JP2001262088A - Pressure-sensitive adhesive tape for protecting antireflection film, antireflection film with protective film, and method for producing antireflection film with transparent conductive thin-film circuit pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an antireflection film with a transparent conductive thin-film pattern at cost reduced by mass production and to provide a pressure-sensitive adhesive tape for an antireflection film, excellent in heat resistance and chemical resistance required in protecting an antireflection film in the above method and excellent in, especially, chemical resistance on exposure to a treating solution used for the development peel of a photoresist in a photoetching process and on exposure to a treating solution used for etching a transparent conductive thin-film. SOLUTION: An antireflection film 21 is protected with a pressure-sensitive film 1 prepared by forming a pressure-sensitive adhesive layer 11 having excellent chemical resistance and formed by curing an acrylic copolymer comprising essentially consisting of a (meth)acrylic ester monomer with a 1-12C alkyl and a functional-group-containing monomer with a curing agent on a support 12, and a circuit pattern is formed on the back transparent conductive thin-film 23.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an antireflection film having a transparent conductive thin film, and more particularly to a method for protecting an antireflection film in a step of forming a circuit pattern of the transparent conductive thin film, and a method for protecting the same. It relates to a suitable adhesive film.

[0002]

2. Description of the Related Art In recent years, a liquid crystal display element has attracted attention as an image display device, and one of its uses is expected to be applied to a portable electronic notebook, an information terminal, and the like. Screen input devices such as these portable electronic notebooks and information terminals are generally used in which a transparent touch panel is mounted on a liquid crystal display element, particularly in combination with a resistive touch panel in terms of price and the like. ing.

As a film used on the input surface of such a resistive touch panel, a hard coat layer having excellent scratch resistance is provided on one surface of a transparent polymer film, and a transparent conductive thin film circuit is provided on the other surface. A film provided with a pattern is generally used.

On the other hand, in a liquid crystal display device without a screen input device, an anti-reflection treatment is performed on the outermost surface of the display device as a method of improving a decrease in visibility due to surface reflection.

However, when these antireflection treatments are applied to the film surface of the touch panel, the scratch resistance of the surface provided with the antireflection film is reduced, and a film which can be practically used cannot be obtained. The fact is that it is not applied to the surface.

In recent years, attempts have been made to improve the abrasion resistance of the anti-reflection film, and some high-end models have performed a surface treatment of the anti-reflection film in the final step. In reality, it is not very popular.

In recent years, attempts have been made in recent years to mass-produce such an anti-reflection film by continuously performing surface treatment in an initial stage of a production process, thereby realizing a low price of the anti-reflection treatment. I have.

However, such an antireflection film also has insufficient scratch resistance and chemical resistance, and its performance can be maintained in the step of forming a circuit pattern of the transparent conductive thin film as described above. It was impossible.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a method capable of reducing the cost by mass-producing an antireflection film with a transparent conductive thin film circuit pattern, and Heat treatment and chemical resistance required for protecting the anti-reflection film in the method, in particular, a treatment liquid used for developing and removing a photoresist in a photoetching method and a treatment liquid used for etching a transparent conductive thin film An object of the present invention is to provide an adhesive film for protecting an anti-reflection film having excellent chemical resistance to the film.

[0010]

The pressure-sensitive adhesive film for protecting an anti-reflection film of the present invention which achieves the above object is provided with a processing solution used for developing and removing a photoresist on a substrate and for etching a transparent conductive thin film. Characterized in that a pressure-sensitive adhesive layer having resistance to the processing liquid used for the above is provided.

Further, in the pressure-sensitive adhesive film for protecting an antireflection film of the present invention, the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer obtained by curing at least an acrylic copolymer with a curing agent, and the acrylic copolymer is at least an alkyl compound. It is characterized by comprising a (meth) acrylate monomer having 1 to 12 carbon atoms and a functional group-containing monomer.

The pressure-sensitive adhesive film for protecting an antireflection film of the present invention is characterized in that the polymerization ratio of the (meth) acrylate monomer and the functional group-containing monomer constituting the acrylic copolymer is (meth) acrylate monomer. The functional group-containing monomer is used in an amount of 1 to 30 parts by weight with respect to 100 parts by weight.

Further, the pressure-sensitive adhesive film for protecting an antireflection film of the present invention is characterized in that a macromonomer is copolymerized as another monomer copolymerized with the acrylic copolymer.

In the pressure-sensitive adhesive film for protecting an antireflection film according to the present invention, the macromonomer has a monoethylenically unsaturated group as a terminal polymerizable functional group and a polydimethylsiloxane having a polydimethylsiloxane as a high molecular weight skeleton component. It is characterized by being siloxane methacrylate.

Further, the antireflection film with a protective film of the present invention is characterized in that the antireflection film is protected by an adhesive film for protecting the antireflection film.

Further, the antireflection film with a protective film of the present invention is characterized in that the outermost layer of the antireflection film is a silicon oxide-based thin film.

Further, the antireflection film with a protective film of the present invention is characterized in that the antireflection film is provided on a transparent polymer film.

The antireflection film with a protective film of the present invention is characterized in that a transparent conductive thin film is provided on the back surface of the surface of the transparent polymer film on which the antireflection film is provided. It is.

Further, the antireflection film with a protective film of the present invention is characterized in that the transparent conductive thin film is mainly composed of indium oxide, tin oxide or indium tin oxide.

Further, the antireflection film with a protective film of the present invention is characterized in that the transparent conductive thin film is formed by removing unnecessary portions by photoetching to form a transparent conductive thin film circuit pattern. Things.

Further, the method for producing an antireflection film with a transparent conductive thin film circuit pattern according to the present invention comprises the steps of: providing an antireflection film having an antireflection film on one surface of a transparent polymer film; After affixing the adhesive film for film protection, a transparent conductive thin film is provided on the back surface of the transparent polymer film on which the antireflection film is provided, and then unnecessary portions of the transparent conductive thin film are removed by etching using a photoetching method. And forming a circuit pattern on the transparent conductive thin film.

Further, the method for producing an antireflection film with a transparent conductive thin film circuit pattern according to the present invention is directed to a reflection method in which a transparent polymer film has an antireflection film on one surface and a transparent conductive thin film on the other surface. After sticking an adhesive film for protecting the anti-reflection film on the anti-reflection film of the anti-reflection film, an unnecessary portion of the transparent conductive thin film is removed by etching using a photo-etching method to form a circuit pattern on the transparent conductive thin film. It is a feature.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an adhesive film 1 for protecting an antireflection film according to the present invention will be described with reference to FIG.

The pressure-sensitive adhesive film 1 for protecting an antireflection film of the present invention.
Is provided with a pressure-sensitive adhesive layer 11 having a resistance to a processing liquid used for developing and peeling a photoresist and a processing liquid used for etching a transparent conductive thin film on a base material 12 and supporting the pressure-sensitive adhesive layer if necessary. The body is provided on the adhesive layer 11 so as to be peelable.

Therefore, as a specific embodiment of the pressure-sensitive adhesive film 1 for protecting an antireflection film of the present invention, the pressure-sensitive adhesive layer 11 obtained by curing at least an acrylic copolymer with a curing agent is used as the base material 1.
2. The protective adhesive film 1 provided on 2 above, wherein the acrylic copolymer has at least one alkyl group having 1 carbon atom.
(Meth) acrylic acid ester monomers having a molecular weight of 12 and a functional group-containing monomer. Thus, at least the alkyl group has 1 to 12 carbon atoms (meth)
By curing an acrylic copolymer composed of an acrylate monomer and a functional group-containing monomer with a curing agent, the adhesive layer 11 can have excellent heat resistance and chemical resistance, and can have a transparent conductive thin film. Good removability can be maintained even after the circuit pattern formation step.

Here, the photoresist is a photosensitive resin for forming an etching-resistant thin film by light irradiation to partially etch a metal or the like. The transparent conductive thin film is a transparent conductive thin film described later. A substance formed into a thin film. Therefore, the treatment liquid used for developing and removing the photoresist refers to an alkali such as sodium carbonate and sodium hydroxide, and the treatment liquid used for etching the transparent conductive thin film refers to an acid such as hydrochloric acid.

Here, as a method of providing the pressure-sensitive adhesive layer 11 on the base material 12, a coating solution is prepared by appropriately adding an organic solvent or the like to a mixture of an acrylic copolymer and a curing agent. A method obtained by applying the composition on the base material 12 and curing by heating and drying can be adopted.

Here, the substrate 12 on which the pressure-sensitive adhesive layer 11 obtained by curing at least the acrylic copolymer with a curing agent is not particularly limited as long as it has excellent heat resistance, chemical resistance and the like. However, a transparent polymer film such as a biaxially stretched polyethylene terephthalate film which is excellent in mechanical strength and the like is preferable.

The support provided on the pressure-sensitive adhesive layer 11 in a releasable manner is not particularly limited as long as it can be peeled off without impairing the performance of the pressure-sensitive adhesive layer 11, but is preferably not limited to the above. Those obtained by subjecting the surface of a transparent polymer film or the like to a release treatment such as a silicone release agent can be used.

The monomer for copolymerizing the acrylic copolymer has at least an alkyl group having 1 to 1 carbon atom.
It is preferable that the copolymer is composed of a (meth) acrylic acid ester monomer and a monomer having a functional group of 12, and it is more preferable to copolymerize another monomer, and it is particularly preferable to copolymerize a macromer. As described above, the performance as a basic acrylic pressure-sensitive adhesive is maintained by the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, and the functional group-containing monomer is crosslinked and cured by the curing agent. Thus, heat resistance and chemical resistance can be obtained in the pressure-sensitive adhesive layer 11. Further, those having another monomer such as a macromonomer can easily improve the heat resistance and the chemical resistance of the pressure-sensitive adhesive layer 11.

The (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms includes methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, and 2- (meth) acrylate. Ethyl hexyl, octyl acrylate, cyclohexyl acrylate, acrylates such as benzyl acrylate, and methacrylates such as butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and the like. These can be used alone or in combination of two or more.

Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid. ) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, N-methylolacrylamide, hydroxy-containing monomers such as allyl alcohol, dimethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Amino-group-containing monomers, amide group-containing monomers such as acrylamide and methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylia De, N-t-butyl acrylamide, N- substituted amide group-containing monomers such as N- octyl acrylamide.

The polymerization ratio of the (meth) acrylate monomer and the functional group-containing monomer constituting these acrylic copolymers is such that the functional group-containing monomer is 1 to 100 parts by weight of the (meth) acrylate monomer. ~ 30
It is desirable that the amount be 5 parts by weight, preferably 5 to 15 parts by weight. If it is less than 1 part by weight, heat resistance may be impaired, and if it exceeds 30 parts by weight, chemical resistance may be poor.

The acrylic copolymer has a weight average molecular weight of 200,000 to 3,000,000, preferably 300,000 to 2,000,000. When the weight average molecular weight is 200,000 or more, a decrease in cohesive strength can be prevented, and when the weight average molecular weight is 3,000,000 or less, a sufficient initial adhesive strength can be obtained.

Other monomers to be copolymerized include vinyl acetate, vinyl propionate, vinyl ether, styrene, acrylonitrile, methacrylonitrile and the like, and preferably high molecular weight monomers having a polymerizable functional group at the terminal. Macromonomers can be mentioned.

The terminal polymerizable functional group includes a monoethylenically unsaturated group, and the high molecular weight skeleton component includes polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, and polymethacrylic. Butyl acrylate, polyisobutyl methacrylate, methyl methacrylate-hydroxymethyl methacrylate copolymer,
Examples include 2-ethylhexyl methacrylate-hydroxyethyl methacrylate copolymer, polydimethylsiloxane, and the like. The monoethylenically unsaturated group, which is a polymerizable functional group at the terminal, and a high molecular weight skeleton component can be freely combined. be able to.

Here, particularly suitable as the pressure-sensitive adhesive film for protecting the antireflection film of the present invention are those having a monoethylenically unsaturated group as a terminal polymerizable functional group and a polydimethylsiloxane as a high molecular weight skeleton component. And polydimethylsiloxane methacrylate having the formula: Thus, the pressure-sensitive adhesive layer 11 obtained by curing the acrylic copolymer obtained by copolymerizing polydimethylsiloxane methacrylate as another monomer component with a curing agent can enhance the water repellency of the pressure-sensitive adhesive layer 11 itself. In the step of forming a circuit pattern on the transparent conductive thin film on the back surface of the surface provided with the anti-reflection film 21 by protecting the anti-reflection film 21 using the adhesive film for protecting the anti-reflection film provided with the same. An anti-reflection film 21 can be more effectively removed from a processing solution such as an alkali used for developing and removing a photoresist and an acid used for etching a transparent conductive thin film.
Can be protected.

The polymerization ratio of the other monomer copolymerized with the acrylic copolymer is a total of 100% of the (meth) acrylate monomer and the functional group-containing monomer.
It is desirable that the amount is 0 to 30 parts by weight, preferably 1 to 15 parts by weight based on parts by weight. If it exceeds 30 parts by weight, it may be difficult to control the adhesive strength.

As the curing agent contained in the pressure-sensitive adhesive layer 11, an appropriate one such as an isocyanate compound, an epoxy compound, a metal chelate compound, a metal salt, an amine compound, a hydrazine compound and an aldehyde compound is used. It can be used in accordance with the type of the functional group-containing monomer to be copolymerized with the copolymer, whereby the acrylic copolymer is cured and becomes excellent in heat resistance and chemical resistance.

The thickness of the pressure-sensitive adhesive layer 11 and the substrate 12 is not particularly limited, but the thickness of the substrate 12 is 4 to 250 μm, preferably 25 to 200 μm.
And the thickness of the pressure-sensitive adhesive layer 11 is 1 to 30 μm,
Preferably it is 5 to 15 μm.

Next, the antireflection film 2 with a protective film of the present invention will be described with reference to FIGS.

The antireflection film 2 with a protective film of the present invention is one in which the antireflection film 21 is protected by the antireflection film protecting adhesive film 1 of the present invention. As a result, the anti-reflection film 21 is made of an alkali or transparent conductive thin film 23 used for developing and removing the photoresist in the step of forming a transparent conductive thin film circuit pattern provided on the back surface of the surface on which the anti-reflection film 21 is provided. Is suitably protected from a processing solution such as an acid used for etching.

The anti-reflection film 21 of the present invention is provided on the transparent polymer film 22, has transparency in the visible light range, and reflects light by utilizing the interference of light at the layer interface. Is a layer having the ability to cancel out. Here, the transparent polymer film 22 is not particularly limited as long as it has excellent transparency, and the above-described biaxially stretched polyethylene terephthalate film is suitably used, and appropriately improves the scratch resistance of the antireflection film 21. A material provided with a hard coat layer for the purpose, a material provided with an undercoat layer for improving the adhesiveness to the antireflection film 21, and the like can be used.

As such an anti-reflection film 21, a low-refractive-index layer having high transparency is formed by simply providing an optical film thickness of １ ／ of the wavelength with respect to a specific wavelength (a main wavelength for anti-reflection). In addition to the layer anti-reflection film, a multi-layer anti-reflection film in which a high refractive index layer, a medium refractive index layer, and a low refractive index layer having an optical thickness based on a specific wavelength are appropriately laminated on the low refractive index layer. Can be. Here, the optical film thickness is a film thickness determined by a product nd of a refractive index n of the film and a mechanical film thickness d.

Examples of the method for forming the antireflection film 21 include a vacuum film forming method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a coating method such as a blade coater method, a rod coater method, and a gravure coater method. Can be adopted.

Here, in the vacuum film forming method, as a material constituting the low refractive index layer, oxides of Si, Li, Na, M
g, Al, Ca and other fluorides. Examples of the material constituting the high refractive index layer include Ti, Cr, Zr, Ni, and Mo.
Alone, Ti, Zn, Y, Zr, In, Sn, Sb,
Oxides such as Hf, Ta, Ce, Pr, and Nd;
Materials constituting the middle refractive index layer include La, Nd, and Pb.
And the like.

In the coating method, as a material constituting the low refractive index layer, a resin into which a fluorine atom is introduced, an organic silicon compound, a resin in which low refractive index fine particles such as magnesium fluoride and silica are dispersed, and the like. Examples include silicon oxide sol prepared by hydrolyzing silicon alkoxide, and as a material constituting the high refractive index layer, an atom such as halogen other than fluorine, sulfur, nitrogen, phosphorus, or an aromatic ring is introduced. Resin, a resin in which high refractive index fine particles composed of a metal oxide or the like are dispersed, a metal oxide sol prepared by hydrolyzing a metal alkoxide other than silicon, and the like, and examples of a material constituting the middle refractive index layer include An appropriate material having an intermediate refractive index between these materials can be employed.

In particular, the effect of protecting the anti-reflection film 21 with the anti-reflection film protective pressure-sensitive adhesive film 1 of the present invention is as follows: the outermost layer of the anti-reflection film is provided with an oxide of Si by a vacuum film forming method; This is exerted when a silicon oxide-based thin film such as one provided with a material such as a silicon oxide sol prepared by hydrolyzing an alkoxide by a coating method.

As shown in FIG. 3, the antireflection film 2 with a protective film of the present invention
The transparent conductive thin film 23 is provided on the back surface of the surface on which the antireflection film 21 is provided.

The transparent conductive thin film 23 is made of a transparent conductive material typified by indium oxide, tin oxide, indium tin oxide, gold, silver, palladium, etc. by a vacuum evaporation method, a sputtering method, an ion plating method, or the like. A material formed by a solution coating method or the like is used, and in particular, a material mainly containing any of indium oxide, tin oxide, and indium tin oxide, which is excellent in transparency and conductivity and obtained at a relatively low cost, is preferably used. Is done. And this transparent conductive thin film 2
3 includes those in which unnecessary portions are removed by etching using a photoetching method to form a transparent conductive thin film circuit pattern.

Here, the photo-etching method is to provide a photoresist layer 4 on a transparent conductive thin film 23 by a solution coating method or a dry film laminating method as shown in FIG. Baking the circuit pattern, developing the photoresist layer 4 using a weak alkali such as sodium carbonate to form an etching resist,
Then, the transparent conductive thin film 23 is etched off using an acid such as hydrochloric acid, and the photoresist layer 4 is peeled off using a strong alkali such as sodium hydroxide to form a transparent conductive thin film circuit pattern. Say.

Next, a method for producing the antireflection film 3 with a transparent conductive thin film circuit pattern of the present invention will be described.

The method for producing the antireflection film 3 with a transparent conductive thin film circuit pattern according to the present invention comprises the steps of: forming an antireflection film 21 having an antireflection film 21 on one surface of a transparent polymer film 22; After the adhesive film 1 for protecting an anti-reflection film is attached, a transparent conductive thin film 23 is provided on the back surface of the transparent polymer film 22 on which the anti-reflection film 21 is provided, and then unnecessary portions of the transparent conductive thin film 23 are removed. The circuit pattern is formed on the transparent conductive thin film 23 by etching and removing by a photoetching method. Alternatively, the antireflection film 2 is formed on one surface of the transparent polymer film 22.
After the adhesive film 1 for protecting the anti-reflection film is adhered on the anti-reflection film 21 of the anti-reflection film having the transparent conductive thin film 23 on the other surface, the transparent conductive thin film 23
The unnecessary portions are removed by etching using a photoetching method to form a circuit pattern on the transparent conductive thin film 23.

By forming a circuit pattern on the transparent conductive thin film 23 as described above, the anti-reflection film 21
In the step of forming a circuit pattern on the transparent conductive thin film 23 on the back surface, a treatment liquid such as an alkali used for development and peeling of the photoresist layer 4 and an acid used for etching the transparent conductive thin film 23 and scratches. As a result, the adhesive film 1 for protecting the anti-reflection film 1 is peeled off from the anti-reflection film 21 so that the anti-reflection film 3 with the transparent conductive thin-film circuit pattern having the anti-reflection film 21 maintaining excellent performance can be obtained. Can be obtained.

[0055]

Embodiments of the present invention will be described below.
The “parts” and “%” are based on weight unless otherwise specified.

1. Synthesis of Acrylic Copolymer [Synthesis Example 1] 15.0 g of butyl acetate and 15.0 g of toluene were placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and stirred while passing through nitrogen.
Heated to ° C. In a separate container, 90.0 g of 2-ethylhexyl acrylate monomer, 6.0 g of 2-hydroxyethyl methacrylate monomer, 4.0 g of acrylic acid monomer,
α, α'-azobis (isobutyronitrile) 0.13
g, 15.0 g of butyl acid acid and 15.0 g of toluene were added dropwise to the reaction vessel over 1 hour and 30 minutes. Thereafter, the reaction was completed over a period of 6 hours and 30 minutes while stirring the reaction solution at 80 ° C. to synthesize an acrylic copolymer. 20.0 g of butyl acetate was added to this reaction solution,
Acrylic copolymer solution A having a solid content of 50% was prepared by adding 20.0 g of toluene.

[Synthesis Example 2] As monomers to be mixed in another container of Synthesis Example 1, 6.0 g of 2-hydroxyethyl methacrylate monomer was changed to 5.0 g, and 4.0 g of acrylic acid monomer was changed to 3.0 g. An acrylic copolymer was synthesized in the same manner as in Synthesis Example 1 except that 2.0 g of polydimethylsiloxane methacrylate macromonomer (AK-32: Toagosei Co., Ltd.) was separately added to prepare an acrylic copolymer solution B. did.

2. Example 1 Preparation of a pressure-sensitive adhesive film for protecting an anti-reflection film [Example 1] A coating solution for a pressure-sensitive adhesive layer having the following composition on one surface of a polyethylene terephthalate film 12 (diafoil T-600E: Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 50 µm. Was applied and dried at 110 ° C. for 5 minutes to form a pressure-sensitive adhesive layer 11 having a dry film thickness of 7 μm, thereby producing the pressure-sensitive adhesive film 1 for protecting the antireflection film shown in FIG. <Coating solution for adhesive layer> ・ Acrylic copolymer solution A 20 parts ・ Isocyanate curing agent (Takenate D110N <solid content 75%>: Takeda Pharmaceutical Co., Ltd.) 0.46 parts ・ Ethyl acetate 30 parts ・ Toluene 30 copies

Example 2 The antireflection coating of FIG. 1 was prepared in the same manner as in Example 1 except that the coating liquid for an adhesive layer having the following composition was used instead of the coating liquid for an adhesive layer used in Example 1. An adhesive film 1 for film protection was produced. <Coating solution for pressure-sensitive adhesive layer>-Acrylic copolymer solution B 20 parts-Isocyanate-based curing agent (Takenate D110N <solid content 75%>: Takeda Pharmaceutical Co., Ltd.) 0.37 parts-Ethyl acetate 30 parts-Toluene 30 copies

3. Production of Antireflection Film with Protective Film [Example 3] On one surface, the outermost layer was made of Si having a thickness of 85 nm.
The anti-reflection film 21 of the polyethylene terephthalate film 22 (Cosmo Shine A4300: Toyobo Co., Ltd.) having the anti-reflection film 21 which is an O ₂ film (refractive index: 1.46)
The anti-reflection film-protecting pressure-sensitive adhesive film 1 obtained in Example 1 was adhered thereon via the pressure-sensitive adhesive layer 11, and the anti-reflection film-protecting pressure-sensitive adhesive film 1 of the present invention protected the anti-reflection film 21. The antireflection film 2 with a protective film of FIG. 2 was produced.

Example 4 A polyethylene terephthalate film 22 opposite to the surface on which the antireflection film 21 of the antireflection film 2 with a protective film of Example 3 was provided.
The surface has a surface resistance of 500Ω using a sputtering method.
A transparent conductive thin film 23 of indium tin oxide (ITO) was provided to prepare the antireflection film 2 with a protective film in FIG.

Example 5 One surface had a surface resistance of 50.
It has a transparent conductive thin film 23 of indium tin oxide (ITO) of 0 Ω / □, and the outermost layer has a thickness of 85 on the other surface.
polyethylene terephthalate film 22 having an antireflection film 21 which is a SiO ₂ film (refractive index: 1.46)
(Cosmo Shine A4300: Toyobo Co., Ltd.), the anti-reflection film protecting pressure-sensitive adhesive film 1 obtained in Example 2 was adhered via the pressure-sensitive adhesive layer 11 on the anti-reflection film 21 to prevent the anti-reflection of the present invention. The antireflection film 2 with the protective film of FIG. 3 in which the antireflection film 21 was protected by the film protecting adhesive film 1 was produced.

4. Production of antireflection film with transparent conductive thin film circuit pattern [Example 6] After sticking the antireflection film protective adhesive film 1 on the antireflection film 21 in the same manner as in Example 3, the same procedure as in Example 4 was performed. A transparent conductive thin film 23 was provided. Next, as shown in FIG. 4, an unnecessary portion of the transparent conductive thin film 23 is removed by etching using a photoetching method as described below to form a circuit pattern on the transparent conductive thin film 23. The anti-reflection film 3 was produced. = Photo-etching method = I. Dry film 4 (ALPHO601Y3) on conductive thin film 23
3: Nippon Synthetic Chemical Industry Co., Ltd.) and then expose the circuit pattern (FIG. 4 (a)), II. Next, the antireflection film 2 with a protective film is spray-treated with a 1.0% sodium carbonate solution at 30 ° C. for 30 seconds to dry the film 4.
(FIG. 4 (b)) and III. Then add hydrochloric acid 1
The transparent conductive thin film 23 was removed by etching by spraying with a 0% solution (FIG. 4C), and IV. Further, the resist of the dry film 4 is removed by spraying with a 3.0% sodium hydroxide solution (FIG. 4D).

Example 7 After the adhesive film 1 for protecting an anti-reflection film was pasted on the anti-reflection film 21 in the same manner as in Example 5, unnecessary portions of the transparent conductive thin film 23 were subjected to a photo-etching method (Example 6). A circuit pattern was formed on the transparent conductive thin film 23 by etching in the same manner as described above, thereby producing an antireflection film 3 with a transparent conductive thin film circuit pattern of the present invention.

[Comparative Example 1] The surface resistance of one surface was 50
It has a transparent conductive thin film 23 of indium tin oxide (ITO) of 0 Ω / □, and the outermost layer has a thickness of 85 on the other surface.
polyethylene terephthalate film 22 having an antireflection film 21 which is a SiO ₂ film (refractive index: 1.46)
(Cosmo Shine A4300: Toyobo Co., Ltd.) An unnecessary portion of the transparent conductive thin film 23 is photo-etched on the antireflection film 21 without attaching a protective film (Example 6).
A circuit pattern was formed on the transparent conductive thin film 23 by etching in the same manner as described above) to produce the antireflection film 3 with a transparent conductive thin film circuit pattern of Comparative Example 1.

[Comparative Example 2] In Example 5, the adhesive film 1 for protecting the anti-reflection film 21 for protecting the anti-reflection film 21 was replaced with a special polyethylene instead of the adhesive film 1 for protecting the anti-reflection film of Example 2, and a synthetic rubber-based adhesive was used. Was applied on the antireflection film 21 in the same manner as in Example 5 except that a protective film (Sanyect MS14: San-A Kaken Co., Ltd.) was used, and the unnecessary portions of the transparent conductive thin film 23 were removed. Was removed by etching using a photoetching method (same method as in Example 6) to form a circuit pattern on the transparent conductive thin film 23, and an antireflection film 3 with a transparent conductive thin film circuit pattern of Comparative Example 2 was produced.

Examples 6 and 7 obtained as described above
When the antireflection film 21 of the antireflection film 3 with the transparent conductive thin film circuit pattern of Comparative Examples 1 and 2 was evaluated (for those having a protective film attached, after the protective film was peeled off), Examples 6 and 7 did not hinder the performance of the anti-reflection film 21 at all, whereas the one of Comparative Example 1
_{2 The} film completely disappeared, and in the case of Comparative Example 2 as well, the treatment liquid entered from the end where the protective film was attached, and SiO ₂
The film eroded, and the performance of the antireflection film 21 was not maintained.

[0068]

According to the method for producing an antireflection film with a transparent conductive thin film circuit pattern of the present invention, there is provided a method capable of reducing the cost by mass production of an antireflection film with a transparent conductive thin film circuit pattern. According to the adhesive film for protecting the antireflection film of the present invention,
Heat treatment and chemical resistance required for protecting the anti-reflection film in the method, particularly a treatment liquid used for developing and removing a photoresist in a photo-etching method and a treatment liquid used for etching a transparent conductive thin film It is possible to provide an adhesive film for protecting an antireflection film, which is excellent in chemical resistance to the film.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of the pressure-sensitive adhesive film for protecting an antireflection film of the present invention.

FIG. 2 is a sectional view showing an embodiment of the antireflection film with a protective film of the present invention.

FIG. 3 is a sectional view showing another embodiment of the antireflection film with a protective film of the present invention.

FIG. 4 is a cross-sectional view of a step illustrating a photoetching method.

[Description of Signs] 1 ... Adhesive film for protecting anti-reflective film 11 ... Adhesive layer 12 ... Base material 2 ... Anti-reflective film with protective film 21 ... Anti-reflective film 22- ..Transparent polymer film 23 ... Transparent conductive thin film 3 ... Transparent conductive thin film Antireflection film with circuit pattern 4 ... Photoresist layer 5 ... Document of circuit pattern 6 ... ·light

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 13/00 503 H01B 17/56 A 5G333 17/56 17/60 A 5G435 17/60 G02B 1/10 A F term (reference) 2K009 AA02 CC03 CC06 CC14 CC24 DD02 DD03 DD04 DD07 EE03 4F100 AA20C AA28D AA33D AK01E AK25B AK25J AK42A AK42E AK52B AK52J AL01B AL06B AR00B AR00D AT00ABABAE12 BA05 BA08 BA01 BA08 BA01 BA08 BA08 BA01 BA08 BA08 BA01 BA08 BA01 BA08 JL02 JL13B JM02C JM02D JN01D JN01E JN06 JN06C 4J004 AA10 AA11 AB01 CC02 FA04 FA05 5G307 FA02 FB01 FC06 FC08 FC10 5G323 CA01 5G333 AA03 AB13 AB22 BA03 CC09 CC20 DA03 DA21 DB02 DC02 FB01 FB02 FB01 FB02 FB01 FB02 FB01 FB02 FB01 FB02 FB01 FB02

Claims (13)

[Claims] An adhesive layer having a resistance to a processing liquid used for developing and removing a photoresist and a processing liquid used for etching a transparent conductive thin film is provided on a base material. An adhesive film for protecting an antireflection film. 2. The pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer obtained by curing at least an acrylic copolymer with a curing agent, wherein the acrylic copolymer has at least 1 to 12 carbon atoms in an alkyl group. The pressure-sensitive adhesive film for protecting an antireflection film according to claim 1, wherein the pressure-sensitive adhesive film is composed of a certain (meth) acrylate monomer and a functional group-containing monomer. 3. The polymerization ratio of the (meth) acrylate monomer and the functional group-containing monomer constituting the acrylic copolymer is 100 parts by weight of the (meth) acrylate monomer. 3. The pressure-sensitive adhesive film for protecting an antireflection film according to claim 2, wherein the amount of the functional group-containing monomer is 1 to 30 parts by weight. 4. The pressure-sensitive adhesive film according to claim 2, wherein a macromonomer is copolymerized as another monomer copolymerized with the acrylic copolymer. 5. The macromonomer is a polydimethylsiloxane methacrylate having a monoethylenically unsaturated group as a terminal polymerizable functional group and having polydimethylsiloxane as a high molecular weight skeletal component. Item 6. An adhesive film for protecting an antireflection film according to Item 4. 6. An anti-reflection film with a protective film, wherein the anti-reflection film is protected by the adhesive film for protecting an anti-reflection film according to claim 1. 7. The anti-reflection film with a protective film according to claim 6, wherein the outermost layer of the anti-reflection film is a silicon oxide-based thin film. 8. The anti-reflection film with a protective film according to claim 6, wherein said anti-reflection film is provided on a transparent polymer film. 9. The anti-reflection film with a protective film according to claim 8, wherein a transparent conductive thin film is provided on the back surface of the transparent polymer film on the surface on which the anti-reflection film is provided. the film. 10. The antireflection film with a protective film according to claim 9, wherein the transparent conductive thin film is mainly composed of indium oxide, tin oxide or indium tin oxide. 11. The antireflection with a protective film according to claim 9, wherein said transparent conductive thin film is formed by removing unnecessary portions by photoetching to form a transparent conductive thin film circuit pattern. the film. 12. An anti-reflection film having an anti-reflection film on one surface of a transparent polymer film,
After adhering the pressure-sensitive adhesive film for protecting the anti-reflection film according to claim 1, a transparent conductive thin film is provided on the back surface of the surface of the transparent polymer film on which the anti-reflection film is provided, and then the transparent conductive thin film is formed. A method for producing an antireflection film with a transparent conductive thin film circuit pattern, wherein an unnecessary portion is etched away by a photoetching method to form a circuit pattern on the transparent conductive thin film. 13. An anti-reflection film according to claim 1, wherein the anti-reflection film has an anti-reflection film on one surface of the transparent polymer film and a transparent conductive thin film on the other surface. After attaching a protective adhesive film, unnecessary portions of the transparent conductive thin film are etched and removed by a photoetching method to form a circuit pattern on the transparent conductive thin film. Production method of the prevention film.