JP2001282459A - Resistive film type touch panel and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resistive film type transparent touch panel where wear and peeling of a transparent conductive thin film due to repetition of an input operation are decreased and its manufacturing method. SOLUTION: The resistive film type transparent touch panel uses a plastic substrate on the touch side which is obtained by depositing, on one side of a transparent plastic base material, a transparent hardened substance layer having a hardened substance layer of activated energy line-hardened composition and having a hardened substance layer of hardened composition including polysilazane, and by depositing a transparent conductive thin film on the surface of the transparent hardened substance layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistive transparent touch panel having a transparent conductive thin film layer excellent in abrasion resistance and adhesion to a substrate, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Transparent touch panels, particularly resistive touch panels, have been used as input devices for portable information terminals whose market has been increasing in recent years.

In general, a resistive touch panel has a touch-side plastic substrate in which a transparent conductive thin film is laminated on one surface of a transparent plastic substrate, and a display-side transparent substrate in which a transparent conductive thin film is laminated on one surface of a transparent substrate such as glass. Board and
It has a structure in which the transparent conductive thin films are opposed to each other with the insulating spacer interposed therebetween.

[0004] Input is performed by pressing the touch input surface of the touch-side plastic substrate (the surface opposite to the transparent conductive thin film side; the same applies hereinafter) with a pen or a finger, and the transparent conductive material of the touch-side plastic substrate is pressed. The conductive thin film is brought into contact with the transparent conductive thin film of the display-side transparent substrate.

[0005]

However, in the resistive touch panel, the input operation is repeated, that is, the touch between the transparent conductive thin film on the touch-side plastic substrate and the transparent conductive thin film on the display-side transparent substrate is repeated. The transparent conductive thin film on the side plastic substrate wears out,
Cracks may be generated or peeled off from the base material, which is problematic in terms of durability.

In order to solve such a problem, a method of forming a hard coat layer made of a synthetic resin or a flexible cushion layer between a transparent plastic substrate and a transparent conductive thin film has been proposed. At present, the performance is not satisfactory.

It is an object of the present invention to provide a resistive transparent touch panel in which abrasion and peeling of a transparent conductive thin film due to repetition of an input operation are reduced, and a method of manufacturing the same.

[0008]

A first aspect of the present invention is a touch-side plastic substrate in which a transparent cured material layer and a first transparent conductive thin film are sequentially formed on one surface of a transparent plastic substrate,
On one surface of a transparent substrate, a display-side transparent substrate having a second transparent conductive thin film formed thereon is opposed to the first transparent conductive thin film so that the second transparent conductive thin film faces each other. In a resistive transparent touch panel constituted by arranging and joining insulating spacers, the transparent cured material layer is formed on the surface of the transparent plastic base material directly or via another layer, and active energy rays A cured product layer (A ′) of an active energy ray-curable composition (A) containing a polyfunctional compound (a) having two or more curable polymerizable functional groups and a photopolymerization initiator, And a cured product layer (B ′) of a curable composition (B) containing polysilazane (b) formed on the surface of the material layer.

A second aspect of the present invention is the resistive transparent touch panel according to the first aspect, wherein a hard coat layer is formed on a touch input surface of the transparent plastic substrate.

In a third aspect of the present invention, in the above-mentioned method for manufacturing a resistive transparent touch panel, the step of forming the transparent cured product layer comprises the step of forming an active layer on the surface of a transparent plastic substrate directly or through another layer. Energy ray curable composition (A)
Forming a layer of the curable composition (B) on the surface of this layer, and curing the layers sequentially or simultaneously. .

According to the present invention, it is possible to provide a transparent resistive touch panel in which the abrasion resistance and the peeling resistance of the transparent conductive thin film of the touch-side plastic substrate are improved and the durability against pen input is excellent.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following description, the active energy ray-curable composition (A) is simply referred to as the curable composition (A).
The polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups is simply referred to as a polyfunctional compound (a). Further, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group, and the same applies to expressions such as a (meth) acryloyloxy group, (meth) acrylic acid, and (meth) acrylate.

In the present invention, the transparent cured material layer formed on one side of the transparent plastic substrate is composed of the curable composition (A).
And two or more cured product layers including a cured product layer (A ′) and a cured product layer (B ′) of the curable composition (B) directly in contact therewith.

A third layer composed of a layer of another synthetic resin, for example, a thermoplastic resin such as a thermoplastic acrylic resin, or an adhesive layer exists between the transparent plastic substrate and the transparent cured material layer. It may be. In the present invention, it is usually preferable that the layer be composed of two layers, a cured layer (A ′) and a cured layer (B ′).

Further, the first transparent conductive thin film may be formed directly on the surface of the transparent cured material layer, or may be formed via an anchor coat layer. As an anchor coating agent,
Epoxy resin, acrylic resin, silicon resin, or the like can be used.

First, the curable composition (A) will be described. Preferred examples of the polyfunctional compound (a) contained in the curable composition (A) include compounds described in JP-A-11-240103, paragraphs 0016 to 0020, 0023 to 0047.

Preferred polyfunctional compounds (a) include:
Compounds having two or more (usually preferably 2 to 50, more preferably 3 to 30) one or more polymerizable functional groups selected from (meth) acryloyl groups are exemplified. Among them, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of a compound having two or more hydroxyl groups such as a polyhydric alcohol and (meth) acrylic acid is preferable. Particularly, having a urethane bond (meth)
An acryloyl group-containing compound (hereinafter, referred to as acrylic urethane) and a (meth) acrylate compound having no urethane bond are preferable.

Examples of the acrylic urethane include acrylic urethane which is a reaction product of pentaerythritol or its polymer, polypentaerythritol, polyisocyanate, and hydroxyalkyl (meth) acrylate, or hydroxyl group-containing polypentaerythritol or polypentaerythritol. An acrylic urethane that is a reaction product of a (meth) acrylate and a polyisocyanate, and a polyfunctional compound having three or more (more preferably 4 to 20) active energy ray-curable polymerizable functional groups, No.

The (meth) acrylate compound having no urethane bond includes pentaerythritol-based poly (meth) acrylate and isocyanurate-based poly (meth) acrylate. In addition, pentaerythritol-based poly (meth) acrylate is
Polyester of pentaerythritol or polypentaerythritol and (meth) acrylic acid (preferably having 4 to 20 active energy ray-curable polymerizable functional groups). Also, isocyanurate-based poly (meth)
Acrylate is a polyester of (meth) acrylic acid with an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate or 1 mol of tris (hydroxyalkyl) isocyanurate. (Preferably having 2 to 3 active energy ray-curable polymerizable functional groups).

In the present invention, the above-mentioned preferred polyfunctional compound and another polyfunctional compound having two or more active energy ray-curable polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol) are used. May be used in combination.

The curable composition (A) is a monofunctional compound having one polymerizable functional group polymerizable by an active energy ray together with the polyfunctional compound (a) (hereinafter simply referred to as a monofunctional compound). ).

As the monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. In addition, other hydroxyl groups,
It may have a functional group such as an epoxy group.

Preferred monofunctional compounds are (meth) acrylates, that is, (meth) acrylates, and specific examples thereof include those described in paragraph No. 0049 of JP-A-11-240103.

When a monofunctional compound is used, the sum of the polyfunctional compound (a) and the monofunctional compound (hereinafter referred to as an active energy ray-curable component) in the curable composition (A). The proportion of the monofunctional compound with respect to is not particularly limited, but is preferably 60% by mass or less,
Particularly, the content is preferably 30% by mass or less. If the proportion of the monofunctional compound is too large, the cured product of the curable composition (A) becomes too soft, and as a result, it is not possible to impart sufficient abrasion resistance to the first transparent conductive thin film.

The curable composition (A) contains a photopolymerization initiator in order to efficiently cure the active energy ray-curable component. As the photopolymerization initiator, known photopolymerization initiators can be used, and commercially available photopolymerization initiators are particularly preferable.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoyl benzoates, α-acyloxime esters, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.),
Examples include acylphosphine oxide-based photopolymerization initiators, diacylphosphine oxide-based photopolymerization initiators, and other photopolymerization initiators.

Specific examples include compounds described in JP-A-11-240103, paragraphs 0081-0085. In the present invention, an acylphosphine oxide-based photopolymerization initiator or a diacylphosphine oxide-based photopolymerization initiator is particularly preferred. Further, a plurality of types of photopolymerization initiators may be used in combination, or may be used in combination with a photosensitizer such as amines.

The amount of the photopolymerization initiator in the curable composition (A) is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the active energy ray-curable component.
Parts by weight are preferred.

Further, the curable composition (A) may contain the following solvents and various functional additives in addition to the above basic components.

In the curable composition (A), a solvent is usually an essential component, and a solvent is used unless the active energy ray-curable component is a liquid having a particularly low viscosity.

As the solvent, JP-A-11-240103
The solvent described in paragraph No. 0089 of the publication and the dispersion medium used for modifying colloidal silica described later described in paragraph 0055 of the publication can be directly used as the solvent. In addition, it is preferable to select and use an appropriate solvent depending on the type of the base material. For example, when the base material is an aromatic polycarbonate resin having low solvent resistance, lower alcohols, cellosolves, esters, or the like. It is preferable to use a mixture of the above. In the present invention, isopropyl alcohol, methyl ethyl ketone, dibutyl ether, ethyl cellosolve, 1-methoxy-2-propanol, and xylene are particularly preferable.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured product layer, the drying temperature conditions, and the like.

The amount of the solvent is usually 100 times or less, preferably 0.1 to 50 times, by mass of the active energy ray-curable component in the curable composition (A).

On the other hand, the functional compounding agents include an ultraviolet absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a defoaming agent, a thickener, a sedimentation inhibitor, an infrared absorber, and a fluorescent enhancer. One or more functional compounding agents selected from the group consisting of whitening agents, dispersants, rust inhibitors, antistatic agents, curable catalysts (acids, alkalis, salts) and colloidal silica are exemplified. In the present invention, it is particularly preferable to use an ultraviolet absorber, a light stabilizer or colloidal silica.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers which are commonly used as ultraviolet absorbers for synthetic resins.
Salicylic acid-based ultraviolet absorbers and the like are preferred. Specifically, JP-A-11-240103, paragraph number 0093
And the compounds described in the above.

As the light stabilizer, a hindered amine light stabilizer (such as a 2,2,6,6-tetraalkylpiperidine derivative) which is also commonly used as a light stabilizer for a synthetic resin is also preferable. Specifically, Japanese Patent Laid-Open No. 11-
Compounds described in paragraph No. 0094 of 240103 publication may be mentioned.

As the colloidal silica, Japanese Patent Application Laid-Open No.
No. 240103, paragraphs [0050] to [0078], unmodified colloidal silica, or surface-modified colloidal silica using a compound having a hydrolyzable silicon group or a silicon group bonded to a hydroxyl group (modifying agent) (Hereinafter simply referred to as modified colloidal silica). In the present invention, it is preferable to use modified colloidal silica. The average particle size of the colloidal silica is preferably 200 nm or less, more preferably 1 to 100 nm, and particularly preferably 1 to 50 nm.

The amount of the colloidal silica used is preferably from 5 to 300 parts by mass, more preferably from 10 to 250 parts by mass, per 100 parts by mass of the active energy ray-curable component. If the amount is too small, it is difficult to obtain sufficient abrasion resistance. If the amount is too large, fogging (haze) is likely to occur, and a crack is easily generated in the formed transparent cured product layer.

The thickness of the cured product layer (A ′) formed from the curable composition (A) is preferably 1 to 50 μm, and more preferably 2 to 50 μm.
-30 μm is preferred. The thickness of the cured product layer (A ') is 50
If it exceeds μm, curing by active energy rays becomes insufficient, and the adhesion to the base material tends to be impaired. On the other hand, when the thickness of the cured product layer (A ′) is less than 1 μm, the abrasion resistance of this layer is insufficient, and the abrasion resistance and scratch resistance of the cured product layer (B ′) described below can be exhibited. Therefore, there is a possibility that sufficient abrasion resistance and peeling resistance cannot be imparted to the first transparent conductive thin film.

Hereinafter, the curable composition (B) will be described. Polysilazane (b) contained in curable composition (B)
Is a compound represented by the following formula 1.

[0041]

Embedded image

(Rx, Ry and Rz each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
Represents an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, or a metal atom, and at least one of Rx, Ry, and Rz is a hydrogen atom. n represents the degree of polymerization. That is, the polysilazane (b) may be a polysilazane having at least a Si—H bond or an N—H bond in a molecule. In addition, polysilazane has a chain form, a cyclic form,
Alternatively, there is a compound having a crosslinked structure or a compound having a plurality of these structures in a molecule at the same time, and these can be used alone or as a mixture.

The molecular weight of the polysilazane (b) is preferably from 100,000 to 50,000 in number average molecular weight. Number average molecular weight is 100
If it is less than 50,000, it is difficult to obtain a uniform cured product even if it is baked.

In the present invention, Rx, Ry, and Rz are used in view of the low firing temperature and the denseness of the cured product after firing.
Are preferably hydrogen atoms. In the case where perhydropolysilazane is used, when the firing is completely advanced, the cured product after firing becomes complete silicon dioxide.

On the other hand, when polysilazane having a substituent other than a hydrogen atom is used for Rx, flexibility can be imparted to the cured product and the thickness can be increased. In this case, the cured product after firing does not become complete silicon dioxide.

The curable composition (B) can contain the following solvents and various functional additives in addition to the polysilazane (b).

As the solvent, hydrocarbons, halogenated hydrocarbons, ethers, esters and ketones can be used. Specifically, a solvent described in paragraph No. 0106 of JP-A-11-240103 is preferably exemplified. In the present invention, xylene is particularly preferred.

In order to adjust the solubility of the polysilazane (b) and the evaporation rate of the solvent, a plurality of types of solvents may be mixed and used.

The amount of the solvent used depends on the coating method to be employed, the structure of polysilazane (b), the average molecular weight, and the like, but is preferably adjusted so that the solid content concentration is 0.5 to 80% by mass. .

As the functional compounding agent, the functional compounding agent described in the coating composition (A) is preferably exemplified.

The thickness of the cured product layer (B ′) formed from the curable composition (B) is preferably 0.05 to 10 μm,
In particular, 0.1 to 3 μm is preferable. When the thickness of the cured product layer (B ′) exceeds 10 μm, the layer becomes brittle, and cracks and the like are easily generated in the cured product layer (B ′) even with slight deformation. If the thickness is less than 0.05 μm, abrasion resistance and abrasion resistance cannot be sufficiently exhibited, and sufficient abrasion resistance and peeling resistance may not be imparted to the first transparent conductive thin film.

Next, the transparent conductive thin film (referred to as both the first transparent conductive thin film and the second transparent conductive thin film, the same applies hereinafter) will be described.

As the material of the transparent conductive thin film, Au, P
Metal oxides such as d, Rh, Sn, In, Ti, Ag and the like, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), and a mixture thereof such as ITO and zinc oxide (ZnO) Things. Also, the transparent conductive thin film,
It may be composed of one layer, TiO ₂ / Ag / T
It may be composed of iO ₂ or a multilayer of metal / metal oxide such as ZnO / Ag / ZnO.

In the present invention, the material of the first transparent conductive thin film and the material of the second transparent conductive thin film may be the same or different.

As a method of forming a transparent conductive thin film,
Various film forming methods such as a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, and a hydrolysis method using a metal alcoholate can be employed. In the present invention,
From the viewpoint of the uniformity of the thin film and the like, a vacuum evaporation method or a sputtering method is preferable.

The thickness of the transparent conductive thin film may be appropriately determined according to the required performance such as transparency and conductivity, and is usually preferably 50 ° or more.

Next, the base material will be described. Various transparent synthetic resins can be used as the transparent plastic substrate used for the touch-side plastic substrate. For example, aromatic polycarbonate, polymethyl methacrylate, polystyrene, aromatic polyester such as polyethylene terephthalate, polyarylate, polyimide, polyethersulfone, polysulfone, polyamide, cellulose triacetate, fluorine resin and the like can be mentioned. In the present invention, a substrate made of polyethylene terephthalate, aromatic polycarbonate or polyarylate is particularly preferred. Since the touch-side plastic substrate needs to have flexibility, a substrate formed into a sheet or film with a thickness of 0.05 to 0.5 mm is used.

On the other hand, as the transparent base material used for the display-side transparent substrate, glass and the above-mentioned various transparent synthetic resins can be used. Further, as the display-side transparent substrate, a base material molded into a flat plate having a certain rigidity is used so as not to be deformed (curved or depressed) by touch pressure from the touch-side plastic substrate.

Next, the insulating spacer will be described. The insulating spacer is for preventing the transparent conductive thin films from coming into contact with each other during normal times when no signal is input, and generally used various insulating synthetic resins are used. Examples of the insulating synthetic resin include a melamine acrylate resin, a urethane acrylate resin, an epoxy acrylate resin, and a (meth) acryl acrylate resin.

There are no particular restrictions on the manufacturing method, size, arrangement position, quantity, and the like. For example, a method of forming a photocurable insulating synthetic resin into fine dots by a photo process, and a method of printing an insulating synthetic resin in dots at predetermined intervals on the surface of one transparent conductive thin film. and so on.

In the present invention, the distance between the plastic substrate on the touch side and the transparent substrate on the display side is not particularly limited, and may be appropriately determined according to the size of the insulating spacer to be used.

FIG. 1 is a schematic diagram showing a cross section of a resistive transparent touch panel as an example of the present invention. The resistive film-type transparent touch panel 12 is composed of a cured plastic layer 2 of a curable composition (A) and a cured substance layer 3 of a curable composition (B) directly in contact with the transparent plastic substrate 1. A touch-side plastic substrate 10 on which a first transparent conductive thin film 4 is formed on a transparent cured material layer 8 and a display-side transparent substrate on which a second transparent conductive thin film 5 is formed on one surface of a transparent substrate 6. The substrate 9 is arranged such that the transparent conductive thin films face each other with a spacer (not shown) interposed therebetween with the insulating spacer 7 interposed therebetween.

The resistive transparent touch panel of the present invention shown in FIG. 1 can be manufactured, for example, as follows.

First, on one side of the transparent plastic substrate 1,
The curable compositions (A) and (B) are applied and cured to form a transparent cured layer 8 composed of the cured layer 2 and the cured layer 3. At this time, a third layer may be formed between the transparent plastic substrate 1 and the transparent cured material layer 8.

The method for applying the curable compositions (A) and (B) on the surface of the transparent plastic substrate 1 is not particularly limited, and a known method can be employed. For example, various methods such as a dip method, a float coat method, a spray method, a bar coat method, a gravure coat method, a roll coat method, a blade coat method, and an air knife coat method can be adopted.

The active energy ray for curing the curable composition (A) is not particularly limited, and ultraviolet rays, electron beams and other active energy rays can be used, but ultraviolet rays are preferred. As the ultraviolet light source, a xenon lamp, a pulse xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, and the like can be used.

As a method for curing the polysilazane (b) contained in the curable composition (B) into silica, JP-A-11-240104, paragraph number 0111
To 0115 can be adopted.

However, in the present invention, the low temperature (180
C. or lower) to cure the polysilazane (b). In order to cure the polysilazane (b) at a low temperature, it is necessary to add a catalyst to the curable composition (B). However, it is preferable to use a catalyst that can be cured at a lower temperature. Depending on the type and amount of the catalyst, Curing at room temperature is also possible. Examples of such catalysts include, for example,
Fine particles of a metal such as gold, silver, palladium, platinum, and nickel described in JP-A-196986;
These include carboxylic acid complexes proposed in JP-A-93275, and amines and acids described in JP-A-9-31333.

The particle size of the metal fine particles is preferably smaller than 0.1 μm, and more preferably smaller than 0.05 μm in order to ensure transparency of the cured product. Further, since the specific surface area increases as the particle diameter decreases, the catalytic ability also increases. Therefore, it is preferable to use a catalyst having a smaller particle diameter from the viewpoint of improving the catalytic performance.

The amines include, for example, monoalkylamine, dialkylamine, trialkylamine, monoarylamine, diarylamine, cyclic amine and the like.

Examples of the above-mentioned acids include organic acids such as acetic acid and inorganic acids such as hydrochloric acid.

For example, when the metal fine particles are previously added to the curable composition (B) as a catalyst, the amount of addition is 0.01 to 100 parts by mass of the polysilazane (b).
It is preferably from 10 to 10 parts by mass, particularly preferably from 0.05 to 5 parts by mass. If the amount is less than 0.01 part by mass, a sufficient catalytic effect cannot be expected. If the amount exceeds 10 parts by mass, aggregation of the catalysts tends to occur, which may impair the transparency.

The above-mentioned amines and acids may be added to the curable composition (B) in advance, and may be used in the form of a solution (including an aqueous solution) of amines or acids, or a vapor thereof (from an aqueous solution). (Including steam).

The combination (timing) of curing of the curable composition (A) and application to curing of the curable composition (B) is described in JP-A-11-240104, paragraphs 0120 to 0127. Timing.

In the present invention, in order to increase the interlayer adhesion between the two cured product layers, it is preferable to perform curing at the following timing. When the curable composition contains a solvent, it is preferable to cure the composition after coating and drying to remove the solvent. Further, the curable composition (A)
It is preferable to shift the absorption peak of the photopolymerization initiator used for the above and the absorption peak of the ultraviolet absorber used for the curable composition (B).

(1) After applying the curable composition (A) to form an uncured material layer of the curable composition (A), the curable composition (B) is coated on the surface of the uncured material layer. ) Is applied to form a layer of the uncured material of the curable composition (B), and thereafter, the curing of the curable composition (A) is completed by irradiating a sufficient amount of active energy rays. In this case, the curable composition (B) cures almost simultaneously with the curable composition (A), or after curing of the curable composition (A), is exposed to a steam atmosphere of a curing catalyst solution.
It is left at room temperature or cured by heating or the like.

(2) After applying the curable composition (A),
The partially cured product of the curable composition (A) is once irradiated with an active energy ray (usually, an irradiation amount of up to about 300 mJ / cm ² ) in an amount until it becomes dry to the touch and does not reach complete curing. After forming the layer, the curable composition (B) is applied to the surface of the partially cured material layer to form an uncured material layer of the curable composition (B), and then completely cured. The curing of the curable composition (A) is completed by irradiating a sufficient amount of active energy rays. The curing of the curable composition (B) is the same as in the above (1).

As described above, the transparent plastic substrate 1
After forming the transparent hardened material layer 8 on one side of the above, the first transparent conductive thin film 4 is formed on the surface of the transparent hardened material layer 8 by the above-described method of forming the transparent conductive thin film. A substrate 10 is obtained. At this time, the first transparent conductive thin film 4 may be formed after forming the anchor coat layer on the surface of the transparent cured material layer 8.

On the other hand, the display-side transparent substrate 9 is obtained by forming the second transparent conductive thin film 5 on one surface of the transparent substrate 6 by the above-described method of forming the transparent conductive thin film.

Then, the touch-side plastic substrate 10
And the display-side transparent substrate 9 are disposed with an insulating spacer 7 interposed therebetween such that both transparent conductive thin films face each other, and are arranged and joined via a spacer (not shown) to obtain a resistive transparent touch panel 12. Can be.

Note that, in order to prevent scratches during pen input,
A hard coat layer may be provided on the touch input surface 11. Examples of the hard coat layer include a cured layer made of a curable resin such as a polyester resin, a urethane resin, a melamine resin, an epoxy resin, a silicon resin, an acrylic resin, and a polyimide resin. In the present invention, it is particularly preferable to form a transparent cured product layer composed of the cured product layer of the curable composition (A) and the cured product layer of the curable composition (B) in the same manner as described above.

[0082]

The present invention will be described below with reference to Synthesis Examples (Example 1), Examples (Examples 2 to 7), and Comparative Examples (Examples 8 to 10).
The present invention is not limited to these. The measurement and evaluation of various physical properties of Examples 2 to 9 were performed by the following methods, and the results are shown in Table 1.

In Examples 2 to 6, 8 and 10,
A transparent aromatic polycarbonate film (200 μm in thickness) was used as a transparent plastic substrate, and in Examples 7 and 9, a transparent polyester film (188 μm in thickness) having a surface easily treated for adhesion was used.

[Adhesion] Cross-cut test (JIS-
K1979), the adhesion of the transparent conductive thin film on the touch-side plastic substrate was evaluated.

[Pen Input Durability] The same location of the touch input surface of the touch panel is repeatedly slid with a pen tip made of polyacetal having a tip of 0.5R with a pen load of 250 gf, and the transparent conductivity of the plastic substrate on the touch side is repeated. The number of slidings at which cracks occurred in the thin film was measured.

[Example 1] Ethyl cellosolve dispersed colloidal silica (silica content: 30% by mass, average particle size: 11 nm)
To 100 parts by mass, 5 parts by mass of 3-mercaptopropyltrimethoxysilane and 3.0 parts by mass of 0.1 mol / L hydrochloric acid were added, and the mixture was heated and stirred at 100 ° C. for 6 hours, and then aged at room temperature for 12 hours. As a result, a mercaptosilane-modified colloidal silica dispersion was obtained.

[Example 2] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 15 g of isopropyl alcohol, 15 g of butyl acetate, 7.5 g of 1-methoxy-2-propanol, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- [4-
(2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4
-Dimethylphenyl) -1,3,5-triazine 100
0 mg, and 1,2,2,6,6-pentamethyl-4
-200 mg of piperidyl methacrylate was added and dissolved. Subsequently, urethane acrylate which is a reaction product of hydroxyl-containing dipentaerythritol polyacrylate and partially nullated hexamethylene diisocyanate (containing an average of 15 acryloyl groups per molecule)
5.0 g and 5.0 g of tris (2-acryloyloxyethyl) isocyanurate were added, and the mixture was stirred at room temperature for 1 hour to obtain a coating liquid 1.

Then, on one side of the transparent plastic substrate,
Apply coating liquid 1 using a bar coater (wet thickness 1
6 μm), dried at 80 ° C., and irradiated with 3000 mJ / cm ² of ultraviolet light (ultraviolet integrated energy in the wavelength range of 300 to 390 nm, the same applies hereinafter) using a high-pressure mercury lamp in an air atmosphere. A cured product layer having a thickness of 5 μm was formed.

Then, on the surface of the cured product layer, a coating liquid 2 consisting of a xylene solution of low-temperature curable perhydropolysilazane (solid content concentration: 20% by mass, trade name “NL110” manufactured by Tonen Corporation) was added. Coating (wet thickness: 5 μm) using a bar coater, holding for 10 minutes in a hot air circulating oven at 80 ° C., and then 12 minutes in a hot air circulating oven at 100 ° C.
Hold for 0 minutes to completely cure. And it was confirmed by IR analysis that silicon dioxide had been completely formed.
Thus, a total film thickness of 6 μm is formed on one side of the transparent plastic substrate.
Was formed.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

On the other hand, a transparent conductive thin film having a thickness of 400 ° was formed on one side of a glass substrate (thickness: 1.1 mm) in the same manner as above to obtain a display-side transparent substrate.

Then, the touch-side plastic substrate and the display-side transparent substrate were arranged with epoxy beads (insulating spacer) having a diameter of 30 μm interposed therebetween such that the respective transparent conductive thin films faced each other, to obtain a resistive transparent touch panel. .

[Example 3] On one side of a transparent plastic substrate,
The coating liquid 1 is applied by a microgravure coating method (wet thickness: 16 μm), dried by heating at 80 ° C., and irradiated with 150 mJ / cm ² ultraviolet light using a high-pressure mercury lamp in an air atmosphere. A partially cured product layer having a thickness of 5 μm was formed.

Then, a 20% by mass xylene solution of perhydropolysilazane (number average molecular weight Mn ≒ 1000, trade name “V-110”, manufactured by Tonen Co., Ltd.) (hereinafter referred to as Coating Solution 3) was formed on the surface of the partially cured product layer. ) Was applied by a microgravure method (wet thickness: 5 μm), dried by heating at 80 ° C., and dried in an air atmosphere using a high-pressure mercury lamp.
Irradiation with ultraviolet rays of 000 mJ / cm ² was carried out for 24 hours in an environment of a relative humidity of 50% to form a transparent cured layer having a thickness of 6 μm.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

Using this touch-side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[Example 4] On one side of a transparent plastic substrate,
Coating the coating liquid 1 using a bar coater (wet thickness 16
μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. Subsequently, the coating liquid 3 is applied thereon (wet thickness 5 μm) using a bar coater, and circulated at 80 ° C. After holding it in the oven for 10 minutes,
Ultraviolet rays of 3000 mJ / cm ² were irradiated using a high-pressure mercury lamp, and further kept in an environment of a relative humidity of 50% for 24 hours to form a transparent cured layer having a thickness of 6 μm.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

Using this touch-side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[Example 5] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 15 g of isopropyl alcohol, 15 g of butyl acetate, 7.5 g of 1-methoxy-2-propanol, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- [4-
(2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4
-Dimethylphenyl) -1,3,5-triazine 100
0 mg, and 1,2,2,6,6-pentamethyl-4
-200 mg of piperidyl methacrylate was added and dissolved. Subsequently, urethane acrylate which is a reaction product of hydroxyl-containing dipentaerythritol polyacrylate and partially nullated hexamethylene diisocyanate (containing an average of 15 acryloyl groups per molecule)
5.0 g and 5.0 g of tris (2-acryloyloxyethyl) isocyanurate were added, and the mixture was stirred at room temperature for 1 hour.

Subsequently, 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added, and the mixture was further stirred at room temperature for 15 minutes to obtain a coating liquid 4.

Then, a coating liquid 4 was applied to the transparent plastic base material using a bar coater (wet thickness 16 μm).
m) and kept in a hot-air circulating oven at 80 ° C. for 5 minutes.
Irradiation with ultraviolet rays of mJ / cm ² was performed to form a partially cured layer having a thickness of 5 μm.

Next, the coating liquid 3 was applied to the surface of the partially cured product layer using a bar coater (wet thickness: 5 μm).
Then, it was kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then kept in an air atmosphere for 3000 minutes using a high-pressure mercury lamp.
Irradiation with ultraviolet rays of mJ / cm ² and relative humidity of 50%
, And a transparent cured product layer having a thickness of 6 μm was formed.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

Using this touch-side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[Example 6] On one side of a transparent plastic substrate,
The coating liquid 1 is applied by a microgravure coating method (wet thickness: 16 μm), dried by heating at 80 ° C., and irradiated with 150 mJ / cm ² ultraviolet light using a high-pressure mercury lamp in an air atmosphere. A partially cured product layer having a thickness of 5 μm was formed.

Next, a coating liquid 3 was applied to the surface of this partially cured product layer by a microgravure method (wet thickness 5 μm).
m), and after drying by heating at 80 ° C., this was irradiated with ultraviolet rays of 3000 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere, and further kept for 24 hours in an environment of a relative humidity of 50%. A 6 μm transparent cured product layer was formed.

On the other side of the transparent plastic substrate, a transparent cured product layer having a total film thickness of 6 μm was formed in the same manner as described above.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of one of the transparent cured material layers by a sputtering method to obtain a touch-side plastic substrate.

Using this touch-side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[Example 7] On one surface of a transparent plastic substrate,
The coating liquid 1 is applied by a microgravure coating method (wet thickness: 16 μm), dried by heating at 80 ° C., and irradiated with 150 mJ / cm ² ultraviolet light using a high-pressure mercury lamp in an air atmosphere. A partially cured layer having a thickness of 5 mm was formed.

Next, a coating liquid 3 was applied to the surface of the partially cured product layer by a microgravure method (wet thickness 5 μm).
m), and after drying by heating at 80 ° C., this was irradiated with ultraviolet rays of 3000 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere, and further kept for 24 hours in an environment of a relative humidity of 50%. A 6 μm transparent cured product layer was formed.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

Using this touch-side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[Example 8] On one side of a transparent plastic substrate,
Coating the coating liquid 2 using a bar coater (wet thickness 5μ)
m) and kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then kept in a hot air circulating oven at 100 ° C. for 120 minutes to form a cured product layer having a thickness of 1 μm.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the cured product layer by a sputtering method.
A touch-side plastic substrate was obtained.

Using this touch-side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[Example 9] On one surface of a transparent plastic substrate,
Coating the coating liquid 2 using a bar coater (wet thickness 5μ)
m) and kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then kept in a hot air circulating oven at 100 ° C. for 120 minutes to form a cured product layer having a thickness of 1 μm.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

Using this touch side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

Example 10 One side of a transparent plastic substrate was coated with a coating liquid 1 using a bar coater (wet thickness 16 μm), dried at 80 ° C., and then dried in an air atmosphere under high pressure. Ultraviolet rays of 3000 mJ / cm ² were irradiated using a mercury lamp to form a cured layer having a thickness of 5 μm.

Then, an ITO thin film having a thickness of 300 ° was formed on the surface of the transparent cured material layer by a sputtering method to obtain a touch-side plastic substrate.

Using this touch side plastic substrate,
A resistive transparent touch panel was obtained in the same manner as in Example 2.

[0124]

[Table 1]

[0125]

According to the present invention, by forming the above-mentioned transparent cured material layer between the transparent plastic substrate and the transparent conductive thin film, the abrasion resistance and the anti-wear property of the transparent conductive thin film are formed. It is possible to provide a resistive transparent touch panel having improved peelability and excellent durability against pen input.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a resistive transparent touch panel which is an example of the present invention.

[Explanation of symbols]

 1. 1. transparent plastic substrate 2. Cured product layer of curable composition (A) 3. Cured product layer of curable composition (B) 4. First transparent conductive thin film Second transparent conductive thin film 6. Transparent substrate 7. 7. Insulating spacer Transparent cured product layer 9. Display side transparent substrate 10. 10. Touch-side plastic substrate Touch input surface 12. Resistive transparent touch panel

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Shibuya 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. (72) Inventor Hiroshi Shimoda 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co. 72) Inventor Hiroshi Yamamoto 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd.F-term (reference) 5B087 AA04 CC11 CC13 5G307 FA02 FB01 FB02 FC01 FC05

Claims (3)

[Claims] 1. A touch-side plastic substrate in which a transparent cured material layer and a first transparent conductive thin film are sequentially formed on one surface of a transparent plastic substrate, and a second transparent conductive thin film is formed on one surface of the transparent substrate. A display-side transparent substrate, so that the first transparent conductive thin film and the second transparent conductive thin film face each other, and an insulating spacer is arranged and joined between them. In the transparent touch panel of the formula, the transparent cured material layer is formed on the surface of the transparent plastic substrate directly or through another layer, and has two or more active energy ray-curable polymerizable functional groups. A cured product layer (A ′) of the active energy ray-curable composition (A) containing the compound (a) and the photopolymerization initiator, and a polysilazane (b) formed on the surface of the cured product layer Hardening Resistive transparent touch panel characterized by having a cured product layer of Narubutsu (B) and (B '). 2. The resistive transparent touch panel according to claim 1, wherein a hard coat layer is formed on a touch input surface of the plastic substrate on the touch side. 3. The method for producing a resistive transparent touch panel according to claim 1, wherein the step of forming the transparent cured material layer comprises directly or via another layer on the surface of a transparent plastic substrate. Forming a layer of the active energy ray-curable composition (A), forming a layer of the curable composition (B) on the surface of this layer, and curing them sequentially or simultaneously. A method for manufacturing a resistive transparent touch panel.