KR102063061B1 - Conductive laminate - Google Patents

Abstract

The present application relates to a conductive laminate and its use. Since the conductive laminate of the present application can effectively suppress the generation of bubbles around the stepped portion even when attached to a substrate having a surface level difference, the appearance and performance of the product to which the conductive laminate is applied can be maintained. Such a conductive laminate can be usefully used, for example, in a touch panel.

Description

Conductive Laminate {CONDUCTIVE LAMINATE}

The present application relates to a conductive laminate and its use.

The touch panel or touch screen is applied to various information processing terminals such as mobile communication terminals or ATMs, and display devices such as TVs and monitors. In addition, as the application to small portable electronic devices increases, the demand for smaller and lighter touch panels or screens increases.

In the configuration of the touch panel or screen, for example, a conductive laminate as disclosed in Patent Documents 1 or 2 is used. Such a conductive laminate may include an adhesive layer. It is important that the conductive laminate does not generate bubbles when laminated to another substrate through the pressure-sensitive adhesive layer. This is because if bubbles are generated, the design of the screen may be remarkably impaired, which may affect the appearance and may cause a decrease in performance.

Patent Document 1: Republic of Korea Patent Publication No. 2002-0036837 Patent Document 2: Republic of Korea Patent Publication No. 2001-0042939

The present application relates to a conductive laminate and its use.

The present application relates to a conductive laminate. 1 exemplarily shows a structure of a conductive laminate according to a first embodiment of the present application. As shown in FIG. 1, the electroconductive laminated body 1 is the base material layer 101; And a conductive layer 201 formed on one surface of the base layer. And an adhesive layer 30 attached to a surface on which the first conductive layer of the first base layer is not formed. Hereinafter, the conductive laminated body of this application is demonstrated concretely.

[Base layer]

The kind of base material layer 101 is not specifically limited, For example, a glass base material or a plastic base material can be used. As the plastic substrate, a polyester film, a polyamide film, a polyvinyl chloride film, a polystyrene film, or a polyolefin film may be used, and a polyester film such as polyethylene terephthalate, an acrylic resin film, or a polycarbonate film may be used. However, it is not limited thereto.

The thickness of the base material layer 101 is not specifically limited, It can set suitably as long as it can function as an electroconductive laminated body. For example, the thickness of the substrate layer may be in the range of about 1 μm to 500 μm, about 3 μm to 300 μm, about 5 μm to 250 μm, or about 10 μm to 200 μm.

The substrate layer 101 may be, for example, a suitable adhesion treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment or sputter etching treatment, but is not limited thereto.

[Conductive layer]

The conductive layer 201 may be formed on one surface of the base layer 101. Examples of the material constituting the conductive layer 201 include metals such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, alloys of two or more thereof, indium oxide, Tin oxide, titanium oxide, cadmium oxide or a metal oxide composed of a mixture of two or more thereof, copper iodide, and the like may be used, and the conductive layer may be a crystalline layer or an amorphous layer. In one example, the material constituting the conductive layer may use Indium Tin Oxide (ITO), but is not limited thereto.

The thickness of the conductive layer 201 may be adjusted in a range of about 10 nm to 300 nm, about 10 nm to 200 nm, or about 10 nm to 100 nm in consideration of the possibility of forming a continuous film, conductivity, transparency, and the like, but is not limited thereto.

The method of forming the conductive layer 201 is not particularly limited, but for example, a vacuum thin film deposition method, a sputtering method, an ion plating method, a spray pyrolysis method, a chemical plating method, an electroplating method, or a conventional thin film formation method combining two or more of the above methods may be employed. It can form, and can be formed by a vacuum vapor deposition method or sputtering method normally.

The conductive layer 201 may be formed on one surface of the base layer through an anchor layer or a dielectric layer if necessary. The anchor layer or the dielectric layer may improve adhesion between the conductive layer and the base layer, and may improve scratch resistance or flex resistance.

In addition, the anchor layer or the dielectric layer may be, for example, an inorganic material such as SiO ₂ , MgF ₂ or Al ₂ O ₃ ; It can be formed using an organic substance such as an acrylic resin, a urethane resin, a melamine resin, an alkyd resin, or a siloxane polymer, or a vacuum deposition method, a sputtering method, an ion plating method, or a coating method using a mixture of two or more of the above. The anchor layer or dielectric layer may be typically formed to a thickness of about 100 nm or less, specifically 15 nm to 100 nm or 20 nm to 60 nm.

[Adhesive Layer]

The adhesive layer 30 may be attached to a surface on which the conductive layer 201 of the base layer 101 is not formed. The pressure-sensitive adhesive layer may include an adhesive polymer. As used herein, the term “polymer” may refer to a polymer in which one or more monomers different from each other are mixed and polymerized. In one example, the pressure-sensitive adhesive layer may include the pressure-sensitive adhesive polymer in a crosslinked state. Hereinafter, the storage modulus or loss modulus of the pressure-sensitive adhesive layer refers to the storage modulus or loss modulus of the pressure-sensitive adhesive layer including the pressure-sensitive adhesive polymer in a crosslinked state unless otherwise specified. When the pressure-sensitive adhesive layer is attached to another substrate having a surface step, its physical properties and composition may be controlled as follows in terms of suppressing bubble generation at the periphery of the step.

The pressure-sensitive adhesive layer 30 has a loss modulus at a temperature of 50 ° C. and a frequency of 1 rad / sec of 1.0 x 10 ⁴ Pa or less, 0.98 x 10 ⁴ Pa or less, 0.96 x 10 ⁴ Pa or less, 0.94 x 10 ⁴ Pa Or less than or equal to 0.92 x 10 ⁴ Pa or less, or less than or equal to 0.90 x 10 ⁴ Pa, less than or equal to 0.80 x 10 ⁴ Pa, less than or equal to 0.70 x 10 ⁴ Pa, less than or equal to 0.60 x 10 ⁴ Pa, or less than or equal to 0.50 x 10 ⁴ Pa. The lower limit of the loss modulus at the 50 ° C. temperature and the 1 rad / sec frequency of the pressure-sensitive adhesive layer 30 is not particularly limited, and may be, for example, 0.1 × 10 ⁴ Pa or more. As used herein, the term "loss modulus" refers to the commonly known "dynamic loss modulus". That is, when the sine type shear deformation is applied to the elastic body as described above, the portion of the phase delayed by pi / 2, that is, the energy that is irreversibly lost by being converted into heat or the like due to elasticity, is referred to as "dynamic loss modulus" or "loss." Modulus of elasticity ”. The loss elastic modulus of an adhesive layer can be adjusted in the above-mentioned range, and even if it adheres to the base material which has a surface level | step difference, generation | occurrence | production of the bubble of a peripheral part of a level | step difference can be suppressed.

The pressure-sensitive adhesive layer 30 also has a storage modulus at a temperature of 50 ° C. and a frequency of 1 rad / sec of 1.0 x 10 ⁴ Pa or less, 0.98 x 10 ⁴ Pa or less, 0.96 x 10 ⁴ Pa or less, 0.94 x 10 ⁴ Pa or less, 0.92 x 10 ⁴ Pa or less, 0.90 x 10 ⁴ Pa or less, 0.80 x 10 ⁴ Pa or less, 0.70 x 10 ⁴ Pa or less, or 0.60 x 10 ⁴ Pa or less. The lower limit of the storage elastic modulus at the 50 ° C. temperature and the 1 rad / sec frequency of the pressure-sensitive adhesive layer 30 is not particularly limited, and may be, for example, 0.1 × 10 ⁴ Pa or more. As used herein, the term "storage modulus" refers to the commonly known "dynamic storage modulus". In other words, when sine-type shear deformation is applied to an elastic body, in the case of a viscoelastic material, the stress is delayed to appear in an intermediate form. Mathematically, one component is in the same phase and the other component is delayed by pi / 2. In this case, a portion in the same phase, that is, energy stored without loss by elasticity may be referred to as "dynamic storage modulus" or "storage modulus". By controlling the storage elastic modulus of the pressure-sensitive adhesive layer within the above-described range, bubbles can be effectively suppressed even when adhered to a substrate having a surface level difference.

The adhesive polymer included in the pressure-sensitive adhesive layer 30 may be included as a first monomer polymerization unit having a C5 or more alkyl group and a crosslinkable monomer polymerization unit. As used herein, the term "monomer polymerized unit" may refer to a form in which the monomer forms a skeleton, for example, a main chain or a side chain, of the polymer through a polymerization reaction. When the adhesive polymer includes the monomer polymerization unit, the pressure-sensitive adhesive layer may exhibit the above-described loss or storage modulus range, thereby suppressing bubble generation around the step difference even when the pressure-sensitive adhesive layer is attached to a substrate having a surface level difference. have.

As a 1st monomer, the alkyl (meth) acrylate which has a C5 or more alkyl group can be used, for example. The alkyl group is not particularly limited when it has 5 or more carbon atoms, but may be, for example, a branched or straight chain alkyl group, and more preferably a straight chain alkyl group. As such a 1st monomer, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, or lauryl (meth), for example Acrylate, etc. may be exemplified, and one or more kinds thereof may be used, and 2-ethylhexyl (meth) acrylate may be used as one embodiment of the present application, but is not limited thereto. The upper limit of the carbon number of the alkyl group of the first monomer is not particularly limited, but for example, an alkyl (meth) acrylate having an alkyl group of 20 or less carbon atoms, 18 or less carbon atoms, 16 or less carbon atoms, 14 or less carbon atoms, 12 carbon atoms or 10 carbon atoms. Can be used.

The first monomer polymerization unit may be included in a ratio of more than about 50 parts by weight to 100 parts by weight of the tacky polymer. In the present specification, the unit "parts by weight" may mean a ratio of weights between components. More specifically, the first monomer polymerization unit has a ratio of about 55 parts by weight, 60 parts by weight, 65 parts by weight, about 70 parts by weight, about 75 parts by weight or about 80 parts by weight or more based on 100 parts by weight of the adhesive polymer. It can be included in the adhesive polymer. The upper limit of the content ratio in the tacky polymer of the first monomer polymerizing unit is not particularly limited, but may be, for example, about 95 parts by weight or less or about 90 parts by weight or less. In this range, the pressure-sensitive adhesive layer may exhibit the above-described loss or storage modulus range, and thus, even when adhered to a substrate having a surface step, it is possible to effectively suppress bubble generation around the step difference.

The adhesive polymer may also include crosslinkable monomer polymerization units. As used herein, the term "crosslinkable monomer" may mean a monomer capable of providing a crosslinkable functional group to the polymer when the polymer is included in the polymer unit by having a crosslinkable functional group and another functional group capable of forming an adhesive polymer.

There are various known monomers that can be used as crosslinkable monomers in the manufacture of pressure sensitive adhesives, and all of these monomers can be used in the pressure sensitive adhesive polymer. For example, as a crosslinkable monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate or 8-hydroxyoctyl (meth) acrylate; Poly (alkylene glycol) (meth) acrylates, such as poly (ethylene glycol) (meth) acrylate or poly (propylene glycol) (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxy acetic acid Carboxyl group-containing copolymerizable monomers such as 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid or maleic anhydride can be used. However, it is not limited thereto.

When the crosslinkable monomer polymerization unit is included in the adhesive polymer, for example, the crosslinkable monomer polymerization unit may be included in an amount of 1 part by weight to 30 parts by weight, 5 parts by weight to 30 parts by weight, and 10 parts by weight to 100 parts by weight of the adhesive polymer. It may be included in the ratio of 30 parts by weight or 12 to 30 parts by weight. In this range, the pressure-sensitive adhesive layer may exhibit the above-described loss or storage modulus range, and thus, even when adhered to a substrate having a surface step, it is possible to effectively suppress bubble generation around the step difference.

The adhesive polymer may further include a second monomer polymerization unit having an alkyl group having 1 to 4 carbon atoms. As a 2nd monomer, the alkyl (meth) acrylate which has a C1-C4 alkyl group can be used, for example. The alkyl group is not particularly limited in the case of 1 to 4 carbon atoms, for example, may be a branched or straight chain alkyl group, more preferably a straight chain alkyl group. As such a monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t- Butyl (meth) acrylate or sec-butyl (meth) acrylate, and the like may be exemplified, and methyl (meth) acrylate may be used according to one embodiment of the present application, but is not limited thereto.

When the adhesive polymer further includes a second monomer polymerization unit, for example, the second monomer polymerization unit may be included in an amount of 1 part by weight to 30 parts by weight, 5 parts by weight to 30 parts by weight, and 10 parts by weight based on 100 parts by weight of the adhesive polymer. To 30 parts by weight or 12 parts by weight to 30 parts by weight. In this range, the pressure-sensitive adhesive layer may exhibit the above-described loss or storage modulus range, and thus, even when adhered to a substrate having a surface step, it is possible to more effectively suppress bubble generation around the step difference.

The method for producing the adhesive polymer is not particularly limited and can be prepared in a conventional manner. The adhesive polymer may be polymerized by, for example, LRP (Living Radical Polymerization), for example, an alkali metal or an alkaline earth metal using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator. Anion polymerization method synthesized in the presence of an inorganic acid such as a salt of an anion, an anion polymerization method synthesized in the presence of an organoaluminum compound using an organoalkali metal compound as a polymerization initiator, an atom transfer radical using an atom transfer radical polymerizer as a polymerization control agent Polymerization (ATRP), activators regenerated by electron transfer (ARRP), which uses an atomic transfer radical polymerizer as a polymerization control agent and performs polymerization under an organic or inorganic reducing agent that generates electrons. Initiators for continuous activator regeneration ATRP), a reversible addition-cracking chain transfer polymerization method using an inorganic reducing agent reversible addition-cracking chain transfer agent (RAFT), or a method of using an organic tellurium compound as an initiator, and an appropriate method may be selected and applied. have.

The weight average molecular weight of the adhesive polymer may be, for example, 300,000 to 1 million, 300,000 to 900,000, or 300,000 to 800,000. In this range, the pressure-sensitive adhesive layer may exhibit the above-described loss or storage modulus range, and thus, even when adhered to a substrate having a surface step, it is possible to effectively suppress bubble generation around the step difference.

The pressure-sensitive adhesive layer may further include a crosslinking agent capable of crosslinking the adhesive polymer. The crosslinking agent may have at least one functional group capable of reacting with a crosslinkable functional group included in the adhesive polymer, and having from 1 to 10, 1 to 8, 1 to 6 or 1 to 4 Crosslinking agents can be used. As such a crosslinking agent, an appropriate kind may be selected and used in consideration of the kind of the crosslinkable functional group of the adhesive polymer among conventional crosslinking agents such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent or a metal chelate crosslinking agent.

As an isocyanate crosslinking agent, diisocyanate compounds, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethyl xylene diisocyanate, or naphthalene diisocyanate, and the said diisocyanate compound, Reactants such as polyols such as trimethylolpropane or isocyanurate adducts of the diisocyanate compounds may be exemplified, but preferably xylene diisocyanate or hexamethylene diisocyanate may be used, and epoxy crosslinking agent may be used. , Ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl ethylenediamine and glycerin diglycidyl ether It is at least one selected from can be illustrated.

Examples of aziridine crosslinkers include N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide ), Triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine) or tri-1-aziridinylphosphineoxide and the like can be exemplified, but is not limited thereto. Examples of the compound include a compound in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated with acetyl acetone, ethyl acetoacetate, or the like, but is not limited thereto.

For example, the crosslinking agent may be included in a ratio of 0.01 parts by weight to 10 parts by weight, 0.015 parts by weight to 5 parts by weight, 0.02 parts by weight to 2.5 parts by weight, or 0.025 parts by weight to 1 parts by weight with respect to 100 parts by weight of the adhesive polymer. The crosslinking agent may be adjusted to be included in the adhesive polymer in the aforementioned range so that the aforementioned loss or storage modulus is formed within a desired range.

The pressure-sensitive adhesive layer 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 silane coupling agents can, for example, enable the pressure-sensitive adhesive formed by a low molecular weight polymer to exhibit excellent adhesion and adhesion stability. When the pressure-sensitive adhesive layer further includes a silane coupling agent, the silane coupling agent may be included in an amount of 0.01 to 5 parts by weight or 0.01 to 1 part by weight with respect to 100 parts by weight of the adhesive polymer.

The pressure-sensitive adhesive layer may further contain a tackifier as necessary. As the tackifier, for example, a hydrocarbon resin or a hydrogenated substance thereof, a rosin resin or a hydrogenated substance thereof, a rosin ester resin or a hydrogenated substance thereof, a terpene resin or a hydrogenated substance thereof, a terpene phenol resin or a hydrogenated substance thereof, a polymerized rosin resin or One kind or a mixture of two or more kinds such as a polymerized rosin ester resin may be used, but is not limited thereto. A 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 pressure-sensitive adhesive polymer.

If necessary, the pressure-sensitive adhesive layer may further include one or more additives selected from the group consisting of a curing agent, an ultraviolet stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, and a plasticizer.

The method for producing the pressure-sensitive adhesive layer is not particularly limited and can be produced in a conventional manner. For example, the pressure-sensitive adhesive composition in which the pressure-sensitive polymer is present in a crosslinked state may be prepared by applying a conventional means to an appropriate process substrate and then curing. In the present application, the curing process is preferably performed after sufficiently removing the bubble-inducing components such as volatile components or reaction residues contained in the pressure-sensitive adhesive composition. As a result, the crosslinking density or molecular weight of the pressure-sensitive adhesive is too low, the elastic modulus is lowered, and bubbles present at the pressure-sensitive interface in the high temperature state become large, thereby preventing problems such as forming scattering bodies therein. The method of curing the pressure-sensitive adhesive composition is not particularly limited, and for example, curing through appropriate heating, drying and / or aging processes, or curing by electromagnetic radiation such as ultraviolet (UV) may be employed. Can be.

[2nd base material layer and 2nd electroconductive layer]

The conductive laminate may further include a second base layer and a second conductive layer. Hereinafter, the base material layer and the conductive layer mentioned above are called a 1st base material layer and a 1st conductive layer, respectively, for classification. 2 exemplarily shows a structure of the conductive laminate 2 according to the second embodiment of the present application. As shown in FIG. 2, the conductive laminate 2 includes a first base layer 101; A first conductive layer 201 formed on one surface of the first base layer 101; And the pressure-sensitive adhesive layer 30 adhered to a surface on which the first conductive layer of the first base layer is not formed. In addition, the conductive laminate 2 includes a second substrate layer 102 and a second conductive layer 202 formed on one surface of the second substrate layer 102 and having a surface step 2021. In addition, the surface on which the first conductive layer of the first base layer 101 is not formed and the surface having the step difference between the second conductive layer 202 may be present in a state of being attached by the adhesive layer 30. have.

As used herein, the term "surface step" may mean a difference in height of the surface (illustrated by H in FIG. 2). The level difference of the surface of a 2nd electroconductive layer may be derived from the pattern electrode used for the touch panel mentioned later, for example. The pattern shape of the pattern electrode is not particularly limited and may be, for example, a mesh shape or a shape in which electrodes having a polygonal or circular cross section are spaced apart from each other. In addition, the material of a pattern electrode is not specifically limited, For example, any one of silver (Ag), aluminum (Al), copper (Cu), chromium (Cr), nickel (Ni), and molybdenum (Mo) or these It may be an alloy of. In another example, the step on the surface of the second conductive layer may be a printed step, for example, to improve the design of the screen.

The thickness of the surface step of the second conductive layer is not particularly limited and may be appropriately selected depending on the application to which the configuration causing the surface step is applied, but may generally be in the range of about 1 um to 150 um. The thickness range of the pressure-sensitive adhesive layer is not particularly limited, but may be, for example, within a range of 15 um to 30 um. In another example, the thickness of the pressure-sensitive adhesive layer may have a thickness range of about 2 μm or more, for example, compared to the thickness of the surface step. When the thickness of the pressure-sensitive adhesive layer 30 is in the above range, it is possible to effectively reduce the generation of bubbles in the peripheral portion (shown as A of FIG. 2) of the surface of the second conductive layer.

The conductive laminate includes the above-described base layer, the conductive layer and the pressure-sensitive adhesive layer as basic units, and if necessary, other elements usually applied to the formation of the conductive laminate, for example, a transparent sheet layer, a release film layer, a hard coating layer, or the like. It may further include.

The present application also relates to the use of the conductive laminate. The conductive laminate of the present application can be used, for example, in the configuration of a touch panel. The touch panel may include the conductive laminate as, for example, an electrode plate for a touch panel. In addition, the pattern electrode described above can function as a touch sensor. As long as the touch panel includes the conductive laminate, the touch panel may be formed in a known structure including a capacitive type or a resistive film type. The conductive laminate can be used for forming not only a touch panel but also various devices such as a liquid crystal display.

The conductive laminate of the present application can suppress the generation of bubbles around the stepped portion even when adhered to a substrate having a surface level, so that the appearance and performance of the product to which the conductive laminate is applied can be maintained. Such a conductive laminate can be usefully used, for example, in a touch panel.

1 is a schematic diagram of a conductive laminate of a first embodiment of the present application.
It is a schematic diagram of the electroconductive laminated body of 2nd Example of this application.

Hereinafter, the present application will be described in more detail with reference to examples according to the present application and comparative examples not according to the present application, but the scope of the present application is not limited to the examples given below.

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 under the following conditions using GPC, and the measurement results were converted using standard polystyrene of Agilent system for the production of calibration curves.

<Measurement conditions>

Meter: Agilent GPC (Agilent 1200 series, U.S.)

Column: Connect 2 PL Mixed B

Column temperature: 40 ℃

Eluent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

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

2. Loss modulus evaluation

After coating the pressure-sensitive adhesive composition prepared in Examples and Comparative Examples between the release film and cut to a size of 15 cm × 25 cm, remove the release film on one side, and laminated five times, so that the thickness was about 1mm. Subsequently, the laminate was cut into a circle having a diameter of 8 mm, compressed using glass, and left overnight to improve wetting at the interface between the layers, thereby improving bubbles produced during lamination. The sample was prepared by removal. Subsequently, the sample was placed on a parallel plate, the gap was adjusted, the zero point of Normal & Torque was set, the stability of the normal force was confirmed, and then the loss modulus was measured.

Measuring instruments and measuring conditions

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

Measuring conditions:

geometry: 8 mm parallel plate

Thickness: about 1 mm

test type: dynamic strain frequency sweep

Strain = 10.0 [%], temperature: 50 ° C

Initial frequency: 0.1 rad / s, Final frequency: 1 rad / s

3. Step  Characteristic evaluation (1)

A transparent conductive laminate (thickness: about 50 um) in which an ITO layer (width x length = 10 cm x 10 cm thickness: 2 nm) was formed on a PET film (width x length = 10 cm x 10 cm thickness: 50 um) in a conventional manner was approximately. After annealing in an oven at 150 ° C. for about 1 hour, Ag paste (width × vertical = 1 cm x 10 cm, thickness: 18 μm) was applied onto the ITO layer of the heat-treated transparent conductive laminate, and then in an oven at about 150 ° C. Heat treatment for 30 minutes. Next, after applying the adhesive layer of the conductive laminates prepared in Examples and Comparative Examples to contact the surface on which the Ag paste of the transparent conductive laminate is formed, bubbles were observed in the periphery of the step through an optical microscope.

O: Bubbles are not confirmed by the naked eye.

Δ: fine bubbles are visually observed

X: Large bubbles observed with the naked eye

4. Step  Characteristic evaluation (2)

6 kgf / cm ² of the specimen of step characteristic evaluation (1) for 30 minutes at 50 ℃ After autoclave-processing on conditions, the bubble was observed in the periphery of a step | step through an optical microscope.

O: Bubbles are not confirmed by the naked eye.

Δ: fine bubbles are visually observed

X: Large bubbles observed with the naked eye

Production Example  1. Preparation of Adhesive Polymer (A1)

80 parts by weight of 2-ethylhexyl acrylate (EHA), 10 parts by weight of methyl acrylate (MA), and 2-hydroxyethyl acryl in a 1L reactor equipped with a refrigeration system under nitrogen gas reflux and a cooling device for easy temperature control. 10 parts by weight of HEA was added. Subsequently, 100 parts by weight of ethyl acetate (EAc) was added as a solvent, purged with nitrogen gas for 60 minutes to remove oxygen, and then azobisisobutyronitrile as a reaction initiator while maintaining the temperature at 60 ° C. 0.06 parts by weight of (AIBN) was added to initiate the reaction. Thereafter, the reaction product reacted for about 5 hours was diluted with ethyl acetate (EAc) to prepare a tacky polymer (A1).

Production Example  2 to Production Example  5. Preparation of Sticky Polymers (A2 to A3 and B1 to B2)

Adhesive polymers (A2 to A3 and B1 to B2) were prepared in the same manner as in Preparation Example 1 except that the types of raw materials and additives used in the polymerization of the adhesive polymer (A1) in Preparation Example 1 were adjusted as shown in Table 1 below. ) Was prepared.

Raw material EA
V-65
EHA MA BA IBOA HEA
Sticky
polymer A1 80 10 - - 10 100 0.2 A2 90 - - - 10 100 0.15 A3 90 - - - 10 100 0.2 B1 50 40 - - 10 100 0.06 B2 - - 55 30 15 100 0.06 Content Unit: g
BA: n-butyl acrylate
IBOA: isobornyl acrylate
MA: (meth) acrylate
HEA: 2-hydroxyethyl acrylate
EHA: 2-ethylhexyl acrylate
EA: ethyl acetate
V-65: 2,2'-azobis (2,4-dimethyl valeronitrile)

Example  One

Preparation of pressure-sensitive adhesive composition

The pressure-sensitive adhesive composition was prepared by uniformly mixing 0.25 parts by weight of "Takenate D110N" (Mitsui Chemical Co., Ltd.), which is xylene diisocyanate, as a crosslinking agent with respect to 100 parts by weight of the adhesive polymer (A1) solids prepared in Preparation Example 1.

Conductivity Laminate  Produce

After release treatment with silicone on one surface of the PET film, the pressure-sensitive adhesive layer was formed by coating and curing the prepared pressure-sensitive adhesive composition to have a thickness of about 25 μm. Thereafter, the pressure-sensitive adhesive layer was transferred to an opposite surface of a PET film (thickness: about 25 μm) having an ITO layer formed on one surface in a conventional manner, and the release-treated PET film was peeled off to prepare a conductive laminate.

Example  2

An adhesive composition and an adhesive film were prepared in the same manner as in Example 1 that the adhesive polymer included in the adhesive composition of Example 1 was added as A2.

Example  3

An adhesive composition and an adhesive film were prepared in the same manner as in Example 1 that the adhesive polymer included in the adhesive composition of Example 1 was added to A3.

Comparative example  One

An adhesive composition and an adhesive film were prepared in the same manner as in Example 1 that the adhesive polymer included in the adhesive composition of Example 1 was added to B1.

Comparative example  2

An adhesive composition and an adhesive film were prepared in the same manner as in Example 1 that the adhesive polymer included in the adhesive composition of Example 1 was added to B2.

Physical properties and evaluation results measured for the above Examples and Comparative Examples are as shown in Table 2 below.

division Example Comparative example One 2 3 One 2 Molecular weight (unit: only) 56 42 74 110 120 Storage modulus (× 10 ⁴ )
(Unit: pa) 0.9 0.5 0.6 7.7 8.8 Step evaluation (1) △ ○ ○ X X Step evaluation (2) ○ ○ ○  X X

As confirmed from Table 2, in the case of the conductive laminate of the present application, by having a storage elastic modulus within a specific range, it is possible to effectively suppress the generation of bubbles at the stepped periphery.

101 and 102: first and second substrate layers
201 and 202: second and second conductive layers
2021: step
30: adhesive layer
H: step thickness
A: step periphery

Claims (21)

A first base layer;
A first conductive layer formed on one surface of the first base layer;
An adhesive layer attached to a surface on which the first conductive layer of the first base layer is not formed, and having a loss modulus of 0.50 x 10 ⁴ Pa or less at a temperature of 50 ° C. and a frequency of 1 rad / sec;
Second substrate layer;
A second conductive layer formed on one surface of the second substrate layer and having a surface level difference,
The surface on which the first conductive layer of the first base layer is not formed and the surface having the step difference between the second conductive layer are present in a state of being attached by the pressure-sensitive adhesive layer, and the surface level of the second conductive layer is 2 derived from the pattern electrode formed on the surface of the conductive layer,
The thickness of the first conductive layer and the second conductive layer is in the range of 10nm to 300nm, respectively, the thickness of the surface step is in the range of 1um to 150um,
The pressure-sensitive adhesive layer includes an adhesive polymer in a crosslinked state, the adhesive polymer includes a first monomer polymerization unit and a crosslinkable monomer polymerization unit having an alkyl group having 5 or more carbon atoms, and the first monomer polymerization unit is 100 weight of the adhesive polymer. Electroconductive laminated body contained in the ratio of 70 weight part or more with respect to parts. The method of claim 1,
The first base layer is at least one conductive laminate selected from the group consisting of a glass substrate, a polyester film, a polyamide film, a polyvinyl chloride film, a polystyrene film, and a polyolefin film. The method of claim 1,
The first conductive layer comprises gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, indium oxide, tin oxide, titanium oxide, cadmium oxide or copper iodide. The method of claim 1,
The first conductive layer is a conductive laminate formed on one surface of the first or second substrate layer via an anchor layer or a dielectric layer. The method of claim 1,
The pressure-sensitive adhesive layer is a conductive laminate having a loss modulus of 0.1 × 10 ⁴ Pa or more at a temperature of 50 ° C. and a frequency of 1 rad / sec. The method of claim 1,
The pressure-sensitive adhesive layer is a conductive laminate having a storage modulus at a temperature of 50 ° C. and a frequency of 1 rad / sec of 1.0 × 10 ⁴ Pa or less. delete The method of claim 1,
The adhesive polymer has a weight average molecular weight in the range of 300,000 to 1 million, conductive laminate. delete The method of claim 1,
The first monomer is an alkyl (meth) acrylate having a branched or straight chain alkyl group having 5 or more carbon atoms. delete The method of claim 1,
The crosslinkable monomer is a conductive laminate comprising 1 to 30 parts by weight relative to 100 parts by weight of the adhesive polymer. The method of claim 1,
The adhesive polymer further comprises a second monomer polymerization unit having an alkyl group having 1 to 4 carbon atoms. The method of claim 13,
The second monomer is an alkyl (meth) acrylate having a branched or straight chain alkyl group having 1 to 4 carbon atoms. The method of claim 13,
The second monomer is a conductive laminate comprising 1 to 30 parts by weight relative to 100 parts by weight of the adhesive polymer. The method of claim 1,
The adhesive layer further comprises 0.01 to 10 parts by weight of a crosslinking agent based on 100 parts by weight of the adhesive polymer. delete delete The method of claim 1,
The pattern electrode includes any one of silver (Ag), aluminum (Al), copper (Cu), chromium (Cr), nickel (Ni), molybdenum (Mo), or an alloy thereof. The method of claim 1,
The thickness of an adhesive layer is 2 micrometers or more thick electroconductive laminate compared with the thickness of a surface level | step difference. A touch panel comprising the conductive laminate of claim 1.

Images