JP6702022B2 - Touch panel, multilayer film, and method for manufacturing multilayer film - Google Patents

Description

  The present invention relates to a multilayer film having a substrate and an antifouling layer, a method for producing the multilayer film, and a touch panel including the multilayer film.

  2. Description of the Related Art In recent years, a touch panel that inputs information by pressing a finger or a pen on the surface of a display body such as an organic EL (electroluminescence) display (ELD) or a liquid crystal display (LD) has become widespread. Touch panels are used in various applications such as electronic notebooks, mobile terminals such as mobile phones, and ticket issuing machines.

  Fingerprints, sebum, and other stains may be attached or scratched on the surface of the touch panel during operation, and such stains and scratches may reduce visibility and adversely affect operability. .. For this reason, it is required that the surface of the touch panel be provided with characteristics such as antifouling property of dirt and easiness of wiping off dirt (antifouling property) and scratch resistance (hardness).

On the other hand, by using an optical film provided with an antifouling layer or a hard coat layer on a substrate, it is generally performed to impart antifouling property and scratch resistance (hardness) to the touch panel surface.
For example, in Patent Document 1, a hard coat layer, a high refractive index layer, and a low refractive index layer are sequentially provided on a transparent support, and further, a perfluoroalkyl polyether side chain is provided on the low refractive index layer. An antireflection film having an overcoat layer containing a polymer laminated thereon is disclosed.
Further, in Patent Document 2, an intermediate layer containing a photopolymerization initiator and an acrylate and/or a methacrylate is formed on the surface of a base material, and the intermediate layer is irradiated with light to be cured. There is disclosed an antifouling surface material obtained by applying a mixed solution of a solvent and irradiating it with an active energy ray to form a film containing a fluorine-containing polymer.

JP, 2000-284102, A JP, 2005-231128, A

In Patent Document 1, the excellent slipperiness of the perfluoroalkylpolyether compound is utilized to protect the layer on the surface side of the antireflection film from stains and improve scratch resistance. However, since the perfluoroalkylpolyether compound is simply applied and formed on the surface, it is easily peeled off by repeated rubbing, and there is a problem that the durability of the overcoat layer (antifouling layer) is poor.
Further, in Patent Document 2, since a fluorine-containing monomer that is soluble in a non-fluorine solvent is used, the antifouling property of the cured film (fluorine-containing polymer coating) is not sufficient.

  The present invention has been made in view of such circumstances, high hardness, and excellent in antifouling property, a multilayer film having an antifouling layer excellent in durability, a method for producing the multilayer film, and An object is to provide a touch panel provided with a multilayer film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors intend to solve the above-mentioned problems by using a combination of the component (A) and the component (B) or the component (C) described below. I found it.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [17].
[1] A touch panel comprising a multilayer film having a substrate and an antifouling layer, wherein the antifouling layer comprises (A) an alkoxysilane having a perfluoropolyether structure, (B) a trialkoxysilyl group, and A touch panel, which is a cured product containing a compound having a polymerizable group, or (C) a polycondensation product of at least one alkoxy group and a derivative of the component (B) having a polymerizable group.
[2] The touch panel according to [1], wherein the antifouling layer is a cured product using the condensation polymer and an ionizing radiation curable resin.
[3] The touch panel according to the above [1] or [2], which has a hard coat layer on the surface of the antifouling layer on the substrate side.
[4] The touch panel according to any one of [1] to [3] above, wherein the alkoxysilane having a perfluoropolyether structure is trimethoxysilane having a perfluoropolyether structure.
[5] The touch panel according to any one of the above [1] to [4], wherein a contact angle of pure water on the surface of the antifouling layer is 95° or more and a sliding angle is 30° or less.
[6] The reduction rate of the contact angle of pure water on the surface of the antifouling layer before and after wiping off the surface of the antifouling layer with an alcohol solvent is 0 to 15%, according to any one of the above [1] to [5]. Touch panel described in.
[7] A method for producing a multilayer film having at least a substrate and an antifouling layer, the method comprising:
On the substrate, (A) an alkoxysilane having a perfluoropolyether structure, (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) having at least one alkoxy group and a polymerizable group, Uncured composition for forming an antifouling layer, which comprises a polycondensation product obtained by hydrolyzing and polycondensing a derivative of component (B) with a mixed solvent containing an organic solvent, water and an acid. A method for producing a multilayer film, which comprises forming a layer and curing it to form an antifouling layer.
[8] The method for producing a multilayer film according to the above [7], wherein the uncured layer is cured by irradiation with ionizing radiation to form an antifouling layer.
[9] The method for producing a multilayer film according to the above [7] or [8], wherein the antifouling layer forming composition further contains an ionizing radiation curable resin.
[10] Before the formation of the uncured layer, a coating film of a composition for forming a hard coat layer containing an ionizing radiation-curable resin is formed on a substrate and irradiated with ionizing radiation to form a semi-cured layer. Forming the uncured layer in contact with the surface of the semi-cured layer opposite to the substrate, and simultaneously irradiating the semi-cured layer and the uncured layer with ionizing radiation to cure the hardened layer. The method for producing a multilayer film according to the above [8] or [9], wherein a coat layer and an antifouling layer are formed.
[11] Irradiation dose X _α (mJ/cm ² ) of ionizing radiation to be applied when forming the semi-cured layer, and ionizing radiation dose X of simultaneous irradiation to the semi-cured layer and the uncured layer. _The method for producing a multilayer film according to the above [10], wherein _β (mJ/cm ² ) satisfies the relationship of the following formula (I).
0.01≦X _α /(X _α +X _β )≦0.80 (I)
(However, X _α is 3 or more and 100 or less)
[12] A multilayer film having a substrate and an antifouling layer,
The antifouling layer has (A) an alkoxysilane having a perfluoropolyether structure, (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) at least one alkoxy group and a polymerizable group. A multilayer film, which is a cured product containing a polycondensation product with the derivative of the component (B).
[13] The multilayer film according to the above [12], wherein the antifouling layer is a cured product using the condensation polymer and an ionizing radiation curable resin.
[14] The multilayer film according to the above [12] or [13], which has a hard coat layer on the surface of the antifouling layer on the substrate side.
[15] The multilayer film according to any one of the above [12] to [14], wherein the alkoxysilane having a perfluoropolyether structure is trimethoxysilane having a perfluoropolyether structure.
[16] The multilayer film according to any one of the above [12] to [15], wherein the surface of the antifouling layer has a contact angle of pure water of 95° or more and a sliding angle of 30° or less.
[17] The reduction rate of the contact angle of pure water on the surface of the antifouling layer before and after being wiped off with an alcohol solvent on the surface of the antifouling layer is 0 to 15%, according to any one of the above [12] to [16]. The multilayer film according to.

  According to the present invention, it is possible to provide a multilayer film having a high hardness and excellent antifouling property and having an antifouling layer excellent in durability, a method for producing the multilayer film, and a touch panel provided with the multilayer film. it can.

It is sectional drawing which shows one Embodiment of the resistive film type touch panel of this invention. It is sectional drawing which shows one Embodiment of the electrostatic capacitance type touch panel of this invention. It is a schematic diagram which shows one form of the cross section of the multilayer film of this invention. It is a schematic diagram which shows one form of the cross section of the multilayer film of this invention.

Hereinafter, embodiments of the present invention will be described.
[Touch panel]
The touch panel of the present invention comprises a multilayer film having a substrate and an antifouling layer, the antifouling layer comprising (A) an alkoxysilane having a perfluoropolyether structure, (B) a trialkoxysilyl group and a polymerizable group. A cured product containing a compound having a group, or (C) a polycondensation product of the derivative of the component (B) having at least one alkoxy group and a polymerizable group.
Here, in the present invention, “having a perfluoropolyether structure” means having a group containing a perfluoropolyether bond.

Examples of the touch panel include a capacitive touch panel, a resistive film touch panel, an optical touch panel, an ultrasonic touch panel, an electromagnetic induction touch panel, and the like. These touch panels have a base material such as a glass base material and a plastic film base material, and a layer having various properties such as stain resistance and scratch resistance may be formed on the surface of the base material. ..
The touch panel of the present invention preferably uses a multilayer film described below as a surface member of the touch panel, and is installed so that the surface of the multilayer film on the antifouling layer side faces the surface side.

  As shown in FIG. 1, the resistive film type touch panel 1 has a basic configuration in which conductive films 12 of a pair of upper and lower transparent substrates 11 a and 11 b having a conductive film 12 are arranged via a spacer 13 so as to face each other. A circuit (not shown) is connected. In the case of a resistive film type touch panel, it is preferable to use a multilayer film described below as the upper transparent substrate 11a. The upper transparent substrate 11a and the lower transparent substrate 11b may have a multilayer structure including two or more base materials, and a multilayer film described below may be used as the outermost surface base material of the upper transparent substrate 11a.

The capacitive touch panel includes a surface type and a projection type, and the projection type is often used. The projected capacitive touch panel has a circuit connected to a basic configuration in which an X-axis electrode and a Y-axis electrode orthogonal to the X electrode are arranged with an insulator interposed therebetween. The basic configuration will be described more specifically. A mode in which an X electrode and a Y electrode are formed on separate surfaces of a single transparent substrate, and an X electrode, an insulating layer, and a Y electrode are formed in this order on the transparent substrate. As shown in FIG. 2, the X electrode 22 is formed on the upper transparent substrate 21a, the Y electrode 23 is formed on the lower transparent substrate 21b, and the Y electrode 23 is laminated via the adhesive layer 24 or the like. Be done.
In the case of a capacitive touch panel, it is preferable to use a multilayer film described below as the upper transparent substrate 21a. The upper transparent substrate 21a and the lower transparent substrate 21b may have a multilayer structure including two or more base materials, and a multilayer film described below may be used as the outermost base material of the upper transparent substrate 21a.

[Multilayer film]
FIG. 3 is a schematic view showing one form of a cross section of the multilayer film of the present invention. In the schematic diagram shown in FIG. 3, the scale in the thickness direction (vertical direction in the drawing) is greatly enlarged and exaggerated compared to the scale in the width direction (horizontal direction in the drawing) for ease of explanation. is there. The multilayer film 3 includes a base material 31 and an antifouling layer 32 provided on the base material 31. Further, as shown in FIG. 4, a hard coat layer 43 may be provided on the surface of the antifouling layer 42 on the substrate side.

Hereinafter, embodiments of each layer constituting the multilayer film of the present invention will be described.
<Substrate>
Examples of the substrate used for the multilayer film of the present invention include various inorganic materials such as glass plates, aluminum oxide plates, spin-on-glass (SOG) materials, thermoplastic resins, thermosetting resins, and ionizing radiation curable materials. Examples include various organic resin materials such as resins and organic-inorganic composite materials.
The above-mentioned substrate is preferably one having light transparency, smoothness, heat resistance, and excellent mechanical strength, and is preferably made of an organic resin material. Organic resin materials include triacetyl cellulose (TAC); cellulose resins such as nitrocellulose, cellulose acetate propionate, and ethyl hydroxyethyl cellulose; methyl poly(meth)acrylate, poly(meth)butyl acrylate, (meth) ) Acrylic resins such as methyl acrylate-butyl (meth)acrylate copolymer and methyl (meth)acrylate-styrene copolymer; polycarbonate resins; polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) Examples thereof include olefin resins such as polystyrene, cyclic polyolefin, polyethylene and polypropylene; vinyl resins such as polyvinyl chloride and polyvinylidene chloride; polyamide resins such as nylon-6 and nylon-6,6.
Among these, TAC, PET, acrylic resin, and PEN are preferable, TAC, PET, and PEN are more preferable, and TAC and PET are further preferable from the viewpoint of optical characteristics and strength.
The shape of the base material may be a planar structure or a three-dimensional structure.

The thickness of the substrate is not particularly limited, but from the viewpoint of optical characteristics and strength, it is preferably 1 to 500 μm, more preferably 3 to 300 μm, and further preferably 5 to 200 μm.
On the surface of the base material, in order to improve the adhesiveness, a physical treatment such as a corona discharge treatment or an oxidation treatment, or a coating called an anchor agent or a primer may be applied in advance.

  Further, from the viewpoint of use as a display or the like, the total light transmittance of the above-mentioned substrate is preferably 85% or more, more preferably 90% or more. The transmittance of the base material can be measured by a method according to JIS K7361-1 (Testing method for total light transmittance of plastic-transparent material).

<Anti-fouling layer>
The antifouling layer used in the multilayer film of the present invention is a layer having antifouling properties, and includes (A) an alkoxysilane having a perfluoropolyether structure, and (B) a compound having a trialkoxysilyl group and a polymerizable group, Alternatively, it is a cured product containing (C) a polycondensation product with the derivative of the component (B) having at least one alkoxy group and a polymerizable group (hereinafter, also simply referred to as “polycondensation product”). When the polycondensation product has a perfluoropolyether structure, the surface free energy of the antifouling layer can be reduced and stains can be made difficult to adhere. Further, since the polycondensation product has a structure in which the component (A) is polycondensed with the component (B) or the component (C), the intervals between adjacent perfluoropolyether structural sites are wide and sparse. Since the perfluoropolyether structure part is easy to move and has flexibility, slipperiness is improved, stains are less likely to adhere, and stains attached can be easily wiped off.
Further, since the component (B) and the component (C) have a polymerizable group, the adhesion between the antifouling layer and the adjacent layer (base material or hard coat layer) is increased, and the durability of the antifouling layer is improved. Can be excellent.

  The polycondensation product occupying the antifouling layer is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass. When the antifouling layer is a cured product of the condensation polymer and an ionizing radiation curable resin described later, the proportion of the condensation polymer occupying the antifouling layer is 0.01 to 20. It is preferably mass%, more preferably 0.02 to 20 mass%, still more preferably 0.02 to 10 mass%.

[(A) Alkoxysilane Having Perfluoropolyether Structure]
The alkoxysilane having a perfluoropolyether structure, which is the component (A) used as a raw material for the above condensation polymer, has a perfluoropolyether structure, thereby lowering the surface free energy of the antifouling layer and making it difficult for dirt to attach. To do. Furthermore, the spacing between adjacent perfluoropolyether structural parts becomes wide and sparse, and the perfluoropolyether structural parts are easy to move and have flexibility, thereby making it more difficult for dirt to adhere and wiping off the dirt that has adhered. It is supposed to be easy.
Examples of the alkoxysilane having a perfluoropolyether structure as the component (A) include compounds represented by the following general formulas (1) to (4), and from the viewpoint of antifouling property, the following general formula ( The compound represented by 1) is preferable.

(Wherein, ^{R 1} is an alkyl group having 1 to 6 carbon atoms. However, a plurality of ^{R 1} may optionally be the same or different ^.R 2 to R ⁹ are each independently, a carbon number 1 to 12 Z ¹ is a 1 to 10 valent organopolysiloxane group having a siloxane bond, Z ² is a 2 to 10 valent organopolysiloxane group having a siloxane bond, and Q is a par. Rf is a linear or branched fluorinated alkyl group having a fluoropolyether bond, n is an integer of 1 to 200, and m is an integer of 1 to 10.)

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl. Group, neopentyl group, n-hexyl group, isohexyl group and the like. From the viewpoint of antifouling property and reactivity, methyl group and ethyl group are preferable, and methyl group is more preferable.
R ^{2 to} R ⁹ are each independently a divalent organic group having 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms, and specifically, methylene group, ethylene group, propylene group (trimethylene group). , Methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group and other alkylene groups, phenylene group and other arylene groups, or a combination of two or more of these groups. Be done. Moreover, these groups may contain an ether bond, an amide bond, an ester bond, and a vinyl bond, and may further contain an oxygen atom, a nitrogen atom, and a fluorine atom.

Examples of the divalent to 10-valent organopolysiloxane group having a siloxane bond of Z ² include groups represented by the following general formulas (5-1) to (5-12).

  Among the groups represented by the general formulas (5-1) to (5-12), from the viewpoint of obtaining the antifouling property which is the effect of the present invention, the general formulas (5-1), (5-2), The groups represented by (5-3), (5-4) and (5-7) are preferable.

The group containing a perfluoropolyether bond of the Q, for _{example, -CF 2 O -, - CF} 2 CF 2 O -, - CF 2 CF 2 CF 2 O -, - CF (CF 3) CF 2 O- _{, -OCF 2 OCF 2 CF 2 -} , - CF 2 CF 2 CF 2 CF 2 O -, - CF 2 CF (CF 3) CF 2 O -, - CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O- , -C _{(CF 3)} 2 O- and the like.
Among them, from the viewpoint of antifouling _{property, -CF 2 CF 2 O -,} - CF 2 CF 2 CF 2 O -, - CF (CF 3) CF 2 O -, - OCF 2 OCF 2 CF 2 -, - CF 2 _{CF (CF} 3) CF 2 O- are preferred. These may include only one type or two or more types.

Rf is a linear or branched fluorinated alkyl group, and a linear fluorinated alkyl group is preferable from the viewpoint of obtaining the effect of the present invention.
Examples of the linear fluorinated alkyl group include a trifluoromethyl group, a difluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, and a tridecafluorohexyl group. Examples of the branched alkyl fluoride group include a 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl group and a 1,1-di(trifluoromethyl)-2,2,2 group. -Trifluoroethyl group, 2-(trifluoromethyl)-1,1,3,3,3-pentafluoropropyl group and the like.

The above n is an integer of 1 to 200, and is preferably 2 to 100, more preferably 3 to 60 from the viewpoint of antifouling property. When n is 1 or more, the surface of the base material can be sufficiently covered, the surface free energy of the surface of the antifouling layer is reduced, and the antifouling property can be improved. By setting n to 200 or less, the reactivity of the alkoxysilyl group (—Si(OR ¹ ) ₃ ) can be increased.

  The above m is an integer of 1 to 10, and is preferably 1 to 7, more preferably 1 to 5 from the viewpoint of antifouling property. When m is 1 or more, slipperiness is improved and higher antifouling property is obtained. By setting m to 10 or less, an increase in surface free energy can be suppressed and a decrease in antifouling property can be suppressed.

The alkoxysilane having a perfluoropolyether structure of the component (A) is preferably trimethoxysilane having a perfluoropolyether structure from the viewpoint of antifouling property and reactivity.
Further, as the alkoxysilane having a perfluoropolyether structure as the component (A), there are "X-71-195", "KY-178", "KY-164", and "KY-108" manufactured by Shin-Etsu Chemical Co., Ltd. , “KP-911”, “Optool DSX” manufactured by Daikin Industries, Ltd., “Optool DSX-E”, “Optool UF503” and the like are commercially available, and from the viewpoint of productivity and antifouling property, "X-71-195" is preferable.

[(B) Compound Having Trialkoxysilyl Group and Polymerizable Group]
The compound having a trialkoxysilyl group and a polymerizable group of the component (B) used as a raw material of the condensation polymer is particularly preferably a compound having at least one trialkoxysilyl group and at least one polymerizable group. It is not limited and may be a compound having a plurality of trialkoxysilyl groups or a plurality of polymerizable groups. Among them, a compound having one trialkoxysilyl group and one polymerizable group is preferable from the viewpoint of reactivity and availability.

The polymerizable group contained in the component (B) may be either a radical polymerizable group or a cationic polymerizable group and is not particularly limited. Examples of the cationically polymerizable group include vinyl ether group, oxiranyl group, oxetanyl group and the like, and examples of the radically polymerizable group include (meth)acryloyloxy group, (meth)acrylamide group, vinyl group, styryl group and allyl group. It is illustrated.
From the viewpoint of reactivity, the polymerizable group contained in the component (B) is preferably a radical polymerizable group, and particularly preferably a (meth)acryloyloxy group.

As the alkoxy group in the trialkoxysilyl group contained in the component (B), an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 3 carbon atoms is more preferable, and an alkoxy group having 1 or 2 carbon atoms is further preferable. A methoxy group is preferable and a methoxy group is particularly preferable.
The plural alkoxy groups may be the same or different, but from the viewpoint of synthesis, it is preferable that they are the same.

  Specific examples of the component (B) include vinyltrimethoxysilane, vinyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane. Among them, 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane are preferable, and 3-(meth)acryloxypropyltrimethoxysilane is more preferable.

[(C) Derivative of Component (B) Having At least One Alkoxy Group and Polymerizable Group]
The component (C) used as a raw material for the polycondensation product is a derivative of the component (B) having at least one alkoxy group and a polymerizable group, and includes, for example, the component (B) and the following general formula (D). Examples thereof include a condensate with an alkoxysilane represented by the formula (6).

(In the formula, each R ¹⁰ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 ring atoms, and 6 to 6 ring atoms. 20 aryl group ^{.R 11} are each independently ^{if .R 10} and ^{R 11} is an alkyl group having 1 to 6 carbon atoms is more, a plurality of ^{R 10} and ^{R 11} are each be the same or different X is an integer of 1 to 4.)

R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 ring atoms, or an aryl group having 6 to 20 ring atoms. .. Among them, from the viewpoint of reactivity, an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 8 carbon atoms are preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.

Examples of the alkyl group having 1 to ¹⁰ carbon atoms, preferably 1 to 6 carbon atoms of R ¹⁰ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, Examples thereof include n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. Among them, from the viewpoint of antifouling property and reactivity, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

Examples of the alkenyl group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms for R ¹⁰ include a vinyl group, an allyl group, a butenyl group, a pentenyl group and the like.

Examples of the cycloalkyl group having 3 to 10 ring atoms of R ¹⁰ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like.
Examples of the aryl group having 6 to 20, preferably 6 to 12 ring-forming atoms of R ¹⁰ include a phenyl group, a naphthyl group, an anthryl group and a biphenyl group.

  The alkyl group, alkenyl group, cycloalkyl group, and aryl group may have a substituent. As the substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group. , Neopentyl group, n-hexyl group, isohexyl group and the like. Of these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable, from the viewpoint of antifouling property and reactivity.

  x is an integer of 1 to 4, and is preferably 2, 3 or 4 from the viewpoint of antifouling property and reactivity, and more preferably 3 or 4.

  As the alkoxysilane represented by the general formula (6) of the component (D), a trialkoxysilane or tetraalkoxysilane having an alkyl group is preferable from the viewpoint of reactivity and antifouling property. Specific examples include trimethoxy(methyl)silane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane. Among them, trimethoxy(methyl)silane, ethyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane are preferable, and trimethoxy(methyl)silane and tetramethoxysilane are more preferable.

  The component (C) is preferably a condensate in which part of the alkoxy groups of the component (B) and part of the alkoxy groups of the component (D) have undergone a condensation reaction. As a specific example, as a component (B), a part of a methoxy group of 3-acryloxypropyltrimethoxysilane and a part of a methoxy group of trimethoxy(methyl)silane as a component (D) are subjected to a condensation reaction. Examples of the condensate include

  The weight ratio of the component (B) to the component (D) is preferably 1:0.05 to 10, more preferably 1:0.07 to 8, and even more preferably from the viewpoint of antifouling property and adhesiveness. Is 1:0.1-5.

  From the viewpoint of reactivity with the component (A), the total content of the alkoxy group and the silanol group contained in the component (C) is preferably 1 to 30 mmol/g, more preferably 2 to 25 mmol/g, More preferably, it is 3 to 15 mmol/g.

  The content of the polymerizable group contained in the component (C) is preferably 0.1 to 40 mmol/g, more preferably 0.5 to 30 mmol/g, and further preferably from the viewpoint of improving the adhesiveness. It is 1 to 20 mmol/g.

The antifouling layer is preferably a cured product obtained by using the polycondensation product and an ionizing radiation curable resin, from the viewpoint of increasing hardness and improving adhesion.
As the ionizing radiation curable resin, a radical polymerizable resin which has no alkoxy group and can be crosslinked and cured by irradiation with ionizing radiation (ultraviolet ray or electron beam) can be used. The radical polymerizable resin has a radical polymerizable group in the molecule. Examples of the radically polymerizable group include ethylenically unsaturated bond-containing groups such as (meth)acryloyl group, vinyl group and allyl group. Among them, from the viewpoint of strength and curability of the resulting antifouling layer, the radical-polymerizable resin is preferably a compound having two or more ethylenically unsaturated bond-containing groups in the molecule, and (meth)acryloyl is included in the molecule. A polyfunctional (meth)acrylate compound having two or more groups is more preferable. As the polyfunctional (meth)acrylate compound, any of a monomer, an oligomer and a polymer can be used, but it is preferable to contain at least a polyfunctional (meth)acrylate monomer from the viewpoint of strength and curability of the antifouling layer. ..
Here, in the present invention, "(meth)acrylate" means acrylate or methacrylate.

Among the polyfunctional (meth)acrylate compounds, preferable bifunctional (meth)acrylate monomers include 1,6-hexanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate.
Examples of trifunctional or higher functional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipenta. Examples thereof include erythritol tetra(meth)acrylate and isocyanuric acid-modified tri(meth)acrylate.
Further, the (meth)acrylate monomer may be one in which a part of the molecular skeleton is modified, and modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. Things can also be used.

The polyfunctional (meth)acrylate oligomer is not particularly limited as long as it is a bifunctional or higher functional (meth)acrylate oligomer, and examples thereof include a urethane (meth)acrylate oligomer, an epoxy (meth)acrylate oligomer, and a polyester (meth). Examples include various (meth)acrylate oligomers such as acrylate oligomers and polyether (meth)acrylate oligomers.
The urethane (meth)acrylate oligomer is obtained, for example, by reacting a polyhydric alcohol and an organic diisocyanate with a hydroxy (meth)acrylate.
A preferred epoxy (meth)acrylate oligomer is a (meth)acrylate obtained by reacting a (meth)acrylic acid with a trifunctional or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like, 2 (Meth)acrylate obtained by reacting a polyfunctional acid or more with an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin or the like and a polybasic acid and (meth)acrylic acid, and a bifunctional or more aromatic epoxy resin , (Meth)acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin and the like with phenols and (meth)acrylic acid.

The polyfunctional (meth)acrylate oligomer preferably has a weight average molecular weight (polystyrene-equivalent weight average molecular weight measured by GPC method) of less than 4,000, more preferably more than 1,000 and less than 3,000.
Further, the polyfunctional (meth)acrylate oligomer is more preferably 3 to 12 functional, and further preferably 3 to 10 functional. When the number of functional groups is within the above range, a cured layer having excellent strength can be obtained.

  The polyfunctional (meth)acrylate polymer is not particularly limited as long as it is a bifunctional or higher functional (meth)acrylate polymer, and examples thereof include urethane (meth)acrylate polymers, epoxy (meth)acrylate polymers, polyester (meth)acrylate polymers. Various (meth)acrylate-based polymers such as polyether (meth)acrylate polymers can be used.

From the viewpoint of the refractive index, the polyfunctional (meth)acrylate polymer preferably has a weight average molecular weight (polystyrene-equivalent weight average molecular weight measured by the GPC method) of 4,000 or more, and preferably 10,000 to 100,000. , And more preferably 10,000 to 50,000. When the weight average molecular weight is 100,000 or less, curability and coatability are good.
Further, the number of functional groups of the polyfunctional (meth)acrylate polymer is not particularly limited, but from the viewpoint of curability, it is preferable that the number of functional groups per molecule is large (that is, the functional group equivalent is low). The functional group equivalent of the polyfunctional (meth)acrylate polymer is preferably 400 g/equivalent or less, more preferably 300 g/equivalent or less, further preferably 250 g/equivalent or less.

  The above ionizing radiation curable resins may be used alone or in combination of two or more.

(Composition for forming antifouling layer)
The composition for forming an antifouling layer, which forms the antifouling layer, contains the condensation polymer. The polycondensation product is a compound having the (A) alkoxysilane having a perfluoropolyether structure and the (B) trialkoxysilyl group and a polymerizable group in a mixed solvent of an organic solvent, water and an acid, Alternatively, an embodiment obtained by hydrolyzing and polycondensing the derivative of the component (B) having at least one alkoxy group and the polymerizable group (C) is preferable.
Specifically, in the polycondensation product, the alkoxy group contained in the component (A) and the alkoxy group contained in the component (B) or the component (C) are each hydrolyzed to form a silanol group. Then, each silanol group is obtained by polycondensation.

As the organic solvent, a fluorine-based solvent is preferably used from the viewpoint of dissolving the alkoxysilane having the perfluoropolyether structure of the component (A). Further, from the viewpoint of solubility in water, a mixed organic solvent of a fluorine-based solvent and an amphipathic solvent is preferable.
As the amphipathic solvent, for example, water-soluble organic solvents such as alcohols and ketones are preferably used. Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, tertiary butyl alcohol and the like. Examples of the above-mentioned ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. As other water-soluble organic solvents, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate and the like are used. These can be used alone or in combination of two or more.

  The content of the organic solvent in the antifouling layer forming composition is preferably 90.000 to 99.999% by mass, more preferably 92.00 to 99.99% by mass, and further preferably 95.0 to 99.%. It is 9% by mass. When the content is 90.000% by mass or more, the reaction in the mixed solvent can be uniformly promoted, and the antifouling layer formed from the antifouling layer-forming composition can be made uniform and transparent. When the content is 0.999 mass% or less, a sufficient antifouling layer can be formed on the surface of the base material.

  Examples of water include ion-exchanged water and distilled water. The amount of water contained in the mixed solvent is not particularly limited as long as it is 0.001% by mass or more, but preferably 0.001 to 1.000% by mass, more preferably 0.005% by mass. It is compounded at a rate of 0.500% by mass. When the content is 0.001 mass% or more, the above hydrolysis is promoted, and when the content is 1.000 mass% or less, the precipitation of alkoxysilane having a perfluoropolyether structure can be suppressed.

  The acid is not particularly limited as long as it has an action of promoting the hydrolysis, hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, succinic acid, acetic acid, formic acid, oxalic acid, citric acid, benzoic acid and the like. From the viewpoint of reactivity and removal from the antifouling layer during drying, hydrochloric acid is preferable. The amount of the acid contained in the mixed solvent is preferably 0.000001 to 10.000000 mass%, more preferably 0.00001 to 5.00000 mass% from the viewpoint of promoting the hydrolysis. More preferably, it is 0.0001 to 1.0000 mass %.

The antifouling layer forming composition may further contain the above-mentioned ionizing radiation curable resin.
From the viewpoint of curability, the content of the ionizing radiation-curable resin with respect to the total solid content of the antifouling layer-forming composition is preferably 10 to 99% by mass, and more preferably 20 to 98% by mass.

The composition for forming an antifouling layer may contain a photopolymerization initiator.
Examples of the photopolymerization initiator include acetophenone-based, ketone-based, benzophenone-based, benzoin-based, ketal-based, anthraquinone-based, disulfide-based, thioxanthone-based, thiuram-based, and fluoroamine-based photopolymerization initiators. Among them, acetophenone type, ketone type, and benzophenone type are preferable. These photopolymerization initiators can be used alone or in combination of two or more.
From the viewpoint of curability, the content of the photopolymerization initiator relative to the total solid content of the antifouling layer-forming composition is preferably 1.0 to 15% by mass, and more preferably 1.5 to 10% by mass. ..

In the antifouling layer-forming composition, in addition to the above components, an additive such as an acid generator, a photobase generator, a photopolymerization accelerator, and a leveling agent, in a range that does not impair the effects of the present invention. Further, it can be contained.
By adding a photoacid generator or a photobase generator, a stronger antifouling layer can be formed.
The photopolymerization accelerator is capable of reducing polymerization inhibition by air during curing and accelerating curability, and is selected from, for example, p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. One or more may be mentioned.

  The leveling agent is not particularly limited, but a non-polymerizable fluorine-containing compound having no photopolymerizable group is preferable from the viewpoint of enhancing antifouling property. Among the non-polymerizable fluorine-containing compounds, compounds having a weight average molecular weight of 30,000 to 40,000 are preferable. Examples of commercially available products of such a non-polymerizable fluorine-containing compound include F568 and F477 manufactured by DIC Corporation.

Further, the antifouling layer-forming composition may contain a solvent. The solvent can be used without particular limitation as long as it is a solvent that dissolves each component contained in the antifouling layer forming composition, alcohols, ethers, ketones, esters are preferred, alcohols, ethers Classes are more preferred. Examples of alcohols include methanol, ethanol and isopropyl alcohol, and among them, isopropyl alcohol is preferable. Examples of ethers include hydrofluoroether, which is a fluorine-containing ether compound, and n-propyl ether.
The said solvent can be used individually or in combination of 2 or more types.
The content of the solvent in the antifouling layer-forming composition is preferably 40 to 99% by mass, more preferably 50 to 95% by mass. When the content of the solvent is within the above range, the coating suitability is excellent.

  The solid content concentration of the antifouling layer-forming composition is preferably 0.1 to 60.0% by mass, more preferably 0.5 to 50.0% by mass, and still more preferably 1. It is 0 to 45.0 mass %. When it is 0.1% by mass or more, curing of the antifouling layer can be promoted, and when it is 60.0% by mass or less, coloring of the antifouling layer and deterioration of antifouling property can be suppressed. it can.

  When the multilayer film of the present invention has a hard coat layer described below, the thickness of the antifouling layer is preferably 1 to 50 nm, more preferably 1 to 30 nm from the viewpoint of antifouling property and durability. Moreover, when the multilayer film does not have a hard coat layer described below, the thickness of the antifouling layer is preferably 1 to 30 μm (estimated value), and more preferably 2 to 20 μm (estimated value).

In the past, it has been considered to increase the contact angle between water and fats and oils in order to make it difficult for the antifouling layer to become dirty. On the other hand, in the present invention, by increasing the contact angle between water and fats and oils and decreasing the sliding angle of both, it is possible to obtain high sliding property, so that it is difficult for dirt to adhere, and dirt that adheres can be removed. It is easy to wipe.
The sliding property can be evaluated by measuring the sliding angles of pure water and n-hexadecane. The smaller the sliding angle, the better the sliding property. The sliding angle is such that 10 μL of pure water and 3 μL of n-hexadecane are dropped in a horizontal state on the surface of the antifouling layer of the multi-layer film which is the measurement object, and the multi-layer film is gradually inclined so that the liquid drops start to slide. It is obtained by measuring the inclination angle (sliding angle). As the measuring device, for example, a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd. can be used. The sliding angle can be specifically measured by the method described in Examples.

In the multilayer film of the present invention, the contact angle of pure water on the surface of the antifouling layer is preferably 95° or more, more preferably 112° or more, still more preferably 114° or more. Further, the sliding angle of pure water on the surface of the antifouling layer is preferably 30° or less, more preferably 15° or less, and further preferably less than 8°.
When the contact angle is 95° or more, it indicates that the antifouling layer has low surface free energy, and it is possible to make it difficult for dirt to attach. Further, when the sliding angle is 30° or less, the sliding property of the surface of the antifouling layer is improved, dirt is less likely to adhere, and the adhered dirt can be easily wiped off.
In the present invention, the reason why the contact angle can be 95° or more is considered to be that the polycondensation product has a perfluoropolyether structure site. Further, the sliding angle can be set to 30° or less because the polycondensation product is an alkoxysilane having a perfluoropolyether structure of the component (A) and a trialkoxysilyl group of the component (B). And a compound having a polymerizable group, or at least one alkoxy group of the component (C) and a derivative of the component (B) having a polymerizable group are polycondensed, so that adjacent perfluoropolyether structures It is considered that this is due to the fact that the spacing between the sites becomes wide and sparse, and that the perfluoropolyether structure site easily moves and has flexibility.
The contact angle is measured with a contact angle measuring device (for example, a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd.) with respect to pure water and n-hexadecane by the θ/2 method. Required by that. The contact angle can be specifically measured by the method described in Examples.

  In the multilayer film of the present invention, the contact angle of n-hexadecane on the surface of the antifouling layer is preferably 50° or more, more preferably 55° or more, still more preferably 60° or more. The sliding angle of n-hexadecane on the surface of the antifouling layer is preferably 15° or less, more preferably 10° or less, and further preferably 6° or less.

Further, in the multilayer film of the present invention, the reduction rate of the contact angle of pure water on the surface of the antifouling layer before and after wiping with an alcohol solvent is preferably 0 to 15%, more preferably 0 to 13%. , And more preferably 0 to 10%.
According to the present invention, the reduction rate of the contact angle of pure water on the surface of the antifouling layer can be set within the above range, and the adhesion between the antifouling layer and the adjacent layer (base material or hard coat layer) can be improved. The durability of the antifouling layer can be made excellent.

The present inventors propose that the antifouling layer is a cured product containing a polycondensation product of the component (A) and the component (B) or the component (C). It was found that the coefficient of friction with a cloth or the like used for wiping is reduced to improve the slipperiness. The multi-layer film of the present invention, by lowering the surface free energy of the antifouling layer by increasing the contact angle between water and fats and oils, and by reducing the sliding angle between water and fats and oils, high slidability can be obtained. In addition, the high slip property makes it more difficult for dirt to adhere to the surface of the antifouling layer (the amount of fingerprints attached is small), and makes it easier to wipe off the adhered dirt (good fingerprint wipeability. ) Can be done.
Thus, the multilayer film of the present invention has an extremely excellent antifouling property that cannot be obtained by the conventional antifouling member, because the interval between the adjacent perfluoropolyether structural moieties of the polycondensation product is wide. It is considered that it is sparse and the perfluoropolyether structure site is easy to move and has flexibility.
In particular, in order to obtain the antifouling property of the surface used by sliding with a finger such as a touch panel, it is important to improve the slipperiness.
In addition, in the present invention, "slipperiness" is an index representing the smoothness of the surface of the antifouling layer of the multilayer film. The slipperiness can be evaluated specifically by the method described in Examples.

<Hard coat layer>
The multilayer film of the present invention preferably has a hard coat layer on the surface of the antifouling layer on the substrate side from the viewpoint of increasing the hardness.
The hard coat layer has a role of increasing the surface hardness of the multilayer film and imparting scratch resistance to the multilayer film.
In addition, in the present invention, the hard coat layer refers to one having a hardness of “2H” or more in a pencil hardness test. The hard coat layer in the present invention preferably has a pencil hardness test of 2H to 6H, more preferably 3H to 6H, from the viewpoint of a balance between scratch resistance and crack prevention.

The hard coat layer is preferably formed of an ionizing radiation curable resin composition from the viewpoint of increasing the surface hardness.
The ionizing radiation curable resin composition preferably contains a photopolymerization initiator together with the ionizing radiation curable resin. Further, if necessary, a solvent and additives such as a photopolymerization accelerator and a leveling agent may be contained.
As the ionizing radiation curable resin, photopolymerization initiator, solvent, and additive, those described in the section of the antifouling layer can be used.

  The thickness (when cured) of the hard coat layer can be appropriately selected depending on the strength of the base material and the required performance, and is usually 0.1 to 100 μm, preferably 0.8 to 30 μm. Further, from the viewpoint of exhibiting sufficient hardness and suppressing the occurrence of warpage and cracks, it is more preferably 3 to 20 μm.

  The thickness of the hard coat layer can be calculated, for example, by measuring the thickness at 20 points from an image of a cross section taken by using a scanning transmission electron microscope (STEM) and averaging the values at 20 points. The accelerating voltage of STEM is preferably 10 kV to 30 kV. The STEM magnification is preferably 1000 to 7000 times.

[Method for producing multilayer film]
Next, a method for manufacturing the above-mentioned multilayer film will be described.
The method for producing a multilayer film according to the first aspect of the present invention is a method for producing a multilayer film having at least a substrate and an antifouling layer, wherein (A) alkoxy having a perfluoropolyether structure is provided on the substrate. A silane and (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) a derivative of the component (B) having at least one alkoxy group and a polymerizable group, an organic solvent, water, and an acid. Hydrolyzed in a mixed solvent containing, polycondensation polymer to form an uncured layer of the composition for forming an antifouling layer obtained by blending a polycondensation product, and to form an antifouling layer by curing. Characterize.

First, the component (A) and the component (B) or the component (C) are mixed and stirred in a mixed solvent of an organic solvent, water and an acid, and the component (A) and the component (B) are mixed. Component) or the above component (C) is hydrolyzed and then polycondensed to obtain a polycondensation product.
As the component (A), the component (B), the component (C), the organic solvent, water, and the acid, those described in the section of the above-mentioned multilayer film can be used, and the combination of the organic solvent, water, and the acid can be used. The amount is appropriately adjusted within the range described in the above section of the multilayer film.
The weight average molecular weight of the alkoxysilane having the perfluoropolyether structure can be determined by GPC measurement.

  The weight ratio of the component (A) to the component (B) or the component (C) is preferably 1:0.1 to 10.0, more preferably 1:0.15 to 8.0, and further It is preferably 1:0.2 to 6.0. Within the above range, the effects of the present invention can be exhibited.

  The hydrolysis and polycondensation reactions are preferably carried out under a constant atmosphere in which these reactions occur appropriately. Specifically, it is preferably performed in the range of -25 to 120°C for about 0.1 to 200 hours, more preferably at -10 to 100°C for about 0.5 to 150 hours, and more preferably 0 to 70°C. It is more preferable to carry out the treatment for about 1 to 120 hours.

Next, the antifouling layer-forming composition prepared by blending the polycondensation product obtained above is applied onto the substrate to form an uncured layer, and the composition is cured to form the antifouling layer.
The method of applying the above composition may be any method capable of uniformly applying a desired thickness, and may be appropriately selected from conventionally known methods. For example, gravure coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, curtain coating method, die coating method, casting method, bar coating method, extrusion coating method, etc. Is mentioned.

The uncured layer can be cured by drying treatment, irradiation with ionizing radiation, or the like, and is preferably cured by irradiation with ionizing radiation. Further, a drying treatment may be performed before irradiating the uncured layer with ionizing radiation.
The setting conditions of the drying treatment vary depending on the raw materials, the solvent, the temperature and the humidity of the atmosphere, but it is preferable to carry out the drying treatment under a controlled atmosphere suitable for obtaining the effects of the present invention. For example, it is usually carried out at room temperature (25°C) to 300°C for about 0.1 to 48 hours, and more preferably at 25 to 250°C for about 0.2 to 24 hours. These treatments may be completed in one atmosphere or may be conducted stepwise in two or more atmospheres.

Ultraviolet rays (UV) can be preferably used as the ionizing radiation. As ultraviolet rays, those containing ultraviolet rays having a wavelength of 190 to 380 nm are usually emitted. The ultraviolet source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. can be used. Ultraviolet irradiation is preferably performed in a nitrogen atmosphere having an oxygen concentration of 1000 ppm or less.
The irradiation amount of ultraviolet rays is preferably 50 to 300 mJcm ⁻² , more preferably 50 to 250 mJcm ⁻² .

It is preferable that the composition for forming an antifouling layer further contains an ionizing radiation curable resin from the viewpoint of increasing the hardness and improving the adhesion of the cured product.
The content of the polycondensation product contained in the composition for forming an antifouling layer is preferably 0.1 to 1.0 parts by mass, more preferably 0.2 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. ~0.6 parts by mass. Within the above range, the effects of the present invention can be exhibited.

  As the method for producing the second aspect of the multilayer film of the present invention, a coating film of a composition for forming a hard coat layer containing an ionizing radiation-curable resin is formed on a substrate before the formation of an uncured layer, and an ionizing radiation is used. To form a semi-cured layer, and then the uncured layer is formed so as to be in contact with the surface of the semi-cured layer opposite to the substrate, and the semi-cured layer and the uncured layer are formed. The hard coat layer and the antifouling layer may be respectively formed by simultaneously irradiating and curing with ionizing radiation.

  First, a composition for forming a hard coat layer is prepared by containing the above-mentioned photopolymerization initiator together with the above-mentioned ionizing radiation curable resin. The composition for forming a hard coat layer may further contain additives such as the above-mentioned solvent, photopolymerization accelerator, and leveling agent.

The content of the ionizing radiation-curable resin with respect to the total amount of the composition for forming a hard coat layer is preferably 10 to 99% by mass, and more preferably 15 to 98% by mass, from the viewpoint of hard coat properties and adhesiveness.
The content of the photopolymerization initiator in the composition for forming a hard coat layer is preferably 1 to 10 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the ionizing radiation curable resin from the viewpoint of curability. ~8 parts by mass.

Next, the hard coat layer-forming composition prepared above is applied onto the substrate to form a coating film.
The method of applying the above composition may be any method as long as it can be applied uniformly to a desired thickness, and may be appropriately selected from conventionally known methods. Specifically, the method described in the first aspect can be used.

Next, the coating film is irradiated with ionizing radiation to form a semi-cured layer. As the ionizing radiation, the ultraviolet rays described in the first aspect can be preferably used.
The irradiation amount of ultraviolet rays is preferably 3 to 100 mJcm ⁻² , more preferably 5 to 80 mJcm ⁻² . When the content is within the above range, the ionizing radiation curable resin is appropriately cured and a semi-cured layer can be formed. The ultraviolet irradiation may be carried out under a nitrogen atmosphere or an air atmosphere as long as the semi-cured layer can be formed by selecting the irradiation amount of the ultraviolet light, but it is more preferably carried out under the air atmosphere.

Next, the uncured layer described in the manufacturing method of the first aspect is formed so as to contact the surface of the semi-cured layer opposite to the substrate, and the semi-cured layer and the uncured layer are simultaneously formed. It is irradiated with ionizing radiation and cured to form a hard coat layer and an antifouling layer, respectively. By simultaneously curing the semi-cured layer and the uncured layer, the adhesion between the hard coat layer (semi-cured layer) and the antifouling layer (uncured layer) can be improved.
Ultraviolet rays are preferably used as the ionizing radiation. The irradiation amount of ultraviolet rays is preferably 30 to 300 mJcm ⁻² , more preferably 50 to 200 mJcm ⁻² . Within the above range, each layer can be sufficiently cured, and the adhesion between the hard coat layer and the antifouling layer can be made excellent.

Further, in the manufacturing method of the second aspect, the dose X _α (mJ/cm ² ) of ionizing radiation that is applied when forming the semi-cured layer, and the semi-cured layer and the uncured layer simultaneously. The dose X _β (mJ/cm ² ) of the ionizing radiation to be applied preferably satisfies the relationship of the following formula (I).
0.01≦X _α /(X _α +X _β )≦0.80 (I)
(However, X _α is 3 or more and 100 or less)

The above X _α is preferably 3 or more and 100 or less, more preferably 3 or more and 95 or less, further preferably 4 or more and 90 or less, and still more preferably 5 or more and 80 or less. When it is 3 or more, the semi-cured layer can be appropriately cured, and when the antifouling layer-forming composition is applied onto the semi-cured layer, the semi-cured layer is not dissolved, and scratches and distortions are not generated. It is possible to suppress the contact angle and improve the sliding property of the final film. Further, by setting it to 100 or less, it is possible to suppress the curing of the semi-cured layer from proceeding too much, and then the semi-cured layer and the uncured layer are simultaneously cured to form a hard coat layer (semi-cured layer). The adhesion with the antifouling layer (uncured layer) can be improved.

Further, the above X _α /(X _α +X _β ) is preferably 0.01 or more and 0.80 or less, more preferably 0.011 or more and 0.60 or less, further preferably 0.012 or more and 0.50 or less, and More preferably, it is 0.014 or more and 0.35 or less. When it is 0.01 or more, the semi-cured layer can be appropriately cured, and when the composition for forming an antifouling layer is applied onto the semi-cured layer, the semi-cured layer is dissolved, and scratches and distortions are not generated. It is possible to suppress the generation and improve the contact angle and sliding property of the final film. Further, by setting it to 0.80 or less, it is possible to suppress the curing of the semi-cured layer from proceeding too much. Then, the semi-cured layer and the uncured layer are simultaneously cured to form a hard coat layer (semi-cured layer). ) And the antifouling layer (uncured layer) can be improved in adhesiveness.

The thus obtained multilayer film of the present invention preferably has a total light transmittance (JIS K7361-1:1997) of 90% or more, more preferably 92% or more. The haze (JIS K7136:2000) of the multilayer film of the present invention is preferably 1.0% or less, more preferably 0.5% or less, and further preferably 0.3% or less. preferable.
The light incident surface at the time of measuring the total light transmittance and the haze is the antifouling layer side.

  The arithmetic average roughness Ra (JIS B0601:1994) of the surface (surface on the hard coat layer side) of the multilayer film of the present invention is preferably 10 nm or less, and more preferably 1 to 8 nm.

  Since the multilayer film of the present invention has high hardness and excellent antifouling property and also has an excellent antifouling property, it can be suitably used especially for portable electronic devices having a touch panel display.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the form described in the embodiments.
The multilayer films of Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Tables 5 and 6.

1. Measurement 1-1. Contact angle measurement (contact angle before wiping with isopropyl alcohol)
The contact angle of pure water and n-hexadecane was measured using a contact angle meter “DM 500” manufactured by Kyowa Interface Science Co., Ltd. 1.5 μL of deionized water was dropped on the surface of the antifouling layer of the multilayer film, and 1 second after landing, according to the θ/2 method, contact was made from the angle of the straight line connecting the left and right end points and the vertex of the dropped droplet with respect to the solid surface. The angle was calculated. The average value measured 5 times was used as the value of the contact angle.
(Contact angle after wiping with isopropyl alcohol)
Using a nonwoven fabric impregnated with isopropyl alcohol (IPA) (manufactured by Asahi Kasei Corp., trade name: Bencotton), the surface of the antifouling layer of the multilayer film was wiped 5 times under a load of 500 g. .. After that, the contact angle after wiping with IPA was obtained in the same manner as the contact angle before wiping with IPA.

1-2. Surface Free Energy From the contact angle before wiping with IPA measured in the above 1-1, the surface free energy was evaluated according to the following criteria. The larger the contact angle, the lower the surface free energy and the better.
⊚: Pure water 110° or more and n-hexadecane 60° or more ○: Pure water less than 110° 95° or more and n-hexadecane less than 60° 50° or more ×: Pure water less than 95° or n-hexadecane less than 50°

1-3. Measurement of sliding angle Using a contact angle meter "DM 500" manufactured by Kyowa Interface Science Co., Ltd., the sliding angles of pure water and n-hexadecane were measured. The multilayer film is placed horizontally, 10 μL of pure water and 3 μL of n-hexadecane are dropped on the surface of the antifouling layer of the multilayer film, respectively, and the multilayer film is gradually tilted, and the tilt angle ( The sliding angle) was measured. The average value measured 5 times was taken as the value of the sliding angle.

1-4. Sliding property From the sliding angle measured in 1-3 above, the sliding property was evaluated according to the following criteria. When the evaluation results differ between pure water and n-hexadecane, the lower result was adopted. The smaller the sliding angle, the better the sliding property.
[Pure water]
◎: Less than 15° ○: 15° or more and 30° or less ×: Over 30° [n-hexadecane]
◎: Less than 10° ○: 10° or more and 15° or less ×: Over 15°

1-5. Evaluation of Sliding Property 10 subjects contacted their fingers with the surface of the antifouling layer of each of the multilayer films prepared in Examples 1 to 23 and Comparative Examples 1 to 2, and laid the finger parallel to the surface of the antifouling layer. Moved back and forth in a direction (movement like sliding on a smartphone). At that time, the tactile sensation due to the friction between the finger and the surface of the antifouling layer was judged by the following evaluation criteria, and the average value of 10 test subjects was obtained. This average value was judged according to the following judgment criteria.
<Evaluation criteria>
5 points: always smooth 3 points: smooth 0 point: bad <criteria>
○: 4.4 points or more △: 2.1 points or more and less than 4.4 points ×: Less than 2.1 points

1-6. Fingerprint adhesion A fingerprint is obtained by pressing an artificial fingerprint liquid (made by Isekyu Co., Ltd., according to Annex 4 of JIS C9606) onto a silicone resin plate (columnar shape of 10 mmφ×30 mm) to the antifouling layer surface of the multilayer film. Was attached. The adhered state of fingerprints was visually observed and evaluated according to the following criteria.
◎: Fingerprint is strongly repelled and the amount of adhesion is very small ○: Fingerprint is repelled and the amount of adhesion is small Δ: Fingerprint is repelled but adhered ×: Fingerprint is widely adhered

1-7. Fingerprint wiping property A silicone resin plate (cylindrical shape of 10 mmφ x 30 mm) to which an artificial fingerprint liquid (made by Isekyu Co., Ltd., conforming to Annex 4 of JIS C9606) is attached is pressed against the antifouling layer surface of the multilayer film. Fingerprints were attached. The adhered fingerprint was wiped with a non-woven fabric (Asahi Kasei Co., Ltd., trade name: Ben Cotton), and the residual traces of the fingerprint were visually observed and evaluated according to the following criteria.
⊚: Fingerprint sticking marks are not completely visible after wiping up to 3 times ○: Fingerprint sticking marks are not completely visible after 4 to 7 times wiping Δ: 8 to 10 times wiping And, the traces of fingerprint sticking are not completely visible. ×: The traces of fingerprint wipe are clearly visible after 10 times of wiping.

1-8. Pencil hardness test The pencil hardness of the antifouling layer surface of the multilayer film was measured according to JIS K5600-5-4.

1-9. SW test The substrate surface of the multilayer film was adhered to a glass plate so as not to cause wrinkles, and #0000 steel wool was brought into contact with the surface of the antifouling layer at a load of 9.8 N, and a 10 cm one-way movement distance was repeated 10 times. .. Then, the presence or absence of scratches on the surface of the antifouling layer was visually confirmed.

2. Production of multilayer film (without hard coat layer) 2-1. Production of Polycondensation Polymer of Component (A) and Component (B) In a mixed solution of the component (A), the component (B), and a solvent, which are obtained by mixing the respective compounding amounts of the components shown in Table 1, are shown in Table 1. Mixing amounts of water and 1M hydrochloric acid were added, and the mixture was stirred at 25° C. for 3 hours to obtain a composition containing a polycondensation product of the component (A) and the component (B) (Production Examples 1 to 4).
The details of each component shown in Table 1 used for the production of the condensation polymer are as follows.

[(A) component]
X-71-195 (alkoxysilane solution having a perfluoropolyether structure): manufactured by Shin-Etsu Chemical Co., Ltd., trade name, solid content 20%
[(B) component]
KBM-5103 (3-acryloxypropyltrimethoxysilane): manufactured by Shin-Etsu Chemical Co., Ltd., trade name [solvent]
-Novec 7300 (fluorine-based organic solvent): 3M, trade name-2-propanol (amphiphilic solvent): Kanto Chemical Co., Inc., trade name

2-2. Preparation of Antifouling Layer-Forming Composition The respective amounts of the components shown in Table 2 were mixed to prepare an antifouling layer-forming composition. In addition, in Table 2, a blank column represents no compounding.
Details of each component shown in Table 2 used for preparing the composition for forming an antifouling layer are as follows.

X-71-195 (alkoxysilane solution having a perfluoropolyether structure): manufactured by Shin-Etsu Chemical Co., Ltd., trade name, solid content 20%
・KAYARAD-PET-30 (pentaerythritol triacrylate): manufactured by Nippon Kayaku Co., Ltd., trade name ・Irgacure 184 (photopolymerization initiator): manufactured by Ciba Japan Co., Ltd., trade name ・Isopropyl alcohol: Kanto Kagaku ( Ltd.-Novec 7300 (fluorine-based organic solvent): 3M, trade name-Methyl isobutyl ketone (MIBK): Showa Ink Industry Co., Ltd., trade name

2-3. Completion of the multilayer films of Examples 1 to 4 and Comparative Example 1 Substrate: PET film (manufactured by Toyobo Co., Ltd., trade name: A4100, thickness 100 μm) was used and a bar coater was used to show the antifouling properties shown in Table 2. The layer forming composition was applied at a coating speed of 6 m/min to form a coating film. The coating film was dried at 70° C. for 1 minute to remove the solvent. Then, the coating film was irradiated with ultraviolet rays at an irradiation dose of 100 mJ/cm ² using an ultraviolet irradiation device to cure the coating film, thereby obtaining a multilayer film having an antifouling layer with a film thickness of 5 μm after curing. The obtained multilayer film was placed in a thermo-hygrostat at a temperature of 80° C. and a relative humidity of 95% and treated for 1 hour.

3. Production of multilayer film (with hard coat layer) (Example 5)
3-1. Preparation of Hard Coat Layer Forming Composition The following components were mixed to prepare a hard coat layer forming composition.
-Pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., KAYARAD PET-30) 100 parts by mass-Photopolymerization initiator (Ciba Japan Co., Ltd., Irgacure 184) 4 parts by mass-Leveling agent (DIC Co., Ltd.) Manufactured by F568) 0.1 part by mass Methyl isobutyl ketone (MIBK) (manufactured by Showa Ink Industry Co., Ltd., trade name) 187 parts by mass

3-2. Formation of Semi-Cured Layer Substrate: PET film (manufactured by Toyobo Co., Ltd., trade name: A4100, thickness 100 μm), using a bar coater, the composition for forming a hard coat layer prepared in 3-1 above, Coating was performed at a coating speed of 6 m/min to form a coating film. The coating film was dried at 70° C. for 1 minute to remove the solvent. Then, the coating film was irradiated with ultraviolet rays at an irradiation dose of 10 mJ/cm ² using an ultraviolet irradiation device to form a semi-cured layer.

3-3. Preparation of antifouling layer forming composition (Production Example 5)
Fluorine-based organic solvent (3M, trade name: Novec 7300) 12.1 g, amphiphilic solvent (Kanto Chemical Co., Inc., trade name: 2-propanol) 2.1 g, and a perfluoropolyether structure Alkoxysilane solution (Shin-Etsu Chemical Co., Ltd., trade name "X-71-195", solid content 20%) 0.30 g and 3-acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product Alkoxysilane having a perfluoropolyether structure was prepared by adding 2.3 mg of water and 13 mg of 1M hydrochloric acid into a mixed solution prepared by mixing 0.047 g of "KBM-5103") and stirring at 25°C for 3 hours. A composition containing a polycondensation product of 3-acryloxypropyltrimethoxysilane was obtained.

Then, the following components were mixed to prepare an antifouling layer-forming composition.
291 parts by mass of the composition (solid content: 0.7% by mass) obtained in 3-3 above (ratio to 100 parts by mass of pentaerythritol triacrylate in the composition for forming a hard coat layer of 3-1 above)
-Photopolymerization initiator (Ciba Japan Co., Ltd., Irgacure 184) 0.085 parts by mass

3-4. Completion of the multilayer film of Example 5 On the semi-cured layer formed in 3-2 above, a bar coater was used to apply the antifouling layer-forming composition prepared in 3-3 above at a coating speed of 6 m/min. Then, an uncured layer was formed. Then, the semi-cured layer and the uncured layer were irradiated with ultraviolet rays at an irradiation amount of 100 mJ/cm ² using an ultraviolet irradiation device, and a hard coat layer (film thickness after curing 5 μm) and an antifouling layer (after curing) were formed on the substrate. A multilayer film having a film thickness of 30 nm) was obtained.

3-5. Production of Multilayer Films of Examples 6 to 23 and Comparative Example 2 Compositions containing polycondensates (Production Examples 5 to 17) and (A) component were mixed by mixing the compounding amounts of the components shown in Table 3. A composition (Comparative Production Example 1) was obtained. Further, a multilayer film was obtained in the same manner as in Example 5 except that the components shown in Table 4 and the compounding amounts were used and the ultraviolet irradiation amount shown in Table 4 was used. In addition, in Tables 3 and 4, the blank column represents no compounding.

Details of each component shown in Table 3 are as follows.
[(A) component]
X-71-195 (alkoxysilane solution having a perfluoropolyether structure): manufactured by Shin-Etsu Chemical Co., Ltd., trade name, solid content 20%
[(B) component]
-KBM-5103 (3-acryloxypropyltrimethoxysilane): manufactured by Shin-Etsu Chemical Co., Ltd., trade name-KBM-1003 (vinyl trimethoxysilane): manufactured by Shin-Etsu Chemical Co., Ltd., trade name [(C) component〕
KP-513 (polymer of 3-acryloxypropyltrimethoxysilane and trimethoxy(methyl)silane): manufactured by Shin-Etsu Chemical Co., Ltd., trade name [other components]
-Novec 7300 (fluorine-based organic solvent): 3M, trade name-2-propanol (amphiphilic solvent): Kanto Chemical Co., Inc., trade name

(Summary of results)
In Examples 1 to 23 in which the component (A) and the component (B) or the component (C) are used in combination, fingerprints are unlikely to adhere to the surface of the antifouling layer, and even if fingerprints adhere, they can be easily wiped off. In addition, no scratch was confirmed on the surface of the antifouling layer in the SW test.

  Since the multilayer film of the present invention has high hardness and excellent antifouling property and also has an excellent antifouling property, it can be suitably used especially for portable electronic devices having a touch panel display.

1 Resistive Touch Panel 11a Upper Transparent Substrate 11b Lower Transparent Substrate 12 Transparent Conductive Film 13 Spacer 2 Capacitive Touch Panel 21a Upper Transparent Substrate 21b Lower Transparent Substrate 22 Transparent Conductive Film (X Electrode)
23 Transparent conductive film (Y electrode)
24 Adhesive layer 3,4 Multilayer film 31,41 Base material 32,42 Antifouling layer 43 Hard coat layer

Claims (20)

A touch panel comprising a multilayer film having a base material and an antifouling layer,
The antifouling layer has (A) an alkoxysilane having a perfluoropolyether structure, (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) at least one alkoxy group and a polymerizable group. A touch panel, which is a cured product containing a condensation polymer with the derivative of the component (B).   The touch panel according to claim 1, wherein the antifouling layer is a cured product obtained by using the condensation polymer and an ionizing radiation curable resin.   The touch panel according to claim 1, which has a hard coat layer on the surface of the antifouling layer on the substrate side.   The touch panel according to claim 1, wherein the alkoxysilane having a perfluoropolyether structure is trimethoxysilane having a perfluoropolyether structure.   The touch panel according to claim 1, wherein a contact angle of pure water on the surface of the antifouling layer is 95° or more and a sliding angle is 30° or less.   The touch panel according to any one of claims 1 to 5, wherein a reduction rate of a contact angle of pure water on the surface of the antifouling layer before and after wiping the surface of the antifouling layer with an alcohol solvent is 0 to 15%. A method for producing a multilayer film having at least a substrate and an antifouling layer,
On the substrate, (A) an alkoxysilane having a perfluoropolyether structure, (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) having at least one alkoxy group and a polymerizable group, Uncured composition for forming an antifouling layer, which is obtained by blending a polycondensation product obtained by hydrolyzing and polycondensing a derivative of component (B) with a mixed solvent containing an organic solvent, water, and an acid. A method for producing a multilayer film, which comprises forming a layer and curing it to form an antifouling layer.   The method for producing a multilayer film according to claim 7, wherein the uncured layer is cured by irradiation with ionizing radiation to form an antifouling layer.   The method for producing a multilayer film according to claim 7, wherein the composition for forming an antifouling layer further contains an ionizing radiation curable resin.   Before the formation of the uncured layer, a coating film of a composition for forming a hard coat layer containing an ionizing radiation curable resin is formed on a substrate and irradiated with ionizing radiation to form a semi-cured layer. The uncured layer is formed so as to be in contact with the surface of the cured layer opposite to the substrate, and the semi-cured layer and the uncured layer are simultaneously irradiated with ionizing radiation to be cured to form a hard coat layer. The method for producing a multilayer film according to claim 8 or 9, which comprises forming an antifouling layer. Irradiation dose X _α (mJ/cm ² ) of the ionizing radiation irradiated when the semi-cured layer is formed, and ionizing radiation dose X _β (mJ of the semi-cured layer and the uncured layer simultaneously. /Cm< ² >) satisfy|fills the relationship of following formula (I), The manufacturing method of the multilayer film of Claim 10.
0.01≦X _α /(X _α +X _β )≦0.80 (I)
(However, X _α is 3 or more and 100 or less) A multilayer film having a base material and an antifouling layer,
The antifouling layer has (A) an alkoxysilane having a perfluoropolyether structure, (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) at least one alkoxy group and a polymerizable group. A multilayer film, which is a cured product containing a polycondensation product with the derivative of the component (B).   The multilayer film according to claim 12, wherein the antifouling layer is a cured product obtained by using the condensation polymer and an ionizing radiation curable resin.   The multilayer film according to claim 12, which has a hard coat layer on the surface of the antifouling layer on the substrate side.   The multilayer film according to any one of claims 12 to 14, wherein the alkoxysilane having a perfluoropolyether structure is trimethoxysilane having a perfluoropolyether structure.   The multilayer film according to any one of claims 12 to 15, wherein a contact angle of pure water on the surface of the antifouling layer is 95° or more and a sliding angle is 30° or less.   The multilayer film according to any one of claims 12 to 16, wherein a reduction rate of a contact angle of pure water on the surface of the antifouling layer before and after wiping the surface of the antifouling layer with an alcohol solvent is 0 to 15%. A multilayer film having a base material and an antifouling layer,
The antifouling layer has (A) an alkoxysilane having a perfluoropolyether structure, (B) a compound having a trialkoxysilyl group and a polymerizable group, or (C) at least one alkoxy group and a polymerizable group. A cured product containing a polycondensation product of the derivative of the component (B), wherein the weight ratio of the component (A) to the component (B) or the component (C) is 1:0.1 to 10.0. The multilayer film according to claim 12. The polymerizable group contained in the component (B) and the component (C) is a vinyl ether group, an oxiranyl group, an oxetanyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinyl group, a styryl group or an allyl group. Item 12. A multilayer film according to item 12. The multilayer film according to claim 12, wherein the component (C) is a condensate of the component (B) and (D) an alkoxysilane represented by the following general formula (6).

(In the formula, R ¹⁰ Are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 10 ring atoms, and an aryl group having 6 to 20 ring atoms. .. R ¹¹ Are each independently an alkyl group having 1 to 6 carbon atoms. R ¹⁰ And R ¹¹ If there are multiple R ¹⁰ And R ¹¹ May be the same or different. x is an integer of 1 to 4. )