JP2007301773A - Surface material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface material which is improved in the water/oil repelling characteristics on its surface and thus exhibits excellent anti-staining properties, and also to provide its manufacturing method. <P>SOLUTION: The surface material 17 is arranged for use on the surface of a target inclusive of a touch panel 10 or the like being an image display requiring anti-staining properties and has uneven part 20 on its surface. When the width of the protruded parts constituting the uneven part 20 is a(μm), the height thereof is c(μm) and the width of the recessed parts of the uneven part 20 is b(μm), (a), (b) and (c) satisfy a formula (1): 0<c/a≤30, a formula (2): 0.01≤b/a≤10 and a formula (3): 0.01 μm≤a≤500 μm. A hydrophobic treatment layer is further formed on the uneven part 20. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is arranged on the surface of objects such as wallpaper, kitchen tiles, glass cases, etc. in addition to image displays such as automatic teller machines (ATMs) and cash dispensers (CDs). In addition, the present invention relates to a surface material capable of exhibiting excellent antifouling property on an object itself and a method for producing the same.

2. Description of the Related Art Conventionally, as information terminals, for example, navigation devices, automatic cash withdrawal and deposit devices, automatic teller machines, vending machines, security system terminals, and the like are equipped with an image display in the input / output unit. However, when these information terminals are used, the display surface is touched with a finger to operate, and fingerprints or the like due to biological lipid components such as sebum adhere to the surface. It was difficult to do. In addition, displays for display such as wallpaper, kitchen tiles, show glass, glass cases, plastic cases and the like are exposed to contamination due to adhesion of organic substances and the like, and the appearance tends to be impaired. Therefore, examples of measures for preventing fingerprints and various organic contaminants from adhering to the surface of the display have been proposed. As one of these, a surface treatment agent comprising a hydrolyzable metal alkoxide, a fluorine compound having a functional group that reacts with the metal alkoxide, and an adhesion improver is known (see, for example, Patent Document 1).
Republished Patent No. W02002 / 077116 (pages 2-7)

  However, the surface treatment agent described in Patent Document 1 has the advantage that the fingerprint can be easily wiped off by the fluorine compound, but there is a limit to flipping lipid, which is the main component of the fingerprint, so that it does not cause a problem. I couldn't. Therefore, there is a problem that dirt due to the adhesion of fingerprints remains and the visibility of the display surface cannot be satisfied at a practical level.

  Accordingly, an object of the present invention is to provide a surface material capable of improving the water and oil repellency characteristics on the surface and exhibiting excellent antifouling properties and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by making the outermost surface layer a resin layer having specific irregularities, and have completed the present invention. . That is, the surface material of the first invention in the present invention is a surface material that is required to have antifouling properties, has a concavo-convex portion on the surface, and the width of the bulge portion constituting the concavo-convex portion is a (μm), When the height is c (μm) and the width of the recess is b (μm), the a, b, and c satisfy the relationship of the following expressions (1), (2), and (3). A hydrophobic treatment layer is formed on the uneven portion.

Formula (1): 0 <c / a ≦ 30
Formula (2): 0.01 ≦ b / a ≦ 10
Formula (3): 0.01 μm ≦ a ≦ 500 μm
The manufacturing method of the surface material of the second invention is the manufacturing method of the surface material of the first invention, and is an uncured active energy ray curable type disposed on the concave and convex pattern surface of the original plate and the outermost surface of the surface material. The first step of closely adhering the resin, the second step of curing the uncured active energy ray-curable resin while pressurizing the adhering site, and the uneven part by peeling the original plate from the cured active energy ray-curable resin And a fourth step of forming a hydrophobic treatment layer by subjecting the uneven portion to a hydrophobic treatment.

  The manufacturing method of the surface material of the third invention is the manufacturing method of the surface material of the first invention, wherein the concave-convex pattern surface of the original plate and the thermoplastic resin arranged on the outermost surface of the surface material are in close contact with each other. 1st step, 2nd step of cooling to room temperature after pressurizing with the temperature of the adhered part being equal to or higher than the softening point of the thermoplastic resin, 3rd step of peeling the original plate to obtain a surface material having uneven portions, And a fourth step of forming a hydrophobic treatment layer by applying a hydrophobic treatment on the uneven portion.

According to the present invention, the following effects can be exhibited.
In the surface material of the first invention, the width a, the height c, and the width b of the concave portion constituting the concave-convex portion satisfy the relationship of the above formulas (1), (2), and (3). Set to That is, the range of the width of the convex portion is defined, the ratio of the height of the convex portion to the width and the ratio of the width of the concave portion is set to a predetermined range, and the concave / convex shape of the concave / convex portion is regular within a certain range. . Therefore, it is estimated that a gap is formed between the surface material surface and water or oil adhering to the surface, and water or oil is repelled. In addition, a hydrophobic treatment layer is formed on the concavo-convex portion, and the water and oil repellency characteristics can be enhanced based on the hydrophobicity of the hydrophobic treatment layer.

Therefore, the surface material has improved water and oil repellency on the surface and can exhibit excellent antifouling properties.
In the method for manufacturing the surface material of the second or third invention, the surface material having the effect of the first invention can be easily manufactured, and the obtained surface material is clear because the uneven portion is formed by transfer. In addition, uniform irregularities can be formed.

In the following, embodiments that are considered to be the best of the present invention will be described in detail.
The surface material of this embodiment is required to have antifouling properties, and is for ensuring visibility by suppressing contamination due to fingerprints and the like adhering to the surface. Such a surface material is divided into a first form arranged on the surface of an object as a film or the like, and a second form which is an object itself that requires antifouling properties. Generally, the surface material is often used in the first form, but the second form is also employed. The above objects include navigation devices, automatic cash deposit / deposit devices, cash dispensers, vending machines, security system terminals, personal computers, televisions, mobile phones, and other image displays, as well as glass cases and plastic cases. For example, a display is included.

  This surface material has only a base material (preferably a transparent base material) or a resin layer on the surface thereof, and an uneven portion is formed on the surface of the base material or the resin layer. The uneven | corrugated | grooved part which concerns is comprised by a specific shape. That is, when the width of the convex portion constituting the concave and convex portion is a (μm), the height is c (μm), and the width of the concave portion is b (μm), those a, b and c are the following formulas: It is set so as to satisfy the relationships of (1), Equation (2), and Equation (3).

Formula (1): 0 <c / a ≦ 30
Formula (2): 0.01 ≦ b / a ≦ 10
Formula (3): 0.01 μm ≦ a ≦ 500 μm
In other words, the shape of the concavo-convex part is set such that the width a of the convex part is set to a certain range, and the height c of the convex part and the width b of the concave part (interval of the convex part) are within a certain range with respect to the width a. Is set to be regular. The range of formula (1) is preferably 0.1 ≦ c / a ≦ 25, more preferably 0.5 ≦ c / a ≦ 10, and the range of formula (2) is preferably 0.05 ≦ b / a ≦ 5. More preferably, 0.1 ≦ b / a ≦ 0.4, and the range of the formula (3) is preferably 0.05 ≦ a ≦ 100 μm, more preferably 0.1 ≦ a ≦ 50 μm.

  When c / a is larger than 30, it is substantially difficult to produce, and when b / a is larger than 10, water or oil easily penetrates into the recesses. Voids formed between water and oil are reduced. Therefore, water and oil are hardly repelled, and the antifouling property of the surface material is lowered. In addition, when b / a is smaller than 0.01, the width of the concave portion (interval between the convex portions) is not an appropriate width, and is formed between the surface material surface and water or oil adhering to the surface. When the gaps are reduced, water and oil are hardly repelled, and the function of repelling water and oil is not exhibited. Further, when a is smaller than 0.01 μm, the production is substantially difficult. On the other hand, when it is larger than 500 μm, the width of the convex portion is not an appropriate width, and water or oil is reduced by reducing the gap formed between the surface material surface and water or oil adhering to the surface. It becomes difficult to play, and the function to play water and oil will not be demonstrated.

  The planar shape and cross-sectional shape of the convex portions, the arrangement of the convex portions, and the like can be appropriately selected as long as the object of the present invention can be achieved, but the entire shape of the surface material is covered by the columnar shape constituting the convex portions as a repeating unit. It is necessary. Examples of the columnar form of the convex portion include a polygonal column such as a cylinder, an elliptical column, and a quadrangular column, and similar shapes are included as long as the object of the present invention can be achieved. Among these, a rectangular quadrangular prism in a plan view is preferable from the viewpoint of easy fabrication of the uneven shape. The columnar upper end surface is preferably flat, but may be concave or convex as long as the object of the present invention can be achieved.

  A hydrophobic treatment layer is provided on the concavo-convex portion as described above to increase the hydrophobicity of the surface. This hydrophobic treatment layer is formed by subjecting the uneven surface to a hydrophobic treatment with a hydrophobic treatment agent such as a fluorine-containing compound or a silane compound, and a fluorine-containing compound is more preferred from the viewpoint of oil repellency.

  The substrate is not particularly limited as long as a predetermined uneven portion can be formed on both the inorganic substance and the organic substance. Examples of the inorganic substance include a silicon wafer or quartz glass, and examples of the organic substance include a resin molded product and a film. It is done. The thickness of the film is preferably 10 to 500 μm from the viewpoint of transparency and workability. A resin film is preferably used as the substrate. Examples of the resin film include polyesters such as polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, regenerated cellulose, diacetyl cellulose, triacetyl cellulose, acrylonitrile / styrene / butadiene terpolymer, polyvinyl chloride, polyvinylidene chloride, and polyvinyl chloride. Examples include alcohol, nylon, polyethylene, cellulose acetate, polypropylene, polyamide, polyimide, polysulfone, polyethersulfone, and norbornene resin. In these, what has favorable transparency, such as a polyethylene terephthalate, a triacetyl cellulose, a polycarbonate, is preferable.

  As the resin for forming the resin layer, for example, an active energy ray curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. Among these, it is preferable to use an active energy ray-curable resin or a thermoplastic resin from the viewpoints of productivity and various physical properties.

  When an active energy ray-curable resin is used, a polymerizable component is essential as a constituent component of the coating agent. That is, the polymerizable component is one or two of a monofunctional monomer, a polyfunctional monomer, an oligomer having a vinyl group or a (meth) acryloyl group, and a polymer having a vinyl group or a (meth) acryloyl group. More than species are selected and used. Other polymerization initiators such as photodecomposition type or thermal decomposition type, oligomers not containing vinyl groups or (meth) acryloyl groups, polymers not containing vinyl groups or (meth) acryloyl groups, surfactants, dilution as required You may add suitably additives, such as a solvent, a photosensitizer, a stabilizer, a ultraviolet absorber, an infrared absorber, and antioxidant.

  As the monofunctional monomer, all known monofunctional monomers can be used. For example, the following monofunctional monomers are preferable. That is, (meth) acrylic acid ester, itaconic acid ester, and fumaric acid ester are mentioned as a compound which is an ester compound with an alcohol having 1 to 20 carbon atoms and does not contain a fluorine atom. Furthermore, (meth) acrylic acid amide which is an amide compound with an amine having 1 to 10 carbon atoms and does not contain a fluorine atom can be mentioned. In addition, styrene and substituted styrene containing no fluorine atom can be mentioned. Moreover, the compound containing a fluorine atom can also be used with the said ester compound, an amide compound, or substituted styrene. Other examples include N-vinyl-2-pyrrolidone and substituted N-vinyl-2-pyrrolidone.

  Specifically, the following monofunctional monomers can be exemplified. That is, monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, ( Isobutyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Cetyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyloxy (meth) acrylate Ethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid N-methylpiperidyl, ethyl (meth) acrylate hexahydrophthalate, ethyl (meth) acrylate 2-hydroxypropyl phthalate, 2-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acryl (Meth) acrylic acid esters such as phenoxyethyl acid, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate, styrene, α-methylstyrene, p (m ) -Methoxystyrene, di-t-butyl fumarate, di-n-butyl fumarate, diethyl fumarate, mono (di) methyl itaconate, mono (di) ethyl itaconate, N-isopropylacrylamide, N-vinyl-2- Preferably contains pyrrolidone Yes.

  Examples of the polyfunctional monomer include esterified products of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified (meth) acrylate, and the like. . Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, Divalent alcohols such as hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedimethanol; trimethylolpropane, glycerol, pentaerythritol, di Examples thereof include trivalent or higher alcohols such as glycerol, dipentaerythritol, and ditrimethylolpropane.

  The urethane-modified (meth) acrylate can be obtained by a urethanization reaction between an organic isocyanate having a plurality of isocyanate groups in one molecule and a (meth) acrylic acid derivative having a hydroxyl group. Examples of organic isocyanates having a plurality of isocyanate groups in one molecule include two isocyanates in one molecule such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Organic isocyanate having a group, organic isocyanate having three isocyanate groups in one molecule obtained by subjecting these organic isocyanates to isocyanurate modification, adduct modification, biuret modification, and the like.

  Among them, di (meth) acrylate hexanediol, di (meth) acrylate neopentyl glycol, di (meth) acrylate diethylene glycol, di (meth) from the viewpoint of improving the strength of the resin layer and availability. (Meth) acrylates such as tripropylene glycol acrylate, polymethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexamethylene diisocyanate and (meth ) Adduct of 2-hydroxyethyl acrylate, adduct of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate, adduct of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate, adduct-modified isophorone Diisocyanate Doo and (meth) adducts of adduct and biuret modified isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl acrylate is preferable.

  Oligomers that do not contain vinyl or (meth) acryloyl groups include acrylic oligomers, polyester oligomers, epoxy oligomers, urethane oligomers, polyether oligomers, alkyd oligomers, polybutadiene oligomers, polythiol polyene oligomers and spiroacetal oligomers, polyvalent oligomers. The oligomer which consists of polyfunctional (meth) acrylic acid ester of alcohol is mentioned.

  Examples of the oligomer having a vinyl group or (meth) acryloyl group include an oligomer obtained by adding a vinyl group or (meth) acryloyl group to the above oligomer. Examples of the polymer that does not contain a vinyl group or (meth) acryloyl group include polymer types of oligomers that do not contain the vinyl group or (meth) acryloyl group. Examples of the polymer having a vinyl group or a (meth) acryloyl group include polymer types of oligomers having the vinyl group or the (meth) acryloyl group.

  Examples of the polymerization initiator include known compounds that start polymerization upon irradiation with active energy rays such as ultraviolet rays and light. For example, benzophenones, acetophenones, α-amyloxime esters, Michler benzoylbenzoate, tetramethylchuram mono Examples thereof include sulfide and thioxanthone. Specifically, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-Morferinopropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy- 1,2-diphenylethane-1-one, benzophenone, [4- (methylphenol Nylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothioxanthone, 2,4-diethylthioxanthone , Α-amyloxime ester, Michler benzoylbenzoate, tetramethylchuram monosulfide and the like.

  Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin, poly A siloxane resin or the like can be used. In addition, surfactants, diluent solvents, stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, and the like may be added as necessary.

  As the thermoplastic resin, a polymer obtained by polymerizing a monofunctional monomer used when the raw material component is the active energy ray-curable resin, a polymer containing no acrylic functional group is essential. In addition, surfactants, diluent solvents, stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants, and the like may be added as necessary.

  As described above, an uneven portion can be provided on the surface of the substrate itself. In that case, it is preferable to use a hydrophobic material (hydrophobic resin) as the substrate. In such a case, it is not necessary to provide a resin layer on the substrate, and the substrate and the resin layer can be used together. As such a substrate, for example, a fluororesin (polytetrafluoroethylene or the like), an active energy ray-curable resin containing a fluorine atom as the above-mentioned monofunctional monomer, or the like can be used.

  The surface material is a desired functional layer such as a pressure-sensitive adhesive layer, an ultraviolet absorbing layer, an infrared absorbing layer, an antireflection layer, a soft (impact-resistant layer), if necessary, between the back surface of the substrate or between the substrate and the resin layer. ) Each layer such as a layer, a hard coat layer, a conductive layer, an antistatic layer, a heat insulating layer, a reflective layer, and a primer layer can be provided as a single layer or a plurality of layers.

  Next, when the above surface material is manufactured, the following two transfer methods are preferable, but an uneven portion can be directly formed on the surface of the surface material (material). The first transfer method is a first step in which the concavo-convex pattern surface of the original plate and the uncured active energy ray-curable resin disposed on the outermost surface of the surface material are in close contact with each other. A second step of curing the active energy ray-curable resin, a third step of peeling the original plate from the cured active energy ray-curable resin to obtain a surface material having an uneven portion, and a hydrophobic treatment on the uneven portion This is a method including a fourth step of forming a hydrophobized layer by applying the step.

  The second transfer method is a first step in which the concave / convex pattern surface of the original plate and the thermoplastic resin disposed on the outermost surface of the surface material are brought into close contact with each other, and the temperature of the contacted portion is set to a temperature equal to or higher than the softening point of the thermoplastic resin. A second step of cooling to room temperature after pressurizing, a third step of peeling the original plate to obtain a surface material having a concavo-convex portion, and forming a hydrophobic treatment layer by applying a hydrophobic treatment on the concavo-convex portion It is a method including a fourth step.

  The method for forming the concavo-convex portion by the first to third steps is not particularly limited, and a conventionally known method can be used. For example, a lithographic method (photolithographic method, photomechanical method), A transfer method using the unevenness-imparted substrate obtained as a master is a preferable method. The lithographic method is generally a method in which the surface of a material is cut using light, an electron beam or the like. That is, first, a resist is applied to one surface of a material for preparing an original plate, exposure drawing is performed on each region of the resist with an electron beam exposure apparatus, and an uneven pattern can be obtained after development. Next, the original plate on which the concave / convex pattern capable of shaping the specific concave / convex pattern is formed can be obtained by performing plasma etching on the original plate preparation material at a predetermined etching rate ratio using the concave / convex pattern as a masking material. For example, when the original plate production material is a quartz glass substrate, the etching rate can be adjusted using a gas in which a predetermined amount of oxygen is mixed in a fluorine-based gas as an etching gas. As the original plate, for example, a commercially available shaping film, a shaping roll, a flat plate mold for shaping press or the like having a predetermined uneven shape can be prepared and used.

  Moreover, the method for transferring the original plate to form the uneven portion on the surface material is not particularly limited, and a conventionally known method can be applied. In the case of a thermoplastic resin having a softening point, the concavo-convex pattern surface of the original plate is pressed against the substrate or the resin layer at a temperature equal to or higher than the softening point to deform the surface (first step), and then cooled (second). A method of transferring the original plate by a process) is preferable.

  On the other hand, in the case of an active energy ray curable resin, the original plate is pressed against the base material or the resin layer in a liquid state before the curing (first step) and is cured in the state (second step). As the curing method, a known curing method such as a curing method using an active energy ray such as an ultraviolet curing method or a curing method using a thermal decomposition polymerization initiator is employed. After the curing, the original plate is peeled off (third step) to obtain a surface material to which the concave / convex pattern of the original plate is transferred. You may make it harden | cure in the state which peeled the original plate before hardening resin. Before the resin is cured, the original plate may be peeled off and cured in that state.

  Next, as a method of forming the hydrophobized layer by the fourth step, it is performed by a hydrophobizing treatment using a water / oil repellent treating agent such as a fluorine-containing compound and a silane compound which are usually used. it can. As the water / oil repellent treatment agent, conventionally known ones can be used without problems. From an industrial viewpoint, a copolymer obtained by copolymerizing a monomer containing a perfluoroalkyl group or a perfluoroether group with another monomer as a fluorine-containing compound is preferably used.

Examples of the silane compound include conventionally known fluorinated silane coupling agents. Specific examples include compounds represented by the following chemical formula.
_{CF 3 - (CF 2) n} -R-Si (X p Y 3-P)
[Wherein, n is an integer of 0 to 12, preferably 3 to 12, and R is a divalent organic group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group) or a silicon atom and oxygen. X is a substituent selected from hydrogen or a monovalent hydrocarbon group having 1 to 4 carbon atoms (for example, an alkyl group or an allyl group) or a derivative thereof, and p is 0, 1 or 2 and Y is an alkoxyl group having 1 to 4 carbon atoms. ]
Among these compounds, one or a plurality of compounds can be used in combination. Among the fluoroalkylsilanes, for example, n = 7, R = ethylene group, p = 0, Y = ethoxy group heptadecafluorodecyltriethoxysilane, n = 7, R = ethylene group, p = 0, Particularly preferred is heptadecafluorotrimethoxysilane or the like where Y = methoxy group.

  As a method for forming the hydrophobic treatment layer, a conventionally known method can be used without any problem. For example, a dry coating method such as a gas phase adsorption method or a wet coating method can be used. Among these, the wet coating method is preferable from an industrial viewpoint. Examples of wet coating methods include roll coating, spin coating, dip coating, brush coating, spray coating, bar coating, knife coating, die coating, gravure coating, curtain flow coating, and reverse coating. Any known method such as kiss coating method or comma coating method may be used. At the time of application, some pretreatment such as corona treatment may be performed in advance in order to improve interlayer adhesion as necessary. For the purpose of improving the adhesion between the hydrophobized layer and the resin layer having a concavo-convex portion, the resin layer is preferably subjected to UV treatment, plasma treatment, corona treatment, etc. on the surface of the resin layer before forming the hydrophobized layer. .

  The hydrophobized layer preferably further contains fine particles having an average particle size of 0.001 to 10 μm. In that case, the penetration of water or oil can be suppressed as compared with the hydrophobized layer containing no fine particles, and as a result, the effect of water / oil repellency can be further enhanced. The average particle diameter of the fine particles is preferably 0.001 to 0.20 μm, more preferably 0.005 to 0.05 μm.

  The fine particles to be used are not particularly limited, and examples thereof include inorganic fine particles and plastic beads. It is preferable to use colloidal silica as the inorganic fine particles. Colloidal silica is available, for example, as a colloidal solution in which ultrafine particles of polymeric inorganic silicic acid are dispersed in water or an organic solvent. Representative examples include “Snowtex” manufactured by Nissan Chemical Industries, Ltd., and Catalyst Chemical Industry Co., Ltd. “OSCAL” manufactured by the company can be mentioned. When using such inorganic fine particles, the surface of the fine particles is preferably hydrophobized in advance. Examples of the material of the plastic beads include vinyl chloride resin, acrylic resin, acrylic-styrene copolymer resin, polystyrene resin, melamine resin, polyethylene resin, polycarbonate resin, and fluororesin (PTFE).

  The compounding amount of the fine particles is usually 10 to 70 parts by mass, preferably 20 to 60 parts by mass with respect to 100 parts by mass of the constituent components of the hydrophobic treatment layer. When the blending amount of the fine particles is less than 10 parts by mass, the effect of the fine particles cannot be sufficiently exhibited in the resin layer, the water repellency / oil repellency is lowered, and when it is more than 70 parts by mass, the strength of the hydrophobized layer is increased. It tends to decrease.

  Examples of the object include automatic cash withdrawal and deposit device (ATM), cash dispenser (CD), navigation device, personal computer, TV, mobile phone display (display device), wallpaper, kitchen tile, Examples include show window glass, glass cases, and plastic cases. Among these objects, a touch panel and a display with a touch panel are preferable for imparting antifouling properties and improving visibility.

  Specific examples of the display include all known displays such as CRT (CRT), LCD (Liquid Crystal Display), PDP (Plasma Display), FED (Field Emission Display), ELD (Electroluminescence Display), and Projection Display.

  In addition to the integrated type incorporated in various displays as described above, there are separate types of touch panels that are arranged on the display surface of various display devices. As a touch panel system, a known system is adopted and is not particularly limited. Specifically, 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 can be given. 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. 1 (a), a resistive touch panel 10 has a transparent resin on the fixed side (lower side in the figure) and movable side (upper side in the figure) provided with transparent conductive thin films 11 and 12 on one side. The base materials 13 and 14 made of a sheet are arranged so that the transparent conductive thin films 11 and 12 face each other, and the periphery is adhered by an adhesive reinforcing material 15 so that a constant interval can be maintained. On one transparent conductive thin film 11, a large number of insulating spacers 16 are provided in a dot shape so that the opposing transparent conductive thin films 11 and 12 are insulated. A touch panel body is constituted by the base materials 13 and 14, the transparent conductive thin films 11 and 12, the insulating spacer 16, and the like. The surface material 17 is provided on the movable base 14.

  Alternatively, in the touch panel 10 shown in FIG. 1B, in the configuration of FIG. 1A, a transparent base material 19 is bonded to the surface of the movable base material 14 by a pressure-sensitive adhesive layer 18 as a surface material 17, An uneven portion 20 is provided on the surface. And, by pressing the surface material 17 with the input pen 21 or the finger, the movable conductive film 12 on the movable side is brought into contact with the transparent conductive film 11 on the fixed side so as to be electrically connected to allow input. Yes.

  As shown in FIG. 2, the electromagnetic induction type touch panel 10 has a transparent base material 19 bonded to the surface of the base material 14 by a pressure-sensitive adhesive layer 18 as a surface material 17, and an uneven portion 20 is provided on the surface. Yes. On the back surface of the base material 14, a pen position detector 22 in which a receiving circuit is stretched around a liquid crystal element (LCD) is provided. Further, an electromagnetic input pen 21 having a transmission coil (not shown) is provided. Then, by pressing the concavo-convex portion 20 with the input pen 21, electromagnetic waves generated by electromagnetic induction are detected by the pen position detector 22 and the input position is recorded. In any of the resistive film type and electromagnetic induction type touch panels 10, a finger, a hand, or the like comes into contact with the surface of the surface material 17 during an input operation or the like, and a biological lipid component adheres.

  From the viewpoint of not impairing the visibility on the surface of the display such as the touch panel 10, the total light transmittance is preferably 80% or more, more preferably 85% or more. When the total light transmittance is less than 80%, the display surface feels dark and the visibility is deteriorated. The haze value is preferably 40% or less, more preferably 30% or less. When the haze value exceeds 40%, the opacity is felt and the visibility is deteriorated.

  By forming the pressure-sensitive adhesive layer on the surface of the surface material opposite to the concavo-convex portion, it can be easily installed on the front surface of a display such as a touch panel. In this case, as the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, for example, an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and the like can be used. In terms of transparency, an acrylic pressure-sensitive adhesive is used. In view of removability, it is preferable to use a silicone-based adhesive.

  In addition to the adhesive polymer component, the adhesive can contain a plasticizer, a tackifier component, etc., but it is more desirable not to 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 alcohols having an alkyl group 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, and hydroxyethyl methacrylate is preferred. As the adhesive polymer which is the main component of the rubber adhesive, styrene-butadiene random copolymer, styrene-isoprene block copolymer, natural rubber and the like are preferable. It is preferable that the thickness of the adhesive layer by these components is 5-100 micrometers.

  Now, the operation of this embodiment will be described. For example, a concavo-convex pattern is formed on the surface of the object itself by a lithographic method, or a concavo-convex portion is formed on the surface by a transfer method using it as a master plate. And the hydrophobization process using a fluorine-containing compound etc. is given to the surface of these uneven | corrugated | grooved parts, and the hydrophobization process layer is formed. The width “a”, the height “c”, and the width “b” of the concave portion constituting the concave-convex portion of the surface material are set so as to satisfy the relationship of the above formulas (1), (2), and (3). For this reason, the range of the width of the convex portion is defined, the ratio of the height of the convex portion to the width and the ratio of the width of the concave portion is set to a predetermined range, and the concave-convex shape of the concave-convex portion is regular within a certain range. Become. Then, when water or oil adheres to the surface material surface in a state where the concavo-convex portion satisfies the above relational expression, a gap is formed between the attached water or oil and the concavo-convex portion, and water and oil are repelled well. It is presumed that water and oil repellency characteristics are exhibited. In addition, hydrophobicity is manifested on the surface based on the properties of the hydrophobized layer formed on the uneven portion of the surface material.

The effects exhibited by the above embodiment will be described collectively below.
-In the surface material of this embodiment, the width a of the convex part which comprises an uneven | corrugated | grooved part, height c, and the width | variety b of a recessed part satisfy | fill the relationship of said Formula (1), Formula (2), and Formula (3). Set to That is, the range of the width of the convex portion is defined, the ratio of the height of the convex portion to the width and the ratio of the width of the concave portion is set to a predetermined range, and the concave / convex shape of the concave / convex portion is regular within a certain range. . In addition, a hydrophobic treatment layer is formed on the uneven portion. Therefore, the surface material has improved water and oil repellency on the surface and can exhibit excellent antifouling properties.

-By forming the said uneven | corrugated | grooved part with hydrophobic resin, water-repellent | oil-repellent property can be improved based on the hydrophobicity of hydrophobic resin.
-By including fine particles having an average particle size of 0.001 to 10 μm in the hydrophobic treatment layer on the uneven portion, finer particles in the hydrophobic treatment layer are formed on the uneven portion of the uneven portion. Unevenness is formed, and the water and oil repellency characteristics can be further improved.

  -By adopting a transfer method using an original plate as a method for producing a surface material, it is possible to easily produce a surface material having the above-mentioned effects, and the obtained surface material is formed with uneven portions by transfer. Therefore, clear and uniform irregularities can be formed.

Hereinafter, the embodiment will be described more specifically with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. The width a of the convex portion, the width b of the concave portion, the height c of the convex portion, the water / oil repellency and the antifouling property in each example were measured and evaluated by the following methods.
1) Width of convex part a and width b of concave part
The width a (μm) of the convex portion and the width b (μm) of the concave portion were measured with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-3000N).
2) Convex height c
The height c (μm) of the convex part was measured with a surface roughness measuring machine (manufactured by Kosaka Laboratory, Surfcoder SE4000).
3) Water / oil repellency Contact angle measurement using a contact angle measuring device (Kyowa Interface Science Co., Ltd., Model: Drop Master 500) using 4 μl droplets, water repellency is achieved by contact angle with pure water. The oil repellency was evaluated by the contact angle with respect to dodecane.
4) Antifouling property In the evaluation of the water / oil repellency, the higher the contact angle with pure water and the contact angle with dodecane, the higher the antifouling property.
(Production Example 1)
A silicon wafer was prepared as a base material, and a silicon oxide film of about 0.1 μm was formed on one surface of the silicon substrate using a thermal oxidation method. Next, photosensitive resin ZEP520A (solution) manufactured by Nippon Zeon Co., Ltd. is dropped onto the silicon oxide film of the single crystal silicon substrate, and spin coated at a speed of 4000 revolutions per minute for 1 minute. Formed. Under this spin coating condition, the photosensitive resin could be applied with an average film thickness of about 0.1 μm and a wafer surface variation of 10%. The coating film thickness can be appropriately changed depending on the size of the groove to be processed.

Next, the substrate was dried in an oven at 180 ° C. for 30 minutes, the substrate was cooled to room temperature, and a concavo-convex pattern was formed by a photolithographic method. Subsequently, after etching the silicon oxide film in the groove planned region with hydrofluoric acid, the photosensitive resin was removed with a stripping solution. Next, using a dry etching apparatus, a plasma synthesis film using a gas containing C and F was formed. Subsequently, after the dry etching apparatus was evacuated, silicon was etched by plasma of chemical formula SF ₆ or CF ₄ gas. . By repeating the above plasma polymerization and plasma etching, the surface of the silicon substrate was etched to form concave and convex portions. Through the above procedure, a material having a concavo-convex pattern of a = 10 μm, b = 2 μm, and c = 5 μm was produced.
(Production Examples 2 to 11)
A material having a concavo-convex pattern as shown in Table 1 was produced by the same procedure as in Production Example 1.
Example 1
The material of Production Example 1 was subjected to a hydrophobization treatment by a gas phase adsorption reaction of heptadecafluorodecyltriethoxysilane to form a hydrophobization treatment layer to obtain a surface material. The contact angles on the surface of the obtained surface material were a contact angle with water of 140 degrees and a contact angle with dodecane of 128 degrees. The uneven pattern on the surface of the hydrophobized layer was substantially the same as the uneven pattern of the material of Production Example 1.
(Examples 2 to 11)
In Example 1, except that the material was changed to the material of the production example shown in Table 1, an uneven resin layer was formed in the same procedure as in Example 1, and the surface treatment material was formed by forming a hydrophobic treatment layer on the surface. Obtained. Then, the contact angle with water and the contact angle with dodecane were evaluated in the same manner as in Example 1. Each evaluation result is shown in Table 1. In addition, the uneven | corrugated pattern of the hydrophobic treatment layer surface in Examples 2-11 was substantially the same as the uneven | corrugated pattern of the original material (material of each manufacture example shown in Table 1).
(Examples 12 to 16)
100.0 parts by mass of tetraethoxysilane, colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtech IPA-ST, 30% isopropanol solution, average particle size: 12 nm), 50.0 parts by mass, heptadecafluorodecyltri 43.0 parts by mass of ethoxysilane and 19.3 parts by mass of 0.1N hydrochloric acid aqueous solution were stirred to prepare a mixed solution. The mixed solution was coated on the materials of Production Examples 3, 4, 9, 10, and 11 by a spin coating method. Then, the contact angle with water and the contact angle with dodecane were evaluated in the same manner as in Example 1. The obtained evaluation results are shown in Table 1.

表１に示した結果より、実施例１〜１１においては、凸部の幅ａ、高さｃ及び凹部の幅ｂに関する前記関係式が本発明の範囲に入っているため、比較例１の場合に比べて対水接触角及び対ドデカン接触角が大きく、撥水・撥油性に優れ、防汚性が向上した。特に、実施例１、３、５、７では、凸部の幅ａ、高さｃ及び凹部の幅ｂの関係式が前述の好ましい範囲にあるため、撥水・撥油性、さらには防汚性の評価が最も優れていた。

From the results shown in Table 1, in Examples 1 to 11, the relational expressions related to the width a of the convex portion, the height c, and the width b of the concave portion are within the scope of the present invention. Compared to, the contact angle with water and contact angle with dodecane are large, and it has excellent water and oil repellency and improved antifouling property. In particular, in Examples 1, 3, 5, and 7, since the relational expression of the width a of the convex portion, the height c, and the width b of the concave portion is in the above-described preferable range, the water and oil repellency, and further, the antifouling property The rating was the best.

In addition, in Examples 12 to 16, since the hydrophobized layer contains silica fine particles, the contact angle with water and the contact angle with dodecane are generally large, and the water and oil repellency and further the antifouling property are increased. It was excellent.
(Example 17)
Active energy ray-curable resin (pentaerythritol triacrylate / 1-hydroxycyclohexyl phenyl ketone / methyl ethyl ketone = 100/2/150, each amount unit: parts by mass) blended on a polyethylene terephthalate (PET) substrate It apply | coated so that it might become 3 micrometers, and dried for 60 second at 70 degreeC. On top of that, the material produced in Production Example 9 was pressed and pressed as the original plate, and fixed so that the active energy ray-curable resin located between the original plate and the base material had a predetermined shape.

Thereafter, the film was cured by irradiation with ultraviolet rays (integrated light amount 400 mJ / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nippon Batteries Co., Ltd.). A concavo-convex resin layer (concavo-convex part) having a width a of 10 μm, c / a of 5 and b / a of 0.1 was formed. The surface was hydrophilized by corona treatment, and then hydrophobized by a gas phase adsorption reaction of heptadecafluorodecyltriethoxysilane to form a hydrophobized layer to obtain a surface material. The contact angle of the surface was 142 ° contact angle with water and 122 ° contact angle with dodecane. The uneven pattern on the surface of the hydrophobized layer in Example 17 was substantially the same as the uneven pattern of the original material.
(Comparative Example 1)
An active energy ray-curable resin (pentaerythritol triacrylate / 1-hydroxycyclohexyl phenyl ketone / methyl ethyl ketone = 100/2/150, representing a mass ratio) formulation was applied onto a PET film so that the dry film thickness was 3 μm. And dried at 70 ° C. for 60 seconds. Then, after irradiating with ultraviolet rays (accumulated light amount: 400 mJ / cm ² ) with a 120 W high-pressure mercury lamp (manufactured by Nihon Battery Co., Ltd.), the surface is corona-treated to be hydrophilized. Hydrophobized by the phase adsorption method. The obtained surface material was smooth with no irregularities on the surface. The contact angles on the surface were a water contact angle of 120 degrees and a dodecane contact angle of 70 degrees.

In addition, this embodiment can also be changed and embodied as follows.
-The range of the height of the convex part which comprises the uneven | corrugated | grooved part of a surface material can be prescribed | regulated, and the range of the ratio of the width | variety of a convex part with respect to the height and the width | variety of a recessed part can also be set.

In order to specify the uneven shape of the uneven portion, it is possible to consider the maximum height (Ry) and the average interval (Sm) of the unevenness specified in JIS B 0601-1994.
-When evaluating oil repellency, the contact angle with respect to oleic acid or the like can be employed instead of the contact angle with respect to dodecane.

Further, the technical idea that can be grasped from the embodiment will be described below.
The surface material according to claim 1, wherein a, b, and c constituting the concavo-convex portion satisfy a relationship of the following formulas (4), (5), and (6).

Formula (4): 0.1 ≦ c / a ≦ 25
Formula (5): 0.05 ≦ b / a ≦ 5
Formula (6): 0.05 ≦ a ≦ 100 μm
When comprised in this way, the effect of invention of Claim 1 can be improved further.

The surface material according to claim 1, wherein a, b, and c constituting the concavo-convex portion satisfy a relationship of the following formulas (7), (8), and (9).
Formula (7): 0.5 ≦ c / a ≦ 10
Formula (8): 0.1 ≦ b / a ≦ 0.4
Formula (9): 0.1 ≦ a ≦ 50 μm
When comprised in this way, the effect of invention of Claim 1 can be improved most.

  A surface having a concavo-convex portion formed of a hydrophobic resin, the width of the convex portion constituting the concavo-convex portion is a (μm), the height is c (μm), and the width of the concave portion is b (μm). In this case, the surface material is characterized in that a, b, and c satisfy the relationship of the following formulas (1), (2), and (3).

Formula (1): 0 <c / a ≦ 30
Formula (2): 0.01 ≦ b / a ≦ 10
Formula (3): 0.01 μm ≦ a ≦ 500 μm
When configured in this manner, the concavo-convex portion is formed of a hydrophobic resin, so that the hydrophobic treatment can be omitted.

  The surface material according to claim 1, wherein fine particles having an average particle diameter of 0.001 to 10 µm are contained in the hydrophobic treatment layer. When comprised in this way, the finer unevenness | corrugation by the microparticles | fine-particles in a hydrophobization process layer is formed on the unevenness | corrugation of the said uneven | corrugated | grooved part, and the effect of invention of Claim 1 can be improved.

  The surface material according to claim 1, wherein the surface material is a film-like material disposed on the surface of the object. When comprised in this way, the effect of the invention which concerns on Claim 1 can be easily exhibited by arrange | positioning a surface material on the surface of a target object.

(A) is sectional drawing which shows typically a resistive film type touchscreen, (b) is sectional drawing which shows typically the resistive film type touchscreen of another form. Sectional drawing which shows an electromagnetic induction type touchscreen typically.

Explanation of symbols

  17 ... surface material, 20 ... uneven portion.

Claims (3)

It is a surface material that requires antifouling properties, and has a concavo-convex portion on the surface, the width of the convex portion constituting the concavo-convex portion is a (μm), the height is c (μm), and the width of the concave portion is b ( μm), a, b, and c satisfy the relationship of the following formulas (1), (2), and (3), and a hydrophobic treatment layer is formed on the concavo-convex portion. A surface material characterized by
Formula (1): 0 <c / a ≦ 30
Formula (2): 0.01 ≦ b / a ≦ 10
Formula (3): 0.01 μm ≦ a ≦ 500 μm The first step of closely attaching the concavo-convex pattern surface of the original plate and the uncured active energy ray curable resin disposed on the outermost surface of the surface material, an uncured active energy ray curable resin while pressing the adhered portion A second step of curing, a third step of peeling the original plate from the cured active energy ray-curable resin to obtain a surface material having a concavo-convex portion, and a hydrophobic treatment layer by applying a hydrophobizing treatment on the concavo-convex portion The method for producing a surface material according to claim 1, further comprising a fourth step of forming the surface material. The first step of closely attaching the concavo-convex pattern surface of the original plate and the thermoplastic resin disposed on the outermost surface of the surface material, pressurizing the temperature of the contacted part to a temperature equal to or higher than the softening point of the thermoplastic resin, to normal temperature Including a second step of cooling, a third step of obtaining a surface material having an uneven portion by peeling the original plate, and a fourth step of forming a hydrophobized layer by subjecting the uneven portion to a hydrophobic treatment. The manufacturing method of the surface material of Claim 1 characterized by the above-mentioned.

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