KR20150104532A - Adhesive composition, a comprising anti-scattering film and decor film - Google Patents

Abstract

The present invention relates to adhesive composition and an adhesive film manufactured by using the same. When applied to an adhesive film such as an anti-scattering film or a decoration film as an adhesive layer, the adhesive composition according to the present invention can maximize productivity for the adhesive film manufactured including the same by preventing the adhesive film from being steamed when the adhesive film is cut by laser or computer numerical control (CNC) to minimize a failure rate during a manufacturing process.

Description

TECHNICAL FIELD [0001] The present invention relates to a pressure-sensitive adhesive composition, an anti-scattering film and a decolor film containing the same,

The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive film produced using the pressure-sensitive adhesive composition, an anti-fire film containing the same, and a deco film.

BACKGROUND ART Adhesive films produced by forming a pressure-sensitive adhesive layer on one side or both sides of a base film are widely used in various industrial fields including advertising adhesive films for decorative purposes, industrial protective films, optical adhesive films, and adhesive films for electronic components .

The decorative adhesive film is referred to as a deco film, and a shatterproof film is often used as one of the industrial protective films.

In the case of the shrink-preventive film and the decolorized film, cutting is usually performed with a laser or CNC (computer numerical control). In performing the cutting process, the shrink- There is a problem that a phenomenon occurs and defects are generated.

Patent Documents 1 and 2 disclose a pressure-sensitive adhesive composition used for producing such a pressure-sensitive adhesive or film.

Patent Document 1: Korean Patent Publication No. 2013-0113373 Patent Document 2: Korean Patent Publication No. 2013-0101988

The present application provides a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film produced using the pressure-sensitive adhesive composition.

The present application relates to a pressure-sensitive adhesive composition.

In one example, the pressure sensitive adhesive composition may comprise a tacky polymer.

As used herein, the term " polymer " may refer to a polymer in which one or more different monomers are mixed and polymerized.

In one example, the tacky polymer may comprise a first monomer having a glass transition temperature of less than 0 ° C and a second monomer having a glass transition temperature of 0 ° C or higher as polymerized units.

As used herein, the term "first monomer having a glass transition temperature of less than 0 ° C" may mean that the glass transition temperature measured or calculated from a "homopolymer" type polymer formed solely of the first monomers is less than 0 ° C. The term "second monomer having a glass transition temperature of 0 ° C or higher" may also mean that the glass transition temperature measured or calculated from a polymer of the "homopolymer" type formed solely of the second monomers is 0 ° C. or higher. Also, in the present specification, when a monomer is contained in a polymer as a polymerized unit, it may mean that the monomer undergoes a polymerization reaction to form a skeleton of the polymer, for example, a main chain or a side chain.

The glass transition temperature of the first monomer may be, for example, less than 0 占 폚, less than -10 占 폚, less than -20 占 폚, less than -30 占 폚, or less than -40 占 폚. The lower limit of the glass transition temperature of the first monomer is not particularly limited and may be, for example, about -100 ° C, -90 ° C, -80 ° C, or -70 ° C.

The first monomer may be an alkyl (meth) acrylate having an alkyl group of 1 to 5 carbon atoms in consideration of the glass transition temperature and the storage modulus to be described later. The alkyl group may be a branched chain or straight chain alkyl group. Examples of the first monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate and the like can be mentioned, and preferably n-butyl acrylate, ethyl acrylate or isopropyl acrylate May be used, but is not limited thereto.

In consideration of the ease of controlling the glass transition temperature and the like, the monomers contained in the polymerized form of the adhesive polymer include methacrylic acid ester monomers such as alkyl methacrylates, for example, alkyl groups having 1 to 5 carbon atoms Alkyl methacrylate may be used.

The glass transition temperature of the second monomer may be, for example, 0 占 폚 or higher, 10 占 폚 or higher, 20 占 폚 or higher, 30 占 폚 or higher, or 40 占 폚 or higher. The upper limit of the glass transition temperature of the second monomer is not particularly limited and may be, for example, about 200 ° C, 190 ° C, 180 ° C, 170 ° C or 160 ° C. The glass transition temperature of the second monomer may suitably be formed within a range of 0 占 폚 to 200 占 폚, 50 占 폚 to 150 占 폚, or 80 占 폚 to 110 占 폚.

The second monomer may include, for example, a linear monomer and a cyclic monomer in consideration of the above-mentioned range of the glass transition temperature and the control of the storage elastic modulus range to be described later.

The linear monomers used as the second monomer include, for example, t-butyl (meth) acrylate, N-vinylformamide, acrylamide, t Butyl acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (Meth) acrylate, N, N-dimethyl acrylamide, N, N-dimethyl (meth) acrylamide, (Meth) acrylamide, N- (n-dodecyl) (meth) acrylamide, 1-hexadecyl (meth) acrylate, Acrylates such as 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, Methyl acrylate or N- (Meth) acrylate, t-butyl acrylate, isobutyl (meth) acrylate, and the like. Isobutyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, 1- Acrylates such as 1-hexadecyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, or methyl acrylate. However, the present invention is not limited thereto.

Also, the cyclic monomer used as the second monomer may be dihydrodicyclopentadienyl acrylate, cyclohexyl (meth) acrylate, benzyl acrylate, , Benzyl (meth) acrylate, 4-cyclopropyl acrylate, cyclohexyl acrylate, cyclohexyl (meth) acrylate, ), N, N-diphenyl (meth) acrylamide, N-naphthyl acrylate, 2-phenoxyethyl (meth) acrylate (meth) acrylate, phenyl acrylate, phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, styrene (styrene), isobornyl acrylate ), Isobornyl (meth) acrylate or (meth) acrylic acid dicyclopentanyl ester, and preferably isobornyl (meth) acrylate, acrylate or isobornyl (meth) acrylate may be used, but the present invention is not limited thereto.

The pressure-sensitive adhesive polymer containing the first and second monomers whose glass transition temperature is within the above-mentioned range has a storage elastic modulus within a specific range in a high-frequency range described later in the pressure-sensitive adhesive composition; And / or a viscosity higher than a specific range at a specific temperature. The pressure-sensitive adhesive composition having such a storage elastic modulus minimizes the outflow of the adhesive composition as a pressure-sensitive adhesive after curing, thereby preventing occurrence of defects due to steaming in the cutting process .

In one example, the tacky polymer may further comprise, in addition to the first monomer and the second monomer, a third monomer having a cyclic structure including nitrogen as a ring-constituting atom, as polymerization units.

The third monomer is not particularly limited as long as it has a cyclic structure containing nitrogen as a ring constituting atom. For example, the number of ring constituting atoms of the cyclic structure is in the range of 3 to 8, 4 to 8, or suitably 5 to 8 Lt; / RTI >

The third monomer having a cyclic structure containing nitrogen as a ring-constituting atom is, for example, 4-acryloylmorpholine, 1-vinyl-2-pyrrolidone 2-isopropenyl-2-oxazoline, N-vinylcaprolactam, and 1-vinylimidazole. , Preferably 1-vinyl-2-pyrrolidone, but is not limited thereto.

The tacky polymer may further comprise a crosslinkable monomer as a polymerization unit. As used herein, the term " crosslinkable monomer " may mean a polymerizable monomer having a crosslinkable functional group.

As the crosslinkable monomer, for example, a compound having a moiety capable of being polymerized with the above-mentioned monomer contained in the adhesive polymer, such as an acrylic acid ester monomer, and having the crosslinkable functional group can be used. In the production of pressure-sensitive adhesives, various crosslinking monomers as described above are widely known, and all of these monomers can be used in the adhesive polymer. Examples of the copolymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate such as hydroxyalkyl (meth) acrylate or 8-hydroxyoctyl (Meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloylglycol (meth) acrylate and the like. Examples of the copolymerizable monomer having a carboxyl group include (Meth) acryloyloxybutyric acid, acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride, and the like, and preferably 2-hydroxyethyl (meth) acrylate Late or 2-hydroxypropyl (meth) acrylate, but you can use the like, without being limited thereto.

When the crosslinkable monomer is contained in the tacky polymer, the tacky polymer is used in an amount of 40 to 70 parts by weight of the first monomer, 10 to 50 parts by weight of the second monomer, 1 to 20 parts by weight of the third monomer, 5 to 25 parts by weight of the monomer may be contained as a polymerization unit. In the present specification, the unit " part by weight " may mean the ratio of the weight between each component. It is possible to provide a pressure-sensitive adhesive composition having a storage elastic modulus and / or viscosity of a specific range or more, which will be described later, by controlling the pressure-sensitive adhesive polymer to include the crosslinkable monomer in the above-mentioned range as polymerization units.

The tacky polymer may further include any other comonomer, for example, when necessary for controlling the glass transition temperature, and the monomer may be included as a polymerization unit. Examples of the comonomer include a third monomer such as (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide and other nitrogen-containing monomers; Styrene-based monomers such as methylstyrene; Glycidyl group-containing monomers such as glycidyl (meth) acrylate; And carboxylic acid vinyl esters such as vinyl acetate, but are not limited thereto. These comonomers may be included in the adhesive polymer by selecting one kind or more than two kinds of suitable comonomers as needed. Such comonomers may be included, for example, in the tacky polymer in an amount of 20 parts by weight or less, or 0.1 parts by weight to 15 parts by weight, based on the weight of the other monomers.

In one example, the tacky polymer comprises 40 to 70 parts by weight of the first monomer; From 10 parts by weight to 50 parts by weight of the second monomer and from 1 part by weight to 20 parts by weight of the third monomer.

The ratio of the weight between the first monomer, the second monomer and the third monomer is not particularly limited, but it is preferable that the ratio of the weight between the monomers mentioned above is adjusted to the above ratio so that the storage elastic modulus and / In the pressure-sensitive adhesive composition of the present invention. In another example, the tacky polymer may comprise 45 to 60 parts by weight of the first monomer, 20 to 40 parts by weight of the second monomer and 25 to 20 parts by weight of the third monomer.

The method for producing the pressure-sensitive adhesive polymer is not particularly limited and can be produced in a usual manner. The sticky polymer is polymerized by, for example, an LRP (Living Radical Polymerization) method. Examples of the polymer include an organic rare earth metal complex as a polymerization initiator, an organic alkali metal compound as a polymerization initiator, and an alkali metal or alkaline earth metal Anion polymerization which is synthesized in the presence of an inorganic acid salt such as a salt, an anionic polymerization method in which an organic alkali metal compound is used as a polymerization initiator and synthesized in the presence of an organoaluminum compound, an atomic transfer radical polymerization (ATRP), Atomic Transfer Radical Polymerization (ATRP), ICAR (Initiators), which conducts polymerization under an organic or inorganic reducing agent that generates electrons using an atom transfer radical polymerization agent as a polymerization initiator for continuous activator regeneration) Atom Transfer Radical Polymerization (ATRP ), A polymerization method (RAFT) using a reversible addition-cleavage chain transfer agent using an inorganic reducing agent addition-cleavage chain transfer agent, or a method using an organic tellurium compound as an initiator. Among these methods, an appropriate method can be selected and applied .

In one example, the tacky polymer may have a weight average molecular weight of from 300,000 to 250,000, from 300,000 to 2,000,000, or from 300,000 to 150. When the weight average molecular weight is within this range, the effect of adding the pressure-sensitive adhesive polymer can be increased, and thus the storage elastic modulus and / or viscosity of the pressure-sensitive adhesive composition containing the pressure-sensitive adhesive polymer described later can be adjusted to a specific range or more.

The tacky polymer may have, for example, a glass transition temperature of -80 캜 to 30 캜, -65 캜 to 15 캜, or -50 캜 to 0 캜. When the glass transition temperature is within this range, the effect of adding the pressure-sensitive adhesive polymer can be increased, and thus the storage elastic modulus and / or viscosity of the pressure-sensitive adhesive composition containing the pressure-sensitive adhesive polymer described below can be adjusted to a specific range or more.

The pressure-sensitive adhesive composition may further comprise a crosslinking agent capable of crosslinking the pressure-sensitive adhesive polymer. The cross-linking agent includes at least one functional group capable of reacting with the crosslinkable functional group contained in the tacky polymer, and having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 functional groups Crosslinking agents may be used. As such a cross-linking agent, an appropriate type may be selected and used from among conventional cross-linking agents such as an isocyanate cross-linking agent, an epoxy cross-linking agent, an aziridine cross-linking agent or a metal chelate cross-linking agent considering the kind of the cross-linkable functional group of the adhesive polymer.

Examples of the isocyanate crosslinking agent include diisocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate, and naphthalene diisocyanate; And a reaction product of a polyol such as trimethylolpropane or an isocyanurate adduct of the above diisocyanate compound. Of these, xylene diisocyanate or hexamethylene diisocyanate can be preferably used. As the epoxy crosslinking agent Is preferably at least one selected from the group consisting of ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'- tetraglycidylethylenediamine and glycerin diglycidyl ether There is at least one selected from the group true can be exemplified.

As the aziridine crosslinking agent, N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'- (2-methyl aziridine) or tri-1-aziridinyl phosphine oxide, and the like, but not limited thereto, and the metal chelate Examples of the crosslinking agent include compounds in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated to acetylacetone or ethyl acetoacetate.

The crosslinking agent may be contained in an amount of, for example, 0.01 to 10 parts by weight, 0.015 to 5 parts by weight, 0.02 to 2.5 parts by weight or 0.025 to 1 part by weight based on 100 parts by weight of the adhesive polymer . The cross-linking agent may be adjusted to be included in the tacky polymer in the above-mentioned range so that the storage elastic modulus and / or viscosity described below are formed within a desired range.

The pressure-sensitive adhesive composition may further include a silane coupling agent. As the silane coupling agent, for example, a silane coupling agent having a beta-cyano group or an acetoacetyl group can be used. Such a silane coupling agent can make the pressure-sensitive adhesive formed by, for example, a polymer having a low molecular weight exhibit excellent adhesion and adhesion stability.

As the silane coupling agent having a beta-cyano group or an acetoacetyl group, for example, a compound represented by the following formula (1) or (2) can be used.

[Chemical Formula 1]

(R ₁ ) _n Si (R ₂ ) _(4-n)

(2)

(R ₃ ) _n Si (R ₂ ) _(4-n)

Wherein R ₁ is a beta-cyanoacetyl group or a beta-cyanoacetylalkyl group, R ₃ is an acetoacetyl group or an acetoacetylalkyl group, R ₂ is an alkoxy group and n is 1 to 3 ≪ / RTI >

In the general formula (1) or (2), the alkyl group may be an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be linear, branched or cyclic.

In the general formula (1) or (2), the alkoxy group may be an alkoxy group having 1 to 5 carbon atoms, and the alkoxy group may be linear, branched or cyclic.

In Formula 1 or 2, n may be, for example, 1 to 3, 1 to 2, or 1.

Examples of the compound represented by the general formula (1) or (2) include acetoacetylpropyltrimethoxysilane, acetoacetylpropyltriethoxysilane, beta-cyanoacetylpropyltrimethoxysilane or beta-cyanoacetylpropyltriethoxysilane But is not limited thereto.

In the pressure-sensitive adhesive composition, the silane coupling agent may be contained in an amount of 0.01 to 5 parts by weight or 0.01 to 1 part by weight based on 100 parts by weight of the pressure-sensitive adhesive polymer. Within this range, the storage modulus and / Can be effectively implemented.

The pressure-sensitive adhesive composition may further include a tackifier as necessary. Examples of the tackifier include a hydrocarbon resin or hydrogenated product thereof, a rosin resin or hydrogenated product thereof, a rosin ester resin or hydrogenated product thereof, a terpene resin or hydrogenated product thereof, a terpene phenol resin or hydrogenated product thereof, Polymerized rosin ester resin, and the like, or a mixture of two or more of them may be used, but the present invention is not limited thereto. The tackifier may be included in the pressure-sensitive adhesive composition in an amount of 100 parts by weight or less based on 100 parts by weight of the tacky polymer.

The pressure-sensitive adhesive composition may further include, if necessary, at least one additive selected from the group consisting of a curing agent, a UV stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, a defoamer, a surfactant and a plasticizer.

In one example, the pressure-sensitive adhesive composition may have a coating solid content of 20 wt% or more or 25 wt% or more, if necessary, in consideration of storage elastic modulus and / or viscosity to be described later. As used herein, the term " coating solids " may refer to the solids content of the coating solution at the time the pressure-sensitive adhesive composition is applied to the coating process to form the pressure-sensitive adhesive. Such a coating solid content can be measured, for example, by a commonly known measurement method. Usually, at the time of application to the coating process, the pressure-sensitive adhesive composition, that is, the coating liquid contains the above-mentioned pressure-sensitive adhesive polymer, cross-linking agent, initiator and other additives, and may also include a solvent. When the solid content of the coating is 20% by weight or more, the productivity of the pressure-sensitive adhesive or the pressure-sensitive adhesive film to which the pressure-sensitive adhesive is applied can be maximized. The upper limit of the coating solid content is not particularly limited and can be suitably controlled within a range of, for example, 50 wt% or less, 40 wt% or less, or 30 wt% or less, taking into consideration the viscosity for application to the coating process.

In addition, the pressure-sensitive adhesive composition may have a gel fraction of 80% by weight or more. The gel fraction can be calculated by the following general formula (1).

[Formula 1]

Gel fraction (%) = B / A x 100

In the general formula 1, A represents the mass of the pressure-sensitive adhesive composition, and B represents the mass of the pressure-sensitive adhesive composition obtained by immersing the pressure-sensitive adhesive composition of mass A in a mesh having a mesh size of 200 mesh for 72 hours at room temperature, It represents the dry mass of sea water.

The gel fraction can be maintained at 80% by weight or more, so that workability and reworkability can be kept excellent, and the storage elastic modulus and / or viscosity to be described later can be suitably realized in a specific range or more. The lower limit of the gel fraction is not particularly limited, and may be, for example, 0% by weight. However, when the gel fraction is 0% by weight, it does not mean that no crosslinking has proceeded to the pressure-sensitive adhesive composition at all. For example, a pressure-sensitive adhesive composition having a gel fraction of 0 wt% has some degree of crosslinking or crosslinking, but the degree of crosslinking is low, so that the gel can not be retained in the mesh having a size of 200 mesh Leakage may also be included.

The pressure-sensitive adhesive composition includes a tacky polymer and may have a storage elastic modulus at a temperature of 30 DEG C and a frequency of 500 rad / sec of 0.5 MPa or more, 0.55 MPa or more, or 0.6 MPa or more. The upper limit of the storage elastic modulus of the pressure-sensitive adhesive composition measured at a temperature of 30 DEG C and a frequency of 500 rad / sec is not particularly limited and may be, for example, about 1.2 MPa, 1.5 MPa, 1.1 MPa or 1.0 MPa. More preferably, the storage modulus of the pressure-sensitive adhesive composition measured at a temperature of 30 DEG C and a frequency of 500 rad / sec can be suitably implemented within a range of 0.55 MPa to 1 MPa or 0.6 MPa to 0.95 MPa. The term " storage elastic modulus " as used herein generally means " dynamic storage modulus ". That is, when a sine-shaped shear strain is applied to an elastic body, a stress is delayed in an intermediate form in the case of a viscoelastic material. Mathematically, one component is in the same phase and the other component is delayed by pi / 2 In this case, energy stored in the same phase, i.e., without loss by elasticity, may be referred to as "dynamic storage modulus" or "storage modulus".

In another example, the pressure-sensitive adhesive composition may have a storage elastic modulus of 0.05 MPa or more, 0.055 MPa or more, 0.06 MPa or more, 0.065 MPa or more, or 0.07 MPa or more at 30 ° C to 100 ° C and 1 rad / sec. The upper limit of the storage elastic modulus of the pressure-sensitive adhesive composition measured at a temperature of 30 to 100 DEG C and a frequency of 1 rad / sec is not particularly limited and may be, for example, about 0.12 MPa, 0.11 MPa, 0.1 MPa or 0.095 MPa. The pressure-sensitive adhesive composition may exhibit the storage elastic modulus as described above at any one of the temperatures of 30 ° C to 100 ° C. For example, the pressure-sensitive adhesive composition may exhibit the storage elastic modulus as described above at 80 占 폚, and may exhibit the storage elastic modulus as described above at all temperatures ranging preferably from 30 占 폚 to 100 占 폚.

By adjusting the storage elastic modulus of the pressure-sensitive adhesive composition within the above-mentioned range, it is possible to prevent the occurrence of steam phenomenon that may occur when the pressure-sensitive adhesive film using the pressure-sensitive adhesive composition is cut by laser or CNC, thereby minimizing the defective rate Thereby maximizing the productivity.

In one example, the pressure-sensitive adhesive composition has a composite viscosity at a temperature of from 30 DEG C to 100 DEG C and at a rad / sec frequency of from 0.05 MPa.s to 0.055 MPa.s, from 0.06 MPa.s to 0.065 MPa.s, 0.07 MPa.s or higher. The upper limit of the viscosity of the pressure-sensitive adhesive composition measured at a temperature of 30 ° C to 100 ° C and a frequency of 1 rad / sec is not particularly limited, but is preferably about 3 MPa.s, 2.5 MPa.s, 2.0 MPa.s or 1.5 MPa.s . The term complex viscosity refers to a frequency-dependent viscosity function determined at the time of forced harmonic oscillation of shear stress. The pressure-sensitive adhesive composition may exhibit such a complex viscosity at any one of the temperatures of 30 캜 to 100 캜. The pressure-sensitive adhesive composition may exhibit such a complex viscosity at 80 캜, for example, and may exhibit the above-described complexity at all temperatures ranging from 30 캜 to 100 캜.

By controlling the complex viscosity of the pressure-sensitive adhesive composition within the above-mentioned range, it is possible to prevent the occurrence of steam generated when the pressure-sensitive adhesive film applied with the pressure-sensitive adhesive composition is cut by laser or CNC, thereby minimizing the defective rate Thereby maximizing the productivity.

The present application also relates to an adhesive film. In one example, the adhesive film may be an adhesive film having a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition comprising a crosslinked pressure-sensitive adhesive polymer. The above-mentioned pressure-sensitive adhesive composition may be applied in the same manner as described in the item of the pressure-sensitive adhesive composition.

The method of curing the above-described pressure-sensitive adhesive composition in the present application and incorporating the pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer on the pressure-sensitive adhesive film to produce the pressure-sensitive adhesive composition is not particularly limited. The pressure-sensitive adhesive layer can be produced, for example, by applying the pressure-sensitive adhesive composition or the coating liquid prepared by using the pressure-sensitive adhesive composition to an appropriate processing base material by a conventional means such as a bar coater and then curing. In the present application, it is preferable that the curing process is performed after sufficiently removing the bubble-inducing component such as volatile components or reaction residues contained in the pressure-sensitive adhesive composition or coating solution. Accordingly, the crosslinking density or the molecular weight of the pressure-sensitive adhesive is too low to lower the elastic modulus, and bubbles existing in the pressure-sensitive adhesive interface at high temperature are increased to form a scattering body therein.

The method for curing the pressure-sensitive adhesive composition or the coating liquid is not particularly limited. For example, the pressure-sensitive adhesive composition or the coating liquid may be cured by suitable heating, drying and / or aging processes or curing by electromagnetic wave irradiation such as ultraviolet Method can be employed.

In the present application, the pressure-sensitive adhesive layer is produced through the above-described processes and laminated on the base film to produce the pressure-sensitive adhesive film. Alternatively, one pressure-sensitive adhesive layer may be formed first, and another pressure- To form a pressure-sensitive adhesive film. Further, if necessary, corona treatment may be appropriately performed in the process of forming the pressure-sensitive adhesive layer, and the corona treatment may be carried out using well-known means commonly used in this field.

In one example, the adhesive film may further include a base film present on one side or both sides of the pressure-sensitive adhesive layer. The specific type of the base film is not particularly limited, and for example, a general plastic film in this field can be used. In one example, the base film may be a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polyvinyl chloride film, a polyurethane film, Acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, or a polyimide film.

The thickness of the base film is not particularly limited and may be suitably selected according to the application to which it is applied. For example, the thickness of the base film may be about 12 탆 to 50 탆, preferably about 20 탆 to 40 탆, but is not limited thereto.

In one example, the pressure-sensitive adhesive film may further include a protective film present on one side or both sides of the pressure-sensitive adhesive layer. The specific kind of the protective film is not particularly limited, and for example, a polyester film such as cellulose, polycarbonate, or polyethylene terephthalate having transparency; Polyether-based films such as polyethersulfone; Or a polyolefin-based film such as polyethylene, polypropylene, a polyolefin having a cyclonanorbornene structure, or an ethylene propylene copolymer. The protective film may be a single layer or a laminate of two or more layers. The thickness of the protective film may be appropriately selected depending on the application, but may be, for example, 5 to 500 탆 or 10 to 100 탆, but is not limited thereto . In addition, the protective film may be subjected to a surface treatment or a primer treatment on one side or both sides in order to improve the adhesion of the substrate to a pressure-sensitive adhesive, and an antistatic layer, an antifouling layer or the like may be provided.

In one example, the adhesive film may be a anti-scattering film or a decolor film. The anti-scattering film or the decolor film may include a base film and a protective film, and a pressure-sensitive adhesive layer present between the base film and the protective film. In the above, the content of the base film, the protective film and the pressure-sensitive adhesive layer may be the same as those described in the item of the pressure-sensitive adhesive film. The anti-scattering film or the decolor film may further include a hard coat layer, and the hard coat layer may be present on the opposite side of the base film on which the adhesive layer is formed. Fig. 1 is a cross-sectional view of a base film of the present invention, which includes a base film 101, a protective film 102, a pressure-sensitive adhesive layer 103 existing between the base film and the protective film, and a hard coating layer 104 present on the side opposite to the pressure- A shatterproof film or a deco film is exemplarily shown.

The thickness of the hard coating layer may be appropriately selected depending on the specific use of the anti-scattering film or the decolorizing film. For example, the thickness of the hard coating layer may be in the range of 0.5 to 15 占 퐉, but is not limited thereto. The hard coating layer can have a sufficient surface hardness when the thickness is within the above range, thereby preventing the hard coating layer from being damaged or the scratch resistance from being deteriorated. Further, cracks due to stress such as bending can be reduced, Can be prevented. The material of the hard coat layer is not particularly limited and may be selected to have an appropriate hardness depending on the specific use of the anti-scattering film or the decolor film. The hard coating layer may be formed by curing a composition including, for example, a curable resin mixture, but is not limited thereto. As the curable resin mixture, for example, a thermosetting resin mixture or a photo-curable resin mixture, for example, an ultraviolet curable resin mixture, may be used.

In the present application, the thickness of the adhesive film may be 30 μm to 200 μm, specifically 50 μm to 150 μm, more preferably 50 μm to 100 μm. In the present application, by controlling the thickness of the adhesive film to a certain range, the product to which the adhesive is applied can be realized in a thin shape, and an adhesive film excellent in optical or mechanical properties can be provided depending on the product to which it is applied.

When the pressure-sensitive adhesive composition according to the present application is applied as a pressure-sensitive adhesive layer to an adhesive film such as a shrinkage-preventing film or a decolorizing film, it is possible to prevent the occurrence of steam, which may be caused by laser or CNC cutting, It is possible to maximize the productivity of the adhesive film produced thereby.

Fig. 1 exemplarily shows a light-scattering film or a decolor film.

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 embodiments.

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

1. Molecular weight measurement

The weight average molecular weight (Mw) was measured using GPC under the following conditions, and the measurement results were converted using standard polystyrene of Agilent system for the calibration curve.

<Measurement Conditions>

Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

Column: Two PL Mixed B connections

Column temperature: 40 ° C

Eluent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

Concentration: ~ 1 mg / mL (100 μL injection)

2. Evaluation of storage modulus (A)

The pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was coated between release films and cut to a size of 15 cm x 25 cm. The release film on one side was removed and laminated five times to have a thickness of about 1 mm. Subsequently, the laminate was cut into a circular shape having a diameter of 8 mm, compressed using glass, and allowed to stand overnight to improve wetting at the interface between the respective layers, To prepare a sample. Then, the sample was placed on a parallel plate, the gap was adjusted, the zero point of Normal & Torque was set, and the normal force was stabilized. Then, the storage elastic modulus was measured.

Measuring instruments and measuring conditions

Measuring instrument: ARES-RDA, TA Instruments Inc. with forced convection oven.

Measuring conditions:

geometry: 8 mm parallel plate

Thickness: about 1 mm

test type: dynamic strain frequency sweep

Strain = 10.0 [%], Temperature: 30 [deg.] C

Initial frequency: 0.1 rad / s, Final frequency: 500 rad / s

3. Evaluation of storage modulus (B)

The pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was coated between release films and cut to a size of 15 cm x 25 cm. The release film on one side was removed and laminated five times to have a thickness of about 1 mm. Subsequently, the laminate was cut into a circular shape having a diameter of 8 mm, compressed using glass, and allowed to stand overnight to improve wetting at the interface between the respective layers, To prepare a sample. Then, the sample was placed on a parallel plate, the gap was adjusted, the zero point of Normal & Torque was set, and the normal force was stabilized. Then, the storage elastic modulus was measured.

Measuring instruments and measuring conditions

Measuring instrument: ARES-RDA, TA Instruments Inc. with forced convection oven.

Measuring conditions:

geometry: 8 mm parallel plate

Thickness: about 1 mm

test type: dynamic strain frequency sweep

Strain = 10.0 [%], Frequency: 1 rad / sec

Initial temperature: 30 占 폚, Final temperature: 100 占 폚

4. Evaluation of Viscosity

The pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was coated between release films and cut to a size of 15 cm x 25 cm. The release film on one side was removed and laminated five times to have a thickness of about 1 mm. Subsequently, the laminate was cut into a circular shape having a diameter of 8 mm, compressed using glass, and allowed to stand overnight to improve wetting at the interface between the respective layers, To prepare a sample. Then, the sample was placed on a parallel plate, the gap was adjusted, the zero point of Normal & Torque was set, and the normal force was stabilized. Then, the storage elastic modulus was measured.

Measuring instruments and measuring conditions

Measuring instrument: ARES-RDA, TA Instruments Inc. with forced convection oven.

Measuring conditions:

geometry: 8 mm parallel plate

Thickness: about 1 mm

test type: dynamic strain frequency sweep

Strain = 10.0 [%], Frequency: 1 rad / sec

Initial temperature: 30 占 폚, Final temperature: 100 占 폚

5. Evaluation of Steaming Condition (1)

The pressure-sensitive adhesive films prepared in Examples and Comparative Examples were cut using a laser or CNC with a size of 100 mm x 100 mm (width x length), and then friction force of 1 Kgf was uniformly applied to both specimens, Was visually observed and evaluated according to the following criteria.

<Evaluation Criteria>

○: The adhesive on the surface of the film was not visually confirmed.

X: The adhesive on the surface of the film was observed visually.

6. Evaluation of Steam Phenomena (2)

The pressure-sensitive adhesive films prepared in Examples and Comparative Examples were subjected to a force of 10 kgf at 60 캜 for 24 hours, and the degree of the pressure-sensitive adhesive exiting between the films was visually observed and evaluated according to the following criteria.

<Evaluation Criteria>

○: It is not visually confirmed that the adhesive is released between the films.

X: The viscous agent was observed to be evacuated from the film to the naked eye.

Manufacturing example  1. Preparation of adhesive polymer (A1)

Butyl acrylate (BA) isobornyl acrylate (IBOA), 2-hydroxyethyl acrylate (HEA) and 1-hydroxyethyl acrylate (HEA) were added to a 1 L reactor equipped with a cooling device, Vinyl-2-pyrrolidone (VP) was added in a weight ratio of 50: 30: 15: 5 (BA: IBOA: HEA: VP). Subsequently, 100 parts by weight of ethyl acetate (EAc) was added to 100 parts by weight of the monomer, and a nitrogen gas was purged for 60 minutes to remove oxygen. While the temperature was maintained at 60 占 폚, And 0.06 part by weight of bisisobutyronitrile (AIBN) were added to initiate the reaction. The reaction product was reacted for about 5 hours and diluted with ethyl acetate (EAc) to prepare a viscous polymer (A1).

Manufacturing example  2 to Manufacturing example  4. Production of sticky polymers (A2 to A5 and B1 to B2)

(A 2 to A 5 and B 1 to B 2) were obtained in the same manner as in Production Example 1, except that the raw materials and additives used in the production of the pressure-sensitive adhesive polymer (A1) ).

Raw material EA V-65 BA IBOA MA MMA HEA VP ACMO EHA

cohesion
Mature
coalescence A1 50 30 - 15 5 - - 100 0.06 A2 50 30 - 15 - 5 - 100 0.06 A3 55 30 - - 15 - - - 100 0.06 A4 55 - 30 - 15 - - - 100 0.06 A5 55 - - 30 15 - - - 100 0.06 B1 - 30 - - 15 - - 55 100 0.06 B2 - - 40 - 10 - - 50 100 0.06 Content Unit: g
BA: n-butyl acrylate
IBOA: isobornyl acrylate
MA: (meth) acrylate
MMA: methyl (meth) acrylate
HEA: 2-hydroxyethyl acrylate
VP: 1-vinyl-2-pyrrolidone
ACMO: 4-acryloylmorpholine
EHA: 2-ethylhexyl acrylate
EA: ethyl acetate
V-65: 2,2'-azobis (2,4-dimethyl valeronitrile)

Example  One

Preparation of pressure-sensitive adhesive composition

To 100 parts by weight of the solid content of the adhesive polymer (A1) prepared in Preparation Example 1, 0.5 part by weight of "Takenate D110N" xylene diisocyanate (manufactured by Mitsui Chemicals) as a crosslinking agent was uniformly mixed to prepare a pressure-sensitive adhesive composition.

Production of adhesive film

The pressure-sensitive adhesive composition thus prepared was coated on a PET (heavy-weight) film subjected to silicone release treatment so as to have a thickness of about 50 탆 and dried to form a pressure-sensitive adhesive layer. Then, a silicone release PET (light- .

hard  Coating layer formation

(MIBK: DHPA: IRAGACURE) at a weight ratio of 300: 100: 5 (MIBK: methyliso-butylketone), DHPA (dipentaerythritol hexaacrylate, manufactured by Sanofco) and IRAGACURE 184 Then, the hard coat layer composition was coated on both sides of a 125 μm thick PET film so as to have a thickness of 1 μm, dried at 100 ° C. for 2 minutes, and then cured using a UV curing machine (Fushion, Power 50%, speed: 10 m / min ) To form a hard coat layer.

arsenic acid  Prevention film and Deco  Production of film

The produced adhesive film was peeled off, and the resulting double-sided hard coat layer having a thickness of 125 탆 was laminated on the side of the PET (heavyweight) film to prepare a shatterproof film.

Example  2

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive polymer contained in the pressure-sensitive adhesive composition of Example 1 was changed to A2.

Example  3

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive polymer contained in the pressure-sensitive adhesive composition of Example 1 was changed to A3.

Example  4

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive polymer contained in the pressure-sensitive adhesive composition of Example 1 was changed to A4.

Example  5

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive polymer contained in the pressure-sensitive adhesive composition of Example 1 was changed to A5.

Comparative Example  One

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive polymer contained in the pressure-sensitive adhesive composition of Example 1 was charged as B1.

Comparative Example  2

A pressure-sensitive adhesive composition and a pressure-sensitive adhesive film were prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive polymer contained in the pressure-sensitive adhesive composition of Example 1 was charged with B2.

The physical properties and evaluation results of the above-mentioned Examples and Comparative Examples are shown in Table 2 below.

division Example Comparative Example One 2 3 4 5 One 2 Molecular weight (unit: million) 74 90 148 149 40 130 140 Storage elastic modulus (1) (× 10 ⁵ )
(Unit: pa) 7.9 6.2 6.4 6.9 9.1 4.1 2.8 The storage elastic modulus (2) (x 10 ⁴ )
(Unit: pa) 8.2 6.9 7.4 7.2 9.4 3.6 4.4 Viscosity (× 10 ⁴ )
(Unit: pa · s) 8.6 7.3 7.8 6.7 9.5 3.8 4.6 Steam Evaluation (1) ○ ○ ○ ○ ○ × × Steam Assessment (2) ○ ○ ○ ○ ○ × ×

As can be seen from the above Table 2, the pressure-sensitive adhesive composition of the present application has a storage modulus and / or viscosity exceeding a specific range to prevent the steam phenomenon that may occur in the laser or CNC cutting process, It is possible to maximize the productivity and to provide an adhesive film containing it as a pressure-sensitive adhesive layer.

101: base film
102: protective film
103: Pressure-sensitive adhesive layer
104: Hard coating layer

Claims (23)

And a storage elastic modulus at 30 ° C and 500 rad / sec of 0.5 MPa or more. The pressure-sensitive adhesive composition according to claim 1, wherein the storage elastic modulus at 30 ° C and 500 rad / sec is 0.55 MPa to 1.1 MPa. The pressure-sensitive adhesive composition according to claim 1, wherein the storage elastic modulus at 30 ° C to 100 ° C and 1 rad / sec is 0.05 MPa or more. The pressure-sensitive adhesive composition according to claim 1, wherein the compound viscosity at 30 ° C to 100 ° C and 1 rad / sec is 0.05 MPa.s or more. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive polymer comprises, as polymerized units, a first monomer having an alkyl group of 1 to 5 carbon atoms and a glass transition temperature of lower than 0 ° C and a second monomer having a glass transition temperature of 0 ° C or higher. 6. The pressure-sensitive adhesive composition according to claim 5, wherein the first monomer has a glass transition temperature in a range of -100 DEG C to less than 0 DEG C. The pressure-sensitive adhesive composition according to claim 5, wherein the second monomer has a glass transition temperature in the range of 0 ° C or higher to 200 ° C or lower. The pressure-sensitive adhesive composition according to claim 5, wherein the pressure-sensitive adhesive polymer further comprises, as polymerized units, a third monomer having a cyclic structure containing nitrogen as a ring-constituting atom. The pressure-sensitive adhesive composition according to claim 8, wherein the number of ring-constituting atoms of the ring structure of the third monomer is in the range of 3 to 8. 9. The composition of claim 8, wherein the tacky polymer comprises from 40 parts by weight to 70 parts by weight of the first monomer; 10 to 50 parts by weight of the second monomer and 1 to 20 parts by weight of the third monomer as polymerized units. The pressure-sensitive adhesive composition according to claim 5, wherein the first monomer is an alkyl (meth) acrylate having a branched or straight-chain alkyl group having 1 to 5 carbon atoms. 6. The composition of claim 5 wherein the first monomer is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) t-butyl (meth) acrylate, sec-butyl (meth) acrylate, or pentyl (meth) acrylate. 6. The composition of claim 5, wherein the second monomer is selected from the group consisting of t-butyl (meth) acrylate, N-vinylformamide, acrylamide, t-butyl acrylate, isobutyl (meth) acrylate, (meth) acrylate, N, N-dimethylacrylamide, N, N-dimethyl (meth) acrylamide, N- Linear monomers composed of acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, methyl acrylate and N-hydroxyl acrylamide; (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-cyclopropyl acrylate, cyclohexyl acrylate, cyclohexyl (Meth) acrylate, N, N-diphenyl (meth) acrylamide, N-naphthyl acrylate, 2-phenoxyethyl Wherein the pressure-sensitive adhesive composition is at least one selected from the group consisting of styrene, isobornyl acrylate, isobonyl (meth) acrylate, and cyclic monomers composed of dicyclopentanyl (meth) acrylate. 6. The composition of claim 5 wherein the second monomer is selected from the group consisting of t-butyl (meth) acrylate, t-butyl acrylate, isobutyl (meth) acrylate, n- butyl (meth) (Meth) acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate and methyl acrylate; And cyclic monomers composed of isobonyl acrylate and isobonyl (meth) acrylate. 9. The composition of claim 8 wherein the third monomer is selected from the group consisting of 4-acryloylmorpholine, 1-vinyl-2-pyrrolidone, 2- isopropenyl- 2- oxazoline, N- vinylcaprolactam, And at least one selected from the group consisting of sols. The pressure-sensitive adhesive composition according to claim 8, wherein the third monomer is 1-vinyl-2-pyrrolidone. The pressure-sensitive adhesive composition according to claim 8, wherein the pressure-sensitive adhesive polymer further comprises a crosslinkable monomer as a polymerization unit. 9. The composition of claim 8, wherein the tacky polymer comprises from 40 parts by weight to 70 parts by weight of the first monomer; 10 to 50 parts by weight of a second monomer, 1 to 20 parts by weight of a third monomer and 5 to 25 parts by weight of a crosslinkable monomer as polymerized units. The pressure-sensitive adhesive composition according to claim 18, further comprising 0.01 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of the pressure-sensitive adhesive polymer. 1. A light-scattering film comprising a base film, a protective film, and a pressure-sensitive adhesive composition comprising the pressure-sensitive adhesive composition according to claim 1 present between the base film and the protective film. The anti-scattering film according to claim 20, further comprising a hard coating layer present adjacent to an opposite side of the pressure sensitive adhesive layer of the base film. A decoy film comprising a base film, a protective film, and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to claim 1 present between the base film and the protective film. 23. The decoy film of claim 22, further comprising a hard coat layer present adjacent the opposite side of the pressure sensitive adhesive layer of the substrate film.

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