KR102235979B1 - Adhesive film and manufacturing method of adhesive film - Google Patents

Abstract

An exemplary embodiment of the present application is a base film; A barrier film provided on one side of the base film; And an adhesive sheet provided on a surface opposite to a surface of the barrier film in contact with the base film, wherein the adhesive strength of the surface in contact with the barrier film and the adhesive sheet is 600 gf/in or more and 1000 gf/in or less, and the The pressure-sensitive adhesive sheet is an acrylate resin; A polymer containing at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by the following formula (1); And a composition comprising a curing agent or a cured product thereof, wherein the storage modulus of the adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less.

Description

Adhesive film and manufacturing method of adhesive film {ADHESIVE FILM AND MANUFACTURING METHOD OF ADHESIVE FILM}

The present application relates to an adhesive film and a method of manufacturing an adhesive film.

Conventionally, a pressure-sensitive adhesive sheet having a high adhesive strength from the initial stage of adhesion has been known. In addition, when using such an adhesive sheet to fix a substrate, an adhesive sheet having sufficient adhesive strength to fix the substrate is selected.

On the other hand, air bubbles or unexpected foreign matter generated in the process of bonding the pressure-sensitive adhesive sheet to the substrate may be introduced, which is not desirable from the viewpoint of aesthetics or adhesiveness, and re-adhesion of the pressure-sensitive adhesive sheet may be required. However, in the case of a pressure-sensitive adhesive sheet having high adhesion, such a re-adhesion operation is difficult.

Therefore, a technique for reducing such air bubbles has been devised. For example, a technique has been devised to form an uneven surface shape on the adhesive surface of a pressure-sensitive adhesive by using an embossed liner. In this case, even if air bubbles are mixed between both when the pressure-sensitive adhesive is bonded to the substrate, since air easily flows out to the outside through the surface grooves of the pressure-sensitive adhesive, it becomes easy to remove the air bubbles without performing re-adhesion. However, the above-described pressure-sensitive adhesive needs a certain thickness in order to form grooves. In addition, when this pressure-sensitive adhesive is lightly adhered to the substrate, the adhesive area becomes small due to the presence of grooves, making it easier to perform operations such as rework or position refresh, but sufficient adhesive strength cannot be obtained. There is also a possibility.

In addition, in order to secure adhesion and to be applied to a flexible device at the same time, it is necessary to maintain a storage elastic modulus that can be folded even under high and low temperature conditions.

Therefore, in consideration of this situation, the adhesive force required for fixing the substrate can be expressed, and foreign substances and air bubbles can be efficiently removed if there are any foreign substances and bubbles between the adhesive sheet and the substrate, and can be applied to a flexible device. It is necessary to develop an adhesive sheet.

Japanese Patent Publication No. 2006-299283

The present application is to provide an adhesive film and a method of manufacturing an adhesive film.

An exemplary embodiment of the present application is a base film; A barrier film provided on one side of the base film; And an adhesive sheet provided on a surface opposite to a surface of the barrier film in contact with the base film, wherein the adhesive strength of the surface in contact with the barrier film and the adhesive sheet is 600 gf/in or more and 1000 gf/in or less, and the The pressure-sensitive adhesive sheet is an acrylate resin; A polymer containing at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by the following formula (1); And it provides a composition comprising a curing agent or a cured product thereof, wherein the storage modulus of the pressure-sensitive adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less.

[Formula 1]

In Formula 1,

R ₁ is hydrogen or a methyl group,

n is an integer of 10 to 30.

Another exemplary embodiment is the step of preparing a base film; Forming a barrier film on one surface of the base film; And forming a pressure-sensitive adhesive sheet on a surface opposite to the surface of the barrier film on which the base film is formed, wherein the adhesion between the barrier film and the pressure-sensitive adhesive sheet is 600 gf/in or more and 1000 gf/in or less, and the pressure-sensitive adhesive sheet Is an acrylate resin; A polymer comprising at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by Formula 1; And a curing agent, wherein the storage modulus of the adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less.

The adhesive film according to the exemplary embodiment of the present application can increase the adhesive strength between the adhesive sheet and the barrier film by attaching the adhesive sheet having variable characteristics to the barrier film and then a heat treatment process, and the side where the barrier film of the adhesive sheet contacts later. In the case of adhesion between the opposite side of and the adhered substrate, the pressure-sensitive adhesive sheet according to an exemplary embodiment of the present application has low initial adhesive strength and can be reused when incorrectly attached to the adhered substrate, and the adhesive strength with the adhered substrate increases after the heat treatment process. It has the characteristics of

In addition, the adhesive film according to an exemplary embodiment of the present application has a storage elastic modulus of 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less as an adhesive sheet, so that it can be applied to a flexible device in the future. Have.

In particular, the adhesive film according to an exemplary embodiment of the present application includes a polymer containing at least one selected from the group consisting of a monofunctional polysiloxane and a monomer represented by Formula 1 in the adhesive sheet, so that the variable characteristics are particularly excellent. Will have.

1 is a diagram showing a laminated structure of an adhesive film according to an exemplary embodiment of the present application.

Hereinafter, the present specification will be described in more detail.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

Embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

An exemplary embodiment of the present application is a base film; A barrier film provided on one side of the base film; And an adhesive sheet provided on a surface opposite to a surface of the barrier film in contact with the base film, wherein the adhesive strength of the surface in contact with the barrier film and the adhesive sheet is 600 gf/in or more and 1000 gf/in or less, and the The pressure-sensitive adhesive sheet is an acrylate resin; A polymer containing at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by the following formula (1); And it provides a composition comprising a curing agent or a cured product thereof, wherein the storage modulus of the pressure-sensitive adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less.

The adhesive film according to an exemplary embodiment of the present application includes, in the adhesive sheet, a polymer containing at least one selected from the group consisting of a monofunctional polysiloxane and a monomer represented by Formula 1, so that the variable property of the adhesive sheet is excellent. Has. The excellent variable property means that the difference between the initial adhesive force and the late adhesive force after a specific process occurs significantly, and the change characteristics of the initial and late adhesive force are particularly excellent, and after the heat treatment process, the polymer has a more stable arrangement. So that the adhesive property has particularly excellent properties.

In the exemplary embodiment of the present application, n in Formula 1 may be an integer of 10 to 30.

In another exemplary embodiment, n in Formula 1 may be an integer of 15 to 25.

In another exemplary embodiment, n in Formula 1 may be an integer of 16 to 23.

In the exemplary embodiment of the present application, the storage modulus of the pressure-sensitive adhesive sheet may be 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less, preferably 1.1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less.

When the storage modulus has the above range, stability over time and excellent variable properties are obtained. When the storage elastic modulus is higher than the above range, the adhesive sheet has a hard characteristic, so that the increase in adhesive force after heat treatment is variable, and when the storage elastic modulus is lower than the above range, the adhesive sheet has a soft characteristic. Even if the polymer is used, the initial adhesive strength is high, making it difficult to rework.

The storage modulus value of the pressure-sensitive adhesive sheet has a value that varies depending on the composition ratio of the acrylate resin used in the pressure-sensitive adhesive sheet, the content of the curing agent, or the content/type of the polymer. It means the value measured at °C.

In the exemplary embodiment of the present application, the base film is PET (polyethylene terephthalate), polyester, PC (polycarbonate), PI (polyimide), PEN (polyethylene naphthalate), PEEK (polyether ether ketone), PAR ( polyarylate), polycylicolefin (PCO), polynorbornene, polyethersulphone (PES), and cycloolefin polymer (COP).

In another exemplary embodiment, the base film may be polyethylene terephthalate (PET) or cycloolefin polymer (COP).

In the exemplary embodiment of the present application, the thickness of the base film is 10 μm or more and 100 μm Hereinafter, preferably, it may be 15 µm or more and 90 µm or less, and more preferably 20 µm or more and 75 µm or less.

In addition, it is preferable that the base film is transparent. The meaning that the base film is transparent here indicates that the light transmittance of visible light (400 to 700 nm) is 80% or more.

When the base film has the above range, the laminated adhesive film has a characteristic capable of thinning.

In the exemplary embodiment of the present application, the barrier film may include various inorganic barrier materials, and the inorganic barrier material is, for example, silicon (Si), aluminum (Al), indium (In), tin (Sn), At least one metal selected from the group consisting of zinc (Zn), titanium (Ti), copper (Cu), cerium (Ce) and tantalum (Ta), oxides, nitrides, carbides, oxynitrides or oxidation of the metal And metal compounds such as carbides.

More specific examples of the metal compound include silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), tantalum oxide, zirconium oxide, niobium oxide, aluminum silicate (SiAlOx), boron carbide, tungsten carbide, Metal oxides, metal nitrides, metal carbides such as silicon carbide, oxygen-containing silicon carbide, aluminum nitride, silicon nitride, boron nitride, aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconium oxide, titanium boride oxide and composites thereof , Metal oxynitride, metal oxide boride, diamond-like carbon (DLC), and combinations thereof.

In addition, the barrier film may include an organic layer including an organic polymer. That is, the barrier film may be a laminate of an inorganic layer including the inorganic barrier material and an organic layer.

In the exemplary embodiment of the present application, the thickness of the barrier film is 10 μm or more and 100 μm Hereinafter, preferably, it may be 15 µm or more and 90 µm or less, and more preferably 20 µm or more and 75 µm or less.

In the exemplary embodiment of the present application, the barrier film may be a film excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and the like.

In the exemplary embodiment of the present application, the moisture transmittance of the barrier film ^{may be 10 -2} g/m ² -day or less. More preferably, it may be 10 ^-3 g/m ² -day or less, and 10 ^-5 g/m ² -day or more.

In the exemplary embodiment of the present application, the pressure-sensitive adhesive sheet is an acrylate-based resin; A polymer comprising at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by Formula 1; And a curing agent.

In an exemplary embodiment of the present application, a melting temperature (Tm) of the polymer is provided at 35° C. or higher and 50° C. or lower.

The fact that the polymer has a melting temperature of 35°C or more and 50°C or less means that when one or more selected from the group consisting of the monofunctional polysiloxane and the monomer represented by Formula 1 are copolymerized, the melting temperature of the final polymer is 35°C. It means having a value of more than or equal to 50°C.

In the exemplary embodiment of the present application, the monomer represented by Chemical Formula 1 is STMA (Stearyl methacrylate); Or it may be STA (Stearyl acylate).

In the exemplary embodiment of the present application, the monomer represented by Chemical Formula 1 may be STMA (Stearyl methacrylate).

The melting temperature refers to a temperature at which a material transitions from a solid state to a liquid state, and in particular, in the case of a polymer, as it heats, a large change in the three-dimensional structure occurs at a specific temperature, which becomes equivalent to a phase transition. Changes can be observed, and the temperature at this time can be defined as the melting temperature.

The melting temperature can be measured by differential scanning calorimetry (DSC) or differential thermal analysis (DTA).

In the exemplary embodiment of the present application, the acrylate-based resin may include a (meth)acrylate-based resin having a weight average molecular weight of 100,000 g/mol to 5 million g/mol.

The weight average molecular weight is one of average molecular weights whose molecular weight is not uniform and the molecular weight of a certain polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

The weight average molecular weight can be measured through Gel Permeation Chromatography (GPC) analysis.

In the present specification, (meth)acrylate is meant to include both acrylate and methacrylate. The (meth)acrylate-based resin may be, for example, a copolymer of a (meth)acrylic acid ester-based monomer and a crosslinkable functional group-containing monomer.

The (meth)acrylic acid ester monomer is not particularly limited, but examples thereof include alkyl (meth)acrylate, and more specifically, as a monomer having an alkyl group having 1 to 12 carbon atoms, pentyl (meth)acrylate, n-butyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyl Hexyl (meth) acrylate, dodecyl (meth) acrylate, and may include one or two or more of decyl (meth) acrylate.

The crosslinkable functional group-containing monomer is not particularly limited, but may include, for example, one or more of a hydroxy group-containing monomer, a carboxyl group-containing monomer, and a nitrogen-containing monomer.

Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. ) Acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, or 2-hydroxypropylene glycol (meth)acrylate.

Examples of the carboxyl group-containing compound include (meth)acrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, 4-(meth)acryloyloxybutyric acid, and acrylic acid. Sieve, itaconic acid, maleic acid, or maleic anhydride.

Examples of the nitrogen-containing monomer include (meth)acrylonitrile, N-vinyl pyrrolidone or N-vinyl caprolactam.

At least one of vinyl acetate, styrene, and acrylonitrile may be further copolymerized with the (meth)acrylate-based resin from the viewpoint of improving other functionalities such as compatibility.

In the exemplary embodiment of the present application, the acrylate-based resin may be selected from the group consisting of alkyl (meth)acrylate, hydroxyalkyl acrylate, and nitrogen-containing monomers.

As the alkyl acrylate and the alkyl methacrylate, as a monomer having an alkyl group having 1 to 12 carbon atoms, pentyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylic Rate, hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate and decyl (meth)acrylate It may include one kind or two or more of them.

As the hydroxyalkyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 2 -Hydroxyethylene glycol acrylate, 2-hydroxypropylene glycol acrylate, etc. are mentioned.

As the nitrogen-containing monomer, VP (N-vinyl pyrrolidone, N-vinyl pyrrolidone) may be mentioned.

In the exemplary embodiment of the present application, the acrylate-based resin is based on 100 parts by weight of an acrylate-based resin, 50 to 70 parts by weight of alkyl acrylate, 5 to 40 parts by weight of alkyl methacrylate, 0.1 to 10 parts by weight of a nitrogen-containing monomer Parts and 1 to 30 parts by weight of hydroxyalkyl acrylate.

The meaning of the acrylate-based resin containing 50 to 70 parts by weight of an alkyl acrylate, 5 to 40 parts by weight of an alkyl methacrylate, 0.1 to 10 parts by weight of a nitrogen-containing monomer, and 1 to 30 parts by weight of a hydroxyalkyl acrylate, It means that an alkyl acrylate monomer, an alkyl methacrylate monomer, a nitrogen-containing monomer, and a hydroxyalkyl acrylate monomer are polymerized in the above weight ratio.

In the exemplary embodiment of the present application, the acrylate-based resin is 50 to 70 parts by weight of alkyl acrylate, preferably 55 to 70 parts by weight, more preferably 60 to 70 parts by weight based on 100 parts by weight of the acrylate resin. May contain wealth.

In the exemplary embodiment of the present application, the acrylate-based resin is based on 100 parts by weight of an acrylate-based resin, 5 to 40 parts by weight of alkyl methacrylate, preferably 7 to 35 parts by weight, more preferably 10 to 30 parts by weight. It may include parts by weight.

In the exemplary embodiment of the present application, the acrylate-based resin is based on 100 parts by weight of the acrylate-based resin, 0.1 to 10 parts by weight of a nitrogen-containing monomer, preferably 1 to 10 parts by weight, more preferably 3 to 10 parts by weight. May contain wealth.

In the exemplary embodiment of the present application, the acrylate-based resin is based on 100 parts by weight of the acrylate-based resin, 1 to 30 parts by weight of hydroxyalkyl acrylate, preferably 5 to 25 parts by weight, more preferably 5 to It may contain 20 parts by weight.

When the acrylate-based resin has the above composition and content, the pressure-sensitive adhesive sheet has excellent characteristics in terms of variable properties later.

In the exemplary embodiment of the present application, a release film may be further included on a surface of the pressure-sensitive adhesive sheet opposite to a surface in contact with the barrier film.

The release film may be a hydrophobic film, and is a layer for protecting an adhesive sheet having a very thin thickness, which refers to a transparent layer attached to one side of the adhesive sheet, and has excellent mechanical strength, thermal stability, moisture shielding property, and isotropy. Can be used. For example, acetate-based, polyester-based, polyethersulfone-based, polycarbonate-based, polyamide-based, polyimide-based, polyolefin-based, cycloolefin-based, polyurethane-based and acrylic resin films such as triacetylcellulose (TAC), etc. Can be used, but is not limited to this if it is a commercially available silicone-treated release film.

In the exemplary embodiment of the present application, the polymer may include monofunctional polysiloxane and STMA (Stearyl methacrylate).

As the monofunctional polysiloxane, Chisso's FM-0721, Shin-Etsu's KF2012, and the like may be used, but are not limited thereto.

In the exemplary embodiment of the present application, the polymer may have a weight average molecular weight of 10,000 g/mol to 150,000 g/mol.

In the exemplary embodiment of the present application, the curing agent may include at least one selected from the group consisting of an isocyanate-based curing agent and an epoxy-based curing agent.

In the exemplary embodiment of the present application, the adhesive strength of the surface where the barrier film and the adhesive sheet are in contact may be 600 gf/in or more and 1000 gf/in or less.

In another exemplary embodiment, the adhesive force of the surface of the barrier film and the adhesive sheet in contact may be 620 gf/in or more and 950 gf/in or less, and preferably 650 gf/in or more and 950 gf/in or less.

The adhesive film according to an exemplary embodiment of the present application includes a base film; Barrier film; Adhesive sheet; And it may have a structure in which the release film is sequentially stacked. At this time, when the pressure-sensitive adhesive sheet is subjected to a heat treatment process, the adhesive strength of the barrier film and the pressure-sensitive adhesive sheet increases as in the above range, resulting in excellent adhesion, and at the same time, the adhesive strength of the surface where the pressure-sensitive adhesive sheet and the release film are in contact with each other increases. It has a characteristic that does not.

This is because the polymer of the pressure-sensitive adhesive sheet has a hydrophobic property, and when the polymer is subjected to a heat treatment process, the polymer changes to a liquid state, so that the adhesion with the barrier film having hydrophilic properties increases, but in the case of a release film having hydrophobic properties, the adhesive strength Will not increase.

With the above-described characteristics, it is possible to increase the adhesion between the barrier film and the adhesive film, and at the same time, the adhesion between the substrate and the adhesive sheet is low, so that re-use is possible in case of incorrect attachment.

In the exemplary embodiment of the present application, the pressure-sensitive adhesive sheet includes 70 to 90 parts by weight of the acrylate-based resin based on 100 parts by weight of the pressure-sensitive adhesive sheet; 0.5 to 25 parts by weight of the polymer; And it provides an adhesive film containing 0.3 to 20 parts by weight of the curing agent.

In the exemplary embodiment of the present application, the pressure-sensitive adhesive sheet includes 70 to 90 parts by weight of the acrylate resin, preferably 75 to 90 parts by weight, more preferably 80 to 90 parts by weight, based on 100 parts by weight of the pressure-sensitive adhesive sheet. can do.

In the exemplary embodiment of the present application, the pressure-sensitive adhesive sheet may include 0.5 to 25 parts by weight of the polymer, preferably 0.5 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the pressure-sensitive adhesive sheet. .

In the exemplary embodiment of the present application, the pressure-sensitive adhesive sheet may include 0.3 to 20 parts by weight of the curing agent, preferably 0.3 to 15 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the pressure-sensitive adhesive sheet. .

Acrylate resin contained in the pressure-sensitive adhesive sheet; polymer; And when the curing agent has the above weight range, the initial peel force of the pressure-sensitive adhesive sheet is kept low, so that the re-use (rework) characteristic is excellent, and after the heat treatment is varied, the peel force increase rate is high.

In particular, when the curing agent has the above range, the storage modulus value may be 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less, and when the storage elastic modulus has the above range, stability over time and excellent variable properties are obtained. When the storage elastic modulus is higher than the above range, it has a hard property, and the increase in adhesive strength is small after the heat treatment is variable, and when the storage elastic modulus is lower than the above range, it has a soft property. The high adhesion makes it difficult to rework.

In the exemplary embodiment of the present application, the polymer comprises 5 to 30 parts by weight of a monofunctional polysiloxane based on 100 parts by weight of the polymer; And it provides an adhesive film comprising 60 to 90 parts by weight of the monomer represented by the formula (1).

In the exemplary embodiment of the present application, the polymer may include 5 to 30 parts by weight, preferably 10 to 30 parts by weight, more preferably 15 to 25 parts by weight of the monofunctional polysiloxane based on 100 parts by weight of the polymer. .

In the exemplary embodiment of the present application, the polymer comprises 60 to 90 parts by weight, preferably 65 to 85 parts by weight, more preferably 70 to 85 parts by weight of the monomer represented by Formula 1 based on 100 parts by weight of the polymer. can do.

When the polymer has the above composition and content range, the melting temperature value of the entire polymer may be appropriately maintained, thereby increasing the aging stability of the pressure-sensitive adhesive sheet, and having excellent properties of later variable characteristics.

For the pressure-sensitive adhesive sheet, the component and content of the polymer can be detected by component analysis. Specifically, after dissolving the pressure-sensitive adhesive sheet in a solvent for analysis, component analysis of the monofunctional polysiloxane is possible through NMR analysis, and the formula The monomer represented by 1 can be analyzed for components through GC (Gas Chromatography) analysis.

Ethanol, toluene, etc. may be used as the solvent for analysis, and the type is not limited as long as the pressure-sensitive adhesive sheet can be dissolved.

In the exemplary embodiment of the present application, the pressure-sensitive adhesive sheet may further include at least one selected from the group consisting of a dispersant, a photoinitiator, a thermal initiator, a crosslinkable compound, and a tackifier.

According to an exemplary embodiment of the present specification, the crosslinkable compound is hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethyl Allpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene group Propylene glycol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate with the number of 2 to 14 Compounds obtained by esterifying polyhydric alcohols such as a mixture of pentaerythritol hexa(meth)acrylate (TO-2348, TO-2349, manufactured by Dong-A Synthetic Japan as a brand name) with α,β-unsaturated carboxylic acid; Compounds obtained by adding (meth)acrylic acid to a compound containing a glycidyl group such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; An ester compound of a compound having a hydroxyl group or ethylenically unsaturated bond, such as a phthalic acid diester of β-hydroxyethyl (meth)acrylate and a toluene diisocyanate adduct of β-hydroxyethyl (meth)acrylate, and a polyhydric carboxylic acid , Or adducts with polyisocyanates; (Meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; And 9,9'-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, and is not limited thereto and known in the art. You can use common ones.

According to an exemplary embodiment of the present specification, the photoinitiator is a triazine-based compound, a biimidazole compound, an acetophenone-based compound, an O-acyloxime-based compound, a thioxanthone-based compound, a phosphine oxide-based compound, a coumarin-based compound, and benzope. It may be substituted with one or two or more substituents selected from the group consisting of non-based compounds.

Specifically, according to the exemplary embodiment of the present specification, the photoinitiator is 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-me Toxystyryl)-6-triazine, 2,4-trichloromethyl-(pipelonyl)-6-triazine, 2,4-trichloromethyl-(3',4'-dimethoxyphenyl)-6 -Triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propanoic acid, 2,4-trichloromethyl-(4'-ethyl ratio Triazine compounds such as phenyl)-6-triazine or 2,4-trichloromethyl-(4'-methylbiphenyl)-6-triazine; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole or 2,2'-bis(2,3-dichlorophenyl)-4,4',5 Biimidazole-based compounds such as ,5'-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxye Oxy)-phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl-(4-methylthiophenyl)-2-mol Acetopes such as polyno-1-propan-1-one (Irgacure-907) or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (Irgacure-369) Non-based compounds; O-acyloxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 of Ciba Geigy; Benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone; Thioxanthone compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone, or diisopropyl thioxanthone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide or bis(2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as; 3,3'-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3-benzoyl-7-methoxy-coumarin or 10,10'-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-Cl] Coumarin-based compounds such as -benzopyrano[6,7,8-ij]-quinolizin-11-one, etc. may be used alone or in combination of two or more, but are not limited thereto.

In addition, the thermal initiator may use those known in the art.

In an exemplary embodiment of the present application, the initial adhesive strength after bonding the opposite surface of the adhesive sheet to the barrier film in contact with the barrier film to stainless steel (SUS304 substrate) for 2 hours at 23° C. is 50 gf/inch or less, and then The adhesive strength after heat treatment at 50° C. for 20 minutes may be 500 gf/inch or more.

The initial and late adhesive strength was measured using a texture analyzer (Texture Analyzer (Stable Micro Systems)) at a 180° angle and a peel rate of 1800 mm/min, and the adhesive sheet prepared according to the present invention was measured with a 2 kg rubber roller. After one round trip and attaching to the stainless steel (304 mirror substrate), measurements were made for the initial 2 hours and 2 hours after the heat treatment.

In the exemplary embodiment of the present application, the initial adhesive strength of the pressure-sensitive adhesive sheet may be 50 gf/inch or less, preferably 40 gf/inch or less, and more preferably 35 gf/inch or less.

In another exemplary embodiment, the initial adhesive strength of the pressure-sensitive adhesive sheet may be 5 gf/inch or more.

In the exemplary embodiment of the present application, the late adhesive strength of the pressure-sensitive adhesive sheet may be 500 gf/inch or more, preferably 550 gf/inch or more, and more preferably 600 gf/inch or more.

In another exemplary embodiment, the late adhesive strength of the pressure-sensitive adhesive sheet may be 3000 gf/inch or less, preferably 2500 gf/inch or less.

In the exemplary embodiment of the present application, the late adhesive strength is 3 times or more and 100 times or less, preferably 5 times or more and 100 times or less, and more preferably 10 times or more and 100 times or less of the initial adhesion. do.

In the exemplary embodiment of the present application, the thickness of the pressure-sensitive adhesive sheet is 3 μm or more and 500 μm Hereinafter, preferably, it may be 5 µm or more and 400 µm or less, and more preferably 7 µm or more and 200 µm or less.

When the thickness of the pressure-sensitive adhesive sheet is within the above range, the rework property is excellent in case of incorrect attachment, and in particular, when removing the pressure-sensitive adhesive sheet, foreign matter is not left.

In an exemplary embodiment of the present application, the step of preparing a base film; Forming a barrier film on one surface of the base film; And forming a pressure-sensitive adhesive sheet on a surface opposite to the surface of the barrier film on which the base film is formed, wherein the adhesion between the barrier film and the pressure-sensitive adhesive sheet is 600 gf/in or more and 1000 gf/in or less, and the pressure-sensitive adhesive sheet Is an acrylate resin; A polymer comprising at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by Formula 1; And a curing agent, wherein the storage modulus of the adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less.

In the exemplary embodiment of the present application, after the step of forming an adhesive sheet on a surface opposite to the surface of the barrier film on which the base film is formed, forming a release film on the surface opposite to the surface in which the barrier film of the adhesive sheet is in contact It provides a method of manufacturing an adhesive film that further comprises.

The base film, barrier film, release film, and pressure-sensitive adhesive sheet are the same as described above.

In an exemplary embodiment of the present application, after the step of forming an adhesive sheet on a surface opposite to the surface on which the base film of the barrier film is formed, it provides a method of manufacturing an adhesive film further comprising a heat treatment step.

The heat treatment step refers to heat treatment under a temperature condition of 35°C or more and 60°C or less, and the heat treatment step refers to a process of heat treatment using a chamber.

In the exemplary embodiment of the present application, the heat treatment step may be a temperature condition of 35°C or more and 60°C or less, preferably 35°C or more and 55°C or less, and more preferably 35°C or more and 50°C or less.

In the exemplary embodiment of the present application, the heat treatment step may be a condition of processing for 20 minutes to 50 minutes at the temperature.

When the pressure-sensitive adhesive sheet is subjected to the heat treatment step, the adhesion between the barrier film and the pressure-sensitive adhesive sheet is 600 gf/in or more and 1000 gf/in or less, and the adhesion is increased to improve adhesion.

In addition, when the adherend is later bonded to the side opposite to the barrier film of the pressure-sensitive adhesive sheet, it can be reused in case of mis-adhering, and the adhesive strength with the adherend is increased after an additional heat treatment process.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

< Manufacturing example >

Components, weight ratios, and storage modulus of the pressure-sensitive adhesive sheets used in Examples and Comparative Examples of the present application are shown in Table 1 below.

Hardener
(Part by weight) Acrylate system
Suzy
(Weight ratio) Storage modulus
(Pa) polymer Furtherance
(Weight ratio) Parts by weight Example 1 DR-7030HD
(1.2) EHA/MMA/VP/HEA
(65/20/5/10) 1.6 x 10 ⁵ STMA/FM-0721
(80/20)

Weight average molecular weight:
60,000 g/mol 5 Example 2 DR-7030HD
(2.4) EHA/MMA/VP/HEA
(65/20/5/10) 2.2 x 10 ⁵ 5 Example 3 DR-7030HD(2.4) EHA/MMA/VP/HEA
(65/15/5/15) 1.5 x 10 ⁵ 5 Example 4 DR-7030HD(2.4) EHA/MMA/VP/HEA
(65/20/10/5) 2.5 x 10 ⁵ 5 Example 5 DR-7030HD(5.0) EHA/MMA/VP/HEA
(65/20/5/10) 5.1 x 10 ⁵ 5 Comparative Example 1 DR-7030HD(7.0) EHA/MMA/VP/HEA
(90/0/0/10) 1.1 x 10 ⁶ 5 Comparative Example 2 DR-7030HD
(0.2) EHA/MMA/VP/HEA
(65/15/5/15) 8.9 x 10 ⁴ 5

In Table 1, as the monofunctional polysiloxane, FM-0721 manufactured by Chisso was used, and DR-7030HD, an NCO type curing agent provided by Samyoung Ink, was used as the curing agent.

After attaching the pressure-sensitive adhesive sheet having the composition and weight ratio of Table 1 to the barrier film, a heat treatment process was performed. As the barrier film, an L-BFL product of LG Chem was used, and the barrier film was a silicon-based barrier film having a ^{moisture transmittance of 10 -2} g/m ^{2 -day or less.} The results of measuring the initial adhesion, late adhesion, rework characteristics and variable performance of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 2 below.

Initial adhesion
( gf /in) Late adhesion
( gf /in) Rework Variable performance Example One 42 850 OK OK Example 2 34 820 OK OK Example 3 33 880 OK OK Example 4 35 780 OK OK Example 5 28 740 OK OK Comparative example One 21 30 OK NG Comparative example 2 330 1050 NG OK

1. Initial adhesion (gf/in): After laminating the prepared adhesive sheet on the SUS304 substrate, the adhesion was measured after leaving it for 1 hour.

2. Late adhesion (gf/in): After laminating the prepared adhesive sheet on the SUS304 substrate, the adhesion was measured after treatment at 50° C. for 20 minutes.

3. Rework: After attaching the adhesive sheet to the SUS substrate, when peeling again after 5 minutes, no adhesive remains on the SUS substrate. If it falls off, it is marked as OK, and if the adhesive residue remains, it is marked as NG.

4. Variable performance: If the adhesive force after heat treatment increases more than 3 times than the normal temperature peeling force, the variable performance is OK, and if it is less than 3 times, it is expressed as NG.

In Table 2, the initial and late adhesive strength was measured using a texture analyzer (Stable Micro Systems) at a 180° angle and a peel rate of 1800 mm/min, and the adhesive sheet prepared according to the present invention was 2 kg rubber. Measurements were made for the initial 2 hours after being reciprocated with a roller and attached to the stainless steel (SUS304 substrate) and 2 hours after the heat treatment.

As can be seen from Table 2, the adhesive film according to an exemplary embodiment of the present application includes a polymer including at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by Formula 1 in the adhesive sheet, The variable property of the pressure-sensitive adhesive sheet has excellent properties. The excellent variable property means that the difference between the initial adhesive force and the late adhesive force after a specific process occurs significantly, and the change characteristics of the initial and late adhesive force are particularly excellent, and after the heat treatment process, the polymer has a more stable arrangement. So that the adhesive property has particularly excellent properties.

In particular, in Table 2, in the case of Comparative Example 1, the content of the curing agent was high. In this case, it was confirmed that the pressure-sensitive adhesive sheet had a hard property, so that the initial adhesive strength was low, but the change characteristics of the adhesive force did not appear. In addition, in Table 2, in the case of Comparative Example 2, the content of the curing agent was low, and in this case, the pressure-sensitive adhesive sheet had soft properties and thus variable properties may appear, but the initial adhesive strength was high and the rework property was good. It could be confirmed that it was not.

As can be seen from Tables 1 and 2, when the storage modulus has the above range as in Examples 1 to 5, it was confirmed that stability over time and excellent variable characteristics were obtained. When the storage elastic modulus is higher than the above range as in Comparative Example 1 in Table 2, the adhesive sheet has a hard characteristic, so that the increase in adhesive strength after the heat treatment is variable, and as in Comparative Example 2 in Table 2, the storage elastic modulus is above. If it was lower than the range, it could be confirmed that the pressure-sensitive adhesive sheet had soft properties, and thus the initial adhesive strength was high even when the polymer was used for the pressure-sensitive adhesive sheet, making rework properties difficult.

101: base film
102: barrier film
103: adhesive sheet
104: adhesive film

Claims (14)

Base film;
A barrier film provided on one side of the base film; And
An adhesive film comprising an adhesive sheet provided on a surface opposite to the surface of the barrier film in contact with the base film,
The adhesive strength of the surface where the barrier film and the adhesive sheet are in contact is 600 gf/in or more and 1000 gf/in or less,
The pressure-sensitive adhesive sheet is an acrylate resin; A polymer containing at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by the following formula (1); And a composition comprising a curing agent or a cured product thereof,
The storage modulus of the pressure-sensitive adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less,
The adhesive sheet, based on 100 parts by weight of the adhesive sheet
70 to 90 parts by weight of the acrylate resin;
0.5 to 25 parts by weight of the polymer; And
The adhesive film containing 0.3 to 20 parts by weight of the curing agent:
[Formula 1]

In Formula 1,
R ₁ is hydrogen or a methyl group,
n is an integer of 10 to 30. The method according to claim 1,
An adhesive film further comprising a release film provided on a surface opposite to the surface in contact with the barrier film of the adhesive sheet. The method according to claim 1,
The melting temperature (melting temperature, Tm) of the polymer is 35 ℃ 50 ℃ or less will the adhesive film. The method according to claim 1,
The monomer represented by Chemical Formula 1 is STMA (Stearyl methacrylate); Or STA (stearyl acrylate) that is an adhesive film. delete The method according to claim 1,
The polymer, based on 100 parts by weight of the polymer
5 to 30 parts by weight of the monofunctional polysiloxane; And
The adhesive film containing 60 to 90 parts by weight of the monomer represented by the formula (1). The pressure-sensitive adhesive film of claim 1, wherein the pressure-sensitive adhesive sheet further comprises at least one selected from the group consisting of a dispersant, a photoinitiator, a thermal initiator, and a tackifier. The method according to claim 1, wherein the initial adhesive strength after leaving the pressure-sensitive adhesive sheet opposite to the surface in contact with the barrier film to stainless steel (SUS304 substrate) at 23°C for 2 hours is 50 gf/inch or less, and then 20 at 50°C. An adhesive film that has a late adhesive strength of 500 gf/inch or more after minute heat treatment. The adhesive film according to claim 8, wherein the late adhesive force is 3 times or more and 100 times or less of the initial adhesive force. The method according to claim 1, wherein the thickness of the pressure-sensitive adhesive sheet is 3 ㎛ or more 500 ㎛ The adhesive film which is the following. Preparing a base film;
Forming a barrier film on one surface of the base film; And
Including the step of forming a pressure-sensitive adhesive sheet on a surface opposite to the surface of the barrier film on which the base film is formed,
The adhesive strength of the surface where the barrier film and the adhesive sheet are in contact is 600 gf/in or more and 1000 gf/in or less,
The adhesive sheet is an acrylate resin; A polymer containing at least one selected from the group consisting of monofunctional polysiloxanes and monomers represented by the following formula (1); And a curing agent,
The storage modulus of the pressure-sensitive adhesive sheet is 1 x 10 ⁵ Pa or more and 1 x 10 ⁶ Pa or less,
The adhesive sheet, based on 100 parts by weight of the adhesive sheet
70 to 90 parts by weight of the acrylate resin;
0.5 to 25 parts by weight of the polymer; And
Method for producing an adhesive film containing 0.3 to 20 parts by weight of the curing agent:
[Formula 1]

In Formula 1,
R ₁ is hydrogen or a methyl group,
n is an integer of 10 to 30. The method of claim 11,
After the step of forming the pressure-sensitive adhesive sheet on the opposite side of the surface of the barrier film on which the base film is formed, the method of manufacturing an adhesive film further comprising a heat treatment step. The method of claim 12,
The heat treatment step is a method of manufacturing an adhesive film that is heat-treated at a temperature condition of 35°C or more and 60°C or less. The method of claim 11,
After the step of forming a pressure-sensitive adhesive sheet on a surface opposite to the surface of the barrier film on which the base film is formed, forming a release film on the opposite surface of the surface where the barrier film of the pressure-sensitive adhesive sheet is in contact with the pressure-sensitive adhesive film Manufacturing method.

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