
An optically clear laminate comprising a cured product formed from the curable composition according to claim 1 between said first and second substrates. 17. The optically transparent laminate of claim 16, wherein the first substrate, the second substrate, or both the first substrate and the second substrate are selected from a display panel, a touch panel, an optical film, a cover lens or a window glass. 18. The optically transparent laminate of claim 17, wherein the display panel is selected from a liquid crystal display, a plasma display, an OLED display, an electrowetting display, and a cathode ray tube display. 18. The optically transparent laminate of claim 17, wherein the optical film is selected from a reflector, a polariser, a mirror, an anti-glare or anti-reflection film, a anti-shatter film, a diffuser, or an electromagnetic interference filter.

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