KR102044201B1 - Adhesive film - Google Patents

Abstract

materials; And a pressure-sensitive adhesive layer disposed on both sides of the base material, wherein the peeling force on the adherend of the pressure-sensitive adhesive layer is 2300 gf / cm to 2900 gf / cm, and the peeling force on the base material of the pressure-sensitive adhesive layer is the pressure-sensitive adhesive. An adhesive film is provided that is 120 gf / cm to 1000 gf / cm larger than the peel force on the adherend of the layer.

Description

Adhesive Film {ADHESIVE FILM}

It relates to an adhesive film.

In general, double-sided adhesive films are used to bond and fix various types of display panels, electronic components, etc. in mobile communication terminals and various mobile devices. For example, the double-sided adhesive film may be disposed between the display window and the display assembly and between various accessories to serve to adhere them.

As described above, the double-sided adhesive film may have elasticity while preventing intrusion of external impurities and the like into the edge of the display and appropriately maintaining the distance between internal terminals of the terminal, thereby absorbing external impact.

However, when the double-sided adhesive film has a high adhesive force, when the double-sided adhesive film is removed thereafter, a residue may be formed on the adherend, so that a study on the adhesive film having no adequate peeling force and no residue is needed.

One embodiment of the present invention provides a pressure-sensitive adhesive film that does not leave a residue upon removal while implementing the proper adhesive properties.

In one embodiment of the invention, the substrate; And a pressure-sensitive adhesive layer disposed on both sides of the substrate, wherein the peeling force on the adherend of the pressure-sensitive adhesive layer is 2300 gf / in to 2900 gf / in, and the peeling force on the base material of the pressure-sensitive adhesive layer is the pressure-sensitive adhesive. An adhesive film is provided that is 120 gf / in to 1000 gf / in larger than the peel force on the adherend of the layer.

The adherend may include one selected from the group consisting of plastic, metal, paper, wool, glass, and combinations thereof.

The pressure-sensitive adhesive layer comprises a photocurable of the photocurable pressure-sensitive adhesive composition, the photocurable pressure-sensitive adhesive composition is a photocurable resin; Dilution monomers comprising monomers having a carboxyl group (-COOH); Photocuring and crosslinking agents.

The monomer having a carboxyl group (-COOH) is 3 parts by weight to 10 parts by weight based on 100 parts by weight of the photocurable resin, and the photocuring agent is 0.05 parts by weight to 0.3 parts by weight based on 100 parts by weight of the photocurable resin, and the crosslinking agent. May be 0.1 parts by weight to 0.5 parts by weight based on 100 parts by weight of the photocurable resin.

The photocurable resin may include a first (meth) acrylate having an alkyl group having 1 to 15 carbon atoms; Second (meth) acrylate having a cycloalkyl group having 3 to 25 carbon atoms; Third (meth) acrylate having an alkoxy group having 1 to 10 carbon atoms; And a mixed monomer component comprising a fourth (meth) acrylate containing a hydrophilic functional group.

The mixed monomer component is 40 to 70% by weight of the first (meth) acrylate; 10 wt% to 25 wt% of the second (meth) acrylate; 10 wt% to 25 wt% of the third (meth) acrylate; And the fourth (meth) acrylate may comprise 3 wt% to 10 wt%.

The photocurable resin may have a weight average molecular weight of 2000000 to 6000000.

The monomer having a carboxyl group (-COOH) may be (meth) acrylic acid, acrylic acid duplex, fumaric acid, itaconic acid, maleic acid and maleic anhydride and combinations thereof. It may include one selected from the group consisting of.

The monomer having a carboxyl group (-COOH) may be a monomer including 80 wt% to 99.9 wt% of a carboxyl group.

The crosslinking agent is 3-glycidoxypropyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydrate Hydroxy group-containing monomers such as hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and the like; Acrylic acid, methacrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid Carboxyl group-containing monomers such as the like; 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, (meth) acrylamide, N-vinyl pyrroli And nitrogen-containing monomers such as don, N-vinyl caprolactam and the like, and combinations thereof.

The photocuring agent may include one selected from the group consisting of polyethylene glycol diacrylate, aliphatic urethane acrylate, tris (meth) acryloxyethyl isocyanurate, and combinations thereof.

The photocurable pressure-sensitive adhesive composition may further include one selected from the group consisting of photoinitiators, antioxidants, light stabilizers, organic and inorganic pigments, and combinations thereof.

The dilution monomer is a (meth) acrylate having an alkyl group having 1 to 15 carbon atoms; (Meth) acrylate having a cycloalkyl group having 3 to 25 carbon atoms; And (meth) acrylate having an alkoxy group having 1 to 10 carbon atoms.

The photocurable pressure sensitive adhesive composition may include 10 parts by weight to 70 parts by weight of the dilution monomer based on 100 parts by weight of the photocurable resin.

The viscosity at 25 ° C. of the photocurable pressure-sensitive adhesive composition may be 1500cp to 4000cp.

The gel fraction of the pressure-sensitive adhesive layer may be 40% to 70%.

The glass transition temperature of the pressure-sensitive adhesive layer may be -20 ℃ to -10 ℃.

The pressure-sensitive adhesive layer may have a thickness of 40 μm to 60 μm.

The thickness ratio of the pressure-sensitive adhesive layer to the thickness of the substrate may be 1: 3 to 1: 4.

The material of the substrate may be one selected from the group consisting of polyethylene (PE) foam, polyurethane (PU) foam, acrylic foam, and combinations thereof.

The adhesive film may realize an effect of improving the high temperature shear strength without leaving a residue after removal while having a proper adhesiveness to the adherend.

Specifically, when the pressure-sensitive adhesive layer has appropriate adhesive properties to improve the cohesive force of the pressure-sensitive adhesive layer to remove the pressure-sensitive adhesive film, the pressure-sensitive adhesive layer may be prevented from being separated. In addition, it is possible to implement the effect of improving the high temperature shear strength by preventing the physical property of the pressure-sensitive adhesive layer at a high temperature.

1 schematically illustrates a cross section of an adhesive film according to an embodiment of the present invention.

Advantages and features of the present invention, and methods for achieving the same will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to make the disclosure of the present invention complete, and to fully convey the scope of the invention to those skilled in the art, and the present invention is defined by the scope of the claims. It will be. Like reference numerals refer to like elements throughout.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.

In addition, in this specification, when a part such as a layer, film, region, plate, etc. is said to be "on" or "upper" another part, it is not only when the other part is "directly over" but also another part in the middle. Also includes. On the contrary, when a part is "just above" another part, there is no other part in the middle. In addition, when a part such as a layer, a film, an area, or a plate is "below" or "below" another part, it is not only when the part is "below" but also another part in the middle. Include. In contrast, when a part is "just below" another part, there is no other part in the middle.

In one embodiment of the invention, the substrate; And an adhesive layer disposed on both sides of the substrate, wherein the peeling force of the adhesive layer to the adherend is about 2300 gf / in to about 2900 gf / in, and the peeling force of the adhesive layer to the substrate is It provides an adhesive film of about 120 gf / in to about 1000 gf / in greater than the peel force on the adherend of the pressure-sensitive adhesive layer.

1 schematically illustrates a cross section of an adhesive film according to an embodiment of the present invention.

Referring to FIG. 1, the pressure-sensitive adhesive film 100 may have a shape in which the pressure-sensitive adhesive layer 110 is disposed and attached to both surfaces of the substrate 120.

The pressure-sensitive adhesive film 100 according to an embodiment of the present invention has a range of peeling force on the adherend of the pressure-sensitive adhesive layer 110, and for each of the substrate 120 and the adherend of the pressure-sensitive adhesive layer 110. By satisfying the above-mentioned range at the same time the difference in the peel force, it is possible to obtain the advantage of simultaneously implementing excellent durability and excellent residue prevention function.

In the present specification, the 'adhered body' is a generic term for an article or a base to which the pressure-sensitive adhesive layer of the adhesive film is attached, and satisfies the peel force range for the adherend, without being particularly limited to inside and outside of electronic products and other articles It will be understood to mean the materials used.

The adhesive layer has a peel force of about 2300 gf / in to about 2900 gf / in of the adherend. The peeling force on the adherend of the pressure-sensitive adhesive layer to maintain the above range can act as a pressure-sensitive adhesive film, it is possible to improve the reliability of the adhesive properties for the product with the pressure-sensitive adhesive film. However, if the peeling force on the adherend of the pressure-sensitive adhesive film is less than the above range, the pressure-sensitive adhesive film can be easily peeled off due to external friction or impact, so that a problem cannot be expected to have sufficient adhesive properties as the pressure-sensitive adhesive film, and exceeds the above range. In this case, there is a fear that the residue prevention performance is lowered.

The peeling force of the pressure-sensitive adhesive layer on the substrate in the pressure-sensitive adhesive film is greater than the peeling force on the adherend of the pressure-sensitive adhesive layer can effectively prevent the occurrence of residue.

Specifically, 'residue' means that when the adhesive film is attached to the adherend and peeled off after a predetermined time has elapsed, part of the adhesive layer component is transferred to the adherend and remains.

In one embodiment, the peeling force on the substrate of the pressure-sensitive adhesive layer may be about 120 gf / in to about 1000 gf / in greater than the peeling force on the adherend, for example, 120 gf / in to about 600 gf It can be as large as / in. Since the difference in peeling force satisfies the above range, the residue preventing performance can be effectively ensured, and also excellent impact resistance and interfacial stability can be ensured together.

Therefore, when the difference in the peeling force of the pressure-sensitive adhesive layer to the substrate and the peeling force of the pressure-sensitive adhesive layer to the adherend is less than the above range, there may be a problem that the residue occurs when peeling the pressure-sensitive adhesive film and the interface separation problem.

In the pressure-sensitive adhesive film, one pressure-sensitive adhesive layer of the substrate or both pressure-sensitive adhesive layers of the substrate may be attached to the adherend. The adherend may include one selected from the group consisting of plastic, metal, paper, wool, glass, and combinations thereof.

For example, in one embodiment, when the adherend comprises polycarbonate (PC), the adhesive force of the pressure-sensitive adhesive layer to the polycarbonate is about 2400 gf / in to about 2800 gf / in, When the adherend includes stainless steel (SUS), the adhesive force of the pressure-sensitive adhesive layer to the stainless steel is about 2300 gf / in to about 2900 gf / in at the same time can implement a proper adhesive properties without the occurrence of residue have.

The pressure-sensitive adhesive film is required to reduce the size of the mobile communication terminal and the mobile device, the complex internal structure, as well as the above-described effects as well as excellent high temperature shear strength and impact resistance, such high temperature shear strength and impact resistance improvement effect is It can be implemented by controlling the photocurable pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer.

The pressure-sensitive adhesive layer comprises a photocurable of the photocurable pressure-sensitive adhesive composition, the photocurable pressure-sensitive adhesive composition is a photocurable resin; Dilution monomers comprising monomers having a carboxyl group (-COOH); Photocuring and crosslinking agents.

The photocurable resin may include a first (meth) acrylate having an alkyl group having 1 to 15 carbon atoms; Second (meth) acrylate having a cycloalkyl group having 3 to 25 carbon atoms; Third (meth) acrylate having an alkoxy group having 1 to 10 carbon atoms; And a mixed monomer component comprising a fourth (meth) acrylate containing a hydrophilic functional group.

The photocurable resin may play a role of configuring the basic structure of the pressure-sensitive adhesive layer during photocuring.

The mixed monomer component comprises about 40% to about 70% by weight of the first (meth) acrylate; From about 10% to about 25% by weight of the second (meth) acrylate; From about 10% to about 25% by weight of the third (meth) acrylate; And about 4 wt% to about 10 wt% of the fourth (meth) acrylate. By controlling the mixed monomer component in the above range it is possible to implement the stability of the dimensions during the photocuring and proper adhesion properties and excellent impact resistance, high temperature properties stabilization and deformation resistance.

The photocurable resin may have a weight average molecular weight of about 2000000 to about 6000000.

By maintaining the weight average molecular weight of the photocurable resin in the above range, the durability of the pressure-sensitive adhesive layer can be improved, and excellent high temperature shear resistance and deformation resistance can be easily ensured. When the weight average molecular weight of the photocurable resin is less than the above range may cause a problem of peeling force and durability degradation, when the weight average molecular weight of the photocurable resin is more than the above range, the viscosity is too high, coating property is lowered, adhesive layer The viscosity may decrease, which may cause a problem that the peeling force is lowered.

The photocurable pressure sensitive adhesive composition includes a dilution monomer, and the dilution monomer serves to facilitate the coating property of the photocurable pressure sensitive adhesive composition by controlling the viscosity of the photocurable pressure sensitive adhesive composition.

Specifically, the dilution monomer may include a monomer having a carboxy group (-COOH). The dilution monomer may include a monomer having a carboxyl group (-COOH) to effectively improve the cohesion of the pressure-sensitive adhesive layer, improve the hardness of the pressure-sensitive adhesive layer to implement the effect of improving the durability against physical friction, preventing residue and high temperature Stability can be achieved.

For example, the monomer having a carboxyl group (-COOH) may be (meth) acrylic acid, acrylic acid duplex, fumaric acid, itaconic acid, maleic acid and maleic anhydride. And combinations thereof.

Specifically, the carboxyl group may improve cohesion through hydrogen bonding in the photocurable pressure-sensitive adhesive composition. For example, when the dilution monomer comprises acrylic acid, hydrogen bonds are generated by polar carboxyl groups located in the main chain, and the aggregation of the pressure-sensitive adhesive layer may be greatly improved by repeating such hydrogen bonds.

The monomer having a carboxyl group (-COOH) may be a monomer including about 80% to about 99.9% by weight of the carboxyl group. That is, the content of the carboxyl group in the total weight of the monomer having a carboxyl group (-COOH) may be about 90% to about 99.9% by weight. By having the carboxyl group having a weight% of the above range, even if the diluent monomer does not excessively include a monomer having a carboxyl group, an appropriate level of cohesion may be realized.

The diluent monomer may further include (meth) acrylate having an alkyl group having 1 to 15 carbon atoms; (Meth) acrylate having a cycloalkyl group having 3 to 25 carbon atoms; And (meth) acrylate having an alkoxy group having 1 to 10 carbon atoms. The diluent monomer may include the same monomers as the monomer included in the mixed monomer component for forming the photocurable resin.

Since the dilution monomer includes the same monomer as the monomer included in the mixed monomer component for forming the photocurable resin, dispersibility and compatibility of the photocurable pressure sensitive adhesive composition may be improved, and interfacial adhesion through the low molecular weight body may be improved. This can be secured.

The photocurable pressure sensitive adhesive composition may include about 10 parts by weight to about 70 parts by weight of the dilution monomer based on 100 parts by weight of the photocurable resin.

By the dilution monomer is included in the photocurable pressure-sensitive adhesive composition in the weight part range it can implement the effect of improving the coating property. When the dilution monomer is less than the weight part range, the hardness of the pressure-sensitive adhesive layer is low, there is a fear that the durability is lowered or the interface adhesion is deteriorated, when the dilution monomer is more than the weight part range, dispersibility of the photocurable pressure-sensitive adhesive composition And moldability may be lowered.

The photocurable pressure-sensitive adhesive composition includes a crosslinking agent, which may serve to induce a reaction site of the pressure-sensitive adhesive layer to improve interfacial adhesion with the base layer.

Specifically, the crosslinking agent is 3-glycidoxypropyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Hydroxy group-containing monomers such as 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and the like ; Acrylic acid, methacrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid Carboxyl group-containing monomers such as the like; 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, (meth) acrylamide, N-vinyl pyrroli It may include, but is not limited to, one selected from the group consisting of nitrogen, monomers such as don, N-vinyl caprolactam, and combinations thereof. By using the aforementioned kind of crosslinking agent, interfacial stability can be ensured through covalent bonding of the pressure-sensitive adhesive layer and the base layer.

The photocurable pressure-sensitive adhesive composition may include a photocuring agent, the photocuring agent serves to control the degree of curing of the photocurable resin by light irradiation according to its type and content, excellent high temperature stability and deformation resistance Can be implemented.

Specifically, the photocuring agent may include one selected from the group consisting of polyethylene glycol diacrylate, aliphatic urethane acrylate, tris (meth) acryloxyethyl isocyanurate, and combinations thereof, but is not limited thereto. no. By using a photocuring agent of the kind described above it can ensure excellent compatibility with the photocurable resin, can contribute greatly to secure the appropriate degree of curing, it is possible to implement excellent shear properties and deformation resistance.

As described above, the photocurable pressure-sensitive adhesive composition may include a photocurable resin, a diluent monomer, a photocuring agent, and a crosslinking agent, and the dilution monomer may further include a monomer having a carboxy group (-COOH) and another composition. The photocurable pressure-sensitive adhesive composition can maximize the aforementioned effects by controlling the weight of each of the compositions.

The monomer having a carboxyl group (-COOH) may be about 3 parts by weight to about 10 parts by weight based on 100 parts by weight of the photocurable resin. When the photocurable pressure-sensitive adhesive composition contains a monomer having a carboxyl group in the above weight part range, an appropriate degree of aggregation can be obtained, and an advantage in that peeling force is improved can be obtained.

The photocuring agent may be about 0.05 parts by weight to about 0.3 parts by weight based on 100 parts by weight of the photocurable resin. When the photocurable pressure-sensitive adhesive composition includes a photocuring agent in the above weight part range, appropriate hardness can be obtained, and excellent shear physical properties and deformation resistance can be realized.

The crosslinking agent may be about 0.1 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the photocurable resin. By the photocurable pressure-sensitive adhesive composition includes a crosslinking agent in the above weight part range, excellent durability can be obtained and excellent high temperature stability can be realized. In addition, the monomer, the photocuring agent and the crosslinking agent having the carboxyl group simultaneously satisfy the weight range, and thus the impact resistance and high temperature cohesion of the pressure-sensitive adhesive layer can be greatly improved and excellent peeling force can be realized.

The photocurable pressure-sensitive adhesive composition may further include one selected from the group consisting of photoinitiators, antioxidants, light stabilizers, organic and inorganic pigments, and combinations thereof within a range that does not reduce the physical properties and effects to be implemented, and is limited thereto. It is not.

The photocurable pressure-sensitive adhesive composition may have a viscosity of about 1500cp to about 4000cp at about 25 ℃.

By having a viscosity in the above range, the photocurable pressure-sensitive adhesive composition can implement the excellent dispersibility and moldability to form the pressure-sensitive adhesive layer to a more uniform level.

The photocurable pressure-sensitive adhesive composition may be cured by photocuring to become a pressure-sensitive adhesive layer. In this case, the gel fraction of the pressure-sensitive adhesive layer may be about 40% to about 70%. The gel fraction is derived by gel fraction (%) = (weight after drying / initial weight of adhesive X100) and the formula can be measured under conditions of 2hr dry in 110 ℃ oven after filtration of the adhesive in ethyl acetate solvent for 24 hours, filtered. . By maintaining the gel fraction of the pressure-sensitive adhesive layer can implement a proper durability and tensile strength, it is possible to implement an excellent peel force and high temperature denaturation resistance. When the pressure-sensitive adhesive layer is less than the gel fraction range, the cohesive force may be lowered and the durability and mechanical properties may be weakened. When the pressure-sensitive adhesive layer is greater than the gel fraction range, the cohesive force of the pressure-sensitive adhesive layer may be improved, but the flexibility and tackiness may be reduced. Can be.

The glass transition temperature of the pressure-sensitive adhesive layer may be about -20 ℃ to about -10 ℃. By maintaining the glass transition temperature range of the pressure-sensitive adhesive layer may have excellent impact resistance, thereby improving the stability to high temperature properties. When the glass transition temperature of the pressure-sensitive adhesive layer is less than the above range, the adhesive force may be lowered at room temperature. When the glass transition temperature of the pressure-sensitive adhesive layer exceeds the above range, a problem may occur in that impact resistance is lowered.

The adhesive layer may have a thickness of about 40 μm to about 60 μm. By maintaining the thickness range of the pressure-sensitive adhesive layer can realize sufficiently good adhesion and durability without excessively increasing the overall thickness of the pressure-sensitive adhesive film. When the pressure-sensitive adhesive layer is less than the thickness range, it is difficult to implement sufficient pressure-sensitive physical properties, when the pressure-sensitive adhesive layer is greater than the thickness range, durability may be lowered, and deformation of the pressure-sensitive adhesive film may occur.

Referring to FIG. 1, the pressure-sensitive adhesive film 100 includes the pressure-sensitive adhesive layer 110 on both surfaces of the substrate 120, respectively. The thickness ratio of the substrate to the pressure-sensitive adhesive layer may be about 1: 3 to about 1: 4. By maintaining the thickness ratio of the substrate and the pressure-sensitive adhesive layer, excellent physical properties and impact resistance may be simultaneously achieved without deteriorating the mechanical properties of the pressure-sensitive adhesive film.

The material of the substrate may be one selected from the group consisting of polyethylene (PE) foam, polyurethane (PU) foam, acrylic foam, and combinations thereof, but is not limited thereto. For example, when the material of the base material is polyethylene foam, the compatibility with the adhesive layer is good and the durability of the adhesive film may be improved.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

< Example  And Comparative example >

Example  One

100 parts by weight of the photocurable resin (LG Hausys, CJM 0703), 51 parts by weight of 2-ethylhexyl acrylate (LG Chemical, 2-EHA) as a diluent monomer, 2- (2-ethoxyethoxy) ethyl acrylate ( Miwon, M170) 20 parts by weight, 20 parts by weight of isobonyl acrylate (Rhodia, IBOA) and 9 parts by weight of acrylic acid (LG Chem, AA); 0.3 part by weight of monoacrylphosphine (BASF, TPO) as a photoinitiator, 0.12 part by weight of tetraethylene glycol diacrylate (Sigma Aldrich, TTEGDA) as a photocuring agent; 15 parts by weight of the chemical name (Eastman, Regalrez 3102) and 5 parts by weight of the chemical name (Eastman, Foral 85) as an adhesive; A photocurable pressure-sensitive adhesive composition comprising 0.1 part by weight of 3-glycidoxypropyl trimethoxysilane (Shinetsu, KBM-403) as a crosslinking agent was prepared.

Next, the photocurable adhesive composition was photocured to form an adhesive layer having a thickness of 50 μm, and the adhesive layer was laminated on both surfaces of a polyethylene foam having a thickness of 150 μm.

The pressure-sensitive adhesive layer has a peeling force of 2300 gf / in to the stainless steel and the peeling force of the pressure-sensitive adhesive layer on the polyethylene foam foam of 700 gf / in greater than the peeling force to the stainless steel of the pressure-sensitive adhesive layer to produce do.

Comparative example  One

100 parts by weight of the photocurable resin (LG Hausys, CJM 0703), 55 parts by weight of 2-ethylhexyl acrylate (LG Chemical, 2-EHA) as a diluent monomer, 2- (2-ethoxyethoxy) ethyl acrylate ( Miwon, M170) 20 parts by weight, 20 parts by weight of isobornyl acrylate (Rhodia, IBOA) and 5 parts by weight of acrylic acid (LG Chem, AA); 0.3 part by weight of monoacrylphosphine (BASF, TPO) as a photoinitiator, 0.12 part by weight of tetraethylene glycol diacrylate (Sigma Aldrich, TTEGDA) as a photocuring agent; 15 parts by weight of the chemical name (Eastman, Regalrez 3102) and 5 parts by weight of the chemical name (Eastman, Foral 85) as an adhesive; A photocurable pressure-sensitive adhesive composition comprising 0.15 parts by weight of 3-glycidoxypropyl trimethoxysilane (Shinetsu, KBM-403) as a crosslinking agent was prepared.

Next, the photocurable adhesive composition was photocured to form an adhesive layer having a thickness of 50 μm, and the adhesive layer was laminated on both surfaces of a polyethylene foam having a thickness of 150 μm.

The pressure-sensitive adhesive layer has a peel force of 3000 gf / in for the stainless steel and the peel force for the polyethylene foam of the pressure-sensitive adhesive layer is 500 gf / in less than the peel force for the stainless steel of the pressure-sensitive adhesive layer is prepared do.

Comparative example  2

100 parts by weight of the photocurable resin (LG Hausys, CJM 0703), 55 parts by weight of 2-ethylhexyl acrylate (LG Chemical, 2-EHA) as a diluent monomer, 2- (2-ethoxyethoxy) ethyl acrylate ( Miwon, M170) 20 parts by weight, 20 parts by weight of isobornyl acrylate (Rhodia, IBOA) and 5 parts by weight of acrylic acid (LG Chem, AA); 0.3 part by weight of monoacrylphosphine (BASF, TPO) as a photoinitiator, 0.15 part by weight of tetraethylene glycol diacrylate (Sigma Aldrich, TTEGDA) as a photocuring agent; 15 parts by weight of the chemical name (Eastman, Regalrez 3102) and 5 parts by weight of the chemical name (Eastman, Foral 85) as an adhesive; A photocurable pressure-sensitive adhesive composition including 0.1 part by weight of 3-glycidoxypropyl trimethoxysilane (Shinetsu, KBM-403) as a crosslinking agent was prepared.

Next, the photocurable adhesive composition was photocured to form an adhesive layer having a thickness of 50 μm, and the adhesive layer was laminated on both surfaces of a polyethylene foam having a thickness of 150 μm.

The pressure-sensitive adhesive layer has a peel force of 2700 gf / in for the stainless steel and the peel force for the polyethylene foam of the pressure-sensitive adhesive layer is 500 gf / in less than the peel force for the stainless steel of the pressure-sensitive adhesive layer is prepared do.

Comparative example  3

100 parts by weight of the photocurable resin (LG Hausys, CJM 0703), 55 parts by weight of 2-ethylhexyl acrylate (LG Chemical, 2-EHA) as a diluent monomer, 2- (2-ethoxyethoxy) ethyl acrylate ( Miwon, M170) 20 parts by weight, 20 parts by weight of isobornyl acrylate (Rhodia, IBOA) and 5 parts by weight of acrylic acid (LG Chem, AA); 0.3 part by weight of monoacrylphosphine (BASF, TPO) as a photoinitiator, 0.12 part by weight of tetraethylene glycol diacrylate (Sigma Aldrich, TTEGDA) as a photocuring agent; 15 parts by weight of the chemical name (Eastman, Regalrez 3102) and 5 parts by weight of the chemical name (Eastman, Foral 85) as an adhesive; A photocurable pressure-sensitive adhesive composition comprising 0.1 part by weight of 3-glycidoxypropyl trimethoxysilane (Shinetsu, KBM-403) as a crosslinking agent was prepared.

Next, the photocurable adhesive composition was photocured to form an adhesive layer having a thickness of 50 μm, and the adhesive layer was laminated on both surfaces of a polyethylene foam having a thickness of 150 μm.

The pressure-sensitive adhesive layer has a peel force of 2800 gf / in for the stainless steel and the peel force for the polyethylene foam of the pressure-sensitive adhesive layer is 500 gf / in less than the peel force for the stainless steel of the pressure-sensitive adhesive layer is prepared do.

Comparative example  4

100 parts by weight of the photocurable resin (LG Hausys, CJM 0703), 55 parts by weight of 2-ethylhexyl acrylate (LG Chemical, 2-EHA) as a diluent monomer, 2- (2-ethoxyethoxy) ethyl acrylate ( Miwon, M170) 20 parts by weight, 20 parts by weight of isobornyl acrylate (Rhodia, IBOA) and 5 parts by weight of acrylic acid (LG Chem, AA); 0.3 part by weight of monoacrylphosphine (BASF, TPO) as a photoinitiator, 0.12 part by weight of tetraethylene glycol diacrylate (Sigma Aldrich, TTEGDA) as a photocuring agent; 15 parts by weight of the chemical name (Eastman, Regalrez 3102) and 3 parts by weight of the chemical name (Eastman, Foral 85) as an adhesive; A photocurable pressure-sensitive adhesive composition comprising 0.1 part by weight of 3-glycidoxypropyl trimethoxysilane (Shinetsu, KBM-403) as a crosslinking agent was prepared.

Next, the photocurable adhesive composition was photocured to form an adhesive layer having a thickness of 50 μm, and the adhesive layer was laminated on both surfaces of a polyethylene foam having a thickness of 150 μm.

The pressure-sensitive adhesive layer has a peel force of 2600 gf / in to the stainless steel and the peel force of the pressure-sensitive adhesive layer to the polyethylene foam is 60 gf / in greater than the peel force of the pressure-sensitive adhesive layer to the stainless steel. do.

Comparison of Composition Components According to Examples and Comparative Examples Raw material name Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Suzy CJM-0703 100.00 100.00 100.00 100.00 100.00 Dilution Monomer 2-EHA 51.00 55.00 55.00 55.00 55.00 M170 20.00 20.00 20.00 20.00 20.00 IBOA 20.00 20.00 20.00 20.00 20.00 AA 9.00 5.00 5.00 5.00 5.00 Photoinitiator TPO 0.30 0.30 0.30 0.30 0.30 Photocuring agent TTEGDA 0.12 0.12 0.15 0.12 0.12 adhesive Regalrez 3102 15.00 15.00 15.00 15.00 15.00 Foral 85 5.00 5.00 5.00 5.00 3.00 Crosslinking agent KBM-403 0.10 0.15 0.10 0.10 0.10

<Evaluation>

Experimental Example  One: Of adhesive layer On the adherend  About 180 ° peeling force  And Residue  Measure

After plywood 50 μm on one surface of the adhesive film according to the above Examples and Comparative Examples, a measurement sample having a width of 25 mm and a length of 200 mm was prepared. Each sample was attached to PC (polycarbonate) and SUS (stainless steel) by reciprocating twice with a roller of 2 kg in accordance with ISO 8510-2. Then, after storing for 1 hour under a temperature of 23 ℃ and a relative humidity of 55%, the peel force was measured at a peel rate of 300mm / min using a tensile tester and the results are shown in Table 2 below.

The residue is peeled off after 1 hour, a day after attaching the adhesive film according to the Examples and Comparative Examples to polycarbonate and stainless steel, and visually determine whether the residue is in the polycarbonate and stainless steel, and the results are shown in the following table. 2 is shown.

*: When there is residue 180 ° Peel (gf / in) Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Polycarbonate 1hr 2542 3002 2414 2837 2412 1day 2887 3720 * 2800 * 4023 * 3005 * Stainless steel 1hr 2379 2798 * 2696 2996 2592 1day 2932 3335 * 3198 * 3504 * 3222 *

When the pressure-sensitive adhesive film prepared according to Example 1 is applied to polycapnate and stainless steel, no residue occurs after one day, and it was confirmed that excellent residue prevention performance was realized. In particular, it was found that after one day to maintain a good adhesion of more than 2800 gf / in at the same time to prevent the residue.

On the other hand, in Comparative Examples 1 to 4, when applied to polycarbonate and stainless steel, only to implement the adhesive strength of 2800 gf / in or more, it was confirmed that the residue remains.

Experimental Example  2: high temperature shear strength measurement

The adhesive films according to the above examples and comparative examples were attached according to ASTM D1002. Then, after the heat treatment for 1 hour at 85 ℃ condition using a tensile tester at 85 ℃ to measure the shear strength at a peel rate of 6mm / min and the results are shown in Table 3 below.

Experimental Example  3: impact resistance measurement

The adhesive films according to the Examples and Comparative Examples were measured for impact resistance according to Dupont type impact test (Dupont Normal) and the results are shown in Table 3 below.

Experimental Example  4: rolling ball Rolling ball tack measurement

The adhesive film according to the Examples and Comparative Examples was measured according to the ASTAM D3121-06 (Tack of Pressure-Sensitive Adhesives by Rolling Ball) and the results are shown in Table 3 below.

unit Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 High temperature shear strength Kg 12.5 8.0 9.7 7.8 9.1 Shock mJ 980 1,323 1,029 1,323 1,029 Rolling balltack mm 6.1 4.0 4.7 3.3 5.2

The pressure-sensitive adhesive film prepared according to Example 1 was able to confirm that the measuring length of the rolling ball tack was 6.1 mm to achieve proper adhesive strength and proper impact resistance of 980 mJ or more. In particular, in the case of high temperature shear strength, it can be seen that the improved high temperature properties can be achieved by showing physical properties of more than 12kg.

On the other hand, in the case of Comparative Examples 1 to 4, it is possible to implement the appropriate impact resistance and adhesion, it was found that in the case of high temperature shear strength, it exhibits a significantly low temperature properties of less than 10kg.

100: adhesive film
110: pressure-sensitive adhesive layer
120: substrate

Claims (20)

materials; And pressure-sensitive adhesive layers each disposed on both sides of the substrate,
Peel force on the adherend of the pressure-sensitive adhesive layer is 2300 gf / in to 2900 gf / in,
The peel force of the pressure-sensitive adhesive layer on the substrate is 120 gf / in to 1000 gf / in greater than the peel force on the adherend of the pressure-sensitive adhesive layer,
The pressure-sensitive adhesive layer comprises a photocurable of the photocurable pressure-sensitive adhesive composition,
The photocurable pressure-sensitive adhesive composition is a photocurable resin; Dilution monomers comprising monomers having a carboxyl group (-COOH); Photocuring agent and crosslinking agent,
The monomer having a carboxyl group (-COOH) is 6 parts by weight to 10 parts by weight based on 100 parts by weight of the photocurable resin.
Adhesive film.
The method of claim 1,
The adherend includes one selected from the group consisting of plastic, metal, paper, wool, glass, and combinations thereof.
Adhesive film.
delete The method of claim 1,
The photocuring agent is 0.05 parts by weight to 0.3 parts by weight based on 100 parts by weight of the photocurable resin,
The crosslinking agent is 0.1 parts by weight to 0.5 parts by weight based on 100 parts by weight of the photocurable resin.
Adhesive film.
The method of claim 1,
The photocurable resin may include a first (meth) acrylate having an alkyl group having 1 to 15 carbon atoms; Second (meth) acrylate having a cycloalkyl group having 3 to 25 carbon atoms; Third (meth) acrylate having an alkoxy group having 1 to 10 carbon atoms; And a mixed monomer component comprising a fourth (meth) acrylate containing a hydrophilic functional group.
Adhesive film.
The method of claim 5,
The mixed monomer component is
40 wt% to 70 wt% of the first (meth) acrylate;
10 wt% to 25 wt% of the second (meth) acrylate;
10 wt% to 25 wt% of the third (meth) acrylate; and
The fourth (meth) acrylate comprises 3 wt% to 10 wt%
Adhesive film.
The method of claim 1,
The photocurable resin has a weight average molecular weight of 2000000 to 6000000
Adhesive film.
The method of claim 1,
The monomer having a carboxyl group (-COOH) is (meth) acrylic acid, acrylic acid duplex, fumaric acid, itaconic acid, maleic acid and maleic anhydride and combinations thereof Contains one selected from the group consisting of
Adhesive film.
The method of claim 1,
The monomer having a carboxyl group (-COOH) is a monomer containing 80 to 99.9% by weight of a carboxyl group
Adhesive film.
The method of claim 1,
The crosslinking agent is 3-glycidoxypropyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydrate A hydroxy group-containing monomer which is one selected from hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, and 2-hydroxypropylene glycol (meth) acrylate; Acrylic acid, methacrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid Carboxyl group-containing monomer which is one selected from; 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, (meth) acrylamide, N-vinyl pyrroli DON, a nitrogen-containing monomer which is one selected from N-vinyl caprolactam and one selected from the group consisting of a combination thereof
Adhesive film.
The method of claim 1,
The photocuring agent includes one selected from the group consisting of polyethylene glycol diacrylate, aliphatic urethane acrylate, tris (meth) acryloxyethyl isocyanurate, and combinations thereof
Adhesive film.
The method of claim 1,
The photocurable pressure-sensitive adhesive composition further comprises one selected from the group consisting of photoinitiators, antioxidants, light stabilizers, organic and inorganic pigments, and combinations thereof.
Adhesive film.
The method of claim 1,
The dilution monomer is a (meth) acrylate having an alkyl group having 1 to 15 carbon atoms; (Meth) acrylate having a cycloalkyl group having 3 to 25 carbon atoms; And (meth) acrylates having an alkoxy group having 1 to 10 carbon atoms.
Adhesive film.
The method of claim 1,
The photocurable pressure-sensitive adhesive composition comprises 10 parts to 70 parts by weight of the dilution monomer based on 100 parts by weight of the photocurable resin.
Adhesive film.
The method of claim 1,
The viscosity of the photocurable pressure-sensitive adhesive composition at 25 ℃ 1500 to 4000cp
Adhesive film.
The method of claim 1,
The gel fraction of the pressure-sensitive adhesive layer is 40% to 70%
Adhesive film.
The method of claim 1,
The glass transition temperature of the pressure-sensitive adhesive layer is -20 ℃ to -10 ℃
Adhesive film.
The method of claim 1,
The thickness of the pressure-sensitive adhesive layer is 40㎛ to 60㎛
Adhesive film.
The method of claim 1,
The thickness ratio of the pressure-sensitive adhesive layer to the thickness of the substrate is 1: 3 to 1: 4
Adhesive film.
The method of claim 1,
The material of the substrate is one selected from the group consisting of polyethylene (PE) foam, polyurethane (PU) foam, acrylic foam and combinations thereof
Adhesive film.

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