JP2023121714A - Laminate, window film, and touch panel - Google Patents

Abstract

To provide a laminate of antifouling films with protection films, the protection films featuring high adhesion.SOLUTION: The present invention provides a laminate including a first substrate (SL), an elemental-fluorine-containing layer (r), and a protective layer (P) in the stated order, wherein the protective layer (P) includes a second substrate (SP) and an adhesive layer (ad), the thickness of the adhesive layer (ad) is less than 16 μm, and the contact angle at the surface of the elemental-fluorine-containing layer (r) upon peeling the protective layer (P) while leaving the elemental-fluorine-containing layer (r) on the first substrate (SL) side is 100° or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to laminates and window films and touch panels containing the laminates.

In various fields such as display devices such as touch panel displays, optical elements, semiconductor elements, building materials, window glass of automobiles and buildings, the surface of the base material has antifouling properties and water repellency (hereinafter collectively referred to as antifouling properties). ) is required to be given. Therefore, members with various antifouling coatings are used.

An antifouling film may be applied directly to a member that requires antifouling properties. Such an antifouling film may be attached to a target member such as a display to impart antifouling properties to the target member. At this time, the protective film has a role of protecting the antifouling film during transportation, etc., and is finally peeled off.

For example, in Patent Document 1, an optical film provided with an antifouling layer as the outermost surface layer on the first main surface of a first film substrate, and a surface protective film temporarily attached to the antifouling layer of the optical film wherein the surface protection film comprises an adhesive layer on the second film substrate, the thickness of the adhesive layer is 16 μm or more, the antifouling layer has a water contact angle of 100° or more, and the A protective film, wherein the antifouling layer and the pressure-sensitive adhesive layer are in contact with each other, and the adhesive force between the antifouling layer of the optical film and the pressure-sensitive adhesive layer of the surface protective film is less than 0.07 N/50 mm. A coated optical film is disclosed.

Japanese Patent Application Laid-Open No. 2020-52221

The antifouling film with a protective film is finally used after removing the protective film from the surface of the antifouling layer, but it is required that the protective film does not shift or peel off during transportation.

Accordingly, an object of the present invention is to provide a laminate such as an antifouling film with a protective film, in which the adhesive strength of the protective film is high.

[1] A laminate comprising a first substrate (S _L ), a layer (r) containing a fluorine element, and a protective layer (P) in this order,
The protective layer (P) comprises a second substrate (S _P ) and an adhesive layer (ad),
The adhesive layer (ad) has a thickness of less than 16 μm,
When the protective layer (P) is peeled off leaving the layer (r) containing elemental fluorine on the first substrate (S _L ) side, the contact angle of the surface of the layer (r) containing elemental fluorine is 100° or more. A laminate.
[2] The contact angle of the peeled surface of the protective layer (P) when the protective layer (P) is peeled off leaving the layer (r) containing the fluorine element on the first substrate (S _L ) side is 110°. The laminate described in [1] below.
[3] The laminate according to [1] or [2], further comprising a primer layer (c) between the first substrate (S _L ) and the layer (r) containing elemental fluorine. .
[4] The first substrate (S _L ) comprises two different layers (S _L1 ) and (S _L2 ),
The layer (S _L2 ) is located closer to the layer (r) containing the fluorine element than the layer (S _L1 ),
The layer (S _L1 ) is a resin,
The laminate according to any one of [1] to [3], wherein the layer (S _L2 ) is an acrylic hard coat layer.
[5] The second base material (S _P ) contains at least one of polyester resin and polyolefin resin,
The adhesive layer (ad) contains at least one selected from the group consisting of (meth)acrylic resins, rubber resins, urethane resins, polyester resins, silicone resins, polyvinyl ether resins and polyolefin resins. The laminate according to any one of [1] to [4].
[6] The laminate according to any one of [1] to [5], wherein the layer (r) containing elemental fluorine has a thickness of 50 nm or less.
[7] When the protective layer (P) is peeled off leaving the layer (r) containing the fluorine element on the first substrate (S _L ) side, the amount of F element on the peeled surface of the protective layer (P) is 50. The laminate according to any one of [1] to [6], which is less than atomic %.
[8] The laminate according to any one of [1] to [7], wherein the layer (r) containing elemental fluorine is a cured layer of an organosilicon compound (A) represented by the following formula (a1).
[9] A window film or touch panel comprising the laminate according to any one of [1] to [8].

ADVANTAGE OF THE INVENTION According to this invention, the laminated body with the high adhesive force of a protective film can be provided.

The laminate of the present invention is a laminate comprising a first substrate (S _L ), a layer (r) containing a fluorine element, and a protective layer (P) in this order, wherein the protective layer (P) is a second including a substrate (S _P ) and an adhesive layer (ad), wherein the thickness of the adhesive layer (ad) is less than 16 μm, and the layer (r) containing elemental fluorine is left on the first substrate (S _L ) side The laminate has a contact angle of 100° or more with respect to the surface of the layer (r) containing elemental fluorine when the protective layer (P) is peeled off. In order to satisfy the requirements that the thickness of the adhesive layer (ad) is less than 16 μm and that the contact angle of the surface of the layer (r) containing elemental fluorine is 100° or more when the protective layer (P) is removed, The adhesive strength (hereinafter sometimes referred to as peel strength) of the protective layer can be improved.

As long as the first substrate (S _L ), the layer (r) containing elemental fluorine and the protective layer (P) are laminated in this order, the first substrate (S _L ) and the layer (r) containing elemental fluorine Another layer may be laminated therebetween, and it is preferable to have a primer layer (c) described later between the first substrate (S _L ) and the layer (r) containing elemental fluorine. The layer (r) containing elemental fluorine and the protective layer (P) are usually directly laminated, and particularly the layer (r) and the adhesive layer (ad) are directly laminated.

Hereinafter, the first substrate (S _L ), the layer (r) containing elemental fluorine, and the protective layer (P) will be described in order. Note that the layer (r) containing elemental fluorine may be simply referred to as "layer (r)".

1. First base material (S _L )
The material of the first base material (S _L ) is not particularly limited, and may be either an organic material or an inorganic material, and the shape of the base material may be flat, curved, or a combination thereof. shape may be used. Examples of organic materials include acrylic resins, acrylonitrile resins, polycarbonate resins, polyester resins (e.g. polyethylene terephthalate), styrene resins, cellulose resins, polyolefin resins, vinyl resins (e.g. polyethylene, polyvinyl chloride, vinylbenzyl chloride). resins, polyvinyl alcohol, etc.), polyvinylidene chloride resins, polyamide resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyethersulfone resins, polysulfone resins, polyvinylacetal resins, vinyl ether resins, copolymers thereof, etc. Thermoplastic resins; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, oxetane resins, unsaturated polyester resins, silicone resins and urethane resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, aluminum, titanium, zirconium, niobium, tantalum, and lanthanum, metal oxides thereof, alloys containing these metals, ceramics, and glass. Among these, organic materials are preferred.

The thickness of the first substrate (S _L ) is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, and may be 500 μm or less, preferably 200 μm or less, or more. It is preferably 150 μm or less, more preferably 100 μm or less, and particularly preferably 60 μm or less.

The first base material (S _L ) may be a single layer, or may be a multilayer of two or more layers. When the first base material (S _L ) is a multilayer, the first base material (S _L ) has a layer (S _L2 ) different from the layer (S _L1 ) on the base layer (S _L1 ). It is preferred to have a multilayer structure provided. The layer (S _L2 ) is located closer to the layer (r) containing the fluorine element than the layer (S _L1 ), _{and the layer (S L2 )} is preferably the most layer (r ) is the layer that exists on the side close to When the first substrate (S _L ) includes the layer (S _L1 ) and the layer (S _L2 ), the laminate of the present invention includes the layer (S _L1 ), the layer (S _L2 ), and the layer containing fluorine element ( r) and the protective layer (P). When the laminate of the present invention does not have a primer layer (c), layer (S _L2 ) is preferably laminated directly with layer (r) and has a primer layer (c). In some cases, layer (S _L2 ) is preferably laminated directly with layer (c).

1-1. Layer (S _L1 )
The material of the layer (S _L1 ) may be either the organic material or the inorganic material described above, but it is preferably an organic material, more preferably a resin, and among them acrylic resin, polyester resin, At least one selected from vinylbenzyl chloride resins, epoxy resins, silicone resins, and urethane resins is more preferred, acrylic resins and polyester resins are particularly preferred, and polyethylene terephthalate is most preferred.

The thickness of the layer (S _L1 ) is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, and may be 500 μm or less, preferably 200 μm or less, more preferably 150 μm. Below, more preferably 100 μm or less, particularly preferably 60 μm or less.

1-2. layer (S _L2 )
Examples of the layer (S _L2 ) include layers formed from at least one selected from the group (X1) consisting of active energy ray-curable resins and thermosetting resins. The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays and electron beams can be used as active energy rays. The active energy ray-curable resins include acrylic resins, epoxy resins, oxetane resins, urethane resins, polyamide resins, vinylbenzyl chloride resins, vinyl resins (polyethylene resins, vinyl chloride resins, etc.), UV-curable resins such as styrene-based resins, phenol-based resins, vinyl ether-based resins, silicone-based resins, or mixed resins thereof, and electron beam-curable resins are included, and UV-curable resins are particularly preferred. The layer (S _L2 ) is at least one selected from the group (X2) consisting of titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide, lanthanum oxide, and SiO ₂ . Layers formed from can also be mentioned. As group (X1), acrylic resins, silicone resins, styrene resins, vinyl chloride resins, polyamide resins, phenol resins, and epoxy resins are particularly preferable. The thickness of the layer (S _L2 ) is 0.1 nm or more and 100 μm or less, preferably 1 nm or more and 60 μm or less, more preferably 1 nm or more and 10 μm or less. If the thickness of the layer (S _L2 ) is too thick, it may tend to curl due to heat during subsequent processing.

When the layer (S _L2 ) has a layer formed from at least one selected from the group (X1), the layer (S _L2 ) can function as a hard coat layer (hc) having surface hardness. , can impart scratch resistance to the first substrate (S _L ). The hard coat layer (hc) generally has a pencil hardness of B or higher, preferably HB or higher, more preferably H or higher, and even more preferably 2H or higher. When the layer (S _L2 ) contains the hard coat layer (hc), that is, when the layer (S _L2 ) has the function of a hard coat layer, the hard coat layer (hc) may have a single layer structure or a multi-layer structure. may be The hard coat layer (hc) preferably contains, for example, the above-described UV-curable resin, and particularly preferably contains an acrylic resin or a silicone resin. is preferred. In addition, it is also preferable to contain an epoxy-based resin, since there is a tendency that the adhesion between the first substrate (S _L ) and the layer (r) is improved. A specific method for forming the active energy ray-curable resin and the thermosetting resin constituting the group (X1) will be described in the display device section below. The layer (S _L2 ) can be formed by coating the layer (S _L1 ) with a composition containing a reactive material that forms a crosslinked structure upon irradiation and curing the composition. When the layer (S _L2 ) contains an antistatic agent (AS), which will be described later, a composition obtained by adding the antistatic agent (AS) to the composition containing the reactive material may be used.

When the layer (S _L2 ) contains a hard coat layer (hc), the hard coat layer (hc) may contain additives. Additives are not limited and include inorganic microparticles, organic microparticles, or mixtures thereof. Examples of additives include ultraviolet absorbers, silica, metal oxides such as alumina, and inorganic fillers such as polyorganosiloxane. By including the inorganic filler, the adhesion between the first substrate (S _L ) and the layer (r) can be improved. The thickness of the hard coat layer (hc) is, for example, preferably 1 μm or more, more preferably 1.2 μm or more, still more preferably 1.4 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, It is more preferably 20 μm or less, and still more preferably 10 μm or less. When the thickness of the hard coat layer (hc) is 1 μm or more, sufficient scratch resistance can be ensured, and when it is 100 μm or less, flex resistance can be ensured, and as a result, curling due to curing shrinkage can be suppressed. becomes.

When the layer (S _L2 ) has a layer formed from at least one selected from the group (X2), the layer (S _L2 ) functions as an antireflection layer (ar) that prevents reflection of incident light. can do. When the layer (S _L2 ) includes an antireflection layer (ar), the antireflection layer (ar) exhibits a reflection characteristic in which the reflectance is reduced to about 5.0% or less in the visible light region of 380 to 780 nm. Layers are preferred. The antireflection layer (ar) preferably comprises a layer formed from silica.

The structure of the antireflection layer (ar) is not particularly limited, and may be a single layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which low refractive index layers and high refractive index layers are alternately laminated is preferable, and the number of laminated layers is preferably 2 to 20 in total. Materials constituting the high refractive index layer include titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide and lanthanum oxide, and silica is a material constituting the low refractive index layer. mentioned. As the antireflection layer of multilayer structure, SiO ₂ (silica) and ZrO ₂ or SiO ₂ and Nb ₂ O ₅ are alternately laminated, and the outermost layer on the side opposite to the layer (S _L1 ) is SiO ₂ . is preferred. The antireflection layer (ar) can be formed by vapor deposition, for example. The thickness of the antireflection layer (ar) is, for example, 0.5 nm or more and 1000 nm or less.

The layer (S _L2 ) may contain the hard coat layer (hc), may contain the antireflection layer (ar), and may contain both the hard coat layer (hc) and the antireflection layer (ar). However, at least the hard coat layer (hc) is preferably included, and the layer (S _L2 ) is preferably the hard coat layer. When the layer (S _L2 ) includes both the hard coat layer (hc) and the antireflection layer (ar), the antireflection layer (ar) is preferably laminated on the layer (r) side.

As a combination of the layer (S _L1 ) and the layer (S _L2 ), the layer (S _L2 ) is located on the layer (r) side of the layer (S _L1 ), and the layer (S _L1 ) is made of resin (especially acrylic resin or polyester resin, particularly polyethylene terephthalate), and the layer (S _L2 ) is preferably an acrylic hard coat layer.

The first base material (S _L ) also preferably has conductivity, and preferably exhibits conductivity by containing an antistatic agent (AS) in the first base material (S _L ). When the first substrate (S _L ) contains an antistatic agent (AS) and the first substrate (S _L ) is a multilayer of two or more layers, the antistatic agent (AS) is contained in one of the layers. It may be included in all layers. In particular, when the first substrate (S _L ) has a multilayer structure in which the layer (S _L1 ) is provided on the layer (S _L1 ), the antistatic agent (AS) is added to the layer (S _L1 ). It may be included, or may be included in the layer (S _L2 ), and particularly preferably included in the layer (S _L2 ). When the antistatic agent (AS) is contained in the layer (S _L2 ), the layer (S _L2 ) is preferably a hard coat layer, and the hard coat layer is an acrylic resin, a silicone resin or an epoxy resin. It is more preferably at least one selected from the group consisting of:

Antistatic agents (AS) include, for example, surfactants, conductive polymers, conductive particles, ionic compounds (i.e., salts) such as quaternary ammonium salts, conjugated systems incorporating acceptors and/or donors Examples include polymers. These antistatic agents are used singly or in combination of two or more.

2. Layer (r) containing elemental fluorine
The layer (r) containing elemental fluorine is preferably a cured layer of the organosilicon compound (A) containing elemental fluorine. Since the layer (r) is a cured layer of the organosilicon compound (A), even a thin film can be imparted with good water repellency (hereinafter, the layer (r) is referred to as a "water-repellent layer"). sometimes). Good water repellency makes it difficult for contaminants such as fingerprints, fingerprints, and dust to adhere and tends to be easily removed. The organosilicon compound (A) is an organosilicon compound (A) containing a fluorine element and having a silicon atom to which a hydrolyzable group or a hydroxy group is bonded with or without a linking group. Preferably. The cured layer of the organosilicon compound (A) is usually obtained by coating and curing the mixed composition of the organosilicon compound (A), that is, the layer (r) is the mixed composition of the organosilicon compound (A). It can be said that it is the hardened layer of the material. Hereinafter, the mixed composition of the organosilicon compound (A) may be referred to as a composition for forming a water-repellent layer.

A mixed composition of an organosilicon compound (A) in which the layer (r) contains elemental fluorine and has a silicon atom to which a hydrolyzable group or a hydroxy group is bonded with or without a linking group. In the case of the cured layer of , the layer (r) has a structure derived from the organosilicon compound (A). The organosilicon compound (A) has a hydrolyzable group or a hydroxy group bonded to a silicon atom (which may be bonded via a linking group), and upon curing, the organosilicon compound (A) The —SiOH group of the organosilicon compound (A) generated by hydrolysis (Si and OH may be bonded via a linking group) is the —SiOH derived from the organosilicon compound (A) group (Si and OH may be bonded via a linking group), -SiOH group derived from another compound, or the surface on which the layer (r) is formed in the laminate (preferably a hard coat layer or layer ( It undergoes dehydration condensation with the active hydrogen (such as a hydroxyl group) of c)). Therefore, the layer (r) preferably has a condensed structure derived from the organosilicon compound (A).

The thickness of layer (r) is preferably 50 nm or less, more preferably 20 nm or less, still more preferably 15 nm or less, still more preferably 10 nm or less, and preferably 1 nm or more, more preferably 4 nm. That's it. The thickness of layer (r) is particularly preferably 4 nm to 15 nm, most preferably 4 nm to 10 nm. If the layer (r) is too thick, the appearance tends to deteriorate (white haze), and if the layer (r) is too thin, the adhesion tends to decrease.

The thickness of the layer (r) can be adjusted by the concentration of solids in the composition for forming the layer (r) and the coating conditions of the composition for forming the layer (r). The thickness of the layer (r) can be measured by an ellipsometer, X-ray reflection measurement, scanning transmission electron microscope (STEM) measurement in the cross-sectional direction, X-ray photoelectron spectroscopy (XPS), stylus type thin film profilometer, or the like. The measurement method can be appropriately selected according to the material and thickness of each layer.

In the STEM measurement in the cross-sectional direction, the laminate is sliced so as to include a plane parallel to the thickness direction of the first base material (S _L ) to cut out an ultra-thin section, and the section of the ultra-thin section is subjected to a scanning transmission electron microscope. The thickness of the layer (r) can be measured by observation with (STEM).
As a method for thinning the laminate, it is sufficient that it can be processed into an ultra-thin slice having a thickness of 100 nm or less, and examples thereof include a focused ion beam processing method, an ultramicrotome method, a cryo-ultramicrotome processing method, and the like. For example, when focused ion beam processing is used, the ion source is preferably Ga, and the acceleration voltage is preferably about 30 kV.
For STEM observation, it is preferable to set the acceleration voltage to 20 kV to 30 kV, the current value to 50 pA to 100 pA, and the magnification to 500,000 to 1,000,000 times. In addition, in order to make it easier to understand the interface between the layer (r) and the outside world in STEM observation, the upper surface of the layer (r) may be painted black with a felt pen or the like before the measurement. good.

As described in Examples below, the thickness of the layer (r) can also be calculated based on a calibration curve obtained from a laminate sample using glass as the material of the first base material (S _L ). . Specifically, glass is used as the material of the first base material (S _L ), and a plurality of laminate samples (preferably are 3 or more), and the thickness of each layer (r) is measured using an ellipsometer. Further, XPS measurement is performed on the sample to obtain the ratio of the amount of a specific element derived from the layer (r) and the amount of a specific element derived from the layer (c), and the ratio is calibrated with respect to the thickness of the layer (r). create a line Then, by performing XPS measurement on the actually obtained laminate, the ratio of the specific element amount derived from the layer (r) and the specific element amount derived from the layer (c) is obtained, and according to the above calibration curve , the thickness of layer (r) can be calculated.

In addition, when the material of the first base material (S _L ) is an organic material, the difference in refractive index between the first base material (S _L ) and the layer (r) is small, so it is difficult to measure the film thickness with an ellipsometer. Sometimes. In that case, STEM measurement in the cross-sectional direction or measurement using the calibration curve described above may be performed.

2-1. Organosilicon compound (A)
In a preferred embodiment, the organosilicon compound (A) has a hydrolyzable group or a hydroxy group (hereinafter collectively referred to as a reactive group (h3)) bonded with or without a linking group. It is a compound having a silicon atom that is Through hydrolysis and dehydration condensation reaction, the reactive groups (h3) form a water-repellent layer with the organosilicon compound (A); with the organosilicon compound (A) and another monomer; It has the function of bonding through a condensation reaction with active hydrogens (such as hydroxyl groups) on the surface to which the composition is applied. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group. The reactive group (h3) is preferably an alkoxy group or a halogen atom, more preferably an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and particularly preferably a methoxy group or an ethoxy group.

The organosilicon compound (A) preferably contains a fluoropolyether structure in addition to the silicon atoms. The fluoropolyether structure can also be referred to as a fluorooxyalkylene group, and means a structure in which both ends are oxygen atoms. When the organosilicon compound (A) contains a fluoropolyether structure, liquid repellency such as water repellency or oil repellency becomes better. The fluoropolyether structure is preferably a perfluoropolyether structure. The number of carbon atoms contained in the longest linear portion of the fluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and is, for example, 200, preferably 150. The number of silicon atoms in one molecule of the organosilicon compound (A) is preferably 1-10, more preferably 1-6.

In the embodiment in which the organosilicon compound (A) contains a fluoropolyether structure, a silicon atom and a reactive group (h3), a monovalent group having an oxygen atom of the fluoropolyether structure at the terminal on the bond side (hereinafter referred to as an FPE group ), the silicon atom is bonded with or without a linking group, and the silicon atom and the reactive group (h3) are bonded with or without a linking group Bonding is preferred. When the FPE group and the silicon atom are bonded via a linking group, the silicon atom bonded to the reactive group (h3) via the linking group or not via the linking group is the organosilicon compound (A) may be present in one molecule, and the number thereof is, for example, 1 or more and 10 or less.

The FPE group may be linear or may have a side chain, and preferably has a side chain. As an aspect having a side chain, it is particularly preferable that the fluoropolyether structure in the FPE group has a side chain. It preferably has a fluoroalkyl group as a side chain, and the fluoroalkyl group is more preferably a perfluoroalkyl group, and still more preferably a trifluoromethyl group. The carbon number of the linking group linking the FPE group and the silicon atom is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less. The FPE group described above is preferably a group in which a fluorine-containing group having a fluoroalkyl group at its end and a perfluoropolyether structure are directly bonded. The fluorine-containing group may be a fluoroalkyl group or a group in which a linking group such as a divalent aromatic hydrocarbon group is bonded to a fluoroalkyl group, but is preferably a fluoroalkyl group. The fluoroalkyl group is preferably a perfluoroalkyl group, more preferably a perfluoroalkyl group having 1 to 20 carbon atoms.

Examples of the fluorine-containing group include CF ₃ (CF ₂ ) _p — (p is, for example, 0 to 19, preferably 0 to 10), CF ₃ (CF ₂ ) _m —(CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H ₄ - (m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4) and preferably CF ₃ (CF ₂ ) _p — or CF ₃ (CF ₂ ) _m —(CH ₂ ) _n —.

The reactive group (h3) may be bonded to the silicon atom via a linking group, or may be directly bonded to the silicon atom without the linking group, and is directly bonded to the silicon atom. is preferred. The number of reactive groups (h3) bonded to one silicon atom may be 1 or more, and may be 2 or 3, preferably 2 or 3, particularly 3 preferable. When the number of reactive groups (h3) bonded to one silicon atom is 2 or less, the remaining bonds may be bonded with a monovalent group other than the reactive group (h3), for example, An alkyl group (especially an alkyl group having 1 to 4 carbon atoms), H, NCO, etc. can be bonded.

The organosilicon compound (A) is preferably a compound represented by the following formula (a1).

In the above formula (a1),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group having 1 to 20 carbon atoms in which one ^or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom; When a plurality of Rf a26 are present, a plurality of Rf ^a26 may be different, when a plurality of Rf ^a27 are present, a plurality of Rf ^a27 may be different, and when a plurality of Rf ^a28 are present, a plurality of Rf ^a28 may be different from each other, and when a plurality of Rf ^a29 are present, the plurality of Rf ^a29 may be different,
R ²⁵ and R ²⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl halide having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms; group, at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom, and when a plurality of R ²⁵ are present, the plurality of ^{R 25 may} be different, When doing, multiple R ²⁶ may be different,
R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, ^{or a} single bond; When a plurality of R ²⁸ are present, the plurality of R ²⁸ may be different,
R ²⁹ and R ^{30 are each independently} an alkyl group having 1 to 20 carbon atoms; may have different R ³⁰ ,
^M7 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, -C(=O)NR-, - CH═CH— or —C ₆ H ₄ — (phenylene group), R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and M ⁷ is When a plurality of M 7 are present, the plurality of M ⁷ may be different,
M ⁵ is ^a hydrogen atom, ^a fluorine atom or an alkyl group having 1 to 4 carbon atoms;
M ¹⁰ is a hydrogen atom or a halogen atom,
M ⁸ and M ⁹ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group; or an ethyl group, and when there are a plurality of M ⁸ , the plurality of M ⁸ may be different, and when there is a plurality of M ⁹ , the plurality of M ⁹ may be different,
f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 is an integer from 0 to 20,
f27 is each independently an integer of 0 to 2,
g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, g21 + g22 ≤ 3,
g31 is an integer of 1 to 3, g32 is an integer of 0 to 2, g31 + g32 ≤ 3,
M ¹⁰ -, -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _3-g31-g32 , f21 -{C(R ²⁵ )(R ²⁶ )}-units (U _a1 ), f22 - {C(Rf ^a26 ) (Rf ^a27 )} - unit (U _a2 ), f23 - {Si (R ²⁷ ) (R ²⁸ )} - unit (U _a3 ), f24 - {Si (Rf ^a28 )(Rf ^a29 )}-unit (U _a4 ), f25 -M ⁷ -units (U _a5 ), and f26-[C(M ⁵ ){(CH ₂ ) _f27 -Si(M ⁸ ) _g21 (H) _g22 (R ²⁹ ) _3-g21-g22 }]-unit (U _a6 ) has M ¹⁰ - at one end in formula (a1), and -Si(M ⁹ ) _g31 (H) _g32 ( R ³⁰ ) _3-g31-g32 are the other ends, and are arranged in an order that forms a fluoropolyether structure at least in part, and each unit can be in any order as long as —O— is not continuous with —O— Join side by side. “Arranged in any order and bonded” means that the repeating units are not limited to being arranged consecutively in the order as described in formula (a1) above, and f21 units (U _a1 ) are consecutively arranged It means that f21 units in total need not be bound together, but may be bound through other units in the middle. The same applies to the units (U _a2 ) to (U _a6 ) enclosed by f22 to f26.

Further, when at least one of R ²⁷ and R ²⁸ is a single bond, the single bond portion of the unit enclosed by f23 and —O— in M ⁷ are repeatedly bonded to form a branched or cyclic It can form siloxane bonds.

Rf ^a26 , Rf ^a27 , Rf ^a28 and Rf ^a29 are preferably each independently a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. More preferably, it is a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms.
R ²⁵ and R ²⁶ are preferably each independently a hydrogen atom or a fluorine atom, at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom, more preferably both are hydrogen is an atom.
R ²⁷ and R ²⁸ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
R ²⁹ and R ³⁰ are preferably C 1-5 alkyl groups, more preferably C 1-2 alkyl groups.
M ⁷ is preferably -C(=O)-O-, -O-, -OC(=O)-, more preferably all -O-.
M ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
M ¹⁰ is preferably a fluorine atom.
^M8 and ^M9 are preferably each independently an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom, particularly preferably a methoxy group or an ethoxy group.
Preferably, f21, f23, and f24 are each 1/2 or less of f22, more preferably 1/4 or less, still more preferably f23 or f24 is 0, particularly preferably f23 and f24 are 0 is.
f25 is preferably 1/5 or more of the total value of f21, f22, f23, and f24 and less than or equal to the total value of f21, f22, f23, and f24.
f21 is preferably 0 to 20, more preferably 0 to 15, even more preferably 1 to 15, particularly preferably 2 to 10. f22 is preferably 5 to 600, more preferably 8 to 600, still more preferably 20 to 200, still more preferably 30 to 200, still more preferably 35 to 180, most preferably 40 to 180 is. f23 and f24 are preferably 0 to 5, more preferably 0 to 3, still more preferably 0. f25 is preferably 4-600, more preferably 4-200, even more preferably 10-200, still more preferably 30-60. The total value of f21, f22, f23, f24 and f25 is preferably 20-600, more preferably 20-250, even more preferably 50-230. f26 is preferably 0-18, more preferably 0-15, even more preferably 0-10, still more preferably 0-5. f27 is preferably 0 to 1, more preferably 0. g21 and g31 are each independently preferably 2 to 3, more preferably 3. g22 and g32 are each independently preferably 0 or 1, more preferably 0. g21+g22 and g31+g32 are preferably three.

In the above formula (a1), both R ²⁵ and R ²⁶ are hydrogen atoms, and Rf ^a26 and Rf ^a27 are fluorine atoms or C 1-2 fluorinated alkyl groups in which all hydrogen atoms are substituted with fluorine atoms. wherein M ⁷ is all —O—, M ⁸ and M ⁹ are all methoxy, ethoxy or chlorine atoms (particularly methoxy or ethoxy), M ⁵ is hydrogen and M ¹⁰ is a fluorine atom, f21 is 1 to 10 (preferably 2 to 7), f22 is 30 to 200 (more preferably 40 to 180), f23 and f24 are 0, f25 is 30 to 60, and f26 is 0 to 6 , f27 is 0 to 1 (especially preferably 0), g21 and g31 are 1 to 3 (both are preferably 2 or more, more preferably 3), g22 and g32 are 0 to 2 (any is preferably 0 or 1, more preferably 0), and a compound (a11) in which g21+g22 and g31+g32 are 3 is preferably used as the organosilicon compound (A).

The organosilicon compound (A) is preferably represented by the following formula (a2).

In the above formula (a2),
Rf ^a1 is a divalent fluoropolyether structure having oxygen atoms at both ends,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^{11 , a plurality of R 11 may} be different, and a plurality of R ¹² When present, a plurality of R ¹² may be different, and when a plurality of R ¹³ are present, a plurality of R ¹³ may be different,
E ¹ , E ² , E ³ , E ⁴ and E ⁵ are each independently a hydrogen atom or a fluorine atom,
When a plurality of E ¹ are present, a plurality of E ¹ may be different, when a plurality of E ² are present, a plurality of E ² may be different, and when a plurality of E ³ are present, a plurality of E ³ may be different from each other, when multiple E ⁴ are present, multiple E ⁴ may be different, when multiple E ⁵ are present, multiple E ⁵ may be different,
G ¹ and G ² are each independently a divalent to decavalent organosiloxane group having a siloxane bond,
J ¹ , J ² , and J ³ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group or an ethyl group, and when there are a plurality of J ¹ , the plurality of J ¹ may be different, and when there are a plurality of J ² , the plurality of J ² may be different, and J When there are multiple ³ 's, the multiple J ³ 's may be different,
L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, a silicon atom or a fluorine atom, and -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ),-{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ),-{Si(R ²⁷ )(R ²⁸ )}-unit (U _a3 ) or a linking group in which one or more -M ⁷ - units (U _a5 ) are arranged in any order (R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , Rf ^a26 , Rf ^a27 and M ⁷ are the same as in formula (a1)),
a10 and a14 are each independently 0 or 1,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0 to 9;
a13 is 0 to 4;
When a11 is 0, or when a11 is 1 and G ¹ has a valence of 2, d11 is 1, and when a11 is 1 and G ¹ has a valence of 3 to 10, d11 is the value of G ¹ is one less than the number,
When a15 is 0, or when a15 is 1 and ^G2 is divalent, d12 is 1, and when a15 is 1 and ^G2 is 3-10 valent, d12 is the value of ^G2 is one less than the number,
a21 and a23 are each independently 0 to 2,
e11 is 1 to 3, e12 is 0 to 2, e11 + e12 ≤ 3,
e21 is 1 to 3, e22 is 0 to 2, e21 + e22 ≤ 3,
e31 is 1 to 3, e32 is 0 to 2, and e31+e32≦3.

Note that a10 is 0 means that the portion enclosed with a10 is a single bond, and even if a11, a12, a13, a14, a15, a16, a21 or a23 is 0 It is the same.

Rf ^a1 is preferably -O-(CF ₂ CF ₂ O) _e4 -, -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, -O-(CF ₂ -CF(CF ₃ )O) _e6 - . Both e4 and e5 are 15-80, and e6 is 3-60. Rf ^a1 is also preferably a group in which hydrogen atoms are removed from hydroxyl groups at both ends of a structure obtained by randomly dehydrating and condensing p mol of perfluoropropylene glycol and q mol of perfluoromethanediol, and p+q is It is from 15 to 80, and this aspect of Rf ^a1 is most preferable.

R ¹¹ , R ¹² and R ¹³ are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

Each of E ¹ , E ² , E ³ and E ⁴ is preferably a hydrogen atom, and E ⁵ is preferably a fluorine atom.

L ¹ and L ² are each independently -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ) or -{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ) A divalent linking group having 1 to 12 carbon atoms (preferably 1 to 10, more preferably 1 to 5) containing a fluorine atom in which one or more of are bonded in any order is preferred, and x is 1 to 12 (preferably 1 to 10, more preferably 1 to 5) is more preferably -(CF ₂ ) _x -.

G ¹ and G ² are each independently preferably a divalent to pentavalent organosiloxane group having a siloxane bond.

J ¹ , J ² and J ³ are each independently preferably methoxy, ethoxy or --(CH ₂ ) _e7 --Si(OR ¹⁴ ) ₃ , more preferably methoxy or ethoxy.

a10 is preferably 1, a11 is preferably 0, a12 is preferably 0 to 7, more preferably 0 to 5, a13 is preferably 1 to 3, a14 is preferably 1, a15 is preferably 0, a16 is preferably 0 to 6, more preferably 0 to 3, both a21 and a23 are preferably 0 or 1 (more preferably both are 0), d11 is preferably 1, d12 is preferably 1, e11, Both e21 and e31 are preferably 2 or more, and 3 is also preferable. Each of e12, e22 and e32 is preferably 0 or 1, more preferably 0. Preferably, e11+e12, e21+e22, and e31+e32 are all three. These preferred ranges may be satisfied singly or in combination of two or more.

As the organosilicon compound (A), Rf ^a1 in the above formula (a2) is a structure in which p mol of perfluoropropylene glycol and q mol of perfluoromethanediol are randomly dehydrated and condensed. A group left after being removed (p + q = 15 to 80), both L ¹ and L ² are perfluoroalkylene groups having 1 to 5 carbon atoms (preferably 1 to 3), and E ¹ , E ² , and ^E3 is a hydrogen atom, ^E4 is a hydrogen atom, ^E5 is a fluorine atom, and ^J1 , ^J2 , and ^J3 are all a methoxy group or an ethoxy group (especially a methoxy group); , a10 is 1, a11 is 0, a12 is 0 to 7 (preferably 0 to 5), a13 is 2, a14 is 1, a15 is 0, a16 is 0 to 6 (especially 0), a21 and a23 are each independently 0 or 1 (more preferably both a21 and a23 are 0), d11 is 1, d12 is 1, e11, Compound (a21) wherein e21 and e31 are all 2 to 3 (especially 3), e12, e22 and e32 are all 0 or 1 (especially 0), and e11+e12, e21+e22, and e31+e32 are all 3 is preferably used.

As the organosilicon compound (A), Rf ^a1 in the above formula (a2) is —O—(CF ₂ CF ₂ CF ₂ O) _e5 —, e5 is 25 to 40, and L ¹ is a fluorine atom and an oxygen atom. a divalent linking group having 3 to 6 carbon atoms containing atoms, L ² is a perfluoroalkylene group having 2 to 10 carbon atoms, both E ² and E ³ are hydrogen atoms, and E ⁵ is fluorine an atom, J ² is —(CH ₂ ) _e7 —Si(OCH ₃ ) ₃ , e7 is 2 to 4, a10 is 1, a11 is 0, a12 is 0, a13 is 2, a14 is 1, a15 is 0, a16 is 0, d11 is 1, d12 is 1 and e21 is 3. It is also preferred to use the compound (a22).

More specific examples of the organosilicon compound (A) include compounds of the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ³¹ is a structure obtained by randomly dehydrating condensation of p mol of perfluoropropylene glycol and q mol of perfluoromethanediol. A group (p+q is 15 to 80) left after hydrogen atoms are removed from hydroxyl groups at both ends, R ³² is a perfluoroalkylene group having 1 to 10 carbon atoms, and R ³³ is a C 2 to 6 It is a trivalent saturated hydrocarbon group, and R ³⁴ is an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms in R ³⁰ is preferably 1-4, more preferably 1-3. The carbon number of R ³² is preferably 1-5. h1 is 1 to 10, preferably 1 to 8, more preferably 1 to 6. h2 is 1 or more, preferably 2 or more, and may be 3.

In particular, organosilicon compounds (A) represented by formulas (a1), (a2), and (a3), including preferred ranges, are useful for increasing the peel strength of the protective layer.

Examples of the organosilicon compound (A) include compounds represented by the following formula (a4).

In the above formula (a4), R ⁴⁰ is a C 2-5 perfluoroalkyl group, R ⁴¹ is a C 2-5 perfluoroalkylene group, and R ⁴² is a C 2-5 a fluoroalkylene group in which some of the hydrogen atoms of the alkylene group are substituted with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group; be. k1 is an integer of 1-5. k2 is an integer of 1 to 3, preferably 2 or more, and may be 3;

The number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, and particularly preferably 7,000 or more. 000 or more, preferably 40,000 or less, more preferably 20,000 or less, and still more preferably 15,000 or less.

As the organosilicon compound (A), only one type may be used, or two or more types may be used.

In the layer (r), the structure derived from the organosilicon compound (A) is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, and may be 100% by mass, preferably 95% by mass. % by mass or less, more preferably 90% by mass or less. Here, the structure derived from the organosilicon compound (A) refers to the residue after dehydration condensation of the organosilicon compound (A) and the organosilicon compound (A).

2-2. Organosilicon compound (B)
The layer (r) may have a structure derived from the organosilicon compound (A) as well as a structure derived from the organosilicon compound (B) represented by the following formula (b1). The layer (r) having the structure derived from the organosilicon compound (A) and the structure derived from the organosilicon compound (B) is a mixed composition in which the water-repellent layer-forming composition is further mixed with the organosilicon compound (B). It can be obtained by coating and curing a substance.

As will be described later, the organosilicon compound (B) has a hydrolyzable group or a hydroxy group bonded to a silicon atom, and usually the -SiOH group possessed by the organosilicon compound (B) or the organic The -SiOH group of the silicon compound (B) is a -SiOH group derived from the organosilicon compound (B), a -SiOH group derived from another compound, or a surface on which the layer (r) is formed in the laminate (preferably a hard coat Since dehydration condensation occurs with the active hydrogen (such as a hydroxyl group) of the layer or layer (c)), in a preferred embodiment, the layer (r) contains the organosilicon compound (B)-derived It has a dehydration condensation structure. Since the layer (r) has a dehydration-condensation structure derived from the organosilicon compound (B), the slipping property of water droplets and the like is further improved.

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom;
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^b11 are present, the plurality of R ^b11 are different from each other. When there are a plurality of R ^b12 , the plurality of R ^b12 may be different, when there is a plurality of R ^b13 , the plurality of R ^b13 may be different, and when there is a plurality of R ^b14 may have different R ^b14 ,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^b11 are present When there is a plurality of Rf ^b11 , the plurality of Rf b11 may be different, when there are a plurality of Rf ^b12 , the plurality of Rf ^b12 may be different, and when there is a plurality of Rf ^b13 , the plurality of Rf ^b13 may be different. may be present, and if there are a plurality of Rf ^b14 , the plurality of Rf ^b14 may be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^b15 are present, the plurality of R ^b15 may be different,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- and R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and when there are multiple A ¹ , the multiple A ¹ may be different,
A ² is a hydrolyzable group or a hydroxy group, and when a plurality of A ² are present, the plurality of A ² may be different,
b11, b12, b13, b14, and b15 are each independently an integer of 0 to 100,
c is an integer from 1 to 3,
Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-unit (U _b1 ), b12 -{C(Rf ^b11 ) (Rf ^b12 )}-unit (U _b2 ), b13-{Si(R ^b13 )(R ^b14 )}-unit (U _b3 ), b14-{Si(Rf ^b13 )(Rf ^b14 )} - unit (U _b4 ), b15 -A ¹ - units (U _b5 ), Rf ^b10 - becomes one end of the compound represented by formula (b1), -Si(A ² ) _c (R ^b15 ) Each unit (U _b1 ) to unit (U _b5 ) is optional as long as _3-c is the other end, does not form a fluoropolyether structure, and -O- is not linked to -O- to -F Arrange and join in order.

Each Rf ^b10 is independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).

R ^b11 , R ^b12 , R ^b13 and R ^b14 are preferably hydrogen atoms.

R ^b15 is preferably an alkyl group having 1 to 5 carbon atoms.

A ¹ is preferably -O-, -C(=O)-O-, or -OC(=O)-.

Examples of hydrolyzable groups represented by A ² include alkoxy groups, halogen atoms, cyano groups, acetoxy groups and isocyanate groups.

A ² is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom.

b11 is preferably 1-30, more preferably 1-25, still more preferably 1-10, particularly preferably 1-5, most preferably 1-2.

b12 is preferably 0-15, more preferably 0-10.

b13 is preferably 0-5, more preferably 0-2.

b14 is preferably 0-4, more preferably 0-2.

b15 is preferably 0-4, more preferably 0-2.

c is preferably 2 to 3, more preferably 3.

The total value of b11, b12, b13, b14, and b15 is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more preferably 20. It is below.

In particular, Rf ^b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, both R ^b11 and R ^b12 are hydrogen atoms, A ² is a methoxy group or an ethoxy group, and b11 is 1 to 5, b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.

In the examples described later, when FAS13E used as the organosilicon compound (B) is represented by the above formula (b1), R ^b11 and R ^b12 are both hydrogen atoms, b11 is 2, b13, b14, and b15 are All are 0, c is 3, A ² is an ethoxy group, Rf ^b10 -{C(Rf ^b11 )(Rf ^b12 )} _b12 - is the terminal and is defined to be C ₆ F ₁₃ -.

Specific examples of the compounds represented by the above formula (b1) include C _j F _2j+1 -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is an integer of 1 to 12), among which C ₄ F ₉ —Si—(OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ —Si—(OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ — Si--(OC ₂ H ₅ ) ₃ and C ₈ F ₁₇ --Si--(OC ₂ H ₅ ) ₃ are preferred. _Also , _CF3CH2O ( _{CH2 ) kSiCl3} , _{CF3CH2O ( CH2} ) _{kSi ( OCH3} ) ₃ , _CF3CH2O ( _CH2 ) _kSi ( _{OC2H5 ) 3} , _CF3 ( _CH2 ) _2Si ( _CH3 ) ₂ (CH2 _{) kSiCl3 ,} CF3( _CH2 ) _2Si ( _CH3 ) ₂ ( _CH2 ) _kSi ( _{OCH3 ) 3} , CF3 _{( CH2} ) _2Si ( _CH3 ) ₂ ( _CH2 ) _kSi ( _OC2H5 ) ₃ , _CF3 ( _CH2 ) _6Si ( _{CH3 ) 2} ( _CH2 ) _{kSiCl3 , CF3} ( _CH2 ) _6Si ( _CH3 ) ₂ ( _CH2 ) _kSi ( _OCH3 ) ₃ , _CF3 ( _{CH2 ) 6Si} ( _CH3 ) ₂ ( _CH2 ) _kSi ( _OC2H5 ) ₃ , _CF3COO (CH ₂ ) _k SiCl ₃ , CF ₃ COO(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ COO(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ (k is 5 to 20). and preferably 8 to 15). Also, _CF3 ( _CF2 ) _m- ( _CH2 ) _{nSiCl3 , CF3} ( _{CF2 ) m-} ( _CH2 ) _nSi ( _OCH3 ) ₃ , CF3( _CF2 ) _m- ( _CH2 ) _n Si(OC ₂ H ₅ ) ₃ (where m is 0 to 10, preferably 0 to 7, n is 1 to 5, preferably 2 to 4). ). CF ₃ (CF ₂ ) _p —(CH ₂ ) _q —Si—(CH ₂ CH═CH ₂ ) ₃ may also be mentioned, where p is 2 to 10, preferably 2 to 8, q are all 1 to 5, preferably 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p —(CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p —(CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p —( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (where p is 2 to 10, preferably 3 to 7; q is 1 to 5, preferably 2 to 4); is).

Among the compounds represented by the above formula (b1), compounds represented by the following formula (b2) are preferred.

In the above formula (b2), R ⁶⁰ is a perfluoroalkyl group having 1 to 8 carbon atoms, R ⁶¹ is an alkylene group having 1 to 5 carbon atoms, and R ⁶² is an alkyl group having 1 to 3 carbon atoms. .

As the organosilicon compound (B), only one type may be used, or two or more types may be used.

When the layer (r) contains a structure derived from the organosilicon compound (B), the structure derived from the organosilicon compound (B) is preferably contained in the layer (r) in an amount of 3% by mass or more, more preferably 5% by mass. % by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less. Here, the structure derived from the organosilicon compound (B) refers to the residue after dehydration condensation of the organosilicon compound (B) and the organosilicon compound (B).

The mass ratio of the structure derived from the organosilicon compound (B) to the structure derived from the organosilicon compound (A) in the layer (r) is preferably 0.05 or greater, more preferably 0.08 or greater, and still more preferably 0.08. It is 10 or more, preferably 2.0 or less, more preferably 1.0 or less, and still more preferably 0.6 or less.

In addition, the layer (r) contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, an antiviral agent, a biological Various additives such as anti-adhesion agents, deodorants, pigments, flame retardants and antistatic agents may be included. The amount of the additive, that is, the solid content other than the solid content derived from the organosilicon compounds (A) and (B), in the layer (r) is preferably 0.1% by mass or less, more preferably 0.01. % by mass or less.

3. Protective layer (P)
In the laminate of the present invention, the first substrate (S _L ), the layer (r) containing fluorine element, and the protective layer (P) are laminated in this order, and another However, it is preferable that the layer (r) and the protective layer (P) are directly laminated, _and the adhesive layer (ad) is the layer (r ) side, and the adhesive layer (ad) and the layer (r) are preferably laminated directly.

3-1. Second base material (S _P )
The second substrate (S _P ) is generally a thermoplastic resin film, and includes a cyclic polyolefin resin film; a cellulose acetate resin film made of a resin such as triacetyl cellulose or diacetyl cellulose; polyethylene terephthalate; polyester resins such as polybutylene terephthalate and polyethylene naphthalate; polyolefin resins such as polyethylene and polypropylene; (meth)acrylic resins; polycarbonate resins; is preferred. Among them, the second base material (S _P ) preferably contains at least one of polyester resin and polyolefin resin, and particularly preferably contains polyester resin such as polyethylene terephthalate. As the second base material (S _P ), a separate film obtained by subjecting the above-described resin to a release treatment can be exemplified. The separate film can be, for example, the surface of the second substrate (S _P ) on which the pressure-sensitive adhesive layer is to be formed, which is subjected to release treatment such as silicone treatment.

The thickness of the second substrate (S _P ) is preferably 10 µm or more, more preferably 15 µm or more, still more preferably 20 µm or more, and preferably 100 µm or less, more preferably 80 µm or less, and even more preferably 60 µm or less.

3-2. Adhesive layer (ad)
The thickness of the adhesive layer (ad) is less than 16 μm. By reducing the thickness of the adhesive layer (ad), the peel strength of the protective layer (P) can be increased. Further, when the thickness of the adhesive layer (ad) is less than 16 μm, even when the thickness of the layer (r) is reduced, the contact angle on the surface of the layer (r) after peeling the protective layer (P) is less likely to decrease. can also be effective. The thickness of the adhesive layer (ad) is preferably 15 μm or less, more preferably 13 μm or less. Although the lower limit of the thickness of the adhesive layer (ad) is not particularly limited, it is preferably 3 μm or more, more preferably 5 μm or more.

The thickness ratio of the adhesive layer (ad) to the second substrate (S _P ) is preferably less than 0.55, more preferably 0.5 or less, and still more preferably 0.45 or less. Although not limited, it may be, for example, 0.01 or more, 0.1 or more, or 0.15 or more.

The adhesive layer (ad) may consist of one layer, or may consist of two or more layers, but preferably consists of one layer. Examples of the adhesive layer (ad) include (meth)acrylic resins, rubber resins, urethane resins, polyester resins, silicone resins, polyvinyl ether resins and polyolefin resins. preferably included. The adhesive layer (ad) can be formed from an adhesive composition containing at least one of the resins described above. A pressure-sensitive adhesive composition is preferred. The adhesive composition may be active energy ray-curable or heat-curable.

The (meth)acrylic resin (base polymer) used in the adhesive composition includes butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like. Polymers or copolymers containing one or more of the (meth)acrylic acid esters as monomers are preferably used. Preferably, the base polymer is copolymerized with a polar monomer. Polar monomers include (meth)acrylic acid compounds, 2-hydroxypropyl (meth)acrylate compounds, hydroxyethyl (meth)acrylate compounds, (meth)acrylamide compounds, and N,N-dimethylaminoethyl (meth)acrylate compounds. , glycidyl (meth)acrylate compounds, and other monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like.

The pressure-sensitive adhesive composition may contain only the above base polymer, but usually further contains a cross-linking agent. As a cross-linking agent, a metal ion having a valence of 2 or more and forming a carboxylic acid metal salt with a carboxyl group, a polyamine compound forming an amide bond with a carboxyl group, and a carboxyl group Examples include polyepoxy compounds or polyols that form ester bonds with and polyisocyanate compounds that form amide bonds with carboxyl groups. Among them, polyisocyanate compounds are preferred.

The active energy ray-curable pressure-sensitive adhesive composition has the property of being cured by being irradiated with an active energy ray such as an ultraviolet ray or an electron beam. It has the property that it can be adhered to an adherend and can be cured by irradiation with active energy rays to adjust the adhesion force. The active energy ray-curable pressure-sensitive adhesive composition is preferably UV-curable. The active energy ray-curable pressure-sensitive adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer and the cross-linking agent. If necessary, a photopolymerization initiator, a photosensitizer, etc. may be contained.

The adhesive composition includes fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than base polymers, tackifiers, fillers (metal powders and other inorganic powders, etc.). ), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, photopolymerization initiators, and other additives.

The adhesive layer (ad) can be formed by applying an organic solvent-diluted solution of the above adhesive composition onto the surface of the second substrate (S _P ) and drying. For example, a separate film is used as the second substrate (S _P ), and an adhesive composition is directly applied to the release-treated surface to form an adhesive layer (ad), and this adhesive layer with a separate film (ad) is formed. It may be laminated on the surface of the layer (r). Alternatively, the adhesive composition is directly applied to the surface of the layer (r) to form an adhesive layer (ad), and a separate film is laminated on the outer surface of the adhesive layer (ad) as a second substrate (S _P ). good too. When the adhesive layer (ad) is provided on the surface of the layer (r), the bonding surface of the layer (r) and/or the bonding surface of the adhesive layer (ad) is subjected to a surface activation treatment such as plasma treatment or corona treatment. etc. is also preferable, and corona treatment is more preferable. Also, the adhesive composition was applied on the second separate film to form an adhesive layer (ad), and a separate film (second base material (S _P )) was laminated on the formed adhesive layer (ad). A pressure-sensitive adhesive sheet may be prepared, and the pressure-sensitive adhesive layer (ad) with a separate film after peeling the second separate film from the pressure-sensitive adhesive sheet may be laminated on the layer (r). The second separate film is weaker in adhesion to the adhesive layer (ad) than the separate film (second substrate (S _P )) and is easy to peel off.

4. Primer layer (c)
The laminate of the present invention may have a primer layer (c) between the first substrate (S _L ) and the layer (r) containing elemental fluorine. By having the primer layer (c), the adhesion between the first substrate (S _L ) and the layer (r) containing elemental fluorine can be improved. Hereinafter, the primer layer (c) may be simply referred to as "layer (c)". The primer layer (c) and layer (r) are preferably directly laminated. Further, another layer may be provided between the first substrate (S _L ) and the primer layer (c), but the first substrate (S _L ) and the primer layer (c) are directly laminated. It is preferable that

4-1. Organosilicon compound (C)
The layer (c) is preferably a cured layer of the organosilicon compound (C) having an amino group or amine skeleton. In this case, the layer (c) is usually a mixed composition of the organosilicon compound (C) ( Hereinafter, it may be referred to as a composition for forming layer (c).) is applied and cured. The organosilicon compound (C) is preferably a compound having a silicon atom to which a hydrolyzable group or a hydroxy group is bonded together with an amino group or amine skeleton, and the —SiOH group or silicon atom possessed by the organosilicon compound (C). The -SiOH group of the organosilicon compound (C) generated by hydrolysis of the hydrolyzable group bonded to the -SiOH group derived from the organosilicon compound (C), or the surface where the layer (c) is formed in the laminate layer (c) may have a dehydration condensate of the organosilicon compound (C) (i.e., a condensed structure derived from the organosilicon compound (C)). All of the organosilicon compound (C) contained in the layer (c) may be a dehydration condensate.

In a preferred embodiment, the organosilicon compound (C) has a hydrolyzable group or a hydroxy group (hereinafter both are collectively referred to as a reactive group (h1)) bonded silicon atoms. ) 1 or more and 10 or less, more preferably 1 or more and 5 or less, and still more preferably 2 or more and 5 or less in one molecule. The number of reactive groups (h1) bonded to one silicon atom may be 1 or more, and may be 2 or 3, preferably 2 or 3. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. An alkoxy group is preferred, and an alkoxy group having 1 to 4 carbon atoms is more preferred. An alkoxy group or a hydroxy group is preferably bonded to the silicon atom, and an alkoxy group or a hydroxy group having 1 to 4 carbon atoms is particularly preferably bonded to the silicon atom. When there are a plurality of reactive groups (h1) in the organosilicon compound (C), the plurality of reactive groups (h1) may be the same or different, but they are the same. is preferred.

The organosilicon compound (C) may have either one of an amino group and an amine skeleton, or preferably has both an amino group and an amine skeleton. As the organosilicon compound (C), one having at least one amine skeleton is preferred. The amine skeleton is represented by —NR ¹⁰⁰ —, where R ¹⁰⁰ is a hydrogen atom or an alkyl group. Moreover, when the organosilicon compound (C) contains a plurality of amine skeletons, the plurality of amine skeletons may be the same or different. The number of amino groups or amine skeletons in one molecule of the organosilicon compound (C) may be 1 or more in total, preferably 2 or more in total, more preferably 2 or more and 5 or less amine skeletons, More preferably, the number of amine skeletons is 2 or more and 3 or less, and more preferably 2 amine skeletons.

The organosilicon compound (C) is preferably a compound having no fluoropolyether structure, more preferably a compound having no elemental fluorine.

The organosilicon compound (C) is preferably a compound represented by the following formula (c1) or (c2). That is, the primer layer (c) is preferably a cured layer of an organosilicon compound (C) represented by the following formula (c1) or (c2).

4-1-1. Organosilicon compound (C) represented by the following formula (c1) (hereinafter, organosilicon compound (C1))

In the above formula (c1),
R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple R ^x11 , the multiple R ^x11 may be different. may be different when there are a plurality of R ^{x12 ;} when there are a plurality of R ^{x13 , a plurality of R x13 may} be different; may be different from each other in a plurality of R ^x14 ,
Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^x11 are present; When there is a plurality of Rf ^x11 , the plurality of Rf x11 may be different, when there are a plurality of Rf ^x12 , the plurality of Rf ^x12 may be different, and when there is a plurality of Rf ^x13 , the plurality of Rf ^x13 may be different. may be different, and if there are a plurality of Rf ^x14 , the plurality of Rf ^x14 may be different,
R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x15 are present, the plurality of R ^x15 may be different,
X ¹¹ is a hydrolyzable group or a hydroxy group, and when a plurality of X ¹¹ are present, the plurality of X ¹¹ may be different,
Y ¹¹ is -NH- or -S-, and when a plurality of Y ¹¹ are present, the plurality of Y ¹¹ may be different,
Z ¹¹ is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group;
p1 is an integer of 1 to 20, p2, p3, and p4 are each independently an integer of 0 to 10, p5 is an integer of 0 to 10,
p6 is an integer from 1 to 3,
has at least one Y ¹¹ which is —NH— when Z ¹¹ is not an amino group; when all Y ¹¹ are —S— or when p5 is 0, Z ¹¹ is an amino group;
Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-units (U _c11 ), p2 -{C(Rf ^x11 ) (Rf ^x12 )}-unit (U _c12 ), p3-{Si (R ^x13 ) (R ^x14 )}-unit (U _c13 ), p4-{Si (Rf ^x13 )(Rf ^x14 )} The - unit (U _c14 ) and p5 -Y ¹¹ - units (U _c15 ) form one end of the compound represented by the formula (c1) where Z ¹¹ - is, and -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 is the other terminal, and the respective units (U _c11 ) to (U _c15 ) are aligned and bonded in any order unless —O— is linked to —O—.

R ^x11 , R ^x12 , R ^x13 and R ^x14 are preferably hydrogen atoms.

Rf ^x11 , Rf ^x12 , Rf ^x13 and Rf ^x14 are each independently preferably an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom.

R ^x15 is preferably an alkyl group having 1 to 5 carbon atoms.

X ¹¹ is preferably an alkoxy group, a halogen atom, a cyano group, an isocyanate group, or a hydroxy group, more preferably an alkoxy group or a hydroxy group, and an alkoxy group or a hydroxy group having 1 to 4 carbon atoms. is more preferred, and a methoxy group, an ethoxy group, or a hydroxy group is particularly preferred.

Y ¹¹ is preferably -NH-.

Z ¹¹ is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, particularly preferably an amino group.

p1 is preferably 1-15, more preferably 2-10. Each of p2, p3 and p4 is independently preferably 0-5, more preferably 0-2. p5 is preferably 0-5, more preferably 0-3. p6 is preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), in the above formula (c1), both R ^x11 and R ^x12 are hydrogen atoms, Y ¹¹ is —NH—, and X ¹¹ is an alkoxy group or a hydroxy group (especially a methoxy group). , an ethoxy group, or a hydroxy group), Z ¹¹ is an amino group or a mercapto group, p1 is 1 to 10, p2, p3 and p4 are all 0, p5 is 0 to 5 (especially 0 ∼3) and p6 is 3 is preferably used.

Note that the p1 units (U _c11 ) do not need to be continuously bonded to each other, _and may be bonded via other units in the middle. Just do it. The same applies to the units (U _c12 ) to (U _c15 ) bounded by p2 to p5.

The organosilicon compound (C1) is preferably represented by the following formula (c1-2).

In the above formula (c1-2),
X ¹² is a hydrolyzable group or a hydroxy group, and when a plurality of X ¹² are present, the plurality of X ¹² may be different,
Y ¹² is -NH-,
Z ¹² is an amino group or a mercapto group,
R ^x16 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x16 are present, the plurality of R ^x16 may be different,
p is an integer of 1 to 3, q is an integer of 2 to 5, r is an integer of 0 to 5, s is 0 or 1,
When s is 0, Z ¹² is an amino group.

X ¹² is preferably an alkoxy group, a halogen atom, a cyano group, an isocyanate group, or a hydroxy group, more preferably an alkoxy group or a hydroxy group, and an alkoxy or hydroxy group having 1 to 4 carbon atoms. is more preferred, and methoxy group, ethoxy group, or hydroxy group is particularly preferred.

Z ¹² is preferably an amino group.

R ^x16 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

p is preferably an integer of 2 to 3, more preferably 3.

When s is 1, q is preferably an integer of 2 to 3, r is preferably an integer of 2 to 4, and when s is 0, the sum of q and r is 1 to 5. Preferably.

4-1-2. Organosilicon compound (C) represented by the following formula (c2) (hereinafter, organosilicon compound (C2))

In the above formula (c2),
R ^{x20 and} R ^x21 are each independently a hydrogen atom or an alkyl group having 1 ^to 4 carbon ^atoms ; When a plurality of R x21 are present, the plurality of R ^x21 may be different,
Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms in ^which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom; ^x20 may be different, and when there are multiple Rf ^x21 , multiple Rf ^x21 may be different,
R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x22 and R ^x23 are present, a plurality of R ^x22 and R ^x23 may be different,
X ²⁰ and X ²¹ are each independently a hydrolyzable group or a hydroxy group, and when multiple X ²⁰ and X ²¹ are present, multiple X ²⁰ and X ²¹ may be different,
p20 is an integer of 1 to 30; p21 is an integer of 0 to ³⁰ ; and R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group,
p22 and p23 are each independently an integer of 1 to 3,
p20-{C( ^Rx20 )( ^Rx21 )}-units ( _Uc21 ), p21-{C( ^Rfx20 )( ^Rfx21 )}-units ( _Uc22 ) are p20 units ( U _c21 ) or p21 units (U _c22 ) do not need to be consecutive, and each unit (U _c21 ) and unit (U _c22 ) are lined up in any order and combined to form the formula (c2) One end of the compound is -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

R ^x20 and R ^x21 are preferably hydrogen atoms.

Rf ^x20 and Rf ^x21 are each independently preferably an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom.

R ^x22 and R ^x23 are preferably alkyl groups having 1 to 5 carbon atoms.

X ²⁰ and X ²¹ are preferably an alkoxy group, a halogen atom, a cyano group, an isocyanate group, or a hydroxy group, more preferably an alkoxy group or a hydroxy group, and an alkoxy group having 1 to 4 carbon atoms or a hydroxy is more preferably a group, and particularly preferably a methoxy group, an ethoxy group, or a hydroxy group.

As described above, at least one amine skeleton —NR ¹⁰⁰ — may be present in the molecule, and the amine skeleton may be replaced by either a repeating unit bracketed with p20 or p21. , p20 are preferably part of a bracketed repeating unit. A plurality of the amine skeletons may be present, and in that case, the number of amine skeletons is preferably 1-10, more preferably 1-5, even more preferably 2-5. In this case, it is preferable to have -{C(R ^x20 )(R ^x21 )} _p200 - between adjacent amine skeletons, and p200 is preferably 1 to 10, preferably 1 to 5. is more preferred. p200 is included in the total number of p20s.

In the amine skeleton —NR ¹⁰⁰ —, when R ¹⁰⁰ is an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ - is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

p20 is preferably 1-15, more preferably 1-10, excluding the number of repeating units replaced by the amine skeleton.

p21 is preferably 0 to 5, more preferably 0 to 2, excluding the number of repeating units replaced by the amine skeleton.

p22 and p23 are preferably 2 to 3, more preferably 3.

As the organosilicon compound (C2), in the above formula (c2), both R ^x20 and R ^x21 are hydrogen atoms, and X ²⁰ and X ²¹ are an alkoxy group or a hydroxy group (especially a methoxy group, an ethoxy group, or a hydroxy group), at least one repeating unit bracketed with p20 is replaced with an amine skeleton —NR ¹⁰⁰ —, R ¹⁰⁰ is a hydrogen atom, and p20 is 1 to 10 (with the proviso that , excluding the number of repeating units replaced by the amine skeleton), it is preferable to use a compound in which p21 is 0 and p22 and p23 are 3.

Incidentally, the reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330, which is used as compound (C) in the examples described later ( Product name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) is represented by the above formula (c2), where R ^x20 and R ^x21 are both hydrogen atoms, and p20 is 8 (however, it is replaced by an amine skeleton excluding the number of repeating units), p21 is 0, two amine skeletons (both R ¹⁰⁰ are hydrogen atoms), both terminals are the same, p22 and p23 are 3, and X ²⁰ and X ²¹ are methoxy groups.

The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

In the above formula (c2-2),
X ²² and X ²³ are each independently a hydrolyzable group or a hydroxy group, and when a plurality of X ²² and X ²³ are present, the plurality of X ²² and X ²³ may be different,
R ^x24 and R ^x25 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x24 and R ^x25 are present, a plurality of R ^x24 and R ^x25 may be different,
—C _w H _2w — has at least one of its methylene groups replaced with an amine skeleton —NR ¹⁰⁰ —, where R ¹⁰⁰ is a hydrogen atom or an alkyl group;
w is an integer of 1 to 30 (excluding the number of methylene groups substituted for the amine skeleton),
p24 and p25 are each independently an integer of 1-3.

X ²² and X ²³ are preferably an alkoxy group, a halogen atom, a cyano group, an isocyanate group, or a hydroxy group, more preferably an alkoxy group or a hydroxy group, and an alkoxy group having 1 to 4 carbon atoms or a hydroxy is more preferably a group, and particularly preferably a methoxy group, an ethoxy group, or a hydroxy group.

A plurality of amine skeletons —NR ¹⁰⁰ — may be present, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and more preferably 2 to 5. More preferred. Moreover, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The number of carbon atoms in the alkylene groups between adjacent amine skeletons is included in the total number of w.

In the amine skeleton —NR ¹⁰⁰ —, when R ¹⁰⁰ is an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ - is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

R ^x24 and R ^x25 are preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms.

p24 and p25 are preferably integers of 2 to 3, more preferably 3.

w is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 10 or less.

Further, the layer (c) contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, an antiviral agent, Various additives such as biofouling agents, deodorants, pigments, flame retardants, and antistatic agents may be included. The amount of the additive, that is, the solid content other than the solid content derived from the organosilicon compound (C) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, in the layer (c). be.

The composition for forming the layer (r) may contain the organosilicon compound (C). In this case, the layer (r) may contain the organosilicon compound (C), or the layer ( r) During curing of the forming composition, the primer layer (c) may be formed separately between the first substrate (S _L ) and the layer (r) containing elemental fluorine.

5. Characteristics of Laminate 5-1. Contact Angle of Layer (r) Side Surface after Peeling of Protective Layer (P) The contact angle of the layer (r) side surface after peeling of the protective layer (P) is 100° or more. By doing so, the peel strength of the protective layer (P) can be increased. After peeling off the protective layer (P), the contact angle of the layer (r) side surface is preferably 105° or more, more preferably 110° or more, and the upper limit is not particularly limited, but for example 120° or less. is. The contact angle may be measured by a droplet method (analysis method: θ/2 method) using a 1.5 μL water droplet, as shown in the examples below.

5-2. Peel strength when peeling off the protective layer (P) The peel strength when peeling off the protective layer (P) is preferably 1.7 gf/25 mm or more, more preferably 2.5 gf/25 mm or more, and still more preferably is 4.0 gf/25 mm or more, more preferably 4.5 gf/25 mm or more, may be 9.0 gf/25 mm or less, may be 8.0 gf/25 mm or less, .5 gf/25 mm or less, or less than 7.0 gf/25 mm. The peel strength is the peel strength when a 180° peel test is performed at a moving speed (peeling speed) of 300 mm/min, as in Examples described later.

5-3. Amount of F element on the peeled surface of the protective layer (P) In the laminate of the present invention, when the protective layer (P) is peeled off leaving the layer (r) on the first substrate (S _L ) side, the protective layer It is preferable that the amount of F element on the peeled surface of (P) is less than 50 atomic %. By doing so, it is possible to further improve the peel strength when the protective layer (P) is peeled off. The amount of the F element is more preferably 45 atomic % or less, still more preferably 40 atomic % or less, and even more preferably 35 atomic % or less. Although the lower limit of the amount of the F element is not particularly limited, it may be, for example, 5 atomic % or more, 8 atomic % or more, or 13 atomic % or more.

The amount of the F element can be obtained by measuring the elements constituting the peeled surface of the protective layer (P) and their amounts by X-ray photoelectron spectroscopy (XPS). Elements constituting the surface (W) measured by XPS are typically B, C, N, O, F, Si, P, S, Cl, particularly C, N, O, F, Si is. The contents of B, C, N, O, F, Si, P, S, and Cl are respectively B1s spectrum, C1s spectrum, N1s spectrum, O1s spectrum, F1s spectrum, Si2p spectrum, P2p spectrum, S2p spectrum, Cl2p Calculated based on the spectrum.

5-4. Contact angle of peeled surface of protective layer ( _P ) The contact angle of the release surface is preferably 110° or less. By doing so, it is possible to further improve the peel strength when the protective layer (P) is peeled off. The contact angle is more preferably 109° or less, more preferably 105° or less, and the lower limit is not particularly limited, but may be 90° or more, 93° or more, or 95° or more. The contact angle can be measured by a droplet method (analytical method: θ/2 method) using a 1.5 μL water droplet, as shown in Examples below.

6. Method for producing a laminate A preferred method for producing the laminate of the present invention is to (i) apply a composition for forming a water-repellent layer to the first substrate (S _L ) or a laminate intermediate containing the first substrate (S _L ) 1, (ii) a water-repellent layer curing step for curing the coating layer of the water-repellent layer-forming composition to obtain a laminated intermediate 2, and (iii) on the laminated intermediate 2 includes a protective layer lamination step of laminating a protective layer (P) on the
In the (i) water-repellent layer coating step, the composition for forming a water-repellent layer may be directly applied to the first substrate (S _L ), or the primer layer (c) may be applied to the first substrate (S _L ). , and the composition for forming a water-repellent layer may be applied on the other layer. In the case of forming the primer layer (c), (pr1-i) a step of applying a composition for forming the layer (c) to the first substrate (S _L ); and (pr2-i) the layer (c) a step of curing the coating layer of the forming composition to obtain the laminated intermediate 1; (ii) a water-repellent layer curing step to obtain a laminated intermediate 2 by curing the coating layer of the water-repellent layer-forming composition, and (iii) on the laminated intermediate 2 The laminate of the present invention may be produced by a step including a protective layer lamination step of laminating a protective layer (P) on the . In the manufacturing method described above, the layer (c) is formed from the coating layer of the layer (c)-forming composition, and the layer (r) is formed from the coating layer of the water-repellent layer-forming composition.
In addition, in the above manufacturing method, a step of forming another layer may be included between the (ii) water-repellent layer curing step and (iii) protective layer lamination step, but (ii) the water-repellent layer After the curing step, (iii) protective layer lamination step is preferably performed directly on the laminated intermediate 2 having the water-repellent layer as the outermost surface without forming other layers.

The composition for forming the layer (c) is a mixed composition of the organosilicon compound (C). The mixed composition of the organosilicon compound (C) is obtained by mixing the organosilicon compound (C), and when components other than the organosilicon compound (C) are mixed, the organosilicon compound (C) and Obtained by mixing other ingredients. The composition for forming the layer (c) includes those that have undergone a reaction after mixing, for example, during storage. Examples include compounds in which the hydrolyzable group bonded to the silicon atom of the compound (C) is hydrolyzed to a —SiOH group (hereinafter sometimes referred to as a hydrolyzate of the organosilicon compound (C)). Further, as an example in which the reaction has progressed, the composition for forming layer (c) may contain a condensate of the organosilicon compound (C), and the condensate may include the organosilicon compound (C). The -SiOH group having or the -SiOH group of the organosilicon compound (C) generated by hydrolysis is formed by dehydration condensation with the -SiOH group derived from the organosilicon compound (C) or the -SiOH group derived from another compound. and dehydrated condensates.

The layer (c) forming composition is preferably mixed with a solvent (E). The solvent (E) is not particularly limited, and for example, water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, ester solvents and the like can be used, with alcohol solvents being particularly preferred.

Alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
Ether solvents include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane and the like.
Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as pentane and hexane, alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.
Examples of ester solvents include ethyl acetate, propyl acetate, and butyl acetate.

The amount of the organosilicon compound (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on 100% by mass of the composition for forming the layer (c). , and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. The amount of the above organosilicon compound (C) can be adjusted during preparation of the composition. Also, the amount of the organosilicon compound (C) may be calculated from the analysis results of the composition. As a method of specifying from the analysis results of the composition, for example, the type of each compound contained in the composition is analyzed by gas chromatography mass spectrometry, liquid chromatography mass spectrometry, etc., and the obtained analysis The results can be identified by library searching, and the amount of each compound contained in the composition can be calculated from the above analytical results using the calibration curve method. In this specification, when ranges of amounts, mass ratios, or molar ratios of each component are described, the ranges can be adjusted during preparation of the composition. The amount of the organosilicon compound (C) is preferably 85% by mass or more, more preferably 95% by mass or more, based on 100% by mass of the solid content in the layer (c)-forming composition.

The amount of the solvent (E) is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass when the entire composition for forming the layer (c) is 100% by mass. % by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and may be 99.99% by mass or less.

In addition, the composition for forming layer (c) contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, and an antiviral agent, as long as the effects of the present invention are not impaired. Various additives such as agents, biofouling agents, deodorants, pigments, flame retardants, and antistatic agents may be mixed. The amount of the additive, that is, the amount of the substance other than the organosilicon compound (C) and the solvent (E) is preferably 5% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the composition for forming the layer (c). It is 1% by mass or less.

Examples of methods for applying the composition for forming layer (c) include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating.

Before applying the composition for forming the layer (c), it is preferable to subject the coated surface of the first substrate (S _L ) to an easy-adhesion treatment. Hydrophilic treatment such as corona treatment, plasma treatment, ultraviolet treatment, etc., can be mentioned as the easy-adhesion treatment, and plasma treatment is more preferable. Formation of functional groups such as OH groups (especially when the base material is an epoxy resin) or COOH groups (especially when the base material is an acrylic resin) on the surface of the base material by performing adhesion treatment such as plasma treatment. can be formed, and when such functional groups are formed on the substrate surface, the adhesion between the layer (c) and the first substrate (S _L ) can be further improved.

After applying the layer (c)-forming composition, the coating layer of the layer (c)-forming composition is dried by allowing it to stand at room temperature in the air for, for example, 10 seconds or more (usually 24 hours or less). , the layer (c) can be formed from the coating layer. In the present invention, normal temperature is 5 to 60°C, preferably 15 to 40°C. The humidity condition for standing at room temperature may be 50 to 90% RH. Further, after applying the layer (c) forming composition, it is heated to a temperature exceeding 60° C. (usually 120° C. or less, and may be 100° C. or less) for 10 seconds to 60 minutes (preferably 30 seconds to 40 minutes).

The composition for forming a water-repellent layer is a mixed composition of the organosilicon compound (A), and is obtained by mixing the organosilicon compound (A). When components other than the organosilicon compound (A) are mixed, the water-repellent layer-forming composition can be obtained by mixing the organosilicon compound (A) with the other components. The composition for forming a water-repellent layer includes those that have undergone reaction after being mixed, for example, during storage. As an example in which the reaction has progressed, for example, the composition for forming a water-repellent layer has a hydrolyzable group bonded (which may be bonded via a linking group) to the silicon atom of the organosilicon compound (A). is a compound (hereinafter sometimes referred to as a hydrolyzate of the organosilicon compound (A)) that has become a —SiOH group (Si and OH may be bonded via a linking group) by hydrolysis. mentioned. Further, the composition for forming a water-repellent layer may contain a condensate of the organosilicon compound (A). The -SiOH group (Si and OH may be bonded via a linking group) of the resulting organosilicon compound (A) is a -SiOH group derived from the organosilicon compound (A) (Si and OH are linking groups. may be bonded via), or dehydration condensates formed by dehydration condensation with —SiOH groups derived from other compounds.

The amount of the organosilicon compound (A) is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, and It is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

The composition for forming a water-repellent layer preferably contains an organosilicon compound (B) mixed together with the above-described organosilicon compound (A). This allows the layer (r) to contain a structure derived from the organosilicon compound (B). As described above, the composition for forming a water-repellent layer includes a composition that has undergone a reaction after mixing the organosilicon compound (A) and the optionally used organosilicon compound (B), and the reaction has proceeded. For example, the composition for forming a water-repellent layer is a compound in which the hydrolyzable group bonded to the silicon atom of the organosilicon compound (B) is hydrolyzed to become a —SiOH group (hereinafter referred to as the organosilicon compound (B ) may be referred to as a hydrolyzate). Further, the composition for forming a water-repellent layer may contain a condensate of the organosilicon compound (B), and the condensate may be a —SiOH group possessed by the organosilicon compound (B) or a hydrolyzed A dehydration condensate formed by dehydration condensation of —SiOH groups of the organosilicon compound (B) with —SiOH groups derived from the organosilicon compound (B) or —SiOH groups derived from other compounds can be mentioned.

The amount of the organosilicon compound (B) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and It is preferably 0.3% by mass or less, more preferably 0.2% by mass or less.

The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) in the water-repellent layer-forming composition is preferably 0.2 or more, more preferably 0.4 or more, and 3.0 or less. is preferred, and more preferably 1.5 or less.

The total amount of the organosilicon compounds (A) and (B) is preferably 0.05% by mass or more, more preferably 100% by mass of the entire water-repellent layer-forming composition. It is 0.10% by mass or more, preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less. The total amount of the organosilicon compounds (A) and (B) is preferably 85% by mass or more, more preferably 90% by mass or more when the total solid content in the water-repellent layer-forming composition is 100% by mass. and more preferably 95% by mass or more.

The water-repellent layer-forming composition is usually mixed with a solvent (D). As the solvent (D), it is preferable to use a fluorine-based solvent. For example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, a fluorinated hydrocarbon-based solvent, etc. can be used. is preferred. As the fluorinated ether-based solvent, hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl (especially methyl group or ethyl group) ether are preferable. Fluoroisobutyl ether may be mentioned. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec® 7200 (manufactured by 3M, molecular weight about 264). As the fluorinated amine-based solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferable, and a tertiary Secondary amines are preferred, specifically tris(heptafluoropropyl)amine, and Fluorinert® FC-3283 (manufactured by 3M, molecular weight about 521) corresponds to this. Fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane and perfluorohexane, and 1,3-bis(trifluoromethylbenzene). Examples include fluorinated aromatic hydrocarbon solvents. Examples of 1,1,1,3,3-pentafluorobutane include Solv 55 (manufactured by Solvex).

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC) and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by AGC) can be used. .

As the solvent (D), it is preferable to use at least a fluorinated amine solvent.

The amount of the solvent (D) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass when the entire composition for forming a water-repellent layer is 100% by mass. It is at least 98% by mass, more preferably at least 98% by mass, and may be at most 99.9% by mass.

In addition, the water-repellent layer-forming composition contains a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, and an antiviral agent, as long as the effects of the present invention are not impaired. , biofouling inhibitors, deodorants, pigments, flame retardants, antistatic agents and the like may be mixed. The amount of the additive, that is, the amount of substances other than the organosilicon compounds (A) and (B) and the solvent (E) is preferably 5% by mass or less in 100% by mass of the composition for forming a water-repellent layer, More preferably, it is 1% by mass or less.

Examples of methods for applying the water-repellent layer-forming composition (1) include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating.

After applying the composition for forming a water-repellent layer, the laminate of the present invention can be produced by allowing the composition to stand at room temperature in the air for, for example, 10 seconds or more (usually 24 hours or less). The humidity condition for standing at room temperature may be 50 to 90% RH. Further, after applying the water-repellent layer-forming composition, it is heated to a temperature exceeding 60° C. (usually 120° C. or lower, and may be 100° C. or lower) for 10 seconds to 60 minutes (preferably 30 seconds to 40 minutes).

In the protective layer lamination step, when the protective layer includes the second substrate (S _P ) and the adhesive layer (ad), a film including the second substrate (S _P ) and the adhesive layer (ad) is prepared and It may be laminated on the laminated intermediate 2, or the adhesive composition may be applied on the laminated intermediate 2 to form an adhesive layer (ad), and the second substrate (S _P ) may be laminated.

7. Display Device The laminate of the present invention is suitably used for display devices, for example, as an optical film, and is particularly suitably used for flexible display devices. The laminate of the present invention can preferably be used as a front panel in a display device, and the front panel is sometimes called a window film.

The display device preferably comprises a display device laminate containing a window film (that is, the laminate of the present invention) and an organic EL display panel. body is placed. Further, in the flexible display device, it is preferable that the laminate for a flexible display device including a window film having flexible characteristics and an organic EL display panel are provided. A laminate is arranged and configured to be foldable. The laminate for a display device (preferably a laminate for a flexible display device) may further contain a polarizing plate (preferably a circularly polarizing plate), a touch sensor, etc. to constitute a touch panel display, and the order of lamination thereof is arbitrary. However, it is preferable that the layers are laminated in the order of the window film, the polarizing plate and the touch sensor, or in the order of the window film, the touch sensor and the polarizing plate from the viewing side. When the polarizing plate is present on the viewing side of the touch sensor, the pattern of the touch sensor becomes less visible and the visibility of the displayed image is improved, which is preferable. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. Also, the display device (preferably flexible display device) can comprise a light shielding pattern formed on at least one surface of any one of the window film, the polarizing plate and the touch sensor.

(window film)
The window film is arranged on the viewing side of the display device (preferably the flexible image display device) and plays a role of protecting other components from external shocks or environmental changes such as temperature and humidity. Glass may be used as such a protective layer, and in a flexible image display device, a material having flexible characteristics may be used for the window film instead of being rigid and hard like glass. Therefore, when the laminate of the present invention is used as a window film in a flexible display device, the first substrate (S _L ) preferably has a layer made of a flexible transparent substrate, and the first substrate (S _L ) may have a multilayer structure in which a hard coat layer is laminated on at least one surface.

The transparent substrate has a visible light transmittance of, for example, 70% or more, preferably 80% or more. Any transparent polymer film can be used as the transparent substrate. Specifically, polyolefins such as polyethylene, polypropylene, polymethylpentene, norbornene, or cycloolefin derivatives having a monomer unit containing cycloolefin, (modified) cellulose such as diacetyl cellulose, triacetyl cellulose, and propionyl cellulose acrylics such as methyl methacrylate (co)polymers, polystyrenes such as styrene (co)polymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers Polyvinyl chlorides, polyvinylidene chlorides, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polycarbonate and polyarylate, polyamides such as nylon, polyimides, polyamideimides, polyetherimides, Films formed of polymers such as polyethersulfones, polysulfones, polyvinyl alcohols, polyvinyl acetals, polyurethanes, and epoxy resins may be used, and unstretched uniaxially or biaxially stretched films may be used. can be done. These polymers can be used alone or in combination of two or more. Among the transparent substrates described above, polyamide films, polyamideimide films, polyimide films, polyester films, olefin films, acrylic films, and cellulose films, which are excellent in transparency and heat resistance, are preferred. It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles, etc. in the polymer film. In addition, colorants such as pigments and dyes, optical brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. may contain a compounding agent. The thickness of the transparent substrate is 5 μm or more and 200 μm or less, preferably 20 μm or more and 100 μm or less. Particularly when used in a flexible image display device, the thickness of the transparent substrate is preferably 5 μm or more and 60 μm or less.

The hard coat layer when the laminate of the present invention is used as a window film is also the same as the hard coat layer (hc) described above. As described above, the hard coat layer (hc) is preferably formed from an active energy ray-curable resin and a thermosetting resin. It can be formed by curing a hardcoat composition containing the forming reactive material. The hard coat composition contains at least one polymer of a radically polymerizable compound and a cationic polymerizable compound.

The radically polymerizable compound is a compound having a radically polymerizable group. The radically polymerizable group possessed by the radically polymerizable compound may be any functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group and a (meth)acryloyl group. When the radically polymerizable compound has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different. The number of radically polymerizable groups in one molecule of the radically polymerizable compound is preferably two or more from the viewpoint of improving the hardness of the hard coat layer. The radically polymerizable compound is preferably a compound having a (meth)acryloyl group from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth)acryloyl groups in one molecule. Compounds called epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and oligomers having several (meth) acryloyl groups in the molecule and having a molecular weight of several hundred to several thousand are preferred. Available. It preferably contains one or more selected from epoxy (meth)acrylate, urethane (meth)acrylate and polyester (meth)acrylate.

The cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group. The number of cationically polymerizable groups in one molecule of the cationically polymerizable compound is preferably two or more, more preferably three or more, from the viewpoint of improving the hardness of the hard coat layer. As the cationically polymerizable compound, among others, a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable. A cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that shrinkage accompanying a polymerization reaction is small. In addition, among the cyclic ether groups, compounds having epoxy groups are readily available in various structures, do not adversely affect the durability of the resulting hard coat layer, and are easy to control compatibility with radically polymerizable compounds. There is an advantage. In addition, among the cyclic ether groups, the oxetanyl group tends to have a higher degree of polymerization than the epoxy group, is less toxic, accelerates the rate of network formation obtained from the cationically polymerizable compound in the resulting hard coat layer, and radicals It has the advantage of forming an independent network without leaving unreacted monomers in the film even in a region mixed with a polymerizable compound.

Examples of cationic polymerizable compounds having an epoxy group include polyglycidyl ethers of polyhydric alcohols having an alicyclic ring, or compounds containing cyclohexene rings or cyclopentene rings, which are treated with a suitable oxidizing agent such as hydrogen peroxide or peracid. Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth)acrylate, Aliphatic epoxy resins such as copolymers; bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or their derivatives such as alkylene oxide adducts and caprolactone adducts, and glycidyl ethers produced by reaction with epichlorohydrin, and glycidyl ether type epoxy resins derived from bisphenols such as novolac epoxy resins.
The hard coat composition may further include a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., and can be appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cationic polymerization.

Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by at least one of active energy ray irradiation and heating. Examples of thermal radical polymerization initiators include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile.
As active energy ray radical polymerization initiators, Type 1 type radical polymerization initiators that generate radicals by decomposition of molecules and Type 2 type radical polymerization initiators that generate radicals by hydrogen abstraction type reaction in coexistence with tertiary amines are used. Yes, each can be used alone or in combination.

The cationic polymerization initiator may be capable of releasing a substance that initiates cationic polymerization by at least one of active energy ray irradiation and heating. As cationic polymerization initiators, aromatic iodonium salts, aromatic sulfonium salts, cyclopentadienyl iron (II) complexes and the like can be used. These can initiate cationic polymerization by either or both of active energy ray irradiation and heating depending on the difference in structure.

The polymerization initiator may be included in an amount of 0.1-10% by weight based on 100% by weight of the hard coat composition. If the content of the polymerization initiator is less than 0.1% by weight, curing may not proceed sufficiently, and it may be difficult to realize the mechanical properties and adhesion of the finally obtained coating film. If the content is more than % by weight, adhesion failure, cracking, and curling may occur due to cure shrinkage.

The hard coat composition may further include one or more selected from the group consisting of solvents and additives. The solvent is capable of dissolving or dispersing the polymerizable compound and the polymerization initiator, and any solvent known as a solvent for hard coat compositions in this technical field can be used without limitation. The additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

(Circularly polarizing plate)
As described above, the display device (preferably flexible display device) of the present invention preferably includes a polarizing plate, especially a circularly polarizing plate. A circularly polarizing plate is a functional layer having a function of transmitting only a right-handed or left-handed circularly polarized light component by laminating a λ/4 retardation plate on a linearly polarizing plate. For example, by converting external light into right-handed circularly polarized light and blocking left-handed circularly polarized light reflected by the organic EL panel, only the luminescent component of the organic EL is transmitted, thereby suppressing the influence of the reflected light and creating an image. used to make it easier to see In order to achieve the circular polarization function, the absorption axis of the linear polarizer and the slow axis of the λ/4 retardation plate should theoretically be 45 degrees, but in practice they are 45±10 degrees. The linear polarizing plate and the λ/4 retardation plate do not necessarily have to be laminated adjacent to each other as long as the relationship between the absorption axis and the slow axis satisfies the above range. Although it is preferable to achieve perfect circular polarization at all wavelengths, it is not always necessary in practice, so the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a λ/4 retardation film on the viewing side of the linear polarizing plate to circularly polarize the emitted light, thereby improving the visibility when wearing polarized sunglasses.

A linear polarizing plate is a functional layer having a function of transmitting light oscillating in the direction of the transmission axis, but blocking polarized light of an oscillating component perpendicular thereto. The linear polarizing plate may have a configuration including a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface of the linear polarizer. The thickness of the linear polarizing plate may be 200 μm or less, preferably 0.5 μm or more and 100 μm or less. When the thickness of the linear polarizing plate is within the above range, the flexibility of the linear polarizing plate tends to be less likely to decrease.

The linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) film. A dichroic dye such as iodine is adsorbed on a PVA-based film that has been oriented by stretching, or the film is stretched while adsorbed to PVA, thereby aligning the dichroic dye and exhibiting polarizing performance. The production of the film-type polarizer may include other steps such as swelling, cross-linking with boric acid, washing with an aqueous solution, and drying. The stretching and dyeing processes may be carried out on the PVA-based film alone, or may be carried out while it is laminated with another film (stretching resin base material) such as polyethylene terephthalate. The thickness of the PVA-based film used is preferably 3 to 100 μm, and the draw ratio is preferably 2 to 10 times. As a method for producing a laminate of a stretchable resin base material and a PVA-based resin layer, a method of applying a coating liquid containing a PVA-based resin to the surface of the stretchable resin base material and drying it is preferable.

In particular, if the manufacturing method includes the step of stretching and dyeing the PVA-based resin layer and the resin substrate for stretching in the state of a laminate, even if the PVA-based resin layer is thin, it is supported by the resin substrate for stretching. Thus, the film can be stretched without problems such as breakage due to stretching.

The thickness of the polarizer is 20 μm or less, preferably 12 μm or less, more preferably 9 μm or less, even more preferably 1 to 8 μm, particularly preferably 3 to 6 μm. If it is within the above range, it becomes a preferred embodiment without inhibiting bending.

Further, another example of the polarizer is a liquid crystal coated polarizer formed by applying a liquid crystal polarizing composition. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The liquid crystalline compound only needs to have a property of exhibiting a liquid crystal state, and it is particularly preferable to have a high-order alignment state such as a smectic phase because high polarizing performance can be exhibited. Moreover, the liquid crystalline compound preferably has a polymerizable functional group.
The dichroic dye compound is a dye that exhibits dichroism by aligning with the liquid crystalline compound, and may have a polymerizable functional group, and the dichroic dye itself has liquid crystallinity. You may have
Any one of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group. The liquid crystal polarizing composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent, and the like.
The liquid crystal polarizing layer is manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed thinner than the film-type polarizer, and the thickness is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.

The alignment film is produced, for example, by applying an alignment film-forming composition onto a substrate and imparting alignment properties by rubbing, polarized light irradiation, or the like. The alignment film-forming composition contains an alignment agent, and may further contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. Examples of the alignment agent include polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides. When using an alignment agent that imparts alignment properties by polarized light irradiation, it is preferable to use an alignment agent containing a cinnamate group. The weight average molecular weight of the polymer used as the alignment agent is, for example, about 10,000 to 1,000,000. The thickness of the alignment film is preferably 5 nm or more and 10,000 nm or less, and more preferably 10 nm or more and 500 nm or less in terms of sufficiently expressing the alignment control force.
The liquid crystal polarizing layer can be laminated by peeling from the base material and transferring, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a protective film, a retardation plate, or a transparent base material for a window film.

As the protective film, any transparent polymer film may be used, and the same materials and additives as those used for the transparent base material of the window film can be used. Cellulose-based films, olefin-based films, acrylic films, and polyester-based films are preferred. It may also be a coating-type protective film obtained by applying and curing a cationic curable composition such as an epoxy resin or a radical curable composition such as an acrylate. The protective film may optionally contain plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, and antioxidants. , a lubricant, a solvent, and the like. The thickness of the protective film is preferably 200 μm or less, more preferably 1 μm or more and 100 μm or less. When the thickness of the protective film is within the above range, the flexibility of the film tends to be less likely to decrease. The protective film can also serve as the transparent substrate of the window film.

The λ/4 retardation plate is a film that provides a λ/4 retardation in a direction (in-plane direction of the film) perpendicular to the traveling direction of incident light. The λ/4 retardation plate may be a stretched retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film. The λ / 4 retardation plate, if necessary, retardation modifiers, plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers agents, antistatic agents, antioxidants, lubricants, solvents, and the like.
The thickness of the stretched retardation plate is preferably 200 μm or less, more preferably 1 μm or more and 100 μm or less. When the thickness of the stretched retardation plate is within the above range, the flexibility of the stretched retardation plate tends to be less likely to decrease.

Another example of the λ/4 retardation plate is a liquid crystal coated retardation plate formed by coating a liquid crystal composition.
The liquid crystal composition includes a liquid crystal compound exhibiting a liquid crystal state such as nematic, cholesteric, or smectic. The liquid crystalline compound has a polymerizable functional group.
The liquid crystal composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent, and the like.
The liquid crystal-coated retardation plate can be produced by applying a liquid crystal composition on a base and curing to form a liquid crystal retardation layer in the same manner as the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed to be thinner than the stretching type retardation plate. The thickness of the liquid crystal polarizing layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.
The liquid crystal-coated retardation plate can be laminated by peeling from the base material and transferred, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a protective film, a retardation plate, or a transparent base material for a window film.

In general, many materials exhibit larger birefringence at shorter wavelengths and smaller birefringence at longer wavelengths. In this case, it is not possible to achieve a retardation of λ / 4 in the entire visible light region, so that the in-plane retardation is preferably 100 nm or more so that it becomes λ / 4 near 560 nm where visibility is high. It is designed to be 180 nm or less, more preferably 130 nm or more and 150 nm or less. A reverse-dispersion λ/4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to that of a normal one is preferable in terms of good visibility. As such materials, for example, those described in JP-A-2007-232873 can be used as the stretched retardation plate, and those described in JP-A-2010-30979 can be used as the liquid crystal-coated retardation plate. .
As another method, a technique of obtaining a broadband λ/4 retardation plate by combining with a λ/2 retardation plate is also known (for example, Japanese Unexamined Patent Publication No. 10-90521). The λ/2 retardation plate is also manufactured by a material method similar to that of the λ/4 retardation plate. The combination of the stretched retardation plate and the liquid crystal-coated retardation plate is arbitrary, but the thickness of both can be reduced by using the liquid crystal-coated retardation plate.
A method is known in which a positive C plate is laminated on the circularly polarizing plate in order to improve visibility in the oblique direction (for example, Japanese Patent Laid-Open No. 2014-224837). The positive C-plate may be either a liquid crystal-coated retardation plate or a stretched retardation plate. The retardation in the thickness direction of the retardation plate is preferably −200 nm or more and −20 nm or less, more preferably −140 nm or more and −40 nm or less.

(touch sensor)
A display device (preferably a flexible display device) including the laminate of the present invention preferably includes a touch sensor as described above. A touch sensor is used as an input means. As the touch sensor, there are various types such as a resistive film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and a capacitance type, and the capacitive type is preferable.
A capacitive touch sensor is divided into an active area and a non-active area located outside the active area. The active area is an area corresponding to the area (display part) where the screen is displayed on the display panel, and is an area where a user's touch is sensed. display area). The touch sensor preferably includes a flexible substrate, a sensing pattern formed in an active region of the substrate, and an external driving circuit formed in a non-active region of the substrate through the sensing pattern and a pad portion. Each sensing line can be included for connecting to a As the flexible substrate, the same material as the transparent substrate of the window film can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa % or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness is 2,000 MPa% or more and 30,000 MPa% or less. Here, the toughness is defined as the lower area of a stress-strain curve obtained through a tensile test of a polymeric material, up to the breaking point.

The sensing patterns may include first patterns formed in a first direction and second patterns formed in a second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed in the same layer, and each pattern must be electrically connected to sense a touched point. The first pattern has a form in which a plurality of unit patterns are connected to each other through joints, but the second pattern has a structure in which a plurality of unit patterns are separated from each other in an island form. A separate bridge electrode is required for direct connection. A well-known transparent electrode can be applied to the electrode for connection of the second pattern. Materials for the transparent electrode include, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), and indium gallium zinc oxide (IGZO). , cadmium tin oxide (CTO), PEDOT (poly(3,4-ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire, etc., preferably ITO. These can be used singly or in combination of two or more. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, terenium, chromium, etc. These may be used alone or in combination of two or more. can be done.
A bridge electrode may be formed on the insulating layer above the sensing pattern with an insulating layer interposed therebetween, and the bridge electrode may be formed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be made of the same material as the sensing pattern, and may be made of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. can.
Since the first pattern and the second pattern should be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer can be formed only between the joints and bridge electrodes of the first pattern, or can be formed as a layer covering the entire sensing pattern. In the case of a layer covering the entire sensing pattern, the bridge electrode can connect the second pattern through contact holes formed in the insulating layer.

The touch sensor is induced by a difference in transmittance between a patterned area where a sensing pattern is formed and a non-patterned area where no sensing pattern is formed, specifically by a difference in refractive index in these areas. An optical adjustment layer may further be included between the substrate and the electrode as a means for properly compensating for differences in optical transmittance. The optical modulating layer can comprise an inorganic insulating material or an organic insulating material. The optical control layer may be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. The inorganic particles can increase the refractive index of the optical adjustment layer.
The photocurable organic binder includes a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, and a carboxylic acid-based monomer within a range that does not impair the effects of the present invention. be able to. The photocurable organic binder may be, for example, a copolymer containing different repeating units such as epoxy group-containing repeating units, acrylate repeating units, and carboxylic acid repeating units.
Examples of the inorganic particles include zirconia particles, titania particles, and alumina particles.
The photocurable composition may further include additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.

(adhesive layer)
Each layer (window film, circularly polarizing plate, touch sensor) forming the laminate for the display device (preferably flexible image display device) and film members (linear polarizing plate, λ/4 retardation plate, etc.) constituting each layer are It can be joined with an adhesive. Examples of the adhesive include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatile adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic-curable adhesives, and active energy ray-curable adhesives. Commonly used adhesives such as adhesives, curing agent-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), and rewetting adhesives can be used, preferably water-based solvent volatilization. type adhesives, active energy ray-curable adhesives, and pressure-sensitive adhesives can be used. The thickness of the adhesive layer can be appropriately adjusted according to the desired adhesive strength and the like, and is preferably 0.01 to 500 μm, more preferably 0.1 to 300 μm. A plurality of adhesive layers are present in the laminate for a display device (preferably a flexible image display device), and the respective thicknesses and types may be the same or different.

As the water-based solvent volatilization type adhesive, water-soluble polymers such as polyvinyl alcohol-based polymers and starch, and polymers in a water-dispersed state such as ethylene-vinyl acetate-based emulsions and styrene-butadiene-based emulsions can be used as main polymers. In addition to the main polymer and water, crosslinking agents, silane compounds, ionic compounds, crosslinking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, and the like may be added. When bonding with the water-based solvent volatilization type adhesive, adhesion can be imparted by injecting the water-based solvent volatilization type adhesive between the layers to be adhered, laminating the layers to be adhered, and then drying. When the water-based solvent volatilization type adhesive is used, the thickness of the adhesive layer is preferably 0.01 to 10 μm, more preferably 0.1 to 1 μm. When the water-based solvent volatilization type adhesive is used for multiple layers, the thickness and type of each layer may be the same or different.

The active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that forms an adhesive layer upon irradiation with an active energy ray. The active energy ray-curable composition can contain at least one polymer of the same radically polymerizable compound and cationic polymerizable compound as those contained in the hard coat composition. As the radically polymerizable compound, the same compound as the radically polymerizable compound in the hard coat composition can be used.
As the cationic polymerizable compound, the same compound as the cationic polymerizable compound in the hard coat composition can be used.
Epoxy compounds are particularly preferred as the cationic polymerizable compound used in the active energy ray-curable composition. It is also preferred to contain a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.

The active energy ray composition can contain a monofunctional compound to reduce viscosity. Examples of the monofunctional compound include acrylate-based monomers having one (meth)acryloyl group in one molecule, compounds having one epoxy group or oxetanyl group in one molecule, such as glycidyl (meth) ) acrylates and the like.
The active energy ray composition can further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, and these are appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cationic polymerization. In the description of the hard coat composition, an initiator capable of initiating at least one of radical polymerization and cationic polymerization upon exposure to active energy rays can be used.
The active energy ray-curable composition further includes an ion scavenger, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming agent solvent, an additive, and a solvent. can include When two layers to be adhered are bonded with the active energy ray-curable adhesive, the active energy ray-curable composition is applied to one or both of the layers to be adhered, and then laminated to either adherend layer. Alternatively, both layers to be adhered can be adhered by irradiating them with active energy rays for curing. When the active energy ray-curable adhesive is used, the adhesive layer preferably has a thickness of 0.01 to 20 μm, more preferably 0.1 to 10 μm. When the active energy ray-curable adhesive is used to form a plurality of adhesive layers, the thickness and type of each layer may be the same or different.

As the pressure-sensitive adhesive, any one classified into an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and the like can be used according to the main polymer. In addition to the base polymer, the adhesive may contain a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like. An adhesive layer is formed by dissolving and dispersing each component constituting the adhesive in a solvent to obtain an adhesive composition, applying the adhesive composition on a substrate and then drying it. be. The adhesive layer may be formed directly, or may be transferred after being separately formed on the substrate. It is also preferable to use a release film to cover the adhesive surface before adhesion. When the active energy ray-curable adhesive is used, the adhesive layer preferably has a thickness of 0.1 to 500 μm, more preferably 1 to 300 μm. When using a plurality of layers of the pressure-sensitive adhesive, the thickness and type of each layer may be the same or different.

(Shading pattern)
The light shielding pattern can be applied as at least part of a bezel or housing of the display device (preferably a flexible image display device). The visibility of the image is improved by hiding the wiring arranged at the peripheral portion of the display device (preferably the flexible image display device) by the light shielding pattern and making it difficult to see. The light shielding pattern may be in the form of a single layer or multiple layers. The color of the light-shielding pattern is not particularly limited, and may be various colors such as black, white, and metallic. The light-shielding pattern may be formed of pigments for realizing colors and polymers such as acryl-based resin, ester-based resin, epoxy-based resin, polyurethane, and silicone. These may be used singly or as a mixture of two or more. The light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is preferably 1-100 μm, more preferably 2-50 μm. It is also preferable to impart a shape such as an inclination in the thickness direction of the light shielding pattern.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. The present invention is not limited by the following examples, and it is of course possible to make appropriate modifications within the scope that can be adapted to the spirit of the above and the following. Included in scope.

Example 1-1
A reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330, represented by the following formula as an organosilicon compound (C) (trade name ; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 0.05% by mass and 99.95% by mass of isopropyl alcohol as a solvent (E) was stirred at room temperature to form a layer (c). A composition was obtained. In _{addition ,} the first substrate (S _L ) (hard coat layer thickness: 5 μm, first substrate thickness: 50 μm) was prepared, and an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.) was used to prepare the hard coat layer of the first substrate (S _L ). The (layer (S _L2 )) plane was activated. After that, the composition for forming the layer (c) obtained above was applied onto the hard coat layer (layer (S _L2 )) of the substrate (S _L ) using an OPTICOAT MS-A100 (bar coater) manufactured by MIKASA Co., Ltd. , #2 bar, 0.5 ml, 100 mm/sec, and dried at 100° C. for 30 seconds to obtain Lamination Intermediate 1 on which layer (c) was formed.

Next, the compound (a10) satisfying the above formula (a1) as the organosilicon compound (A), and FAS13E (C ₆ F ₁₃ —C ₂ H ₄ —Si(OC ₂ H ₅ ) as the organosilicon compound (B) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.) is mixed with FC-3283 ( _C9F21N , _Fluorinert , manufactured by 3M) as a solvent (D), stirred at room temperature for a predetermined time, and used for forming layer (r). A composition was obtained. The ratio of the organosilicon compound (A) in the layer (r)-forming composition was 0.085% by mass, and the ratio of the organosilicon compound (B) was 0.05% by mass. Layer (r) forming composition on layer (c) in laminated intermediate 1, OPTICOAT MS-A100 (bar coater) manufactured by MIKASA Co., Ltd., using #5 bar, 0.5 ml, 100 mm / sec conditions and dried at 100° C. for 30 seconds to obtain a laminate intermediate 2 having a layer (r) formed thereon. The thickness of layer (r) measured by the method described below was about 4.7 nm. The compound (a10) used as the organosilicon compound (A) satisfies the requirements of the above-described compounds (a11) and (a21), and also satisfies the requirements of formula (a3) including preferred embodiments.

Thickness Measurement of Layer (r) The thickness of layer (r) was measured using X-ray photoelectron spectroscopy (XPS) as described below. First, layers (c) and (r) were formed in the same manner as in Example 1 on a glass substrate treated with atmospheric pressure plasma. At that time, the composition for forming a water-repellent layer was applied in four different coating amounts to prepare a total of four laminates with the same thickness of the layer (c) and different thicknesses of the layer (r).
Next, the film thickness of each layer (r) was measured using an ellipsometer. In addition, the amount of the F element and the amount of the C element other than the F element are measured using the XPS method for the same layer, and the ratio (F / C (other than CF)) is calculated. A calibration curve was prepared for the film thickness of the layer (r). In this case, the amount of the F element is derived from the layer (r), and the amount of the C element other than the C element bonded to the F element is derived from the layer (c).
Next, XPS measurement was performed on the laminates produced in Examples, and the film thickness of the layer (r) was calculated according to the calibration curve produced above.
<XPS measurement conditions>
Apparatus name: Thermofisher Scientific K-alpha
X-ray source: monochrome Al Kα
Output: 72W (12kV, 6mA)
Spot size: 400 μm
Pass energy: 50 eV
Dwell time: 50ms
Mode (element): narrow (F, C)
Neutralization gun: on

Lamination was carried out by expulsion of air with a hand sealer so that the adhesive layer of the protective film NSA-33T (manufactured by San A Kaken Co., Ltd.) was in contact with the layer (r) side of the laminated intermediate 2 after drying. After that, the laminated body was kept under normal temperature and humidity for a whole day and night in the state of bonding, and a laminate having the protective layer (P) laminated thereon was obtained.

Example 1-2
A laminate was produced in the same manner as in Example 1-1, except that bar #2 was used as the condition for forming the layer (r). The thickness of layer (r) measured in the same manner as in Example 1-1 was about 2.8 nm.

Example 2-1
A laminate was produced in the same manner as in Example 1 except that AY-638 (manufactured by Fujimori Kogyo Co., Ltd.) was used as the protective film.

Example 2-2
A laminate was produced in the same manner as in Example 2-1, except that bar #2 was used as the condition for forming the layer (r).

Example 3-1
A laminate was produced in the same manner as in Example 1-1, except that Toraytech 7H52 (manufactured by Toray Advanced Film Co., Ltd.) was used as the protective film.

Example 3-2
A laminate was produced in the same manner as in Example 3-1, except that bar #2 was used as the condition for forming the layer (r).

Comparative Example 1-1
A laminate was produced in the same manner as in Example 1-1 except that AS3-304 (manufactured by Fujimori Kogyo Co., Ltd.) was used as the protective film.

Comparative example 1-2
A laminate was produced in the same manner as in Comparative Example 1-1, except that bar #2 was used as the condition for forming the layer (r).

The laminates obtained in Examples and Comparative Examples were evaluated in the following manner.

(1) Method for measuring the amount of F element on the peeled surface of the protective layer (P) By X-ray photoelectron spectroscopy (XPS), using JFS-9010 type manufactured by JEOL Ltd., excitation X-ray: MgKα, X-ray output At 110 W, the photoelectron escape angle is 45°, and the pass energy is 50 eV, carbon (C1s) on the peeled surface of the protective layer (P) when peeled off: 260 to 300 eV, nitrogen (N1s: 390 to 410 eV), oxygen (O1s): 525 to 545 eV, fluorine (F1s): 680 to 698 eV, silicon (2p): 92 to 112 eV. The atomic ratio of the amount of F (fluorine) to the measured total amount of carbon, nitrogen, oxygen, fluorine and silicon was defined as the amount of elemental F in the peeled surface of the protective layer (P).

(2) Method for measuring the peel strength of the protective layer (P) Using the resistance measurement of Tribogear (surface property measuring instrument TYPE: 38) manufactured by Sintokagaku Co., Ltd., using a peel force measurement jig, the measurement conditions are as follows. As a condition, the peel strength was measured when the protective layer (P) was peeled off from the laminates obtained in Examples and Comparative Examples.
Load transducer: 1.442mV/V
Travel distance: 70mm
Movement speed: 300mm/min
Peeling angle: 180°
Sampling number: 14100

(3) Contact angle measurement method The layer (r) film side surface from which the protective layer (P) was removed from the obtained laminate and the protective layer (P) surface in contact with the layer (r) (protective layer (P) surface 1.5 μL of water droplets are dropped on each peeled surface), and a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM700) is used to measure the contact angle of water by a droplet method (analysis method: θ / 2 method). was measured.

Table 1 shows the results.

According to Table 1, the thickness of the adhesive layer (ad) is less than 16 μm, and the contact angle of the surface of the layer (r) containing elemental fluorine when the protective layer (P) is removed is 100° or more. In Example 1-1, Example 1-2, Example 2-1, Example 2-2, Example 3-1 and Example 3-2, the thickness of the adhesive layer (ad) is 16 μm or more Comparison Better peel strength was achieved than in Example 1-1 and Comparative Example 1-2.

Further, by comparing Examples 1-1 and 1-2, Examples 2-1 and 2-2, and Examples 3-1 and 3-2, the thickness of the layer (r) There was a tendency that the thicker the layer (r) after peeling, the higher the contact angle of the layer (r). It can be seen that such a tendency becomes conspicuous particularly when the thickness of the adhesive layer (ad) exceeds 10 μm.

From another point of view, by comparing Examples 1-1 and 1-2, Examples 2-1 and 2-2, and Examples 3-1 and 3-2, the layer The thinner the thickness of (r), the less fluorine is transferred to the protective layer (P), and the peel strength tends to increase when the protective layer (P) is peeled off, especially the thickness of the adhesive layer (ad). It can be seen that such a tendency becomes conspicuous when is exceeds 10 μm. Further, by comparing Comparative Example 1-2 with Examples 1-2, 2-2, and 3-2, it can be seen that, particularly when the thickness of the layer (r) is thin, the layer (r ) tended to suppress the decrease in contact angle.

The laminate of the present invention can be used for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, window glass for automobiles and buildings, metal products such as cookware, ceramic products such as tableware, and plastics. It is industrially useful because it can be suitably used for automotive parts and the like. It is also preferably used for items such as kitchens, bathrooms, washbasins, mirrors, and members around toilets.

Claims (9)

A laminate comprising a first substrate (S _L ), a layer (r) containing a fluorine element, and a protective layer (P) in this order,
The protective layer (P) comprises a second substrate (S _P ) and an adhesive layer (ad),
The adhesive layer (ad) has a thickness of less than 16 μm,
When the protective layer (P) is peeled off leaving the layer (r) containing elemental fluorine on the first substrate (S _L ) side, the contact angle of the surface of the layer (r) containing elemental fluorine is 100° or more. A laminate. The contact angle of the peeled surface of the protective layer (P) is 110° or less when the protective layer (P) is peeled off leaving the layer (r) containing the fluorine element on the first substrate (S _L ) side. The laminate according to claim 1. 3. The laminate according to claim 1, further comprising a primer layer (c) between the first substrate (S _L ) and the layer (r) containing elemental fluorine. said first substrate (S _L ) comprises two different layers (S _L1 ) and a layer (S _L2 ),
The layer (S _L2 ) is located closer to the layer (r) containing the fluorine element than the layer (S _L1 ),
The layer (S _L1 ) is a resin,
3. The laminate according to claim 1, wherein said layer (S _L2 ) is an acrylic hard coat layer. The second base material (S _P ) contains at least one of polyester resin and polyolefin resin,
The adhesive layer (ad) contains at least one selected from the group consisting of (meth)acrylic resins, rubber resins, urethane resins, polyester resins, silicone resins, polyvinyl ether resins and polyolefin resins. The laminate according to claim 1 or 2. 3. The laminate according to claim 1, wherein the layer (r) containing elemental fluorine has a thickness of 50 nm or less. When the protective layer (P) is peeled off leaving the layer (r) containing the fluorine element on the first substrate (S _L ) side, the amount of F element on the peeled surface of the protective layer (P) is less than 50 atomic %. 3. The laminate according to claim 1 or 2. 3. The laminate according to claim 1, wherein the layer (r) containing elemental fluorine is a cured layer of an organosilicon compound (A) represented by the following formula (a1).

In the above formula (a1),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group having 1 to 20 carbon atoms in which one ^or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom; When a plurality of Rf a26 are present, a plurality of Rf ^a26 may be different, when a plurality of Rf ^a27 are present, a plurality of Rf ^a27 may be different, and when a plurality of Rf ^a28 are present, a plurality of Rf ^a28 may be different from each other, and when a plurality of Rf ^a29 are present, the plurality of Rf ^a29 may be different,
R ²⁵ and R ²⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl halide having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms; group, at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom, and when a plurality of R ²⁵ are present, the plurality of ^{R 25 may} be different, When doing, multiple R ²⁶ may be different,
R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, ^{or a} single bond; When a plurality of R ²⁸ are present, the plurality of R ²⁸ may be different,
R ²⁹ and R ^{30 are each independently} an alkyl group having 1 to 20 carbon atoms; may have different R ³⁰ ,
^M7 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, -C(=O)NR-, - CH═CH— or —C ₆ H ₄ — (phenylene group), R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and M ⁷ is When a plurality of M 7 are present, the plurality of M ⁷ may be different,
M ⁵ is ^a hydrogen atom, ^a fluorine atom or an alkyl group having 1 to 4 carbon atoms;
M ¹⁰ is a hydrogen atom or a halogen atom,
M ⁸ and M ⁹ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group; or an ethyl group, and when there are a plurality of M ⁸ , the plurality of M ⁸ may be different, and when there is a plurality of M ⁹ , the plurality of M ⁹ may be different,
f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 is an integer from 0 to 20,
f27 is each independently an integer of 0 to 2,
g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, g21 + g22 ≤ 3,
g31 is an integer of 1 to 3, g32 is an integer of 0 to 2, g31 + g32 ≤ 3,
M ¹⁰ -, -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _3-g31-g32 , f21 -{C(R ²⁵ )(R ²⁶ )}-units (U _a1 ), f22 - {C(Rf ^a26 ) (Rf ^a27 )} - unit (U _a2 ), f23 - {Si (R ²⁷ ) (R ²⁸ )} - unit (U _a3 ), f24 - {Si (Rf ^{a28 .} _{_} ^_ _{_} ^_ _{_ _} ^_ _{_} (H) _g22 (R ²⁹ ) _3-g21-g22 }]-unit (U _a6 ) has M ¹⁰ - at one end in formula (a1), and -Si(M ⁹ ) _g31 (H) _g32 ( R ³⁰ ) _3-g31-g32 are the other ends, and are arranged in an order that forms a fluoropolyether structure at least in part, and the respective units may be arranged in any order as long as —O— is not continuous with —O— Join side by side. A window film or touch panel comprising the laminate according to claim 1 or 2.