JP2005149482A - Pen-input device surface material, pen-input touch panel, and pen-input device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pen-input device surface material, a pen-input touch panel and a pen-input device using the same, excellent in resilience, visibility and a writing feeling. <P>SOLUTION: The pen-input device surface material 23 comprises a substrate 16 and a surface layer 19, wherein a dent formed when an input pen 21 with a weight of 200 g is moved at a speed of 10 cm/sec on the surface of the surface layer 19 in an ambient atmosphere at a temperature of 20°C and with a relative humidity of 50% is resiled in 0.2 to 20 sec. The surface layer 19 is obtained by applying to the surface of the substrate 16 a curable composite containing a specific (meta) acrylyl group as a major constituent and by irradiating the composite with ultraviolet rays to cure the composite. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a pen input device surface material excellent in restoration, visibility and writing feeling, a pen input touch panel, and a pen input device using the same.

  Pen input devices that are provided in front of various displays such as liquid crystal displays and perform input operations based on contact position signals detected by touching the surface with an input pen are fine operations with input pens, curves, straight lines, etc. A continuous line can be input. Therefore, it is possible to input a lot of information even on a relatively small screen. Furthermore, taking advantage of the ability to perform input operations like a paper by writing characters on the display with an input pen, the pen input device is a portable information terminal, electronic notebook. In addition, the range of use of multimedia devices is expanding rapidly.

  Conventionally, as a surface material of the pen input device, a glass plate or a plastic plate having a hard coat layer formed on the surface thereof has been used. However, due to the hard feel of the surface and the feel of sliding, there was a big difference from writing with a pen on normal paper, and the writing feeling was extremely bad.

Several proposals have been made to improve writing feeling.
For example, a pen input device including a panel board using a hard coat material on the outermost surface of a base material and using an adhesive layer having elastic deformability under the base material is disclosed (see Patent Document 1). In addition, a surface material for a pen input device including a surface material of an ionizing radiation curable resin in which an uneven surface layer is formed by fine particles such as an acrylic resin is disclosed (see Patent Document 2). Furthermore, a protective film for a pen input device provided with a transparent soft synthetic resin having self-repairing properties and scratch resistance is disclosed (see Patent Document 3). In addition, a surface material for a pen input device is disclosed that satisfies the three senses of dent, smoothness, and roughness in a well-balanced manner, and in particular has a dynamic friction coefficient and a static friction coefficient in a specific range (see Patent Document 4).

However, the previously disclosed technique has not been fully satisfactory.
That is, in the technique disclosed in Patent Document 1, since the outermost surface is formed of a hard coat layer, the surface becomes hard, and the resilience and smoothness are not appropriate. Further, since the surface of the surface material that the input pen is in direct contact with is not elastically deformed, it is insufficient to obtain a grip feeling of the pen.

  Furthermore, in the technique disclosed in Patent Document 2, there is a rough feeling due to the unevenness of the surface, but the visibility is impaired for that reason. In addition, there is a problem that the surface material has an unsatisfactory feeling on the surface and lacks in dent and resilience.

In the technique disclosed in Patent Document 3, although the soft synthetic resin has a dent feeling, the restorability is not appropriate, and the writing feeling is unsatisfactory. In addition, in the technique disclosed in Patent Document 4, when the surface material is formed with unevenness in order to obtain a rough feeling, the unevenness is so high as to obtain a good writing feeling. There was a problem of impairing visibility.
JP-A-6-309990 (pages 3 to 6) JP 7-244552 A (3-5 pages) JP-A-6-180628 (pages 4-6) International Publication Number WO03 / 067416 (pages 11-16)

  An object of the present invention is to provide a pen input device surface material, a pen input touch panel, and a pen input device using the same, which are excellent in restoration, visibility and writing feeling.

  As a result of intensive studies to achieve the above object, the present inventors have found that the dent restoration time in the surface layer of the surface material for pen input devices is not formed on the surface material for the purpose of obtaining a rough feeling. In the case of being in a specific range, the present invention obtains the knowledge that the writing feeling and the visibility are excellent, preferably by combining the total light transmittance, haze value and slipperiness so as to be in the specific range. Was completed.

  That is, the first invention is a surface material for a pen input device comprising a base material and a surface layer. The surface of the surface layer is 10 cm / cm using an input pen with a load of 200 g in an atmosphere of 20 ° C. and 50% relative humidity. The surface material for a pen input device is characterized in that a dent generated when moved at a speed of sec is restored within a time of 0.2 to 20 sec.

The second invention is the range according to the first invention, wherein the surface layer has a Martens hardness of 0.5 to 50 N / mm ² measured with an ultra-micro hardness tester in an atmosphere of 20 ° C. and 50% relative humidity. It is the surface material for pen input devices which is the inside.

  According to a third invention, in the first or second invention, the elastic energy of the surface layer measured by an ultra micro hardness tester in an atmosphere of 20 ° C. and 50% relative humidity is within a range of 0.1 to 20 nJ. This is a surface material for a pen input device.

A fourth invention is the surface material for a pen input device according to any one of the first to third inventions, wherein the total light transmittance of the surface material for the pen input device is 80% or more.
A fifth invention is a surface material for a pen input device according to any one of the first to fourth inventions, wherein the haze value of the surface material for a pen input device is 5% or less.

  A sixth invention is the method according to any one of the first to fifth inventions, wherein the surface of the surface layer is moved at a speed of 10 cm / sec using an input pen with a load of 200 g in an atmosphere of 20 ° C. and 50% relative humidity. The surface friction material for pen input devices has a dynamic friction coefficient of 0.02 to 0.6 and a static friction coefficient of 0.3 to 2.

  A seventh aspect of the invention is the pen input device according to any one of the first to sixth aspects, wherein the surface layer is formed by applying and curing a curable composition containing a (meth) acryloyl group-containing compound as a main component. Surface material.

  An eighth invention is the curable composition according to any one of the first to seventh inventions, wherein the surface layer contains 10 to 70% by weight of a repeating unit represented by the following chemical formula (1), (2) or (3): Is a surface material for a pen input device formed by coating and curing.

—O — [(CH ₂ ) _j —O] _k − (1)
However, j = 2 to 4 and k = 2 to 30.

但し、ｍ＝３〜１２およびｎ＝１〜１５である。

However, m = 3-12 and n = 1-15.

− (CH ₂ ) _p − (3)
However, p = 10-24.
A ninth invention is the curable composition according to any one of the first to eighth inventions, wherein the surface layer contains a compound having at least one of a carboxyl group and a hydroxyl group within a range of 0.01 to 30% by weight. It is a surface material for pen input devices formed by coating and curing.

  The tenth invention is formed by applying and curing a curable composition whose surface layer contains a polysiloxane compound in a range of 0.01 to 10% by weight in any one of the first to ninth inventions. It is the surface material for pen input devices.

An eleventh aspect of the invention is a pen input touch panel in which the surface material for a pen input device according to any one of the first to tenth aspects of the invention is provided on a touch panel body.
A twelfth aspect of the invention is a pen input device configured by providing the pen input touch panel of the eleventh aspect of the invention on a display.

According to the present invention, the following effects can be exhibited.
In the first invention, since the restoration time of the surface layer is in a specific range, excellent writing feeling and visibility can be obtained when the input pen is brought into contact with the operation surface. As a result, the grip feeling of the pen is different from that of a pen input device that does not take into account the writing feeling, so the input error due to the sliding of the pen tip is reduced to reduce misrecognition, and the soft touch feeling and writing pressure control operation For example, the stress due to the input operation can be reduced.

In the second invention, since the Martens hardness of the surface layer is in a specific range, the dent feeling can be improved.
Since the elastic energy of the surface layer is in a specific range, the third invention can further improve the durability.

In the fourth invention, since the total light transmittance of the surface layer is in a specific range, the visibility can be improved.
In the fifth invention, since the haze value of the surface layer is in a specific range, the visibility can be further improved.

According to the sixth aspect of the present invention, since the dynamic friction coefficient and the static friction coefficient of the surface layer are in a specific range, the smooth feeling can be improved.
In the seventh invention, since the curable composition formed on the surface layer is formed by applying and curing a curable composition containing a (meth) acryloyl group-containing compound as a main component, the durability is good. In addition, it is possible to make a surface material that is easy to handle and excellent in restoring property, visibility and writing feeling.

  According to an eighth aspect of the present invention, there is provided a curable composition for forming a surface layer containing 10 to 70% by weight of the repeating unit represented by the chemical formula (1), (2) or (3), A surface layer is formed by coating and curing on a substrate. For this reason, the surface layer is improved in flexibility and elasticity, and can exhibit excellent resilience, visibility, and writing feeling.

  In a ninth aspect, the curable composition formed on the surface layer is formed by applying and curing a curable composition containing a compound having at least one of a carboxyl group and a hydroxyl group within a specific range. Therefore, it is possible to improve the adhesion with a substrate or the like.

  In the tenth invention, the curable composition formed on the surface layer is formed by applying and curing a curable composition containing a polysiloxane compound within a specific range. It is possible to improve the smoothness.

  In an eleventh aspect of the invention, an input operation with an input pen for a pen input touch panel incorporating the surface material for a pen input device is excellent in writing feeling and good in visibility, so that it is comfortable without feeling tired even if it is repeatedly performed. .

  According to a twelfth aspect of the present invention, the input operation with the contact position signal for the pen input device incorporating the surface material for the pen input device has excellent writing feeling and good visibility. is there.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The pen input device is a device that performs an input operation by performing a drawing operation using a pen-shaped instrument resembling a pencil or a ballpoint pen on the surface of a panel or the like, and at least one of the panel or the pen-shaped instrument. The device is not particularly limited as long as the device has a signal output circuit or a signal recording circuit using electricity or electromagnetic waves.

  For example, a pen input touch panel provided on the front of various displays, a tablet pen input device that is connected to a computer without being provided on the front of the display, and electronic paper can be used. The pen input device has a pen input touch panel on a display surface (display body) such as a liquid crystal display, a plasma display (PDP), an electroluminescent (EL) display, a cathode ray tube (CRT) display, etc. It is an apparatus which performs input operation by the contact position signal detected by touching with. That is, as shown in FIG. 5, the pen input device 10 is configured by assembling a pen input touch panel 12 on the display 11 as described above.

  The (pen input) touch panel includes an integrated type incorporated in various displays as described above and a separate type arranged on the display surface of various display devices. As a touch panel system, any known system can be used and is not particularly limited. Specific examples include touch panel methods such as an ultrasonic method, a resistive film method, a capacitance method, an electric strain method, a magnetostriction method, an infrared method, and an electromagnetic induction method. A resistive touch panel is preferable from the viewpoint of power consumption and price, and an electromagnetic induction touch panel is preferable from the viewpoint of resolution.

  As shown in FIG. 3 (a), the resistive-film-type pen input touch panel 12 includes a fixed side (lower side in the figure) and a movable side (upper side in the figure) provided with transparent conductive thin films 13 and 14 on one side. The base materials 15 and 16 made of a transparent resin sheet are arranged so that the transparent conductive thin films 13 and 14 are opposed to each other, and the periphery is adhered by an adhesive reinforcing material 17 so that a constant interval can be maintained. On one transparent conductive thin film 13, a large number of insulating spacers 18 are provided in a dot shape so that the transparent conductive thin films 13 and 14 facing each other are insulated. A touch panel body is constituted by the base material 15, the transparent conductive thin films 13, 14, the insulating spacer 18, and the like. As shown in FIG. 1, a surface layer 19 made of a soft resin is formed on the movable-side substrate 16. Alternatively, as shown in FIGS. 3B and 2, a surface layer 19 made of a soft resin is provided on the surface of the base material 16 on the movable side, and a transparent adhesive layer 20 is provided on the back surface. It is bonded to the transparent conductive thin film 14 via the material 22. By pressing the surface layer 19 with the input pen 21, the movable transparent conductive thin film 14 is brought into contact with the fixed transparent conductive thin film 13 to be electrically conducted for input.

  As shown in FIG. 4, the electromagnetic induction type touch panel has a pen input device surface material 23 laminated and bonded to the surface of the transparent resin base material 22, and a liquid crystal element (LCD) on the back surface of the transparent resin base material 22. The pen position detector 24 is provided with a receiving circuit. As shown in FIG. 2, the pen input device surface material 23 is configured such that a surface layer 19 made of a soft resin is provided on the surface of a base material 16 made of a transparent resin sheet, and a transparent adhesive layer 20 is provided on the back surface. Has been. Further, an electromagnetic input pen 21 having a transmission coil (not shown) is provided. Then, by pressing the surface layer 19 with the input pen 21, electromagnetic waves generated by electromagnetic induction are detected by the pen position detector 24 and the input position is recorded.

  The surface material 23 for pen input devices is used for the surface which the input pen 21 of the pen input device 10 touches directly. As shown in FIG. 1, the surface material 23 for a pen input device of the present invention includes a base material 16 made of a transparent resin sheet and a surface layer 19 made of a soft resin that the input pen 21 directly touches. Moreover, as shown in FIG. 2, the structure by which the transparent adhesive layer 20 is provided in the back surface of the base material 16 may be sufficient. The surface layer 19 may be a single layer or may be formed of a plurality of layers. The thickness of the surface layer 19 is preferably 5 to 200 μm, more preferably 5 to 100 μm, and particularly preferably 10 to 50 μm. When this thickness is less than 5 μm, the elasticity of the surface layer 19 is insufficient and the restorability and writing feeling are lowered. On the other hand, when it exceeds 200 μm, the surface layer 19 becomes too thick and the writing feeling tends to be lowered. The input pen 21 is not particularly limited as long as it is a pen that can be used for an input operation with the pen input device 10. As the known input pen 21, for example, a material mainly composed of polyacetal resin is used, and the pen tip has a hemispherical shape with a diameter of about 1.6 mm.

  From the viewpoint of resilience related to both writing feeling and visibility, the surface material 23 for a pen input device of the present invention needs to satisfy the following requirements. That is, the dent on the surface material surface generated when the surface of the surface layer 19 is moved at a speed of 10 cm / sec using the input pen 21 with a load of 200 g in an atmosphere of 20 ° C. and 50% relative humidity is 0.2. The surface material 23 for a pen input device is restored within a time of ˜20 sec (seconds), preferably 0.5 to 10 sec. Here, the input pen 21 having a load of 200 g means the total amount of the load (weight) of the input pen 21 itself and the load for pressing the input pen 21 against the surface layer 19. When the dent is restored in less than 0.2 sec, it becomes difficult to feel the softness of the surface material 23, so the writing feeling is not appropriate, and when the dent is restored after 20 sec, the restoration is slow, so when the input pen 21 is further input there Overlap occurs and hinders visibility. The dent is a dent on the surface of the surface layer 19, and the depth of the dent is preferably 1 to 50 μm, more preferably 2 to 30 μm. When the depth of the dent is less than 1 μm, it is difficult to feel the softness of the surface layer 19 and the writing feeling tends to be impaired. On the other hand, when it exceeds 50 μm, the surface layer 19 feels sinking, and the writing feeling is lowered.

Further, the Martens hardness of the surface layer 19 measured with an ultra-micro hardness tester (manufactured by Fisher Instruments Co., Ltd., trade name: Fisherscope H-100) in an atmosphere of 20 ° C. and 50% relative humidity. Is preferably 0.5 to 50 N / mm ² , more preferably 1 to 10 N / mm ² . Such a pen input device surface material 23 is preferable in that an appropriate dent depth can be obtained. Martens hardness is the hardness of the coating film determined from the test load and the indentation surface area when the film surface is indented with a Vickers indenter, and is an index of the hardness of the object surface. When the Martens hardness is less than 0.5 N / m, the surface material 23 is softly dented too much. Conversely, if it exceeds 50 N / m, the surface material 23 is hard and hardly dented.

  Moreover, the surface material 23 for pen input devices whose elastic energy by an ultra micro hardness test apparatus is preferably 0.1 to 20 nJ, more preferably 0.5 to 10 nJ in an atmosphere of 20 ° C. and 50% relative humidity, From the viewpoint of durability. The elastic energy is the amount of elastic deformation work from the indentation of the film surface with the Vickers indenter to the removal of the load, and since the dent hardly returns when the elastic energy is less than 0.1 nJ, it becomes a scratched state. On the other hand, when it exceeds 20 nJ, the dent is well restored, but the surface material 23 becomes too soft and the durability deteriorates. Here, the term “restorability” means that the dent once generated disappears over time and tries to return to its original shape. The dent that is temporarily generated can provide a feeling of dent and absorb the applied force. In order to do so, it is possible to have an anti-scratch performance.

  From the viewpoint of not impairing the visibility, the following surface material 23 for a pen input device is more preferable. That is, the pen input device surface material 23 is composed of the base material 16 and the surface layer 19 and has a total light transmittance of preferably 80% or more, more preferably 85% or more. When the total light transmittance is less than 80%, darkness is felt and visibility is deteriorated. Further, the pen input device surface material 23 having a haze value of preferably 5% or less, more preferably 3% or less is preferred. When the haze value exceeds 5%, the opacity is felt and the visibility is deteriorated.

  In addition to the dent feeling, the slip feeling can be evaluated by measuring the frictional resistance between the tip of the input pen that satisfies the writing feeling and the surface of the surface layer 19 in the pen input device 10 such as a panel. This frictional resistance can be divided into two types: a dynamic frictional resistance corresponding to a sliding feeling during a drawing operation and a static frictional resistance corresponding to a sliding feeling at the beginning of writing. It is important to control both of them, and the following pen input device surface material 23 is more preferable from the viewpoint of improving writing feeling. That is, a value obtained by measuring the frictional resistance with respect to the input pen 21 using a surface property tester (manufactured by Shinto Kagaku Co., Ltd., trade name: Tribogear, TYPE: 14DR) is in a specific range.

  Specifically, when the input pen 21 having a load of 200 g under an atmosphere of 20 ° C. and 50% relative humidity is moved on the surface material 23 for a pen input device at a speed of 10 cm / sec, the dynamic coefficient of friction is preferably about 0.1. It is a surface material 23 for a pen input device that is 02 to 0.6, more preferably 0.1 to 0.4, and the coefficient of static friction is preferably 0.3 to 2, more preferably 0.5 to 1. . When the dynamic friction coefficient of the pen input device surface material 23 with respect to the input pen 21 is less than 0.02 or the static friction coefficient is less than 0.3, the input pen 21 slips too much in any case, resulting in writing feeling. It will be bad. On the contrary, when the dynamic friction coefficient exceeds 0.6 or the static friction coefficient exceeds 2, in any case, the slip of the input pen 21 is bad and feels heavy, resulting in poor writing feeling.

  Moreover, the surface material 23 for pen input devices of the present invention includes an antireflection layer, if necessary, between the base material 16 and the surface layer 19 or on the opposite side of the surface of the base material 16 on which the surface layer 19 is formed. Layers having functions such as a transmitted light control layer, a conductive layer, and an antistatic layer (hereinafter abbreviated as a functional layer) can be formed in a single layer or a plurality of layers. Further, the functional layer may be formed on the outermost surface of the surface layer 19 as long as the writing feeling is not hindered. Further, the substrate 16 can be formed of a plurality of layers and is not particularly limited.

  Examples of the material of the base material 16 used for the surface material 23 for a pen input device of the present invention include polyester such as polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, regenerated cellulose, diacetyl cellulose, triacetyl cellulose, acrylonitrile / Examples include styrene / butadiene terpolymers, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, nylon, polyethylene, cellulose acetate, polypropylene, polyamide, polyimide, polysulfone, polyethersulfone, and norbornene resins. Among these, a transparent base material 16 such as triacetyl cellulose, polyethylene terephthalate, and polycarbonate is cited as a preferable base material 16. The shape of the substrate 16 is usually a film, but may be a thicker sheet or the like.

  The surface layer 19 is usually coated with the curable composition for forming the surface layer on the outermost surface of the substrate 16 or the functional layer laminated on the substrate 16 or the viscosity of the curable composition for forming the surface layer. Is formed by applying a curable composition solution for forming a surface layer diluted with a diluting solvent, removing the solvent, and then curing them. Among such curable compositions for forming the surface layer, there are ultraviolet curable or thermosetting unsaturated acrylic resin compositions, unsaturated polyurethane resin compositions such as urethane-modified (meth) acrylates, unsaturated polyester resins. Compositions, polyamide resin compositions, thermosetting silicone-based, melamine-based, and epoxy-based resin compositions are included.

  More specifically, for example, a curable composition containing a polyfunctional polymerizable compound containing two or more acryloyl groups and methacryloyl groups such as an esterified product of a polyhydric alcohol and (meth) acrylic acid, and a urethane-modified ( Examples thereof include a curable composition containing a (meth) acrylate and a curable composition containing a silicone-based, melamine-based, or epoxy-based polyfunctional polymerizable compound. Among these, in terms of durability and ease of handling, such as esterified products of polyhydric alcohol and (meth) acrylic acid that can be cured by ultraviolet rays, electron beams or heating, and urethane-modified (meth) acrylates. A curable composition containing a (meth) acryloyl group-containing compound as a main component is excellent. The curable composition for forming a surface layer usually contains 50% by weight or more, preferably 60% by weight or more of these (meth) acryloyl group-containing compounds.

  Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentylglycol, 2-ethyl-1,3-hexanediol, 2,2 Examples include divalent alcohols such as' -thiodiethanol and 1,4-cyclohexanedimethanol; trivalent or higher alcohols such as trimethylolpropane, glycerol, pentaerythritol, diglycerol, dipentaerythritol, and ditrimethylolpropane.

  The urethane-modified (meth) acrylate can be obtained by a urethanization reaction between a terminal isocyanate polyurethane and a (meth) acrylic acid derivative having a hydroxyl group.

  Terminal isocyanate polyurethanes are polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, and organic compounds in which these polyisocyanates are isocyanurate-modified, adduct-modified, biuret-modified. An isocyanate etc. can be mentioned as an example. Among these, in order to improve the flexibility and elasticity of the surface layer 19, a modified product of an aliphatic polyisocyanate is preferable.

  Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, and the like. it can.

  Urethane-modified (meth) acrylates include oligomers having a plurality of hydroxyl groups such as polycaprolactone diol and 1,4-butanediol, tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol polyoxyethylene monostearate, poly By including a long-chain alkyl alcohol such as oxyethylene cetyl ether, polyoxyethylene stearyl ether, or glycerol monostearate, the restorability can be improved and the surface smoothness can be made appropriate.

  These components may be used alone or in combination of two or more. In addition, in order to obtain an excellent dent feeling and appropriate restorability, it is preferable to appropriately include a long-chain component among the various compounds such as the polyhydric alcohol and urethane-modified (meth) acrylate.

Examples of the long chain component include a chain containing a repeating unit represented by the following chemical formula (1), (2) or (3).
—O — [(CH ₂ ) _j —O] _k − (1)
However, j = 2 to 4 and k = 2 to 30.

但し、ｍ＝３〜１２およびｎ＝１〜１５である。

However, m = 3-12 and n = 1-15.

− (CH ₂ ) _p − (3)
However, p = 10-24.
The repeating unit or residue of these long chain components is preferably contained in the curable composition in an amount of 10 to 70% by weight, more preferably 20 to 60% by weight. In the case of the component represented by the chemical formula (1), the chain having a repeating unit is preferably 2 to 30 chains, and more preferably 2 to 20 chains. The number j of carbon atoms in the repeating unit of the component of the chemical formula (1) is preferably 2 to 4. In the case of the component of the chemical formula (2), the chain is preferably 1-15, and more preferably 1-10. The number m of carbon atoms in the repeating unit of the component of the chemical formula (2) is preferably 3 to 12, and more preferably 3 to 8. The component of the chemical formula (3) has a long methylene chain, and the carbon number p is preferably 10 to 24, and more preferably 12 to 20.

  Moreover, in order to make the adhesiveness with the base material 16 or the functional layer laminated | stacked on the base material 16 favorable, you may make the curable composition contain the compound which has at least one of a carboxyl group and a hydroxyl group. Although it will not be limited if it is a compound having at least one of a carboxyl group and a hydroxyl group, specifically, a compound having both a hydroxyl group and a carboxyl group such as hydroxysuccinic acid, salicylic acid, lactylic acid, 2-hydroxybutyric acid, ) A compound having both an unsaturated bond and a carboxyl group, such as acrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid monohydroxyethyl acrylate, and a copolymer containing these monomers, allyl alcohol, meta Examples thereof include compounds having both an unsaturated bond and a hydroxyl group, such as ril alcohol, vinyl alcohol, oleyl alcohol and 2-hydroxypropyl acrylate, and copolymers containing these monomers. The content is desirably 0.01 to 30% by weight, and more desirably 0.1 to 15% by weight. If the content of these compounds is less than 0.01% by weight, the adhesion to the substrate is insufficient, and if it exceeds 30% by weight, the restorability becomes unsatisfactory.

  Moreover, you may use together the component which has one unsaturated bond as a reactive diluent. These are not particularly limited as long as they are monomers having good compatibility with the resin used as the main component. For example, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl acrylate, styrene, methylstyrene, N-vinylpyrrolidone, dimethylacrylamide and the like can be mentioned. These may be used alone or in combination of two or more.

  Furthermore, in order to adjust the viscosity of the curable composition for forming a surface layer, a curable composition solution for forming a surface layer may be prepared using a dilution solvent. These are not particularly limited as long as they are non-polymerizable. For example, toluene, xylene, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether , 3-methoxybutanol and the like. These diluent solvents may be used alone or in combination of two or more. The content thereof is usually 0.1 to 80% by weight in the curable composition solution for forming the surface layer, although it depends on the composition of the curable composition for forming the surface layer.

  In order to make the slip feeling of the writing feeling more appropriate, a polysiloxane compound can be contained in the curable composition for forming the surface layer. The polysiloxane compound is preferably a linear or branched polydiorganosiloxane compound. A representative example of polydiorganosiloxane is polydimethylsiloxane. It may have a structure in which part or all of the methyl group is substituted with another organic group (however, the position at which the methyl group is substituted may be a terminal or a chain). .

  Examples of such other organic groups include alkyl groups other than methyl groups, aryl groups, cycloalkyl groups, and chains having repeating units such as polyoxyalkylene chains and polyester chains. Furthermore, these organic groups can have a hydroxyl group, an amino group, an epoxy group, an acyl group, an acyloxy group, a carboxyl group, and other functional groups.

  Examples of the chain having a repeating unit include polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polyoxytetramethylene chains, poly (oxyethyleneoxypropylene) chains, polycaprolactone chains, and polyethylene sebacate chains. And polyester chains such as polyethylene adipate chains.

  Moreover, even if the terminal of these chains is a hydroxyl group, a carboxyl group, a (meth) acryloyl group, or a vinyl group, the terminal may be blocked with an organic group. For example, it may be blocked by alkyl etherification or alkyl esterification. In addition, this chain is usually bonded to a silicon atom via an alkylene group such as a dimethylene group or a trimethylene group, but is not limited thereto.

  The content of the polysiloxane compound used in the present invention in the curable composition for forming a surface layer is usually 0.01 to 10% by weight, particularly preferably 0.01 to 5% by weight. When this content exceeds 10% by weight, the surface layer 19 becomes hard and its restoring property is inhibited, and the surface of the surface layer 19 becomes too slippery, so that an appropriate slip feeling cannot be obtained. On the other hand, when the amount is less than 0.01% by weight, neither smooth feeling nor surface smoothness can be obtained, which is not preferable.

  The curable composition for forming a surface layer used in the present invention contains the above-mentioned (meth) acryloyl group-containing compound, a compound having at least one of a carboxyl group and a hydroxyl group, a polysiloxane compound, and other compounds described later, a solvent and the like. Is obtained. The machine for blending, the blending order, etc. are not particularly limited.

  As a method of applying the curable composition for forming a surface layer directly on the base material 16 or on a functional layer laminated on the base material 16, a roll coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, Any known method such as a coating method, a knife coating method, a die coating method, a gravure coating method, a curtain flow coating method, a reverse coating method, a kiss coating method, or a comma coating method may be used. In addition, when applying, some pretreatment such as corona discharge may be performed in advance in order to improve the adhesion between the base material 16 and the surface layer 19 as necessary.

  The method for curing the curable composition for forming a surface layer, which is applied directly on the base material 16 or on the functional layer laminated on the base material 16 as described above and dried, is not particularly limited and is publicly known. (For example, irradiation with active energy rays such as ultraviolet rays and light and curing by heat).

  In the case of curing by ultraviolet irradiation, a conventionally known photopolymerization initiator is added to the curable composition for forming the surface layer and then cured. Specific examples of photopolymerization initiators include, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoin propyl ether, Benzyldimethyl ketal, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy 2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and other thioxanthates Etc.

As the energy ray source used for the above-mentioned curing, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, or the like is used. The irradiation amount of the energy ray source is preferably 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is less than 50 mJ / cm ² , curing becomes insufficient, so that the wear resistance and hardness of the surface layer 19 are lowered. On the other hand, when it exceeds 5000 mJ / cm ² , the surface layer 19 is colored and the transparency is lowered.

  Moreover, when hardening by heating, it hardens | cures, after adding a conventionally well-known thermal polymerization initiator in the curable composition for surface layer formation. Specific examples of the thermal polymerization initiator include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and the like. These thermal polymerization initiators may be used alone or in combination of two or more.

  In the surface layer forming curable composition, pigments, fillers, surfactants, dispersants, plasticizers, ultraviolet absorbers, antioxidants, and the like are added as necessary within the range that does not impair the performance. can do. These may be used alone or in combination of two or more.

  Further, the pressure-sensitive adhesive layer 20 can be formed on the opposite surface of the base material 16 on which the surface layer 19 is formed. By forming the pressure-sensitive adhesive layer 20, the pen input device is subjected to post-processing on the pen input touch panel 12. 10 can be easily manufactured. As such a pressure-sensitive adhesive layer 20, for example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like can be used, but it is preferable to use an acrylic pressure-sensitive adhesive from the viewpoint of transparency. In terms of releasability, it is preferable to use a silicone-based adhesive. These pressure-sensitive adhesives can contain a plasticizer, a tackifier component and the like in addition to the pressure-sensitive polymer component, but it is more desirable to use an additive that does not impair the transparency.

  Examples of the adhesive polymer that is the main component of the acrylic adhesive include 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate, butyl methacrylate, propyl methacrylate, and other alkyl alcohols having 1 to 10 carbon atoms. A copolymer of an alkyl ester with (meth) acrylic acid and a functional group-containing unsaturated monomer such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferably used. It is done.

  Further, as the adhesive polymer as the main component of the rubber-based adhesive, a styrene-butadiene random copolymer, a styrene-isoprene block copolymer, natural rubber and the like are preferably used. It is preferable to produce an adhesive layer of these components with a thickness of 5 to 100 μm.

As the conductive layer formed on the opposite surface of the base material 16 on which the surface layer 19 is formed, that is, the transparent conductive thin films 13 and 14, tin oxide (SnO ₂ or the like), indium oxide, antimony oxide, zinc oxide Examples thereof include metal oxides such as (ZnO), cadmium oxide, and indium tin oxide (ITO), and metal films such as gold, silver, copper, aluminum, tin, and nickel. Among these, oxides made of a single metal such as zinc oxide and tin oxide are preferable because they can be easily controlled by the stoichiometric ratio and provide a high-performance thin film.

  The method for laminating the conductive layer is not particularly limited, and examples thereof include a sputtering method, a vacuum deposition method, an ion plating method, a low pressure plasma method, a coating method, and an atmospheric pressure chemical vapor deposition (CVD) method. The thickness of the conductive layer is such that the conductive performance and the infrared and electromagnetic wave reducing performance are expressed and the transparency is maintained, that is, the visible light transmittance is 60% or more. It is preferable that it is 30-200 nm.

  When producing the pen input device surface material 23, first, a photopolymerization initiator is added to a composition containing a (meth) acryloyl group-containing compound, a compound having at least one of a carboxyl group and a hydroxyl group, or a polysiloxane compound. Is added to prepare a curable composition. For example, the curable composition is applied to one surface of a polyethylene terephthalate film as the substrate 16 with a roll coater, and cured by irradiating with ultraviolet rays with a high-pressure mercury lamp to form the surface layer 19. In this manner, the pen input device surface material 23 in which the surface layer 19 is formed on the substrate 16 is obtained.

  Next, on the other surface of the polyethylene terephthalate film, for example, a silicone-based adhesive is applied and dried to provide an adhesive layer 20, and the pen input device surface material 23 is pasted on the touch panel body for pen input. A touch panel 12 is obtained. Furthermore, the pen input device 10 is manufactured by assembling the pen input touch panel 12 on the surface of a liquid crystal display, for example.

  Then, the input pen 21 is held in the hand, the pen tip is slid on the surface of the surface layer 19 of the surface material 23, and the input operation is performed so as to draw characters. At this time, the pressed portion of the surface layer 19 is dented by the load of the input pen 21. The surface material 23 is provided with flexibility and elasticity on the surface based on the physical properties of the cured product of the (meth) acryloyl group-containing compound, and as a result, the restoration time for returning the recessed portion of the surface layer 19 to 0 is zero. .2 to 20 sec. Therefore, when the input pen 21 is operated, the smoothness is good and the operation feeling is good.

The effects exhibited by the above embodiment will be described collectively below.
The surface material 23 for the pen input device of the present embodiment is excellent when the input pen 21 is brought into contact with the operation surface of the surface layer 19 because the restoration time of the surface layer 19 is in the range of 0.2 to 20 sec. Written feeling and visibility are obtained. Therefore, since the grip feeling of the pen is different compared to a pen input device that does not consider writing feeling, the input error due to the sliding of the pen tip is reduced to reduce false recognition, and soft touch feeling and writing pressure control operation For example, the stress due to the input operation can be reduced.

In addition, since the Martens hardness of the surface layer 19 is in an appropriate range of 0.5 to 50 N / mm ² , the dent condition is appropriate and the dent feeling can be improved. Furthermore, since the elastic energy of the surface layer 19 is in the range of 0.1 to 20 nJ and the amount of elastic deformation is sufficient, the durability can be further improved.

  -Since the total light transmittance of the surface layer 19 exists in the range of 80% or more, transparency is high and visibility can be improved. At the same time, since the haze value of the surface layer 19 is 5% or less, the haze is low and the visibility can be further improved.

  Since the static friction coefficient of the surface layer 19 is 0.3-2, the resistance at the start of operation of the input pen 21 is small and the dynamic friction coefficient is 0.02-0.6, so that the operation of the input pen 21 is The resistance in the middle is also small, and the smoothness can be improved.

  The curable composition for forming the surface layer 19 contains a (meth) acryloyl group-containing compound as a main component, and the curable composition is applied to the substrate 16 and cured with ultraviolet rays or the like to be cured. By forming the surface material 23, it is possible to make a surface material 23 that is excellent in durability and is easy to handle and excellent in recoverability, visibility, and writing feeling.

  The curable composition contains 10 to 70% by weight of the repeating unit represented by the chemical formula (1), (2) or (3), and the curable composition is applied to the substrate 16 and cured to form a surface layer. By forming 19, the elasticity of the cured product can be increased, and the restoration property, visibility, and writing feeling of the surface material 23 can be further improved.

  The curable composition contains a compound having at least one of a carboxyl group and a hydroxyl group in the range of 0.01 to 30% by weight, and is applied to the substrate 16 and cured to form the surface layer 19. Thereby, the adhesiveness of the surface layer 19 with respect to the base material 16 can be improved based on a carboxyl group or a hydroxyl group.

  The curable composition contains a polysiloxane compound in the range of 0.01 to 10% by weight, and is applied to the base material 16 and cured to form the surface layer 19, thereby restoring. It is possible to improve the property and to make the slipperiness more appropriate.

  -The input operation with the input pen 21 on the pen input touch panel 12 incorporating the pen input device surface material 23 has excellent writing feeling and good visibility, so that even if the input operation is repeated, there is no feeling of fatigue and it is comfortable. . Furthermore, the pen input device 10 incorporating the pen input touch panel 12 can exhibit the effects of the surface layer 19 and the pen input touch panel 12 described above.

EXAMPLES Hereinafter, based on an Example, this invention is demonstrated in detail, comparing with a comparative example. Moreover, each surface material 23 for pen input devices was evaluated by the following method.
1) Restoration time (restorability)
Indentation of the surface of the surface layer 19 in the surface material 23 generated when the surface of the surface layer 19 is moved at a speed of 10 cm / sec using the input pen 21 having a load of 200 g in an atmosphere of 20 ° C. and 50% relative humidity. The restoration time was visually evaluated. The time from when the pen tip of the moved input pen 21 was separated from the surface layer 19 surface to when the dent formed on the surface layer 19 surface was restored was evaluated.

2) Martens hardness and elastic energy Ultrafine hardness test device (manufactured by Fisher Instruments Co., Ltd.) on the surface layer 19 of the pen input device surface material 23 in an atmosphere of 20 ° C. and 50% relative humidity. (Trade name: Fisherscope H-100), the maximum load was 2 mN, the first creep was 5 sec, and the second creep was 5 sec.

3) Static friction coefficient and dynamic friction coefficient On the surface layer 19 of the surface material 23 for the pen input device 23 using an input pen (trade name: stylus, manufactured by Palm Co., Ltd.) having a load of 200 g under an atmosphere of 20 ° C. and 50% relative humidity. The dynamic friction coefficient (μs, no unit) and the static friction coefficient (μk, no unit) when moving the plate at a speed of 10 cm / sec are measured by surface property test equipment (manufactured by Shinto Kagaku Co., Ltd., trade names: Tribogear, TYPE: 14DR).

4) Visibility, total light transmittance and haze value Using a direct reading haze meter (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: direct reading haze meter (No. 206)), total light transmittance (%) as optical characteristics And haze value (%) were measured. In the total visibility, visibility was visually evaluated. The case where the visibility was good was marked with ◯, and the case where the transmission image was difficult to see was marked with x.

5) Writing feeling The writing was actually performed on the surface layer 19 by using the input pen 21, and the writing feeling was evaluated by 10 people from two viewpoints of smooth feeling and dent feeling. And when 6 out of 10 judges as good writing feeling, ○ is evaluated when 3 to 5 out of 10 judges, and x is evaluated when 2 or less out of 10 judges. did. The total writing feeling was evaluated in the same manner by adding a rough feeling to the above two viewpoints.

6) Adhesion A cross-cut peel test was performed based on JIS K5600.
Example 1
Hexamethylene diisocyanate derivative (trimethylene propane adduct modified type of hexamethylene diisocyanate, manufactured by Dainippon Ink & Chemicals, Inc., trade name: Burnock DN-950), 50% by weight, cetyl alcohol (manufactured by Nippon Oil & Fats Co., Ltd., Product name: NAA-44) 9% by weight and polycaprolactone-modified hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., product name: Plaxel FA3) 41% by weight urethane acrylate 87.8% by weight, phthalic acid mono Hydroxyethyl acrylate (trade name: M-5400, manufactured by Toagosei Co., Ltd.), 9.0% by weight, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -Propan-1-one (photopolymerization initiator) 3.0 wt% and polysiloxane Emissions-based compound (produced by BYK (Byk-chemie) Co., Ltd., trade name: BYK-333) for the surface layer consisting of 0.2 wt% resin solution (curable composition) was prepared. The content of the repeating unit represented by the chemical formula (1), (2) or (3) in the curable composition was 33% by weight.

It was uniformly applied to a polyethylene terephthalate film having a thickness of 100 μm with a roll coater to a thickness of 20 μm, and irradiated with ultraviolet rays (1 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.) in a nitrogen atmosphere. The coating was cured. Next, a surface material 23 for a pen input device according to the present invention was prepared by applying a solution containing a silicone-based adhesive on the surface opposite to the cured surface and drying to provide an adhesive layer 20 having a thickness of 50 μm. The pen input touch panel 12 was obtained by bonding the pen input device surface material 23 to the touch panel body. The pen input device 10 was produced by crimping and pasting it on the surface of the liquid crystal display at room temperature. The pen input touch panel 12 employs the resistive film type shown in FIG.

  Using this, restoration time, Martens hardness, elastic energy, coefficient of static friction, dynamic friction coefficient, writing feeling (dent feeling, slip feeling, total writing feeling), visibility (total light transmittance, haze value, total visual feeling) and Evaluation of adhesion was performed. The results are shown in Table 1.

実施例２
ヘキサメチレンジイソシアネート誘導体（ヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ、三井武田ケミカル（株）社製、商品名：タケネートＤ−１７０Ｎ）５０重量％、ステアリルアルコール（日本油脂（株）社製、商品名：ＮＡＡ−４６）９重量％およびポリカプロラクトン変性ヒドロキシエチルアクリレート（ダイセル化学工業（株）社製、商品名：プラクセルＦＡ２Ｄ）４１重量％からなるウレタンアクリレート８９．８重量％と、フタル酸モノヒドロキシエチルアクリレート（東亞合成（株）社製、商品名：Ｍ−５４００）９．０重量％と、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（光重合開始剤）１．０重量％と、ポリシロキサン系化合物（ビックケミー（Ｂｙｋ−ｃｈｅｍｉｅ）社製、商品名：ＢＹＫ−３０６）０．２重量％とからなる表面層用樹脂液（硬化性組成物）を調製した。硬化性組成物中における前記化学式（１）、（２）または（３）に示す繰り返し単位の含有量は、３１重量％であった。

Example 2
Hexamethylene diisocyanate derivative (isocyanurate modified type of hexamethylene diisocyanate, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Takenate D-170N), 50% by weight, stearyl alcohol (manufactured by Nippon Oil & Fats Co., Ltd., trade name: NAA) -46) 89.8% by weight of urethane acrylate consisting of 9% by weight and 41% by weight of polycaprolactone-modified hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Plaxel FA2D), monohydroxyethyl acrylate phthalate ( Toagosei Co., Ltd., trade name: M-5400) 9.0 wt%, 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator) 1.0 wt%, polysiloxane compound (Bic Chemie) (Byk-chemie), product name: YK-306) surface layer resin solution consisting of 0.2 wt% (curable composition) was prepared. The content of the repeating unit represented by the chemical formula (1), (2) or (3) in the curable composition was 31% by weight.

It is uniformly coated on a 50 μm thick polyethylene terephthalate film with a roll coater to a thickness of 30 μm, and irradiated with ultraviolet rays (1 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.) in a nitrogen atmosphere. The coating was cured. Next, the surface material 23 for pen input devices of this invention was produced by apply | coating and drying the solution containing a silicone adhesive on the surface on the opposite side of a hardening surface, and providing the adhesive layer 20 with a thickness of 25 micrometers. Using this surface material 23 for a pen input device, a pen input device 10 was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 3
Hexamethylene diisocyanate isocyanurate-modified type (Mitsui Takeda Chemical Co., Ltd., trade name: Takenate D-170N) 21.7% by weight and polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industries, Ltd., trade name) : Plaxel FA5) 88.8% by weight urethane acrylate consisting of 78.3% by weight, 8.0% by weight itaconic acid, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- From 3.0% by weight of methyl-1-propan-1-one (photopolymerization initiator) and 0.2% by weight of a polysiloxane compound (byk-chemie, trade name: BYK-361N) A surface layer resin solution was prepared. The content of the repeating unit represented by the chemical formula (1), (2) or (3) in the resin liquid for surface layer (curable composition) was 57% by weight.

The film is uniformly coated on a polyethylene terephthalate film having a thickness of 180 μm with a roll coater at a thickness of 30 μm, and irradiated with ultraviolet rays (3 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.). Cured. Next, the surface material 23 for pen input devices of this invention was produced by coating the solution containing an acrylic adhesive on the surface on the opposite side of the cured surface and drying to provide an adhesive layer 20 having a thickness of 50 μm. Using this surface material 23 for a pen input device, a pen input device 10 was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Hexamethylene diisocyanate isocyanurate-modified type (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Takenate D-170N) 40.0% by weight, polycaprolactone-modified hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name) : 96.9% by weight of urethane acrylate comprising 45.5% by weight of Plaxel FA1) and 14.5% by weight of polycaprolactone-modified hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Plaxel FA5), 2- Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (photopolymerization initiator) 3.0% by weight and a polysiloxane compound (byk-chemie, trade name) : BYK-358N) Surface layer resin solution comprising 0.1% by weight Was prepared. The content of the repeating unit represented by the chemical formula (1), (2) or (3) in the resin liquid for surface layer (curable composition) was 32% by weight.

The film is uniformly coated on a 100 μm thick triacetate film with a roll coater to a thickness of 20 μm, and irradiated with ultraviolet rays (3 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.) to cure the coating film. I let you. Next, the surface material 23 for pen input devices of this invention was produced by coating the solution containing an acrylic adhesive on the surface on the opposite side of the cured surface and drying to provide an adhesive layer 20 having a thickness of 25 μm.

Using this surface material 23 for a pen input device, a pen input device 10 was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
Example 5
Hexamethylene diisocyanate isocyanurate-modified type (Mitsui Takeda Chemical Co., Ltd., trade name: Takenate D-170N) 29% by weight and polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industries, Ltd., trade name: Plaxel) FA3) urethane acrylate composed of 71% by weight, 1.0% by weight of monohydroxyethyl acrylate phthalate (manufactured by Toagosei Co., Ltd., trade name: M-5400), 2-hydroxypropyl acrylate (Osaka Organic Chemical Co., Ltd., trade name: HPA) 5.0% by weight, methyl-2-benzoylbenzoate (photopolymerization initiator) 1% by weight, and polysiloxane compound (Byk-chemie) Product name: BYK-306) 0.2% by weight, Hexane compound (BYK (Byk-chemie) Co., Ltd., trade name: BYK-361N) and the surface layer resin solution consisting of 0.025 wt% was prepared. The content of the repeating unit represented by the chemical formula (1), (2) or (3) in the resin liquid for surface layer (curable composition) was 48% by weight.

It was uniformly applied to a 50 μm thick triacetate film with a roll coater at a thickness of 50 μm, and irradiated with ultraviolet light (1 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.) under a nitrogen atmosphere. The coating was cured. Next, the surface material 23 for pen input devices of this invention was produced by apply | coating and drying the solution containing a silicone type adhesive agent on the surface on the opposite side of a hardening surface, and providing an adhesive layer with a thickness of 10 micrometers. Using this surface material 23 for a pen input device, a pen input device 10 was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 6
Polyethylene glycol # 600 diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-600) 78.8% by weight, dipentaerythritol hexaacrylate 9.9% by weight, acrylic acid 1.0 % By weight, 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name: HPA) 9.0% by weight, polysiloxane compound (byk-chemie, trade name: BYK) -306) By sufficiently stirring a liquid mixture consisting of 0.3% by weight and 1.0% by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator) A resin solution for the surface layer was prepared. The content of the repeating unit represented by the chemical formula (1), (2) or (3) in the surface layer resin liquid (curable composition) was 67% by weight.

It is uniformly coated on a 100 μm thick polyethylene terephthalate film with a roll coater to a thickness of 20 μm, and irradiated with ultraviolet rays (3 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.) in a nitrogen atmosphere. The coating was cured. Next, the surface material 23 for pen input devices of this invention was produced by coating the solution containing an acrylic adhesive on the surface on the opposite side of the cured surface and drying to provide an adhesive layer 20 having a thickness of 50 μm. Using this surface material 23 for a pen input device, a pen input device 10 was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
On a polyethylene terephthalate film having a thickness of 125 μm, 100% by weight of dipentaerythritol hexaacrylate and 3% by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator) are added. An acrylic hard coat resin as a component was applied to a thickness of 5 μm and then cured. Further, an acrylic pressure-sensitive adhesive mainly composed of a copolymer of 100% by weight of 2-ethylhexyl acrylate and 10% by weight of acrylic acid is applied to the opposite surface of the base material to a thickness of 40 μm to form a transparent pressure-sensitive adhesive layer. And a surface material was produced by drying. Using this surface material, a pen input device was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A transparent polyethylene terephthalate film having a thickness of 100 μm is composed of 100% by weight of dipentaerythritol hexaacrylate and 3% by weight of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (photopolymerization initiator) on one side. Apply a resin liquid containing acrylic hard coat resin, 2% by weight of acrylic resin beads having a particle size of 5 to 10 μm, and a small amount of silicone resin, and cure by ultraviolet irradiation to form a resin layer having a thickness of 5 μm. Formed. A surface material was prepared by applying an acrylic pressure-sensitive adhesive in the form of a solution to the opposite surface of the polyethylene terephthalate film and drying it. Using this surface material, a pen input device was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
At a thickness of 300 μm, a polyol liquid mainly composed of polycaprolactone triol and a polysiloxane compound and an isocyanate liquid mainly composed of hexamethylene diisocyanate are mixed at a weight ratio of 100: 90 on one side of a polyethylene terephthalate film having a thickness of 100 μm. It was applied and cured by heating at 120 ° C. for 20 minutes. Then, it peeled from the polyethylene terephthalate film and produced the soft resin film. A surface material was prepared by applying an acrylic pressure-sensitive adhesive in the form of a solution to the surface of the soft resin film and drying it. Using this surface material, a pen input device was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
Triethylene diisocyanate derivative (Takeda Pharmaceutical Co., Ltd., trade name: Takenate D-212) 40% by weight and polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industries, trade name: Plaxel FA3) 60% by weight % Urethane acrylate consisting of 77%, polydimethylsiloxane macromonomer (manufactured by Chisso Corporation, trade name: FM0721) 15% by weight, methyl methacrylate 25% by weight, butyl methacrylate 25% by weight, isocyanate ethyl methacrylate (Showa Denko) 20% by weight of an ultraviolet curable silicone copolymer comprising 15% by weight, manufactured by Co., Ltd., trade name: Karenz MOI, and 20% by weight of pentaerythritol triacrylate (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.) And 1 Hydroxy - cyclohexyl - phenyl - ketone (photopolymerization initiator) surface layer resin solution composed of 3 wt% and was prepared.

It was uniformly applied to a polyethylene terephthalate film having a thickness of 100 μm with a roll coater to a thickness of 20 μm, and irradiated with ultraviolet rays (1 J / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.) in a nitrogen atmosphere. The coating was cured. Next, the surface material 23 for pen input devices of this invention was produced by apply | coating and drying the solution containing an acrylic adhesive on the surface on the opposite side to a hardening surface. Using this surface material 23 for a pen input device, a pen input device was produced in the same manner as in Example 1. Using this, various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 6, the restorability was particularly good in all, and the writing feeling and the visibility were also good. In Example 4 using a curable composition not containing a compound having a carboxyl group and a hydroxyl group, the adhesion was insufficient. On the other hand, in all of Comparative Examples 1 to 4, the restorability was not appropriate, and good writing feeling could not be obtained. In Comparative Example 2, the haze value was high and the visibility was poor. In Comparative Examples 3 and 4, the restoration time was early and the feeling of dents could not be fully felt.

It should be noted that the above-described embodiment can be modified as follows.
An elastic material such as a thermoplastic elastomer can be added to the curable composition for forming the surface layer 19 to improve the surface resilience of the surface layer 19.

  A silane coupling agent having a (meth) acryloyl group is added to the curable composition for forming the surface layer 19, and the (meth) acryloyl group-containing compound and the polysiloxane compound are combined. May be.

  A monomer having at least one of a carboxyl group and a hydroxyl group is used as a raw material of the transparent resin constituting the substrate 16 and the adhesion with the surface layer 19 is improved by giving the transparent resin a carboxyl group or a hydroxyl group. You can also

-The shape of the pen tip of the input pen 21 may be a semi-elliptical shape, an irregular curved surface shape, or the like.
Further, the technical idea that can be grasped from the embodiment will be described below.
(1) The (meth) acryloyl group-containing compound is a urethane-modified (meth) acrylate obtained by a urethanization reaction between a terminal isocyanate polyurethane and a (meth) acrylic acid derivative having a hydroxyl group. Item 1. A surface material for a pen input device according to item 1. When comprised in this way, the elasticity of a surface layer can be improved, a restoring property can be improved, and a writing feeling can be made favorable.

  (2) The surface material for a pen input device according to the technical concept (1), wherein the terminal isocyanate polyurethane is a modified product of an aliphatic polyisocyanate. When configured in this manner, the flexibility and elasticity of the surface layer can be further increased, and the effect of the technical idea (1) can be improved.

  (3) The surface material for a pen input device according to the technical concept (1) or (2), wherein the (meth) acrylic acid derivative having a hydroxyl group is polycaprolactone-modified (meth) acrylate. When configured in this way, the flexibility and elasticity of the surface layer can be further increased, and the effect of the technical idea (1) or (2) can be improved.

Sectional drawing which shows the surface material for pen input devices. Sectional drawing which shows the surface material for pen input devices which has an adhesion layer on the back surface. (A) And (b) is sectional drawing which shows typically a resistive film type pen input touch panel. The schematic sectional drawing which shows the pen input touch panel of an electromagnetic induction system. Sectional drawing which shows the concept of a pen input device.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Pen input device, 11 ... Display, 12 ... Pen input touch panel, 13, 14 ... Transparent electroconductive thin film which comprises a touch-panel main body, 15 ... Base material which comprises a touch-panel main body, 16 ... Base material, 18 ... Touch-panel main body Insulating spacers, 19 ... surface layer, 21 ... input pen, 22 ... transparent resin base material constituting touch panel body, 23 ... surface material for pen input device.

Claims (12)

When the surface of the surface layer for a pen input device comprising a base material and a surface layer is moved at a speed of 10 cm / sec using an input pen with a load of 200 g in an atmosphere of 20 ° C. and 50% relative humidity The surface material for pen input devices is characterized in that the dent generated in the surface is restored within a period of 0.2 to 20 seconds. ^2. The pen input device according to claim 1, wherein the Martens hardness of the surface layer measured by an ultrafine hardness tester in an atmosphere of 20 ° C. and 50% relative humidity is within a range of 0.5 to 50 N / mm ^2. Surface material. The surface for a pen input device according to claim 1 or 2, wherein the elastic energy of the surface layer measured by an ultrafine hardness tester in an atmosphere of 20 ° C and 50% relative humidity is in the range of 0.1 to 20 nJ. Wood. The pen input device surface material according to any one of claims 1 to 3, wherein the pen light input device surface material has a total light transmittance of 80% or more. The surface material for pen input devices according to any one of claims 1 to 4, wherein the surface material for pen input devices has a haze value of 5% or less. The dynamic friction coefficient is 0.02 to 0.6 when the surface of the surface layer is moved at a speed of 10 cm / sec using an input pen with a load of 200 g in an atmosphere of 20 ° C. and 50% relative humidity, and static friction. The coefficient is 0.3-2, The surface material for pen input devices of any one of Claims 1-5. The surface material for pen input devices according to any one of claims 1 to 6, wherein the surface layer is formed by applying and curing a curable composition containing a (meth) acryloyl group-containing compound as a main component. The surface layer is formed by applying and curing a curable composition containing 10 to 70% by weight of a repeating unit represented by the following chemical formula (1), (2) or (3). A surface material for a pen input device according to Item.
—O — [(CH ₂ ) _j —O] _k − (1)
However, j = 2 to 4 and k = 2 to 30.

However, m = 3-12 and n = 1-15.
− (CH ₂ ) _p − (3)
However, p = 10-24. The surface layer is formed by applying and curing a curable composition containing a compound having at least one of a carboxyl group and a hydroxyl group within a range of 0.01 to 30% by weight. Surface material for pen input devices as described in 1. The pen input device according to any one of claims 1 to 9, wherein the surface layer is formed by applying and curing a curable composition containing a polysiloxane compound within a range of 0.01 to 10% by weight. Surface material. A pen input touch panel comprising the surface material for a pen input device according to any one of claims 1 to 10 on a touch panel body. 12. A pen input device comprising the pen input touch panel according to claim 11 provided on a display.

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