TW202239611A - Laminate - Google Patents

Abstract

A laminate according to (the first embodiment of) the present invention includes: a substrate that contains an antimicrobial component (K); and a water-repellent layer (r), said laminate being characterized in that the laminate further contains an organosilicon compound (C) that has a silicon atom to which a hydrolyzable group or a hydroxyl group has been bonded, the water-repellent layer (r) is a hardened layer of an organosilicon compound (A) that has a silicon atom to which a hydrolyzable group or a hydroxyl group has been bonded either via a linking group or without the mediation of a linking group, and the thickness of a laminated section including the water-repellent layer (r) provided on the substrate (s)is 1-50 nm, inclusive. This laminate exhibits both good water repellency and antimicrobial properties. A laminate according to (the second embodiment of) the present invention has an electrically conductive substrate (s), a layer (c) that contains elemental nitrogen, and a layer (r) that contains elemental fluorine, wherein the layer (c) is provided between the substrate (s) and the layer (r). This laminate is capable of suppressing increases in the surface resistivity of the surface of the layer that contains elemental fluorine even after use in a high-temperature environment, and providing a laminate that exhibits superior abrasion resistance.

Description

laminate

The present invention relates to an invention of a laminated body, including a first aspect and a second aspect.

(Prior technology related to the first aspect) In various fields such as display devices such as touch panel displays, optical elements, semiconductor elements, building materials, and window glass for automobiles and buildings, it is required to impart water repellency to the surface of the base material. Therefore, various water-repellent films can be used as water-repellent coatings or water-repellent and oil-repellent coatings.

For example, Patent Document 1 describes a water and oil repellent coating composition, which includes: a fluorine-containing group having a perfluoroalkyl group or a perfluoropolyether group on the free end side and a hydrolyzable group bonded to a silicon atom The first organosilicon compound (A), and the hydrolyzable silane oligomer, or the second organosilicon compound (B) in which the group containing carbon fluoride and the hydrolyzable group are bonded to the silicon atom.

(Prior technology related to the second aspect) In various fields such as display devices such as touch panel displays, optical elements, semiconductor elements, building materials, and window glass for automobiles and buildings, it is required to impart water repellency to the surface of the base material. Therefore, members with various water-repellent coatings are used.

As a layer having water repellency, for example, a layer containing fluorine element can be mentioned, but since the surface free energy is very small, it is difficult to ensure the adhesion with various substrates. Also, the layer containing fluorine element has the property of being easily charged.

For example, a water and oil repellent member is disclosed in Patent Document 2, which has an undercoat layer as a first layer on at least one side of the substrate, and has an undercoat layer on the outer surface of the undercoat layer. The second layer is made of a water and oil repellent layer, the primer layer contains a layer with a film thickness of 30 to 500 nm mainly composed of an organosilicon compound having multiple silanol groups in the molecule, and the water and oil repellent layer contains A layer with a film thickness of 0.5 to 30 nm mainly composed of a cured product of a hydrolyzable fluorine-containing compound, and the surface resistance of the outer surface of the water and oil repellent layer is 1.0×10 ¹¹ Ω/□ or less. In the aforementioned Patent Document 2, it is described that the surface resistance value of the outer surface of the water and oil repellent layer formed on the surface of the primer layer can be reduced by setting the main component of the primer layer to a specific one. Prior Art Documents Patent Documents

Patent Document 1: Specification of International Publication No. 2016/076245 (first aspect) Patent Document 2: WO2020/039795 (Second Aspect)

[Problem to be solved by the invention]

(Task of the first aspect) In recent years, attention to the problem of pollution caused by various bacteria has been increasing, and in the above-mentioned various fields, it is also required to have antibacterial properties in addition to good water repellency. However, when the water-repellent coating is applied to an antibacterial substrate to form a laminate, the antibacterial activity on the surface of the laminate may decrease. Therefore, an object of the present invention (first aspect) is to provide a laminate having both good water repellency and antibacterial properties.

(Tasks of the second form) The surface resistance value of the layer containing fluorine element is higher at room temperature, and the surface resistance value tends to increase after being placed in an environment higher than room temperature. It is important to use it at a higher temperature Afterwards, the rise of the surface resistance value can also be suppressed.

Furthermore, depending on the application, the water-repellent coating may apply a physical load to the surface, and in this case, it is also required not to damage the surface.

Therefore, an object of the present invention (aspect 2) is to provide a laminate including a water-repellent layer that suppresses an increase in surface resistivity even after being placed in a relatively high temperature environment and is excellent in scratch resistance. [Technical means to solve the problem]

(Means for solving the problems of the first aspect) The present invention that solves the problems of the above-mentioned first aspect is as follows. [1] A laminate comprising a substrate (s) containing an antibacterial component (K) and a water-repellent layer (r), and the laminate comprises a silicon atom bonded to a hydrolyzable group or a hydroxyl group Organosilicon compound (C), the above-mentioned water-repellent layer (r) is a hardened layer of organosilicon compound (A) having a silicon atom bonded to a hydrolyzable group or a hydroxyl group via a linking group or not via a linking group. The thickness of the layered part of the water-repellent layer (r) of the substrate (s) is not less than 1 nm and not more than 50 nm. [2] The laminate described in [1], wherein a layer (c) is provided between the water-repellent layer (r) and the substrate (s), and the layer (c) contains the organosilicon compound (C). [3] The laminate described in [2], wherein the layer (c) has a thickness of less than 30 nm. [4] The laminate described in [1], wherein the substrate (s) and the water-repellent layer (r) are directly laminated, and the water-repellent layer (r) contains the organosilicon compound (C). [5] The laminate according to any one of [1] to [4], wherein the organosilicon compound (C) is a compound having an amine group or an amine skeleton. [6] The laminate according to any one of [1] to [5], wherein the organosilicon compound (C) is a compound represented by any one of formulas (c1) to (c3) described below, Or a compound in which two or more compounds represented by the formula (c3) are bonded by condensation of at least any one of the following X ³¹ to X ³⁴ . [7] The laminate according to any one of [1] to [6], wherein the antibacterial component (K) contains metal ions. [8] The laminate according to any one of [1] to [7], wherein the antibacterial component (K) contains a quaternary ammonium salt. [9] The laminate described in [8], wherein the quaternary ammonium salt is a compound represented by the formula (k1) described below. [10] The laminate described in any one of [1] to [9], wherein the water-repellent layer (r) surface has a water contact angle of 105° or more and satisfies the following requirements (α) and ( At least one element in the group formed by β). (α) When the antibacterial activity test according to JIS Z 2801:2010 is carried out, the antibacterial activity value against Staphylococcus aureus is 0.1 or more. (β) When the antibacterial activity test according to JIS Z 2801:2010 is carried out, the antibacterial activity value against Escherichia coli is 0.1 or more. [11] The laminate described in any one of [1] to [10], wherein a load of 1000 g is applied in units of a circle with a diameter of 6 mm, and the surface of the water-repellent layer (r) of the laminate is reciprocally rubbed for 1500 Second, the water contact angle on the surface of the water-repellent layer (r) after the abrasion resistance test is 75° or more. [12] The laminate described in any one of [1] to [11], wherein the surface of the water-repellent layer (r) of the laminate is rubbed with steel wool under a pressure of 250 g/cm ² Test until peeling or damage is visually confirmed on the surface of the water-repellent layer (r), the number of times the steel wool reciprocates on the surface of the water-repellent layer (r) is more than 100 times.

(Second aspect of problem solving) The present invention that solves the problems of the above-mentioned second aspect is as follows. [13] A laminate comprising a conductive substrate (s), a layer (c) containing a nitrogen element, and a layer (r) containing a fluorine element, wherein the layer (c) is provided on the substrate Between (s) and the above-mentioned layer (r). [14] The laminate according to [13], wherein the layer (c) has a thickness of less than 30 nm. [15] The laminate described in [13] or [14], wherein the substrate (s) is a substrate containing an antistatic agent, or a substrate containing a surface layer containing an antistatic agent. [16] The laminate according to [15], wherein the substrate (s) includes a resin substrate and the surface layer containing an antistatic agent, and the surface layer is a hard coat layer. [17] The laminate according to [16], wherein the hard coat layer is at least one selected from the group consisting of acrylic resins, silicone resins, and epoxy resins. [18] The laminate according to any one of [15] to [17], wherein the surface layer has a thickness of 10 μm or less. [19] The laminate according to any one of [15] to [18], wherein the antistatic agent is an ionic compound. [20] The laminate according to any one of [15] to [19], wherein the antistatic agent is an ionic compound having a cationic organic group or an anionic organic group. [21] The laminate described in any one of [15] to [20], wherein the antistatic agent is selected from quaternary ammonium salts, pyridinium salts, and compounds having primary to tertiary amino groups At least one of the group. [22] The laminate according to any one of [13] to [21], wherein the total thickness of the layer (c) and the layer (r) is less than 50 nm. [23] The laminate according to any one of [13] to [22], wherein the layer (c) is an organosilicon compound (C) represented by the formula (c1) or (c2) described below. hardened layer.

(Problem solving methods of the first aspect and the second aspect) Moreover, this invention (1st aspect and 2nd aspect) also includes the following invention. [24] The laminate according to any one of [1] to [23], wherein the water-repellent layer (r) is silicon having a hydrolyzable group or a hydroxyl group bonded via a linking group or not. Atoms, and the hardened layer of organosilicon compound (A) containing fluorine element, The above layer (r) is a cured layer of organosilicon compound (A) containing fluorine element. [25] The laminate according to [24], wherein the organosilicon compound (A) is a compound having a fluoropolyether structure. [26] The laminate according to [25], wherein the organosilicon compound (A) is a compound represented by the formula (a1) described below. [27] The laminate according to any one of [1] to [26], wherein the surface of the water-repellent layer (r) or the surface of the layer (r) has a dynamic friction coefficient of 0.1 or less. [28] The laminate according to any one of [1] to [27], wherein the surface resistivity after the heat resistance test of keeping the laminate at 80°C for 36 hours does not reach the surface resistivity before the heat resistance test 6.4 times. [29] A window film or a touch panel display comprising the laminate according to any one of [1] to [28]. [Effect of Invention]

(Effect of the first aspect) According to the present invention (first aspect), it is possible to provide a laminate having both good water repellency and antibacterial properties.

(The effect of the second aspect) According to the present invention (second aspect), it is possible to provide a laminate that suppresses an increase in surface resistivity even after use in a high-temperature environment on the surface of a layer containing a fluorine element and that is excellent in scratch resistance. .

(Mode for implementing the invention related to the first aspect) The laminated system of the present invention (first aspect) includes a substrate (s) containing an antibacterial component (K) and a water-repellent layer (r), and the above-mentioned water-repellent layer (r) has a linking group or does not A cured layer of an organosilicon compound (A) having a silicon atom bonded to a hydrolyzable group or a hydroxyl group as a linking group.

A preferred layered system of the present invention (first aspect) includes a substrate (s) containing an antibacterial component (K) and a water-repellent layer (r), and the above-mentioned layered body includes An organosilicon compound (C) containing silicon atoms, the water-repellent layer (r) is a hardened layer of an organosilicon compound (A) having a silicon atom bonded to a hydrolyzable group or a hydroxyl group via a linking group or not via a linking group .

Also, the preferred laminated system of the present invention (first aspect) includes a substrate (s) containing an antibacterial component (K) and a water-repellent layer (r), and the above-mentioned water-repellent layer (r) has The thickness of the hardened layer of the organosilicon compound (A) containing a silicon atom with a hydrolyzable group or a hydroxyl group bonded to a silicon atom without a linking group, including the layered part of the water-repellent layer (r) provided on the substrate (s), is Above 1 nm and below 50 nm.

Also, a preferred laminate system of the present invention (first aspect) includes a base material (s) containing an antibacterial component (K) and a water-repellent layer (r), and the laminate includes Silicone compound (C) having a silicon atom of a hydroxyl group or a hydroxyl group, the water-repellent layer (r) is an organosilicon compound (A) having a silicon atom bonded to a hydrolyzable group or a hydroxyl group via a linking group or not via a linking group The hardened layer, including the layered part of the water-repellent layer (r) provided on the substrate (s), has a thickness of not less than 1 nm and not more than 50 nm. According to the above laminate, it is possible to provide a laminate having good at least one of abrasion resistance, oil repellency, and scratch resistance in addition to good water repellency and antibacterial properties.

In this specification, the "laminated part" is the part that includes the water-repellent layer (r), and only refers to the water-repellent layer (r) when only the water-repellent layer (r) is laminated on one side of the substrate (s), When there is a water-repellent layer (r) on a single layer of the substrate (s) via a different interlayer from the water-repellent layer (r), it refers to the intermediary layer and the water-repellent layer (r). The spacer layer may be layer (c) described below.

Other layers different from the water-repellent layer (r) and the intervening layer can be laminated on the outer surface of the water-repellent layer (r) (the side where the substrate (s) does not exist). Included in the Lamination Section. In the laminate of the present invention (first aspect), the water-repellent layer (r) is preferably the outermost layer.

When the water-repellent layer (r) is formed on both surfaces of the substrate (s), laminated portions exist on both surfaces, and at least one laminated portion may have a thickness of not less than 1 nm and not more than 50 nm.

The laminate of the present invention (first aspect) can have good water repellency and antibacterial properties (preferably antibacterial and antiviral properties). Also, according to the present invention (the first aspect), it is also possible to provide a water-repellent and antibacterial property, preferably selected from abrasion resistance, anti-fouling properties, oil repellency, scratch resistance, and transparency. At least one good laminate.

Furthermore, in this specification, "antibacterial property" not only means to prevent the proliferation of bacteria such as bacteria and molds, but also includes the meaning of killing or reducing bacteria. As the bacteria, for example, Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus, pneumoniae, Haemophilus influenzae, pertussis, Enteritidis, Klebsiella pneumoniae, Pseudomonas aeruginosa, Vibrio, MRSA (methicillin -resistant staphylloccus aureus, methicillin-resistant Staphylococcus aureus), etc.

Also, "antiviral properties" means inactivating a part of a virus, and specifically, means suppressing virus infectivity. Examples of viruses include rhinovirus, poliovirus, rotavirus, foot-and-mouth disease virus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, type A, type B , and C-type influenza virus, parainfluenza virus, mumps virus (mumps), measles virus, human metapneumovirus, RS (respiratory syncytial, respiratory cell fusion) virus, Nipah virus, Henderson virus La virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, hepatitis B and C virus, eastern and western equine encephalitis virus, o'nyong-nyong virus, rubella virus, Lassa virus, Junin Virus, Machupo virus, Guanarito virus, Sabia virus, Crimean-Congo hemorrhagic fever virus, furode fever, Hantavirus, sinobe virus, rabies virus, Ebola Viruses, Marburg virus, bat Lisa virus, human T-cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS (Severe Acute Respiratory Syndrome, severe acute respiratory syndrome) coronavirus, human parvovirus, polyoma virus, human Papillomavirus, adenovirus, herpes virus, varicella zoster virus, EB (Epstein-Barr) virus, cytomegalovirus, smallpox virus, monkeypox virus, vaccinia virus, molluscum pox virus, para For poxviruses, etc., the laminate of the present invention (first aspect) is more useful for viruses having an envelope.

The laminate of the present invention (first aspect) includes a substrate (s) containing an antibacterial component (K) and a water-repellent layer (r). A layer (hereinafter referred to as layer (c)) different from the base material (s) and the water-repellent layer (r) can be provided between the base material (s) and the water-repellent layer (r), and the base material can also be directly laminated (s) and water-repellent layer (r). Hereinafter, in this specification, the laminate in which the layer (c) is provided between the substrate (s) and the water-repellent layer (r) is referred to as "laminate (1)". In this case, the water-repellent layer (r) and layer (c) become a laminated part. Moreover, in this specification, the laminated body which directly laminated|stacked a base material (s) and a water-repellent layer (r) is called "laminate (2)", and in this case, a water-repellent layer (r) becomes a laminated part.

In the case where the laminate of the present invention (first aspect) contains an organosilicon compound (C) having a silicon atom bonded to a hydrolyzable group or a hydroxyl group, the organosilicon compound (C) may be contained in any layer, and the Preferably, it is included in the water-repellent layer (r) or layer (c). Especially in the case of the laminate (1), the organosilicon compound (C) is preferably contained in the water-repellent layer (r) or layer (c), particularly preferably contained in the layer (c). In addition, in the case of the laminate (2), the organosilicon compound (C) is preferably contained in the water-repellent layer (r).

Hereinafter, the substrate (s), the water-repellent layer (r), and the layer (c) will be described in order.

1-1. Substrate(s) The material of the base material (s) is not particularly limited, and may be any of organic materials and inorganic materials, and the shape of the base material may be either flat or curved, or a combination thereof. shape. Examples of organic materials include: acrylic resins, acrylonitrile resins, polycarbonate resins, polyester resins (such as polyethylene terephthalate, etc.), styrene resins, cellulose resins, polyolefin resins, vinyl Base resin (such as polyethylene, polyvinyl chloride, vinyl benzyl chloride resin, polyvinyl alcohol, etc.), polyvinylidene chloride resin, polyamide resin, polyimide resin, polyamideimide Resins, polyetherimide resins, polyetherimide resins, polyether resins, polyvinyl acetal resins, vinyl ether resins, and thermoplastic resins such as these copolymers; phenol resins, urea resins, melamine resins, epoxy resins Resins, oxetane resins, unsaturated polyesters, silicone resins, urethane resins and other thermosetting resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, aluminum, titanium, zirconium, niobium, tantalum, and lanthanum; metal oxides of these metals, or alloys containing these metals; ceramics, glass, etc. . Among these, organic materials are preferable.

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

The substrate (s) may be a single layer or a multilayer of two or more layers. When the substrate (s) is multilayered, the substrate (s) preferably has a multilayer structure in which a layer (s2) different from the layer (s1) is provided on a matrix layer (s1). When the substrate (s) includes the layer (s1) and the layer (s2), the laminate of the present invention (first aspect) preferably has the layer (s1), the layer (s2), the water repellent layer (r). That is, when the layered body of the present invention (first aspect) is the above-mentioned layered body (1), it is preferable that layer (s1), layer (s2), layer (c), and water-repellent layer are layered in this order. (r), when the laminated body of the present invention (first aspect) is the above-mentioned laminated body (2), it is preferable that the layer (s1), the layer (s2), and the water-repellent layer (r) are sequentially laminated. .

1-1-1. Layer (s1) The material of the layer (s1) can be any one of the above-mentioned organic materials and inorganic materials, preferably an organic material, among which, it is more preferably selected from acrylic resin, polyester resin, vinyl benzyl chloride resin, At least one of epoxy resin, polysiloxane resin, and urethane resin, more preferably acrylic resin, polyester resin, especially preferably polyethylene terephthalate.

The thickness of the layer (s1) is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, further preferably 30 μm or more, may be 500 μm or less, preferably 200 μm or less, more preferably 150 μm or less, more preferably 100 μm or less, especially preferably 60 μm or less.

1-1-2. Layer (s2) The layer (s2) may, for example, be a layer formed of at least one selected from the group (X1) consisting of active energy ray-curable resins and thermosetting resins. The aforementioned active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, and electron beams. The above-mentioned active energy ray-curable resins include: acrylic resins, epoxy resins, oxetane resins, urethane resins, polyamide resins, vinyl benzyl chloride resins, vinyl UV-curable resins (polyethylene, vinyl chloride-based resins, etc.), styrene-based resins, phenol-based resins, vinyl ether-based resins, polysiloxane-based resins, or mixtures thereof, or electron beam-curable resins , especially UV curable resin. Furthermore, as the layer (s2), it is also possible to exemplify the layer (X2) selected from the group (X2) consisting of titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide, lanthanum oxide, and _SiO2 . at least one of the formed layers. As the group (X1), particularly preferred are acrylic resins, silicone resins, styrene resins, vinyl chloride resins, polyamide resins, phenol resins, and epoxy resins. The thickness of the layer (s2) is, for example, from 0.1 nm to 100 μm, preferably from 1 nm to 60 μm, more preferably from 1 nm to 10 μm. If the thickness of the layer (s2) is too thick, it may easily shrink due to heat during subsequent processing.

In the case where the layer (s2) comprises at least one layer formed from the group (X1) above, the layer (s2) can function as a hard coat layer (hc) having surface hardness, and can protect the base The material(s) imparts scratch resistance. The hardness of the hard coat layer (hc) is usually B or higher in pencil hardness, preferably HB or higher, further preferably H or higher, and particularly preferably 2H or higher. When the layer (s2) includes a hard coat layer (hc), that is, when the layer (s2) has the function of a hard coat layer, the hard coat layer (hc) may have a single-layer structure or a multi-layer structure. The hard coat layer (hc), for example, preferably includes the above-mentioned ultraviolet curable resin, more preferably includes an acrylic resin or silicone resin, and preferably includes an acrylic resin in order to express high hardness. Moreover, it is also preferable to contain an epoxy-type resin at the point which shows the tendency for the adhesiveness of a base material (s) and a water-repellent layer (r) to become favorable. Furthermore, in the column of the display device described below, a specific method of forming the active energy ray-curable resin and the thermosetting resin constituting the group (X1) will be described, for example, by including irradiating active energy rays or heat energy. A composition of reactive materials forming a cross-linked structure is coated on layer (s1) and cured to form layer (s2). Furthermore, in the case where the antibacterial component (K) described below is included in the layer (s2), a composition in which the antibacterial component (K) is added to a composition containing the above-mentioned reactive material may be used.

When the layer (s2) contains a hard coat layer (hc), the hard coat layer (hc) may contain additives. The additive is not limited, and examples thereof include inorganic fine particles, organic fine particles, or a mixture thereof. Examples of additives include inorganic fillers such as ultraviolet absorbers, metal oxides such as silica and alumina, and polyorganosiloxane. By including the inorganic filler, the adhesion between the substrate (s) and the water-repellent layer (r) can be improved. The thickness of the hard coat layer (hc), for example, is preferably at least 1 μm, more preferably at least 1.2 μm, further preferably at least 1.4 μm, and preferably at most 100 μm, more preferably at most 50 μm, and still more preferably It is 20 μm or less, more preferably 10 μm or less. When the thickness of the above-mentioned hard coat layer (hc) is 1 μm or more, sufficient scratch resistance can be ensured, and when it is 100 μm or less, bending resistance can be ensured, and as a result, it is possible to suppress the occurrence of curing shrinkage. The generation of curling.

When the layer (s2) includes a layer formed of at least one selected from the group (X2) above, the layer (s2) can function as an antireflection layer (ar) that prevents reflection of incident light. When the layer (s2) includes an anti-reflection layer (ar), the anti-reflection layer (ar) is preferably a layer that exhibits reflective properties such that the reflectance decreases to about 5.0% or less in the visible light region of 380 to 780 nm. The anti-reflection layer (ar) preferably includes a layer formed of silicon dioxide.

The structure of the anti-reflection layer (ar) is not particularly limited, and may be a single-layer structure or a multi-layer 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 total number of laminated layers is preferably 2 to 20. As the material constituting the high refractive index layer, titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide or lanthanum oxide can be cited. As the material constituting the low refractive index layer, two Silicon oxide. As an anti-reflection layer of a multilayer structure, it is preferable to alternately laminate SiO ₂ (silicon dioxide) and ZrO ₂ , or SiO ₂ and Nb ₂ O ₅ , and the outermost layer on the opposite side to layer (s1) is SiO ₂ . The anti-reflection layer (ar) can be formed, for example, by evaporation. The thickness of the antireflection layer (ar) is, for example, not less than 0.5 nm and not more than 1000 nm.

The layer (s2) may comprise a hard coat (hc), may also comprise an anti-reflection layer (ar), may also comprise both a hard coat (hc) and an anti-reflection layer (ar), preferably at least comprises a hard coat layer (hc). When the layer (s2) includes both the hard coat layer (hc) and the antireflection layer (ar), it is preferable to laminate the antireflection layer (ar) on the water-repellent layer (r) side.

The base material (s) contains an antibacterial component (K).

As the antibacterial component (K), a compound exhibiting antibacterial properties (preferably antibacterial and antiviral properties) can be used, and it may be an inorganic antibacterial component or an organic antibacterial component. As an antibacterial component (K), only 1 type may be used, and 2 or more types may be used.

As an inorganic antibacterial component, metal ions (hereinafter referred to as metal ions (K2)) are preferred, and specifically, antimony, silver, iron, nickel, copper, chromium, manganese, gold, gallium, germanium, Ions of mercury, arsenic, aluminum, lead, zinc, bismuth, tin, and palladium. As metal ions (K2), silver ions or copper ions are preferred.

Examples of the organic antibacterial component include various surfactants such as cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants. Among them, cationic surfactants such as quaternary ammonium salts, pyridinium salts, imidazolinium salts, isoquinolinium salts, and phosphonium salts are preferred, and quaternary ammonium salts are particularly preferred.

In addition, as an organic antibacterial component, it is preferable to contain one or more silicon atoms in the molecule that are bonded to hydrolyzable groups or hydroxyl groups (hereinafter both are combined and referred to as reactive groups (h2), and more preferably contain 1 A cationic surfactant with more than one silicon atom bonded to reactive groups (h2), especially a quaternary ammonium salt containing more than one silicon atom bonded to reactive groups (h2). The number of the above silicon atoms is In one molecule of the organic antibacterial component, it is preferably from 1 to 12, more preferably from 1 to 5, and still more preferably from 1 to 3. As the above-mentioned hydrolyzable group, it can be exemplified: an alkoxy group, a halogen atom, A cyano group, an acetyloxy group, an isocyanate group, etc., preferably an alkoxy group, more preferably an alkoxy group with 1 to 4 carbon atoms. It is preferably an alkoxy group or a hydroxyl group bonded to the above-mentioned silicon atom, especially preferably It is bonded with an alkoxy group or a hydroxyl group with a carbon number of 1 to 4. It is considered that the reactive group (h2) between molecules is realized by the organic antibacterial component being a compound containing a silicon atom that is bonded to the reactive group (h2). or the condensation of -SiOH groups derived from silicon atoms bonded to reactive groups (h2) and active hydrogens (hydroxyl groups, etc.) derived from other compounds in the substrate may thus be able to suppress the The rapid exudation of organic antibacterial ingredients caused by environmental changes such as water immersion or temperature rise makes it easier to maintain the organic antibacterial ingredients in the substrate.

The number of reactive groups (h2) bonded to one silicon atom may be 1 or more, may be 2 or 3, and is preferably 2 or 3.

[於式(k1)中， R ^k1～R ^k3分別獨立地表示碳數1～30之烴基， R ^k4及R ^k5分別獨立地表示碳數1～4之烷基，於存在複數個R ^k5之情形時，複數個R ^k5可分別不同， Y ^k1及Y ^k2分別獨立地表示單鍵或碳數1～10之二價烴基， A ^k1及A ^k2分別獨立地表示水解性基或羥基，於存在複數個A ^k1之情形時，複數個A ^k1可分別不同，於存在複數個A ^k2之情形時，複數個A ^k2可分別不同， Z ^k1為水解性基、羥基、碳數1～4之烷基、或式(ki)所表示之基， k3表示1或2， k4表示0～2之整數， k5表示0～10之整數， 於Z ^k1為水解性基、羥基、或碳數1～4之烷基之情形時，n表示1，於Z ^k1為式(ki)所表示之基之情形時，n表示2， X表示鹵素原子； [化2]

[於式(ki)中，R ^k17～R ^k19分別獨立地表示碳數1～30之烴基，*表示鍵結鍵]] The organic antibacterial component is preferably a quaternary ammonium salt represented by formula (k1) (hereinafter sometimes referred to as a quaternary ammonium salt (K1)). [chemical 1]

[In formula (k1), R ^k1 to R ^k3 independently represent a hydrocarbon group with 1 to 30 carbons, R ^k4 and R ^k5 independently represent an alkyl group with 1 to 4 carbons, and where there are a plurality of R ^k5 In this case, a plurality of R ^k5 may be different, Y ^k1 and Y ^k2 independently represent a single bond or a divalent hydrocarbon group with 1 to 10 carbons, A ^k1 and A ^k2 independently represent a hydrolyzable group or a hydroxyl group, in presence In the case of a plurality of A ^k1 , the plurality of A ^k1 may be different, and in the case of a plurality of A ^k2 , the plurality of A ^k2 may be different respectively, and Z ^k1 is a hydrolyzable group, a hydroxyl group, or an alkane having 1 to 4 carbon atoms group, or a group represented by formula (ki), k3 represents 1 or 2, k4 represents an integer of 0 to 2, k5 represents an integer of 0 to 10, and Z ^k1 is a hydrolyzable group, a hydroxyl group, or a carbon number of 1 to 4 In the case of an alkyl group, n represents 1, and in the case where Z ^k1 is a group represented by formula (ki), n represents 2, and X represents a halogen atom;

[In formula (ki), R ^k17 to R ^k19 each independently represent a hydrocarbon group with 1 to 30 carbons, and * represents a bond]]

The hydrocarbon groups represented by R ^k1 to R ^k3 and R ^k17 to R ^k19 may be linear or branched, aliphatic or aromatic, or saturated. It may also be an unsaturated hydrocarbon group, preferably a straight-chain or branched saturated aliphatic hydrocarbon group (hereinafter referred to as an alkyl group), more preferably a straight-chain alkyl group.

The carbon numbers of the hydrocarbon groups represented by R ^k1 ~ R ^k3 and R ^k17 ~ R ^k19 are independently 1 to 30, preferably any one of R ^k1 ~ R ^k3 is a long-chain alkyl group, and the other two are A short-chain alkyl group, and any one of R ^k17 to R ^k19 is a long-chain alkyl group, and the other two are short-chain alkyl groups. The carbon number of the main chain (the longest straight chain) of the long-chain alkyl group is preferably 5 or more, more preferably 8 or more, further preferably 12 or more, and is preferably 25 or less, more preferably 20 or less. The carbon number of the main chain (the longest straight chain) of the short-chain alkyl group is preferably 4 or less, more preferably 1 or 2, and especially preferably 1.

The alkyl group having 1 to 4 carbons represented by R ^k4 , R ^k5 , and Z ^k1 is preferably an alkyl group having 1 to 3 carbons, more preferably methyl or ethyl, and especially preferably methyl. When there are a plurality of R ^k5 , the plurality of R ^k5 may be the same or different.

The divalent hydrocarbon groups represented by Y ^k1 and Y ^k2 may be linear or branched, divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, or divalent saturated hydrocarbon groups, It may also be a divalent unsaturated hydrocarbon group, preferably a linear or branched divalent saturated aliphatic hydrocarbon group (hereinafter referred to as an alkylene group), more preferably a linear chain alkylene group. The carbon number of the divalent hydrocarbon group represented by Y ^k1 and Y ^k2 is preferably 2 or more, and preferably 8 or less, more preferably 5 or less.

The hydrolyzable groups represented by A ^k1 , A ^k2 , and Z ^k1 include, for example, alkoxy groups, halogen atoms, cyano groups, acetyloxy groups, isocyanate groups, etc., preferably alkoxy groups or halogen atoms, It is more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group. When there are a plurality of A ^k1 , the plurality of A ^k1 may be the same or different, but are preferably the same. When there are a plurality of A ^k2 , the plurality of A ^k2 may be the same or different, but are preferably the same.

The halogen atom represented by X is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.

R ^k1 to R ^k3 are preferably alkyl groups with 5 to 25 (preferably 12 to 20) carbon atoms in the main chain (longest straight chain) of any one of R ^k1 to R ^k3 , and the other two It is an alkyl group with 1 to 4 (preferably 1 to 2) carbon atoms in the main chain (longest straight chain), more preferably any one of R ^k1 to R ^k3 has 5 to 25 carbon atoms (preferably 12-25) straight-chain alkyl, and the other two are straight-chain alkyls with 1-4 carbons (preferably 1-2).

R ^k17 to R ^k19 are preferably alkyl groups having 5 to 25 (preferably 12 to 20) carbon atoms in the main chain (longest straight chain) of any one of R ^k17 to R ^k19 , and the other two It is an alkyl group whose main chain (longest straight chain) has 1 to 4 (preferably 1 to 2) carbon atoms, more preferably any one of R ^k17 to R ^k19 has 5 to 25 carbon atoms (preferably 12-25) straight-chain alkyl, and the other two are straight-chain alkyls with 1-4 carbons (preferably 1-2).

Y ^k1 and Y ^k2 are preferably each independently a single bond or an alkylene group having 1 to 10 carbons, more preferably a single bond or a linear alkylene group having 1 to 10 carbons, and still more preferably a single A bond or a straight-chain alkylene group having 2 to 8 carbons, particularly preferably a single bond or a straight-chain alkylene group having 2 to 5 carbons.

A ^k1 and A ^k2 are preferably an alkoxy group, a halogen atom, or a hydroxyl group independently, more preferably an alkoxy group or a hydroxyl group, further preferably an alkoxy group or a hydroxyl group with 1 to 4 carbon atoms, and especially preferably a methyl group. Oxy, Ethoxy, or Hydroxy.

When Y ^k2 is a single bond and k5 is 0, Z ^k1 is more preferably a hydrolyzable group or a hydroxyl group, further preferably a methoxy group, an ethoxy group, or a hydroxyl group. When Y ^k2 is a divalent hydrocarbon group having 1 to 10 carbon atoms or k5 is an integer of 1 or more, Z ^k1 is preferably a hydrolyzable group, a hydroxyl group, or a group represented by the formula (ki), more preferably The base represented by the formula (ki).

Preferably, k3 and k4 are 2.

k5 is preferably an integer of 0-5, more preferably 0 or 1.

[於式(k1-1)中， R ^k11～R ^k16分別獨立地表示碳數1～30之烴基， Y ^k11及Y ^k12分別獨立地表示單鍵或碳數1～10之二價烴基， A ^k11～A ^k14分別獨立地表示水解性基或羥基，於存在複數個A ^k13之情形時，複數個A ^k13可分別不同，於存在複數個A ^k14之情形時，複數個A ^k14可分別不同， k13表示0～10之整數， X表示鹵素原子] The quaternary ammonium salt (K1) is more preferably a compound represented by formula (k1-1). [Chem 3]

[In formula (k1-1), R ^k11 to R ^k16 independently represent a hydrocarbon group with 1 to 30 carbons, Y ^k11 and Y ^k12 independently represent a single bond or a divalent hydrocarbon group with 1 to 10 carbons, A ^k11 to A ^k14 each independently represent a hydrolyzable group or a hydroxyl group. When there are a plurality of A ^k13 , the plurality of A ^k13 may be different, and when there are a plurality of A ^k14 , the plurality of A ^k14 may be different, k13 represents an integer from 0 to 10, and X represents a halogen atom]

Examples of the hydrocarbon groups having 1 to 30 carbon atoms represented by R ^k11 to R ^k16 include the same groups as those described for the hydrocarbon groups having 1 to 30 carbon atoms represented by R ^k1 to R ^k3 and R ^k17 to R ^k19 , and its better form is also the same.

The divalent hydrocarbon groups having 1 to 10 carbon atoms represented by Y ^k11 and Y ^k12 include the same groups as those described for the divalent hydrocarbon groups having 1 to 10 carbon atoms represented by Y ^k1 and Y ^k2 . The better form is the same.

Examples of the hydrolyzable groups represented by A ^k11 to A ^k14 include the same groups as those described for the hydrolyzable groups represented by A ^k1 , A ^k2 , and Z ^k1 , and preferred embodiments are also the same.

The halogen atom represented by X is the same as above.

R ^k11 to R ^k13 are preferably alkyl groups with 5 to 25 (preferably 12 to 20) carbon atoms in the main chain (longest straight chain) of any one of R ^k11 to R ^k13 , and the other two It is an alkyl group with 1 to 4 (preferably 1 to 2) carbon atoms in the main chain (longest straight chain), more preferably any one of R ^k11 to R ^k13 has 5 to 25 carbon atoms (preferably 12-25) straight-chain alkyl, and the other two are straight-chain alkyls with 1-4 carbons (preferably 1-2).

R ^k14 to R ^k16 are preferably alkyl groups with 5 to 25 (preferably 12 to 20) carbon atoms in the main chain (longest straight chain) of any one of R ^k14 to R ^k16 , and the other two It is an alkyl group with 1 to 4 (preferably 1 to 2) carbon atoms in the main chain (longest straight chain), more preferably any one of R ^k14 to R ^k16 has 5 to 25 carbon atoms (preferably 12-25) straight-chain alkyl, and the other two are straight-chain alkyls with 1-4 carbons (preferably 1-2).

A ^k11 to A ^k14 are preferably independently alkoxy groups, halogen atoms, or hydroxyl groups, more preferably alkoxy groups or hydroxyl groups, further preferably alkoxy groups or hydroxyl groups with 1 to 4 carbon atoms, especially preferably all of them For hydroxyl.

Y ^k11 and Y ^k12 are preferably each independently a single bond or an alkylene group having 1 to 10 carbons, more preferably a single bond or a linear alkylene group having 1 to 10 carbons, particularly preferably a single bond .

k13 is preferably an integer of 0-5, more preferably 0 or 1, still more preferably 1.

[於式(k1-2)中， R ^k21～R ^k23分別獨立地表示碳數1～30之烴基， R ^k24表示碳數1～4之烷基，於存在複數個R ^k24之情形時，複數個R ^k24可分別不同， Y ^k21表示單鍵或碳數1～10之二價烴基， A ^k21表示水解性基或羥基，於存在複數個A ^k21之情形時，複數個A ^k21可分別不同， k21表示1～3之整數， X表示鹵素原子] The quaternary ammonium salt (K1) is also more preferably a compound represented by formula (k1-2). [chemical 4]

[In formula (k1-2), R ^k21 ~ R ^k23 independently represent a hydrocarbon group with 1 to 30 carbons, R ^k24 represents an alkyl group with 1 to 4 carbons, and when there are a plurality of R ^k24 , the plural Each R ^k24 may be different, Y ^k21 represents a single bond or a divalent hydrocarbon group having 1 to 10 carbons, A ^k21 represents a hydrolyzable group or a hydroxyl group, and when there are multiple A ^k21s , the multiple A ^k21s may be different, k21 represents an integer of 1 to 3, X represents a halogen atom]

Examples of the hydrocarbon groups having 1 to 30 carbon atoms represented by R ^k21 to R ^k23 include the same groups as those described for the hydrocarbon groups having 1 to 30 carbon atoms represented by R ^k1 to R ^k3 and R ^k17 to R ^k19 , and its better form is also the same.

The alkyl group having 1 to 4 carbon atoms represented by R ^k24 may, for example, be the same group as described for the alkyl group having 1 to 4 carbon atoms represented by R ^k4 , R ^k5 , and Z ^k1 . The good looks are the same.

As the divalent hydrocarbon group having 1 to 10 carbon atoms represented by Y ^k21 , the same group as described as the divalent hydrocarbon group having 1 to 10 carbon atoms represented by Y ^k1 and Y ^k2 can be exemplified, and its preferred form The same is true.

Examples of the hydrolyzable group represented by A ^k21 include the same groups as those described as the hydrolyzable groups represented by A ^k1 , A ^k2 , and Z ^k1 , and preferred embodiments are also the same.

The halogen atom represented by X is the same as above.

R ^k21 to R ^k23 are preferably alkyl groups with 5 to 25 (preferably 12 to 20) carbon atoms in the main chain (longest straight chain) of any one of R ^k21 to R ^k23 , and the other two It is an alkyl group with 1 to 4 (preferably 1 to 2) carbon atoms in the main chain (longest straight chain), more preferably any one of R ^k21 to R ^k23 is 5 to 25 carbon atoms (preferably 12-25) straight-chain alkyl, and the other two are straight-chain alkyls with 1-4 carbons (preferably 1-2).

A ^k21 is preferably an alkoxy group, a halogen atom, or a hydroxyl group independently, more preferably an alkoxy group or a hydroxyl group, further preferably an alkoxy group or a hydroxyl group with 1 to 4 carbon atoms, especially preferably a methoxy group or Ethoxy.

k21 is preferably 2 or 3, more preferably 3.

Y ^k21 is preferably a single bond or an alkylene group having 1 to 10 carbons, more preferably a single bond or a linear alkylene group having 1 to 10 carbons, and further preferably a single bond or an alkylene group having 2 to 10 carbons. 8 (especially C2-5) straight-chain alkylene group, especially preferably C2-5 straight-chain alkylene group.

As the quaternary ammonium salt (K1), it is preferable to use at least the compound represented by the formula (k1-1) and/or the compound represented by the formula (k1-2).

The above-mentioned antibacterial component (K) may be included in the base material (s), and when the base material (s) has two or more layers, it may be included in any layer, or may be included in all layers. Especially when the substrate (s) includes a layer (s1) and a layer (s2), the antibacterial component (K) is preferably contained in the layer (s2) laminated on the side of the water-repellent layer (r), more preferably is included in the hard coat layer (hc) included in the layer (s2).

The content of the antibacterial component (K) is preferably at least 0.001 mass %, more preferably at least 0.005 mass %, further preferably at least 0.01 mass %, and preferably 50 mass % in 100 mass % of the substrate (s). % or less, more preferably 10 mass % or less. Also, when the substrate (s) includes the layer (s1) and the layer (s2), the content of the antibacterial component (K) in the two layers of the layer (s1) and the layer (s2) can be adjusted to the above range, It is preferable to adjust the content of the antibacterial component (K) in any one of the layers to the above-mentioned range, and it is especially preferable to adjust the content of the antibacterial component (K) in the layer (s2) to the above-mentioned range. Especially when the antibacterial component (K) is an inorganic antibacterial component, the content of the inorganic antibacterial component in 100% by mass of the substrate (s), preferably 0.001% by mass or more, more preferably 0.005% by mass or more, Furthermore, it is more preferably at least 0.01% by mass, and more preferably at most 50% by mass, more preferably at most 10% by mass, and still more preferably at most 5% by mass. Also, when the base material (s) comprises a layer (s1) and a layer (s2), the content of the inorganic antibacterial components in the two layers of the layer (s1) and the layer (s2) can be adjusted to the above-mentioned range. Preferably, the content of the inorganic antibacterial component in any one of the layers is adjusted to the above-mentioned range, and it is especially preferable to adjust the content of the inorganic antibacterial component in the layer (s2) to the above-mentioned range. Also, when the antibacterial component (K) is an organic antibacterial component, the content of the organic antibacterial component in 100% by mass of the substrate (s), preferably 0.001% by mass or more, more preferably 0.005% by mass or more, Furthermore, it is preferably at least 0.01% by mass, especially preferably at least 0.1% by mass, and is preferably at most 50% by mass, more preferably at most 25% by mass, and still more preferably at most 10% by mass. Also, when the base material (s) includes the layer (s1) and the layer (s2), the content of the organic antibacterial components in the two layers of the layer (s1) and the layer (s2) can be adjusted to the above-mentioned range, compared with Preferably, the content of the organic antibacterial component in any one of the layers is adjusted to the above-mentioned range, and it is especially preferable to adjust the content of the organic antibacterial component in the layer (s2) to the above-mentioned range.

Also, in addition to the antibacterial component (K), it is also preferable to disperse inorganic particles, organic particles, and rubber particles in the substrate (s), and it may also contain coloring agents such as pigments or dyes, fluorescent whitening Agents, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents and other formulations.

As the substrate (s), commercially available products can be used, for example: Hydro Ag ⁺ Antibacterial Film (manufactured by FUJIFILM Co., Ltd.), Daicel Antiviral Hard Coat S BV01, Daicel Antiviral Hard Coat S BV02 (Daicel Co., Ltd.), etc.

1-2. Water-repellent layer (r) The water-repellent layer (r) is a cured layer of an organosilicon compound (A) having a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded via a linking group or not via a linking group. Since the water-repellent layer (r) is a hardened layer of the organosilicon compound (A), good water-repellency can be imparted even if it is a thin film, and it is preferable that good water-repellency and abrasion resistance can be imparted even if it is a thin film and durability such as scratch resistance. The hardened layer of organosilicon compound (A) is usually obtained by coating a mixed composition of organosilicon compound (A) and hardening it. It can be considered that the water-repellent layer (r) is a mixed combination of organosilicon compound (A) hardened layer. Hereinafter, the mixed composition of the organosilicon compound (A) may be referred to as the composition for water-repellent layer formation.

As mentioned above, the water-repellent layer (r) is a hardened layer of the mixed composition of the organosilicon compound (A), so the water-repellent layer (r) has a structure derived from the organosilicon compound (A). The organosilicon compound (A) has a hydrolyzable group or a hydroxyl group bonded to a silicon atom (it can also be bonded through a linking group). When hardening, the -SiOH group possessed by the organosilicon compound (A) or the organic The -SiOH group of the silicon compound (A) (Si and OH can also be bonded through a linking group) and the -SiOH group derived from the organosilicon compound (A) (Si and OH can also be bonded through a linking group), derived from other The -SiOH group of the compound, or the active hydrogen (hydroxyl group, etc.) on the surface forming the water-repellent layer (r) in the laminate is dehydrated and condensed. Therefore, the water-repellent layer (r) preferably has a condensation structure derived from the organosilicon compound (A).

1-2-1. Organosilicon compound (A) The organosilicon compound (A) is a compound having a silicon atom to which a hydrolyzable group or a hydroxyl group (hereinafter collectively referred to as a reactive group (h3)) is bonded via a linking group or not. The above-mentioned reactive group (h3) has the following functions: through hydrolysis and dehydration condensation reaction, organosilicon compound (A) and other monomers, or organosilicon compound (A) and coated water-repellent layer The active hydrogen (hydroxyl group, etc.) of the surface forming composition is bonded together through condensation reaction. As said hydrolyzable group, an alkoxy group, a halogen atom, a cyano group, an acetyloxy group, an isocyanate group etc. are mentioned. The above-mentioned reactive group (h3) is preferably an alkoxy group or a halogen atom, more preferably an alkoxy group with 1-4 carbon atoms or a chlorine atom, especially preferably a methoxy group or an ethoxy group.

The organosilicon compound (A) preferably contains fluorine in addition to the above-mentioned silicon atoms, and more preferably contains a fluoropolyether structure. The above-mentioned fluoropolyether structure can also be called a fluorooxyalkylene group, which means a structure with oxygen atoms at both ends. 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 above-mentioned carbon number is not particularly limited, for example, it is 200, preferably 150. The number of silicon atoms in 1 molecule of the organosilicon compound (A) is preferably 1-10, more preferably 1-6.

In the aspect where the organosilicon compound (A) includes a fluoropolyether structure, a silicon atom, and a reactive group (h3), it is preferable to have one of the valent groups of the oxygen atom of the fluoropolyether structure at the end of the bonding bond side ( Hereinafter referred to as FPE group) and the silicon atom are bonded via a linking group or not, and the silicon atom and the reactive group (h3) are bonded via a linking group or not. In the case where the above-mentioned FPE group and the silicon atom are bonded via a linking group, the silicon atom bonded to the above-mentioned reactive group (h3) via a linking group or not via a linking group may exist in a molecule of the organosilicon compound (A) 1 or plural, and the number is, for example, 1 or more and 10 or less.

The above-mentioned FPE group may be linear or may have a side chain, but 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, further preferably a trifluoromethyl group. The carbon number of the linking group linking the FPE group and the silicon atom is, for example, 1 to 20, preferably 2 to 15. The above-mentioned FPE group is preferably a group in which a fluorine-containing group having a fluoroalkyl group at the end is directly bonded to a perfluoropolyether structure. The fluorine-containing group may be a fluoroalkyl group, or a group formed by bonding a divalent aromatic hydrocarbon group to the fluoroalkyl group, and 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, 1 to 19, preferably 1 to 10), CF ₃ (CF ₂ ) _m -(CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H ₄ -(m is 1-10, preferably 3-7, n is 1-5, preferably 2-4), preferably CF ₃ (CF ₂ ) _p - or CF ₃ (CF ₂ ) _m -(CH ₂ ) _n -.

The above-mentioned reactive group (h3) may be bonded to the silicon atom through a linking group, or may be directly bonded to the silicon atom without a linking group, and is preferably directly bonded to the silicon atom. The number of reactive groups (h3) bonded to one silicon atom may be at least one, and may be 2 or 3, preferably 2 or 3, and especially preferably 3. When the number of reactive groups (h3) bonded to one silicon atom is 2 or less, a valent group other than the reactive group (h3) may be bonded to the remaining bonds, for example, an alkane may be bonded group (especially an alkyl group with 1 to 4 carbon atoms), H, NCO, etc.

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

於上述式(a1)中， Rf ^a26、Rf ^a27、Rf ^a28、及Rf ^a29分別獨立為1個以上之氫原子被取代為氟原子之碳數1～20之氟化烷基或氟原子，於存在複數個Rf ^a26之情形時，複數個Rf ^a26可分別不同，於存在複數個Rf ^a27之情形時，複數個Rf ^a27可分別不同，於存在複數個Rf ^a28之情形時，複數個Rf ^a28可分別不同，於存在複數個Rf ^a29之情形時，複數個Rf ^a29可分別不同， R ²⁵及R ²⁶分別獨立為氫原子、鹵素原子、碳數1～4之烷基、或1個以上之氫原子被取代為鹵素原子之碳數1～4之鹵化烷基，鍵結於一個碳原子之R ²⁵及R ²⁶之至少一者為氫原子，於存在複數個R ²⁵之情形時，複數個R ²⁵可分別不同，於存在複數個R ²⁶之情形時，複數個R ²⁶可分別不同， R ²⁷及R ²⁸分別獨立為氫原子、碳數1～4之烷基、或單鍵，於存在複數個R ²⁷之情形時，複數個R ²⁷可分別不同，於存在複數個R ²⁸之情形時，複數個R ²⁸可分別不同， R ²⁹及R ³⁰分別獨立為碳數1～20之烷基，於存在複數個R ²⁹之情形時，複數個R ²⁹可分別不同，於存在複數個R ³⁰之情形時，複數個R ³⁰可分別不同， M ⁷為-O-、-C(=O)-O-、-O-C(=O)-、-NR-、-NRC(=O)-、-C(=O)NR-、-CH=CH-、或-C ₆H ₄-(伸苯基)，上述R為氫原子、碳數1～4之烷基或碳數1～4之含氟烷基，於存在複數個M ⁷之情形時，複數個M ⁷可分別不同， M ⁵為氫原子、氟原子或碳數1～4之烷基，於存在複數個M ⁵之情形時，複數個M ⁵可分別不同， M ¹⁰為氫原子、或鹵素原子， M ⁸及M ⁹分別獨立為水解性基、羥基、或-(CH ₂) _e7-Si(OR ¹⁴) ₃，e7為1～5，R ¹⁴為甲基或乙基，於存在複數個M ⁸之情形時，複數個M ⁸可分別不同，於存在複數個M ⁹之情形時，複數個M ⁹可分別不同， f21、f22、f23、f24、及f25分別獨立為0～600之整數，f21、f22、f23、f24、及f25之合計值為13以上， f26為0～20之整數， f27分別獨立為0～2之整數， g21為1～3之整數，g22為0～2之整數，且g21＋g22≦3， g31為1～3之整數，g32為0～2之整數，且g31＋g32≦3， 關於M ¹⁰-、-Si(M ⁹) _g31(H) _g32(R ³⁰) _{3 － g31 － g32}、f21個-{C(R ²⁵)(R ²⁶)}-單元(U _a1)、f22個-{C(Rf ^a26)(Rf ^a27)}-單元(U _a2)、f23個-{Si(R ²⁷)(R ²⁸)}-單元(U _a3)、f24個-{Si(Rf ^a28)(Rf ^a29)}-單元(U _a4)、f25個-M ⁷-單元(U _a5)、及f26個-[C(M ⁵){(CH ₂) _f27-Si(M ⁸) _g21(H) _g22(R ²⁹) _{3 － g21 － g22}}]-單元(U _a6)，M ¹⁰-為式(a1)中之一個末端、-Si(M ⁹) _g31(H) _g32(R ³⁰) _{3 － g31 － g32}為另一個末端，以於至少一部分形成氟聚醚結構之順序排列，只要-O-不與-O-連續，則各單元以任意順序排列而鍵結。以任意順序排列而鍵結意味著不限定於各重複單元相連而以如上述式(a1)所記載之順序排列之含義，又，意味著無需f21個單元(U _a1)連續鍵結，中途亦可介隔其他單元而鍵結，只要合計為f21個即可。以f22～f26括住之單元(U _a2)～(U _a6)亦同樣如此。 [chemical 5]

In the above formula (a1), Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms. When there is a plurality of Rf ^a26 , the plurality of Rf ^a26 can be different, and when there is a plurality of Rf ^a27 , the plurality of Rf ^a27 can be different, and when there is a plurality of Rf ^a28 , the plurality of Rf ^a28 can be different. They are different. When there are multiple Rf ^a29s , the multiple Rf ^a29s can be different. R ²⁵ and R ²⁶ are independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbon atoms, or one or more hydrogen atoms A halogenated alkyl group with 1 to 4 carbon atoms whose atom is replaced by a halogen atom. At least one of ^R25 and ^R26 bonded to a carbon atom is a hydrogen atom. When there are multiple R25s, the multiple ^{R25 25} can be different respectively. When there are multiple R ²⁶ , the multiple R ²⁶ can be different respectively. R ²⁷ and R ²⁸ are independently a hydrogen atom, an alkyl group with 1 to 4 carbons, or a single bond. In the case of one R ²⁷ , the plurality of R ²⁷ may be different, and in the case of a plurality of R ²⁸ , the plurality of R ²⁸ may be different, R ²⁹ and R ³⁰ are independently an alkyl group with 1 to 20 carbons, When there are a plurality of R ²⁹ , the plurality of R ²⁹ may be different, and in the case of a plurality of R ³⁰ , the plurality of R ³⁰ may be different, M ⁷ is -O-, -C(=O)- O-, -OC(=O)-, -NR-, -NRC(=O)-, -C(=O)NR-, -CH=CH-, or -C ₆ H ₄ -(phenylene) , the above R is a hydrogen atom, an alkyl group with 1 to 4 carbons, or a fluorine-containing alkyl group with 1 to 4 carbons. When there are multiple M ⁷ s, the multiple M ⁷ can be different, and M ⁵ is a hydrogen atom , a fluorine atom or an alkyl group with 1 to 4 carbons, when there are multiple ^M5s , the multiple ^M5s can be different, ^M10 is a hydrogen atom or a halogen atom, ^M8 and ^M9 are independently hydrolyzed Native group, hydroxyl group, or -(CH ₂ ) _e7 -Si(OR ¹⁴ ) ₃ , where e7 is 1 to 5, R ¹⁴ is methyl or ethyl, when there are multiple M ⁸ s, the multiple M ⁸ can be are different, when there are multiple ^M9s , the multiple ^M9s can be different respectively, f21, f22, f23, f24, and f25 are independently integers from 0 to 600, f21, f22, f23, f24, and f25 The total value is 13 or more, f26 is an integer from 0 to 20, f27 is an integer from 0 to 2 independently, g21 is an integer from 1 to 3, g22 is an integer from 0 to 2, and g21+g22≦3, g31 is 1 to 2 Integer of 3, g32 is an integer of 0 to 2, and g31+g32≦3, Regarding M ¹⁰ -, -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _{3 - g31 - g32} , f21-{C(R ²⁵ )(R ²⁶ )}-unit (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 -unit (U _a5 ), and f26-[C(M ⁵ ){(CH ₂ ) _f27 -Si(M ⁸ ) _g21 (H) _g22 ( R ²⁹ ) _{3 － g21 － g22} }]-unit (U _a6 ), M ¹⁰ -is one of the terminals in formula (a1), -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _{3 － g31 － g32} The other terminal is arranged in the order that at least a part of the fluoropolyether structure is formed, and as long as -O- and -O- are not consecutive, each unit can be arranged in any order and bonded. Arranging the bonds in any order means not being limited to the meaning that the repeating units are connected but arranged in the order described in the above formula (a1), and also means that there is no need for f21 units (U _a1 ) to be bonded continuously, and also in the middle They may be bonded through other units, as long as the total number is f21. The same is true for the units (U _a2 )-(U _a6 ) enclosed by f22-f26.

Also, when at least one of R ²⁷ and R ²⁸ is a single bond, the single bond part of the unit enclosed by f23 and -O- in M ⁷ can be repeatedly bonded to form a branched or cyclic siloxane bond.

Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently preferably a fluorine atom, or a C1-2 fluorinated alkyl group in which one or more hydrogen atoms are replaced by fluorine atoms, more preferably a fluorine atom , or a fluorinated alkyl group having 1 to 2 carbon atoms in which all hydrogen atoms are substituted by fluorine atoms. R ²⁵ and R ²⁶ are preferably independently hydrogen atoms or fluorine atoms, and at least one of R ²⁵ and R ²⁶ bonded to a carbon atom is a hydrogen atom, more preferably both are hydrogen atoms. R ²⁷ and R ²⁸ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbons, more preferably all of them are hydrogen atoms. R ²⁹ and R ³⁰ are preferably an alkyl group having 1 to 5 carbons, more preferably an alkyl group having 1 to 2 carbons. M ⁷ is preferably -C(=O)-O-, -O-, -OC(=O)-, more preferably all of them are -O-. M ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbons, more preferably all hydrogen atoms. M ¹⁰ is preferably a fluorine atom. M ⁸ and M ⁹ are preferably independently alkoxy and halogen atoms, more preferably methoxy, ethoxy and chlorine atoms, especially preferably methoxy or ethoxy. Preferably, f21, f23, and f24 are 1/2 or less, more preferably 1/4 or less, respectively, of f22, further preferably f23 or f24 is 0, and most preferably f23 and f24 are 0. f25 is preferably not less than 1/5 of the total value of f21, f22, f23, and f24, and is not more than the total value of f21, f22, f23, and f24. f21 is preferably 0-20, more preferably 0-15, still more preferably 1-15, particularly preferably 2-10. f22 is preferably 5-600, more preferably 8-600, still more preferably 20-200, still more preferably 30-200, still more preferably 35-180, most preferably 40-180. It is preferable that f23 and f24 are 0-5, More preferably, they are 0-3, More preferably, they are 0. f25 is preferably from 4 to 600, more preferably from 4 to 200, still more preferably from 10 to 200, still more preferably from 30 to 60. The total value of f21, f22, f23, f24, and f25 is preferably from 20 to 600, more preferably from 20 to 250, and still more preferably from 50 to 230. f26 is preferably 0-18, more preferably 0-15, still more preferably 0-10, still more preferably 0-5. f27 is preferably 0-1, more preferably 0. Preferably, g21 and g31 are each independently 2-3, More preferably, it is 3. Preferably, g22 and g32 are each independently 0 or 1, more preferably 0. Preferably, g21+g22 and g31+g32 are 3.

It is preferable to use the following compound (a11) as the organosilicon compound (A), the compound (a11) in the above formula (a1), R ²⁵ and R ²⁶ are hydrogen atoms, Rf ^a26 and Rf ^a27 are fluorine atoms or all A fluorinated alkyl group with ¹ to 2 carbon atoms in which the hydrogen atom is replaced by a fluorine atom, all of M7 are -O-, all of ^M8 and ^M9 are methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M ⁵ is a hydrogen atom, M ¹⁰ is a fluorine atom, f21 is 1-10 (preferably 2-7), f22 is 30-200 (more preferably 40-180), f23 and f24 are 0, f25 is 30-60, f26 is 0-6, f27 is 0-1 (preferably 0), g21 and g31 are 1-3 (both are preferably 2 or more, more preferably 3), g22 and g32 0 to 2 (both are preferably 0 or 1, more preferably 0), and g21+g22 and g31+g32 are 3.

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

於上述式(a2)中， Rf ^a1為兩端為氧原子之二價氟聚醚結構， R ¹¹、R ¹²、及R ¹³分別獨立為碳數1～20之烷基，於存在複數個R ¹¹之情形時，複數個R ¹¹可分別不同，於存在複數個R ¹²之情形時，複數個R ¹²可分別不同，於存在複數個R ¹³之情形時，複數個R ¹³可分別不同， E ¹、E ²、E ³、E ⁴、及E ⁵分別獨立為氫原子或氟原子，於存在複數個E ¹之情形時，複數個E ¹可分別不同，於存在複數個E ²之情形時，複數個E ²可分別不同，於存在複數個E ³之情形時，複數個E ³可分別不同，於存在複數個E ⁴之情形時，複數個E ⁴可分別不同，於存在複數個E ⁵之情形時，複數個E ⁵可分別不同， G ¹及G ²分別獨立為具有矽氧烷鍵之二～十價有機矽氧烷基， J ¹、J ²、及J ³分別獨立為水解性基、羥基或-(CH ₂) _e7-Si(OR ¹⁴) ₃，e7為1～5，R ¹⁴為甲基或乙基，於存在複數個J ¹之情形時，複數個J ¹可分別不同，於存在複數個J ²之情形時，複數個J ²可分別不同，於存在複數個J ³之情形時，複數個J ³可分別不同， L ¹及L ²分別獨立為可含有氧原子、氮原子、矽原子或氟原子之碳數1～12之二價連結基，且為-{C(R ²⁵)(R ²⁶)}-單元(U _a1)、-{C(Rf ^a26)(Rf ^a27)}-單元(U _a2)、-{Si(R ²⁷)(R ²⁸)}-單元(U _a3)或-M ⁷-單元(U _a5)之一者以上以任意順序排列而鍵結而成之連結基(R ²⁵、R ²⁶、R ²⁷、R ²⁸、Rf ^a26、Rf ^a27、M ⁷與上述式(a1)中者相同)， a10及a14分別獨立為0或1， a11及a15分別獨立為0或1， a12及a16分別獨立為0～9， a13為0～4， 於a11為0時、或a11為1且G ¹為二價時，d11為1，於a11為1且G ¹為三～十價時，d11為較G ¹之價數少一之數， 於a15為0時、或a15為1且G ²為二價時，d12為1，於a15為1且G ²為三～十價時，d12為較G ²之價數少一之數， a21及a23分別獨立為0～2， e11為1～3，e12為0～2，且e11＋e12≦3， e21為1～3，e22為0～2，且e21＋e22≦3， e31為1～3，e32為0～2，且e31＋e32≦3。 [chemical 6]

In the above formula (a2), Rf ^a1 is a divalent fluoropolyether structure with oxygen atoms at both ends, R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group with 1 to 20 carbon atoms. In the case of ¹¹ , the plurality of R ¹¹ may be different, and in the case of a plurality of R ¹² , the plurality of R ¹² may be different, and in the case of a plurality of R ¹³ , the 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 there are multiple E ^1s , the multiple E ^1s can be different. When there are multiple E ^2s , the plurality of E ² can be different respectively, when there is a plurality of E ³ , the plurality of E ³ can be different respectively, in the case of a plurality of E ⁴ , the plurality of E ⁴ can be different respectively, in the case of a plurality of E In the case of ⁵ , the plurality of E ⁵ can be different, G ¹ and G ² are independently di-decavalent organosiloxane groups having siloxane bonds, and J ¹ , J ² , and J ³ are independently hydrolyzed Native group, hydroxyl group or -(CH ₂ ) _e7 -Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, R ¹⁴ is methyl or ethyl, when there are multiple J ^1s , the multiple J ^1s can be respectively Different, when there are multiple J ^2s , the multiple J ^2s can be different, and when there are multiple J ^3s , the multiple J ^3s can be different, and L ¹ and L ² can independently contain oxygen atoms , a nitrogen atom, a silicon atom or a divalent linking group with 1 to 12 carbon atoms of a fluorine atom, which is -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ), -{C(Rf ^a26 )( One or more of Rf ^a27 )}-unit (U _a2 ), -{Si(R ²⁷ )(R ²⁸ )}-unit (U _a3 ), or -M ⁷ -unit (U _a5 ) is arranged in any order and bonded The resulting linking group (R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , Rf ^a26 , Rf ^a27 , M ⁷ are the same as those in the above formula (a1), a10 and a14 are independently 0 or 1, a11 and a15 are independently 0 or 1, a12 and a16 are independently 0 to 9, a13 is 0 to 4, when a11 is 0, or a11 is 1 and G ¹ is divalent, d11 is 1, and a11 is 1 and When G ¹ has a valence of three to ten, d11 is a number less than the valence of G ¹ , when a15 is 0, or when a15 is 1 and G ² is bivalent, d12 is 1, and when a15 is 1 and G When ² is three to ten valences, d12 is a number less than the valence of G ² , a21 and a23 are independently 0 to 2, e11 is 1 to 3, e12 is 0 to 2, and e11+e12≦3, e21 is 1~3, e22 is 0~2, and e21+e22≦3, e31 is 1~3, e32 is 0 to 2, and e31+e32≦3.

Furthermore, a10 being 0 means that the part enclosed by a10 is a single bond, and the same is true when a11, a12, a13, a14, a15, a16, a21 or a23 are 0.

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. In addition, Rf ^a1 is also preferably the group remaining by removing hydrogen atoms from the hydroxyl groups at both ends of the structure formed by the random dehydration condensation of p moles of perfluoropropylene glycol and q moles of perfluoromethanediol, and p+q is 15 ~80, this aspect is the best as Rf ^a1 .

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

E ¹ , E ² , E ³ and E ⁴ are all preferably hydrogen atoms, and E ⁵ is preferably a fluorine atom.

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

G ¹ and G ² are preferably independently di- to pentavalent organosiloxane groups having siloxane bonds.

J ¹ , J ² , and J ³ are preferably independently 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 0-7, more preferably 0-5, a13 is preferably 1-3, a14 is preferably 1, a15 is preferably 0, and 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, e21 and e31 are all relatively Preferably, it is 2 or more, More preferably, it is 3. All of e12, e22 and e32 are preferably 0 or 1, more preferably 0. Preferably, all of e11+e12, e21+e22, and e31+e32 are 3. These preferred ranges can be satisfied individually, or two or more can be satisfied in combination.

As the organosilicon compound (A), it is preferable to use the following compound (a21), the Rf ^a1 of the above-mentioned formula (a2) of the compound (a21) is from p moles of perfluoropropylene glycol and q moles of perfluoromethanediol The hydroxyl groups at both ends of the structure formed by random dehydration condensation of alcohols are the residues left by removing the hydrogen atoms (p+q=15-80), and both L ¹ and L ² have carbon numbers of 1-5 (preferably 1-3) Perfluoroalkylene, E ¹ , E ² , and E ³ are all hydrogen atoms, E ⁴ is hydrogen atom, E ⁵ is fluorine atom, J ¹ , J ² , and J ³ are all methoxy or ethoxy (especially methoxy), a10 is 1, a11 is 0, a12 is 0-7 (preferably 0-5), a13 is 2, a14 is 1, a15 is 0, a16 is 0-6 (especially 0), a21 and a23 are independently 0 or 1 (more preferably a21 and a23 are both 0), d11 is 1, d12 is 1, e11, e21 and e31 are all 2 to 3 (especially 3), e12, Both e22 and e32 are 0 or 1 (especially 0), and e11+e12, e21+e22, and e31+e32 are all 3.

As the organosilicon compound (A), it is also preferable to use the following compound (a22), the Rf ^a1 of the above formula (a2) of the compound (a22) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 15 to 80 (preferably 25 to 40), L1 is a divalent linking group with ³ to 6 carbons containing fluorine atoms and oxygen atoms, L2 is a perfluoroalkylene group with ² to 10 carbons, E ^2. E3 is a hydrogen atom, ^E5 is a fluorine atom, J2 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.

As an organosilicon compound (A), the compound of following formula (a3) is mentioned more specifically.

[chemical 7]

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ³¹ is formed by random dehydration condensation of p moles of perfluoropropylene glycol and q moles of perfluoromethanediol The group left by removing hydrogen atoms from the hydroxyl groups at both ends of the structure (p+q is 15-80) or the group remaining by removing hydrogen atoms from the hydroxyl groups at both ends of perfluorooxyalkylene glycol with carbon number 15-240 ( R ³¹ is more preferably a group of the former), R ³² is a perfluoroalkylene group with 1 to 10 carbons, R ³³ is a trivalent saturated hydrocarbon group with 2 to 6 carbons, R ³⁴ is a perfluoroalkyl group with 1 to 3 carbons alkyl. The carbon number of R ³⁰ is preferably 1-4, more preferably 1-3. The carbon number of R ³² is preferably 1-5. h1 is 1-10, preferably 1-8, more preferably 1-6. h2 is 1 or more, preferably 2 or more, and may be 3.

As the organosilicon compound (A), a compound represented by the following formula (a4) may also be mentioned.

[chemical 8]

In the above formula (a4), R ⁴⁰ is a perfluoroalkyl group with 2 to 5 carbons, R ⁴¹ is a perfluoroalkylene group with 2 to 5 carbons, and R ⁴² is an alkylene group with 2 to 5 carbons. A fluoroalkylene group in which part of the hydrogen atoms is substituted with fluorine, R ⁴³ and R ⁴⁴ are independently a C 2-5 alkylene group, and R ⁴⁵ is a methyl group or an ethyl group. 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 at least 2,000, more preferably at least 4,000, still more preferably at least 5,000, still more preferably at least 6,000, particularly preferably at least 7,000, and more preferably at most 40,000, More preferably, it is 20,000 or less, More preferably, it is 15,000 or less.

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

The water-repellent layer (r) preferably contains a structure derived from the organosilicon compound (A), for example, 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and even more preferably 75% by mass % or more, and may be 100% by mass, preferably 95% by mass or less, more preferably 90% by mass or less. Here, the structure derived from the organosilicon compound (A) refers to the organosilicon compound (A) and the residue after dehydration condensation of the organosilicon compound (A).

1-2-2.Organosilicon compound (B) The water-repellent layer (r) may have a structure derived from the above-mentioned organosilicon compound (A) and a structure derived from the organosilicon compound (B) represented by the following formula (b1). The water-repellent layer (r) having a structure derived from the organosilicon compound (A) and a structure derived from the organosilicon compound (B) can be mixed with organic It is obtained by hardening the mixed composition of the silicon compound (B).

The organosilicon compound (B), as described below, has a hydrolyzable group or a hydroxyl group bonded to a silicon atom. Generally, the -SiOH group of the organosilicon compound (B) or the -SiOH group of the organosilicon compound (B) produced by hydrolysis SiOH group dehydrates and condenses with -SiOH group derived from organosilicon compound (B), -SiOH group derived from other compounds, or active hydrogen (hydroxyl group, etc.) In a preferred aspect, the water repellent layer (r) has a dehydration condensation structure derived from the organosilicon compound (A) and a dehydration condensation structure derived from the organosilicon compound (B). Since the water-repellent layer (r) has the dehydration condensation structure derived from the organosilicon compound (B), the sliding property of water droplets etc. improves further.

[chemical 9]

In the above formula (b1), Rf ^b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms, and R ^b11 , R ^b12 , R ^b13 , and R ^b14 are independently hydrogen Atoms or alkyl groups with 1 to 4 carbons, when there are plural R ^b11 , the plural R ^b11 may be different, and when there are plural R ^b12 , the plural R ^b12 may be different respectively, when there are plural R b11 In the case of a single R ^b13 , the plurality of R ^b13 may be different, and in the case of a plurality of R ^b14 , the plurality of R ^b14 may be different, and Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are each independently one or more The hydrogen atom is replaced by an alkyl group with 1 to 20 carbon atoms or a fluorine atom of a fluorine atom. When there are multiple Rf ^b11 , the multiple Rf ^b11 can be different. When there are multiple Rf ^b12 , the multiple Each Rf ^b12 can be different. When there are multiple Rf ^b13 , the multiple Rf ^b13 can be different. When there are multiple Rf ^b14 , the multiple Rf ^b14 can be different. R ^b15 is carbon number 1～ For the alkyl group of 20, when there are multiple R ^b15s , the multiple R ^b15s can be different, and A1 is -O-, -C( ⁼ O)-O-, -OC(=O)-, -NR -, -NRC(=O)-, or -C(=O)NR-, the above-mentioned R is a hydrogen atom, an alkyl group with 1 to 4 carbons, or a fluorine-containing alkyl group with 1 to 4 carbons. ^In the case of A1, the plural ^A1s may be different, and A2 is ^a hydrolyzable group or a hydroxyl group. In the case of multiple ^A2s , the plural ^A2s may be different, b11, b12, b13, b14, b15 are independently an integer of 0 to 100, c is an integer of 1 to 3, about 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 -unit (U _b5 ), Rf ^b10 -is one terminal of the compound represented by formula (b1),- Si(A ² ) _c (R ^b15 ) _{3 － c} is the other end and does not form a fluoropolyether structure. As long as -O- is not continuous with -O- or -F, each unit (U _b1 )～unit (U _b5 ) are bonded by arranging in any order.

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

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.

A1 is preferably -O-, -C( ⁼ O)-O-, or -OC(=O)-.

^The hydrolyzable group represented by A2 may, for example, be an alkoxy group, a halogen atom, a cyano group, an acetyloxy group or an isocyanate group.

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.

Preferably, b13 is 0-5, More preferably, it is 0-2.

Preferably, b14 is 0-4, More preferably, it is 0-2.

Preferably, b15 is 0-4, More preferably, it is 0-2.

c is preferably 2-3, more preferably 3.

The total value of b11, b12, b13, b14, and b15 is preferably at least 2, more preferably at least 3, more preferably at least 5, and is preferably at most 80, more preferably at most 50, still more preferably at most Below 20.

Especially preferably, Rf ^b10 is a fluorine atom or a perfluoroalkyl group with 1 to 5 carbon atoms, R ^b11 and R ^b12 are both ^hydrogen atoms, A2 is methoxy or ethoxy, and b11 is 1 to 5, and b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.

Furthermore, in the examples described below, if FAS13E used as the organosilicon compound (B) is represented by the above formula (b1), it is determined as follows: R ^b11 and R ^b12 are both hydrogen atoms, and b11 is 2 , b13, b14, and b15 are all 0, c is 3, A ² is ethoxy, Rf ^b10 -{C(Rf ^b11 )(Rf ^b12 )} _b12 - is the terminal, and becomes C ₆ F ₁₃ -.

As the compound represented by the above formula (b1), specifically, C _j F _{2j + 1} -Si-(OCH ₃ ) ₃ , C _j F _{2j + 1} -Si-(OC ₂ H ₅ ) ₃ ( j is an integer from 1 to 12), especially 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 , C ₈ F ₁₇ -Si-(OC ₂ H ₅ ) ₃ . Also, CF ₃ CH ₂ O(CH ₂ ) _k SiCl ₃ , CF ₃ CH ₂ O(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ CH ₂ O(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ COO(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 (all k are 5-20 , preferably 8 to 15). Also, CF ₃ (CF ₂ ) _m -(CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m -(CH ₂ ) _n Si(OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m -(CH ₂ ) _n Si(OC ₂ H ₅ ) ₃ (m is 0-10, preferably 0-7, and n is 1-5, preferably 2-4). CF ₃ (CF ₂ ) _p -(CH ₂ ) _q -Si-(CH ₂ CH=CH ₂ ) ₃ (p is 2-10, preferably 2-8, q is 1-5 , 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 (both p is 2-10, preferably 3-7, and q is 1-5, preferably 2-4).

Among the compounds represented by the above formula (b1), a compound represented by the following formula (b2) is preferred.

[chemical 10]

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

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

When the water-repellent layer (r) contains a structure derived from the organosilicon compound (B), the structure derived from the organosilicon compound (B) is preferably contained in the water-repellent layer (r) at least 3% by mass, and more It is preferably at least 5% by mass, further preferably at least 10% by mass, and is preferably at most 50% by mass, more preferably at most 40% by mass. Here, the structure derived from the organosilicon compound (B) refers to the organosilicon compound (B) and the residue after dehydration condensation of 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 water-repellent layer (r) is preferably at least 0.05, more preferably at least 0.08, further preferably at least 0.10 , and, preferably 2.0 or less, more preferably 1.0 or less, still more preferably 0.6 or less.

1-2-3.Organosilicon compound (C) The organosilicon compound (C) is preferably included in the laminate of the present invention (first aspect), and the organosilicon compound (C) may also be included in the water-repellent layer (r). Especially when the laminate of the present invention (first aspect) is the laminate (2), it is preferable to contain the organosilicon compound (C) in the water-repellent layer (r). When the water-repellent layer (r) contains the organosilicon compound (C), the adhesion of the water-repellent layer (r) to the substrate (s) becomes good, and as a result, the abrasion resistance of the laminate can be improved. In the case where the water-repellent layer (r) contains an organosilicon compound (C), the water-repellent layer (r) can usually be mixed with an organosilicon compound (A), an organosilicon compound (C), and optionally used A composition for forming a water-repellent layer of an organosilicon compound (B) is obtained by hardening it. In the case where the water-repellent layer (r) contains an organosilicon compound (C), the water-repellent layer (r) preferably has a structure derived from the organosilicon compound (A) and a structure derived from the organosilicon compound (C). structure, and a layer derived from the structure of the organosilicon compound (B) used arbitrarily.

As described below, the organosilicon compound (C) is a compound having a silicon atom bonded to a hydrolyzable group or a hydroxyl group. The -SiOH group of the organosilicon compound (C) produced by the hydrolysis and the -SiOH group derived from the organosilicon compound (C), the -SiOH group derived from other compounds, or the laminate to form a water-repellent layer (r) The active hydrogen (hydroxyl group, etc.) on the surface is dehydrated and condensed, so the water-repellent layer (r) may also contain the dehydration condensate of the organosilicon compound (C) (that is, the condensation structure derived from the organosilicon compound (C)). Furthermore, all the organosilicon compounds (C) contained in the water-repellent layer (r) may be dehydration condensates.

The organosilicon compound (C) is a compound having a silicon atom bonded to a hydrolyzable group or a hydroxyl group (hereinafter both are collectively referred to as a reactive group (h1)). The number of the aforementioned silicon atoms is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 2 to 5. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetyloxy group, an isocyanate group, and the like, preferably an alkoxy group, and more preferably an alkoxy group having 1 to 4 carbon atoms. Preferably, an alkoxy group or a hydroxyl group is bonded to the above-mentioned silicon atom, and an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms is particularly preferable.

The number of reactive groups (h1) bonded to one silicon atom may be 1 or more, may be 2 or 3, and is preferably 2 or 3.

The organosilicon compound (C) is preferably a compound having an amine group or an amine skeleton in addition to the silicon atom described above. The organosilicon compound (C) preferably has one or more amine skeletons. Furthermore, the aforementioned amine skeleton is represented by -NR ¹⁰ -, and R ¹⁰ is a hydrogen atom or an alkyl group. R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbons. Moreover, when the organosilicon compound (C) contains a plurality of amine skeletons, the plural amine skeletons may be the same or different.

The organosilicon compound (C) is preferably a compound not having a fluoropolyether structure.

The organosilicon compound (C) is preferably a compound represented by any one of the following formulas (c1) to (c3), or a compound represented by two or more formulas (c3) represented by X ³¹ to X ³⁴ A compound formed by condensation of at least any one of them.

1-2-3-1. Organosilicon compound (C) represented by the following formula (c1) (hereinafter referred to as organosilicon compound (C1)) [Chemical 11]

In the above formula (c1), R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x11 , the multiple R ^x11 can be respectively Different, when there is a plurality of R ^x12 , the plurality of R ^x12 can be different, when there is a plurality of R ^x13 , the plurality of R ^x13 can be different, and when there is a plurality of R ^x14 , the plurality of R x14 R ^x14 can be different respectively, Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group with 1 to 20 carbons or fluorine atoms in which one or more hydrogen atoms are replaced by fluorine atoms, and there are multiple Rf ^x11 In the case of multiple Rf x11, the plurality of Rf ^x11 can be different. In the case of multiple Rf ^x12 , the plurality of Rf ^x12 can be different. In the case of multiple Rf ^x13 , the plurality of Rf ^x13 can be different. In the case of a plurality of Rf ^x14 , the plurality of Rf ^x14 can be different, and R ^x15 is an alkyl group with 1 to 20 carbons. In the case of a plurality of R ^x15 , the plurality of R ^x15 can be different, and X ¹¹ is hydrolyzed In the case of a neutral group or a hydroxyl group, when there are a plurality of X ¹¹ , the plurality of X ¹¹ can be different, Y ¹¹ is -NH-, or -S-, when there is a plurality of Y ¹¹ , the plurality of Y ¹¹ can be are different, Z ¹¹ is vinyl, α-methylvinyl, styrene, methacryl, acryl, amine, isocyanate, isocyanurate, epoxy, urea, or mercapto, 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 of 1 to 3, and when Z ¹¹ is not an amino group , has at least one Y ¹¹ that is -NH-, and when all Y ¹¹ are -S- or p5 is 0, Z ¹¹ is an amino group, and Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _{3 - p6} , p1-{C(R ^x11 )(R ^x12 )}-unit (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 )}-unit (U _c14 ), p5-Y ¹¹ -unit ( U _c15 ), Z ¹¹ - is one terminal of the compound represented by formula (c1), -Si(X ¹¹ ) _p6 (R ^x15 ) _{3 - p6} is the other terminal, as long as -O- is not continuous with -O-, Then each unit (U _c11 )～unit (U _c15 ) is arranged in any order and bonded .

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 carbons 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.

^X11 is preferably an alkoxy group, a halogen atom, a cyano group, an isocyanate group, or a hydroxyl group, more preferably an alkoxy group or a hydroxyl group, further preferably an alkoxy group or a hydroxyl group with 1 to 4 carbon atoms, and especially preferably a methyl group. Oxy, Ethoxy, or Hydroxy.

Y ¹¹ is preferably -NH-.

Z ¹¹ is preferably a methacryl group, an acryl group, a mercapto group or an amine group, more preferably a mercapto group or an amine group, and especially preferably an amine group.

p1 is preferably 1-15, more preferably 2-10. It is preferable that p2, p3, and p4 are each independently 0-5, and it is more preferable that all are 0-2. p5 is preferably 0-5, more preferably 0-3, and still more preferably 1-3. p6 is preferably 2-3, more preferably 3.

As the organosilicon compound (C), it is preferable to use the following compound. In the above formula (c1), R ^x11 and R ^x12 are both hydrogen atoms, Y ¹¹ is -NH-, and X ¹¹ is an alkoxy group or a hydroxyl group. (especially methoxy, ethoxy, or hydroxyl), Z ¹¹ is amino or mercapto, p1 is 1-10, p2, p3 and p4 are all 0, p5 is 0-5 (especially 1-3) , p6 is 3.

Furthermore, the p1 units (U _c11 ) do not need to be bonded consecutively with the units (U _c11 ), and may be bonded via other units on the way, as long as the total is p1. The same applies to units (U _c12 ) to units (U _c15 ) enclosed by p2 to p5.

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

[chemical 12]

In the above formula (c1-2), X ¹² is a hydrolyzable group or a hydroxyl group. When there are plural X ¹² , the plural X ¹² may be different, Y ¹² is -NH-, Z ¹² is an amino group, or mercapto, R ^x16 is an alkyl group with 1 to 20 carbons, and when there are multiple R ^x16s , the multiples of R ^x16 can 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, and when s is 0, Z ¹² is an amino group.

^X12 is preferably an alkoxy group, a halogen atom, a cyano group, an isocyanate group, or a hydroxyl group, more preferably an alkoxy group or a hydroxyl group, further preferably an alkoxy group or a hydroxyl group with 1 to 4 carbon atoms, and especially preferably a methyl group. Oxy, Ethoxy, or Hydroxy.

Z ¹² is preferably an amino group.

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

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

When s is 1, it is preferable that q is an integer of 2-3, and r is an integer of 2-4, and when s is 0, it is preferable that the total of q and r is 1-5.

1-2-3-2. Organosilicon compound (C) represented by the following formula (c2) (hereinafter referred to as organosilicon compound (C2))

於上述式(c2)中， R ^x20及R ^x21分別獨立為氫原子或碳數1～4之烷基，於存在複數個R ^x20之情形時，複數個R ^x20可分別不同，於存在複數個R ^x21之情形時，複數個R ^x21可分別不同， Rf ^x20及Rf ^x21分別獨立為1個以上之氫原子被取代為氟原子之碳數1～20之烷基或氟原子，於存在複數個Rf ^x20之情形時，複數個Rf ^x20可分別不同，於存在複數個Rf ^x21之情形時，複數個Rf ^x21可分別不同， R ^x22及R ^x23分別獨立為碳數1～20之烷基，於存在複數個R ^x22及R ^x23之情形時，複數個R ^x22及R ^x23可分別不同， X ²⁰及X ²¹分別獨立為水解性基或羥基，於存在複數個X ²⁰及X ²¹之情形時，複數個X ²⁰及X ²¹可分別不同， p20為1～30之整數，p21為0～30之整數，標註p20或p21並以括號括住之重複單元之至少一者被取代為胺骨架-NR ¹⁰⁰-，上述胺骨架中之R ¹⁰⁰為氫原子或烷基， p22及p23分別獨立為1～3之整數， p20個-{C(R ^x20)(R ^x21)}-單元(U _c21)、p21個-{C(Rf ^x20)(Rf ^x21)}-單元(U _c22)無需p20個單元(U _c21)或p21個單元(U _c22)連續，各單元(U _c21)及單元(U _c22)以任意之順序排列而鍵結，式(c2)所表示之化合物之一個末端為-Si(X ²⁰) _p22(R ^x22) _{3 － p22}，另一個末端為-Si(X ²¹) _p23(R ^x23) _{3 － p23}。 [chemical 13]

In the above formula (c2), R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x20 , the multiple R ^x20 can be different. In the case of R ^x21 , the plurality of R ^x21 may be different, and Rf ^x20 and Rf ^x21 are each independently an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms. In the case of Rf ^x20 , a plurality of Rf ^x20 may be different, and in the case of a plurality of Rf ^x21 , a plurality of Rf ^x21 may be different, R ^x22 and R ^x23 are independently an alkyl group with 1 to 20 carbon atoms, and When there are multiple R ^x22 and R ^x23 , ^the multiple R ^x22 and R ^x23 can be different respectively, X20 and ^X21 are independently hydrolyzable groups or hydroxyl groups, and when there are multiple ^X20 and ^X21 , A plurality of X ²⁰ and X ²¹ can be different respectively, p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, at least one of the repeating units marked with p20 or p21 and enclosed in brackets is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ in the above-mentioned amine skeleton is a hydrogen atom or an alkyl group, p22 and p23 are independently an integer of 1 to 3, p20 -{C(R ^x20 )(R ^x21 )}-units (U _c21 ), p21-{C(Rf ^x20 )(Rf ^x21 )}-units (U _c22 ) do not need p20 units (U _c21 ) or p21 units (U _c22 ) to be continuous, each unit (U _c21 ) and unit (U _c22 ) Arranging and bonding in any order, one end of the compound represented by formula (c2) 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 carbons in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom.

R ^x22 and R ^{x23 are} preferably an alkyl group having 1 to 5 carbon atoms.

^X20 and ^X21 are preferably alkoxy groups, halogen atoms, cyano groups, isocyanate groups, or hydroxyl groups, more preferably alkoxy groups or hydroxyl groups, and more preferably alkoxy groups or hydroxyl groups with 1 to 4 carbon atoms, especially Preferably it is methoxy, ethoxy, or hydroxy.

Amine skeleton - NR ¹⁰⁰ - as mentioned above, at least one in the molecule is sufficient, and any one of the repeating units marked p20 or p21 and enclosed in brackets is substituted with the above-mentioned amine skeleton, preferably marked p20 part of a repeating unit enclosed in parentheses. The said amine skeleton may exist plurally, and the number of the amine skeleton in this case becomes like this. Preferably it is 1-10, More preferably, it is 1-5, More preferably, it is 2-5. Also, in this case, it is preferable to have -{C(R ^x20 )(R ^x21 )} _p200 - between adjacent amine skeletons, and p200 is preferably 1-10, more preferably 1-5. p200 is included in the total number of p20.

In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the carbon number 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, except for the number of repeating units substituted with amine skeletons.

p21 is preferably 0-5, more preferably 0-2, except for the number of repeating units substituted with amine skeletons.

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

As organosilicon compound (C2), it is preferable to use the following compound. In the above-mentioned formula (c2), R ^x20 and R ^x21 are both hydrogen atoms, and X ²⁰ and X ²¹ are alkoxy groups or hydroxyl groups (especially form oxy, ethoxy, or hydroxyl), at least one of the repeating units marked p20 and enclosed in brackets is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom, and p20 is 1 to 10 (wherein, not Including the number of repeating units substituted with amine backbone), p21 is 0, p22 and p23 are 3.

Furthermore, if the above-mentioned formula (c2) represents N-2-(aminoethyl)-3- The reaction product of aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.), then R ^x20 and R ^x21 are both hydrogen atoms, p20 is 8 (excluding the number of repeating units replaced by amine skeletons), p21 is 0, amine skeletons are 2 (R ¹⁰⁰ are hydrogen atoms), both ends are the same, p22 and p23 are 3, X ²⁰ and X ²¹ is methoxy.

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

[chemical 14]

In the above formula (c2-2), X ²² and X ²³ are independently hydrolyzable groups or hydroxyl groups. When there are multiple X ²² and X ²³ , the multiple X ²² and X ²³ can be different, respectively, R ^x24 and R ^x25 are each independently an alkyl group with 1 to 20 carbon atoms. When there are multiple R ^x24 and R ^x25 , the multiple R ^x24 and R ^x25 may be different from each other, and -C _w H _{2w -part} of methylene At least one of the groups is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom or an alkyl group, w is an integer from 1 to 30 (excluding the number of methylene groups substituted with an amine skeleton), p24 and p25 are each independently an integer of 1-3.

^X22 and ^X23 are preferably alkoxy groups, halogen atoms, cyano groups, isocyanate groups, or hydroxyl groups, more preferably alkoxy groups or hydroxyl groups, and more preferably alkoxy groups or hydroxyl groups with 1 to 4 carbon atoms, especially Preferably it is methoxy, ethoxy, or hydroxy.

There may be a plurality of amine skeletons -NR ¹⁰⁰ -, and in this case, the number of amine skeletons is preferably 1-10, more preferably 1-5, still more preferably 2-5. Also, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. The carbon number of the said alkylene group is preferably 1-10, more preferably 1-5. The carbon number of the alkylene group 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 carbon number 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 an alkyl group having 1 to 10 carbons, more preferably an alkyl group having 1 to 5 carbons.

p24 and p25 are preferably an integer of 2-3, more preferably 3.

w is preferably at least 1, more preferably at least 2, and is preferably at most 20, more preferably at most 10.

1-2-3-3. Organosilicon compound (C) represented by the following formula (c3) (hereinafter referred to as organosilicon compound (C3))

於上述式(c3)中， Z ³¹、Z ³²分別獨立為水解性基及羥基以外之反應性官能基。作為反應性官能基，可例舉：乙烯基、α-甲基乙烯基、苯乙烯基、甲基丙烯醯基、丙烯醯基、胺基、環氧基、脲基、或巰基。作為Z ³¹、Z ³²，較佳為胺基、巰基、或甲基丙烯醯基，尤佳為胺基。 [chemical 15]

In the above formula (c3), Z ³¹ and Z ³² are each independently a hydrolyzable group and a reactive functional group other than a hydroxyl group. The reactive functional group may, for example, be a vinyl group, α-methylvinyl group, styryl group, methacryl group, acryl group, amine group, epoxy group, ureido group, or mercapto group. Z ³¹ and Z ³² are preferably an amino group, a mercapto group, or a methacryl group, and are particularly preferably an amino group.

R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x31s , the multiple R ^x31s can be different. When there are multiple R ^x32 In the case of , the plurality of ^Rx32 can be different, and when there is a plurality of ^Rx33 , the plurality of ^Rx33 can be different, and when there is a plurality of ^Rx34 , the plurality of ^Rx34 can be different. R ^x31 , R ^x32 , R ^x33 , and R ^{x34 are} preferably a hydrogen atom or an alkyl group having 1 to 2 carbons, more preferably a hydrogen atom.

Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms. When there are multiple Rf ^x31 , the multiple Rf ^x31 can be different respectively. When there are multiple Rf ^x32 , the multiple Rf ^x32 can be different. When there are multiple Rf ^x33 , the multiple Rf ^x33 can be different. In the case of multiple Rf ^x34 , the plurality of Rf ^x34 may be different from each other. Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^{x34 are} preferably C 1-10 alkyl groups or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms.

Y ³¹ is -NH-, -N(CH ₃ )- or -O-, and when a plurality of Y ³¹ exists, the plurality of Y ³¹ may be different from each other. Y ³¹ is preferably -NH-.

X ³¹ , X ³² , X ³³ , and X ³⁴ are independently -OR ^c (R ^c is a hydrogen atom, an alkyl group with 1 to 4 carbons, or an amino C _{1-3 alkyldiC 1-3} alkoxy group Silyl group), when there are multiple X ³¹ , the multiple X ³¹ can be different, when there are multiple X ³² , the multiple X ³² can be different, when there are multiple X ³³ , A plurality of X ³³ may be different from each other, and when there are a plurality of X ³⁴ , a plurality of X ³⁴ may be different from each other. X ³¹ , X ³² , X ³³ , and X ³⁴ are preferably -OR ^c in which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbons, and R ^c is more preferably a hydrogen atom.

p31 is an integer of 0-20, p32, p33, and p34 are each independently an integer of 0-10, p35 is an integer of 0-5, p36 is an integer of 1-10, and p37 is 0 or 1. p31 is preferably 1-15, more preferably 3-13, still more preferably 5-10. Preferably, p32, p33, and p34 are each independently 0-5, and all of them are more preferably 0-2. p35 is preferably 0-3. p36 is preferably 1-5, more preferably 1-3. Preferably p37 is 1.

Organosilicon compound (C3) satisfying the condition that at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and the compound represented by formula (c3) One end is Z ³¹ -, the other end is Z ³² -, as long as -O- is not continuous with -O-, p31 -{C(R ^x31 )(R ^x32 )}-units (U _c31 ), p32 pcs-{C(Rf ^x31 )(Rf ^x32 )}-unit(U _c32 ), p33-{Si(R ^x33 )(R ^x34 )}-unit(U _c33 ), p34-{Si(Rf ^x33 ) (Rf ^x34 )}-unit (U _c34 ), p35-Y ³¹ -unit (U _c35 ), p36-{Si(X ³¹ )(X ³² )-O}-unit (U _c36 ), p37- {Si(X ³³ )(X ³⁴ )}-units (U _c37 ) are respectively arranged in an arbitrary order and bonded to form a structure. The p31 units (U _c31 ) do not need to be bonded consecutively by the units (U _c31 ), and may be bonded via other units in the middle, as long as the total is p31. The same applies to the units (U _c32 ) to (U _c37 ) enclosed by p32 to p37.

As the organosilicon compound (C3), the following compounds are preferred. Z ³¹ and Z ³² of the compound are amino groups, R ^x31 and R ^x32 are hydrogen atoms, p31 is 3-13 (preferably 5-10), R ^x33 and R ^x34 are both hydrogen atoms, Rf ^x31 to Rf ^x34 are all hydrogen atoms replaced by fluorine atoms with an alkyl group with 1 to 10 carbons or fluorine atoms, p32 to p34 are all 0 to 5, Y ³¹ is -NH-, p35 is 0-5 (preferably 0-3), X ³¹ -X ³⁴ are all -OH, p36 is 1-5 (preferably 1-3), and p37 is 1.

The organosilicon compound (C3) is preferably represented by the following formula (c3-2).

[chemical 16]

In the above formula (c3-2), Z ³¹ , Z ³² , X ³¹ , X ³² , X ³³ , X ³⁴ , and Y ³¹ have the same meanings as in formula (c3), and p41 to p44 are independently 1 An integer of ~6, p45 and p46 are independently 0 or 1, respectively.

In formula (c3-2), Z ³¹ and Z ³² are preferably amino groups, mercapto groups, or methacryl groups, and are particularly preferably amino groups. X ³¹ , X ³² , X ³³ , and X ³⁴ are preferably -OR ^c in which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbons, more preferably R ^c is a hydrogen atom. Y ³¹ is preferably -NH-. p41 to p44 are preferably at least 1, and are preferably at most 5, more preferably at most 4. Both p45 and p46 are preferably zero.

1-2-3-4. A compound formed by bonding two or more compounds represented by formula (c3) through condensation of at least any one of X ³¹ to X ³⁴ (hereinafter referred to as organosilicon compound (C3') ) The organosilicon compound (C3') is a compound formed by bonding two or more of the above-mentioned organosilicon compounds (C3) through condensation of at least any one of the above-mentioned X ³¹ to X ³⁴ , and two or more of the above-mentioned organosilicon compounds (C3) may be bonded into a chain or may be bonded into a ring. The organosilicon compound (C3') is, for example, a compound formed of an organosilicon compound (C3).

As the organosilicon compound (C3'), for example, one obtained by condensation of the above-mentioned X31 or X32 can be mentioned, specifically, it has two or more structures represented by the following formula ( ^c31-1 ) ( ^c31- 1) In the compound where the above structure (c31-1) is bonded to each other in a chain or a ring by the following *3 or *4, two or more kinds of bonds are used by the following *3 or *4 Condensation of the above-mentioned X ³¹ or X ³² of the above-mentioned organosilicon compound (C3), p31, p32, p31, p32, At least one of the units enclosed by p33, p34, p35, (p36)-1, and p37 is bonded in any order and the terminal is a Z-group, and for each of the plural structures (c31-1) above, bonded to The groups of *1 and *2 may be different, and *3 at the end of a plurality of the above-mentioned structures (c31-1) bonded into a chain is a hydrogen atom, and *4 is a hydroxyl group.

[chemical 17]

[chemical 18]

In the above formula (c31-2), Z is a reactive functional group other than a hydrolyzable group and a hydroxyl group, R ^x31 , R ^x32 , R ^x33 , R ^x34 , Rf ^x31 , Rf ^x32 , Rf ^x33 , Rf ^x34 , Y ³¹ , X ³¹ , X ³² , X ³³ , X ³⁴ , p31 to p37 have the same meanings as those symbols in the above formula (c3).

When the organosilicon compound (C3') is formed, the number of bonds of the organosilicon compound (C3) is preferably 2-10, more preferably 3-8. Moreover, two or more organosilicon compounds (C3) constituting the organosilicon compound (C3') may be different from each other, but all are preferably the same.

When the organosilicon compound (C3) constituting the organosilicon compound (C3') is a compound represented by the above formula (c3-2), as the organosilicon compound (C3'), for example, the following formula (c31 -3) A compound in which the structure represented by the following *3 or *4 is bonded in a chain or a ring. When the structure represented by the following formula (c31-3) is bonded in a chain, *3 at the end is a hydrogen atom, and *4 at the end is a hydroxyl group.

[chemical 19]

All the symbols in the above formula (c31-3) have the same meanings as the symbols in the above formula (c3-2).

The organosilicon compound (C3') is preferably a compound in which 2 to 10 (preferably 3 to 8) structures represented by the above formula (c31-3) are bonded.

As the organosilicon compound (C), only one type may be used, or two or more types may be used. As organosilicon compound (C), it is preferable to use at least one selected from the group consisting of organosilicon compounds (C1) to (C3) and organosilicon compound (C3'), more preferably to use organosilicon compound (C1) and at least one of the group consisting of organosilicon compounds (C2).

When the water-repellent layer (r) contains the organosilicon compound (C), the structure derived from the organosilicon compound (C) is preferably contained in the water-repellent layer (r) at least 5% by mass, more preferably 10% by mass % or more, more preferably at least 15 mass %, and more preferably at most 60 mass %, more preferably at most 50 mass %, further preferably at most 40 mass %, even more preferably at most 30 mass %. Here, the structure derived from the organosilicon compound (C) refers to the organosilicon compound (C) and the residue after dehydration condensation of the organosilicon compound (C). Especially when the laminate of the present invention (first aspect) is the laminate (2), it is preferable to adjust the structure derived from the organosilicon compound (C) to the above range. Also, when the laminate of the present invention (first aspect) is the laminate (1), the structure derived from the organosilicon compound (C) is preferably contained in the water-repellent layer (r) at 5% by mass or less , more preferably 1% by mass or less, and especially preferably does not contain a structure derived from an organosilicon compound (C).

Also, the water-repellent layer (r) may contain a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, and an antifungal agent within the range that does not hinder the effect of the present invention (first aspect) , antibacterial agent, antiviral agent, biological adhesion prevention agent, deodorant, pigment, flame retardant, antistatic agent and other additives. The amount of the above-mentioned additives in the water-repellent layer (r) is preferably at most 0.1% by mass, more preferably at most 0.01% by mass.

The thickness of the water-repellent layer (r) is preferably from 1 nm to 50 nm, more preferably from 1 nm to 40 nm, further preferably from 2 nm to 25 nm, especially preferably from 3 nm to 15 nm. Especially when the laminated body of this invention (1st aspect) is a laminated body (2), it is preferable to make the thickness of a water-repellent layer (r) into the said range. Also, when the laminate of the present invention (first aspect) is the laminate (1), the thickness of the water-repellent layer (r) is preferably from 1 nm to 20 nm, more preferably from 1 nm to 15 nm It is less than or equal to more than 2 nm and not more than 10 nm, and is more preferably not less than 3 nm and not more than 8 nm. By setting the thickness of the water-repellent layer (r) to a predetermined value or more, not only water-repellency, but also excellent durability such as wear resistance and scratch resistance are preferred in this respect. Also, by making the above-mentioned thickness If it is below the specified value, the reduction of the antibacterial activity in the surface of the laminate can be further suppressed (preferably, the antibacterial activity in the surface of the laminate can be further improved), and the transparency is excellent (in other words, the haze can be suppressed to lower) is better. Furthermore, when the thickness of the water-repellent layer (r) is measured below the decimal point, it is preferable that the value obtained by rounding off the decimal point satisfies the above-mentioned range.

The thickness of the water-repellent layer (r) can be adjusted by the concentration of the solid content in the water-repellent layer-forming composition or the coating conditions of the water-repellent layer-forming composition. The thickness of the water-repellent layer (r) can be measured by ellipsometer or X-ray reflection measurement, scanning transmission electron microscope (STEM) measurement of cross-sectional direction, X-ray photoelectron spectroscopy (XPS), probe film profiler, etc. For measurement, a measurement method can be appropriately selected according to the material or thickness of each layer.

In the STEM measurement of the cross-sectional direction, the laminate is thinned along the direction perpendicular to the substrate (s) to cut an ultra-thin section, and the section of the ultra-thin section is observed with a scanning transmission electron microscope (STEM). This can measure the thickness of the water-repellent layer (r). As a method for thinning the laminate, any ultrathin sections with a thickness of 100 nm or less may be processed, and examples thereof include focused ion beam processing, ultramicrotome processing, and cryo-ultramicrotome processing. For example, when using the focused ion beam processing method, the ion source is preferably Ga, and the accelerating voltage is preferably set to about 30 kV. In the case of STEM observation, it is preferable to set the accelerating 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 STEM observation, in order to easily distinguish the interface between the water-repellent layer (r) and the outside world, the upper surface of the water-repellent layer (r) may be blackened with a felt pen or the like prior to sheeting before measurement.

When the laminated body of the present invention (first aspect) is the laminated body (1), it can also be based on a laminated body using glass as the material of the base material (s) as described in the examples described below. Calculate the thickness of the water-repellent layer (r) from the calibration curve obtained from the sample. Specifically, using glass as the material of the substrate (s), prepare a plurality of (preferably 3 or more) laminate samples with the same thickness of the layers (c) and different thicknesses of the water-repellent layer (r), and use an ellipse A polarimeter measures the thickness of the water-repellent layer (r) respectively. In addition, XPS measurement was performed on this sample, and the ratio of the specific element amount derived from the water-repellent layer (r) to the specific element amount derived from the layer (c) was obtained, and the thickness relative to the water-repellent layer (r) was prepared. The calibration curve of the above ratio. Then, XPS measurement is carried out on the actually obtained laminated body, thereby obtaining the ratio of the specific element amount originating from the water-repellent layer (r) to the specific element amount originating from the layer (c), and according to the above-mentioned calibration curve, it can be Calculate the thickness of the water-repellent layer (r).

Furthermore, when the material of the substrate (s) is an organic material, it is difficult to measure the film thickness with an ellipsometer due to the small difference in refractive index between the substrate (s) and the water-repellent layer (r). situation. In this case, STEM measurement in the cross-sectional direction or measurement using the above-mentioned calibration curve may be performed.

1-3. Layer (c) In the laminate of the present invention (first aspect), a layer (c) may be provided between the substrate (s) and the water-repellent layer (r). When the laminate of the present invention (first aspect) includes the layer (c), that is, in the case of the laminate (1), it is preferably an organosilicon compound having a silicon atom bonded to a hydrolyzable group or a hydroxyl group (C) is contained in layer (c). In the case where layer (c) contains organosilicon compound (C), layer (c) can function as a primer layer of water-repellent layer (r), and the adhesion of water-repellent layer (r) to substrate (s) As a result, the wear resistance of the laminate can be improved. The organosilicon compound (C) contained in the layer (c) is the same as the organosilicon compound (C) described above, and its preferred aspects are also the same.

In the case where the layer (c) contains an organosilicon compound (C), the layer (c) can generally be coated with a mixed composition of the organosilicon compound (C) (hereinafter sometimes referred to as layer (c) forming composition ) and harden it. As mentioned above, the organosilicon compound (C) is a compound having a silicon atom bonded to a hydrolyzable group or a hydroxyl group, and a compound bonded to the -SiOH group possessed by the organosilicon compound (C) or a hydrolyzable group of a silicon atom The -SiOH group of the organosilicon compound (C) produced by hydrolysis dehydrates and condenses with the -SiOH group derived from the organosilicon compound (C), or the active hydrogen (hydroxyl group, etc.) on the surface of the layer (c) in the laminate, Therefore, the layer (c) may have a dehydration condensate of the organosilicon compound (C) (ie, a condensation structure derived from the organosilicon compound (C)). Furthermore, all the organosilicon compounds (C) contained in the layer (c) may be dehydration condensates.

The structure derived from the organosilicon compound (C) is preferably contained in layer (c) at least 80% by mass, more preferably at least 90% by mass, still more preferably at least 98% by mass, and may be 100% by mass %.

In addition, the layer (c) may contain a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, antiviral agent, anti-fouling agent, deodorant, pigment, flame retardant, antistatic agent and other additives. The amount of the aforementioned additives is preferably at most 0.1% by mass, more preferably at most 0.01% by mass, in layer (c).

In the case where the laminate of the present invention (first aspect) has layer (c), the thickness of layer (c) can be appropriately adjusted within the range where the thickness of the laminate part does not exceed 50 nm, preferably 1 nm or more 40 nm or less, more preferably 2 nm or more and 35 nm or less, further preferably 3 nm or more and 30 nm or less, most preferably 5 nm or more and 25 nm or less. Moreover, it is also preferable to make the thickness of layer (c) less than 30 nm. By setting the thickness of the layer (c) to 1 nm or more, durability such as wear resistance and scratch resistance is excellent in this point, which is preferable. Also, by making the thickness of the layer (c) below 40 nm (preferably less than 30 nm), the reduction of the antibacterial activity in the surface of the laminate can be further suppressed (preferably, the antibacterial activity in the surface of the laminate can be further increased). Antibacterial activity) and excellent transparency are preferred. Furthermore, when measuring the thickness of the layer (c) below the decimal point, it is preferable that the value obtained by rounding off the decimal point satisfies the above-mentioned range.

The thickness of the layer (c) can be adjusted by the concentration of the solid content in the layer (c) forming composition or the coating conditions of the layer (c) forming composition. The thickness of layer (c) can be measured by ellipsometer or X-ray reflection measurement, X-ray photoelectron spectroscopy (XPS), STEM measurement of cross-sectional direction, probe-type film profiler, etc. It can be measured according to the material or thickness of each layer Choose the measurement method appropriately. In the case of measuring the thickness of the layer (c) by STEM measurement in the cross-sectional direction, the thickness of the water-repellent layer (r) can be measured by placing the laminate along the direction perpendicular to the substrate (s ) in the direction of slicing and cutting ultra-thin slices, and measuring the cross-section of the ultra-thin slices by STEM observation, it can also be measured by using the same method as above before applying the composition for forming a water-repellent layer ( That is, the layered intermediate in the state where only the layer (c) is provided on the substrate (s) is thinned, and the cross-section is observed and measured by STEM. Furthermore, in the case of STEM observation of the cross-section of the laminated intermediate, in order to easily distinguish the interface between the layer (c) and the outside world, the upper surface of the layer (c) can be blackened with a felt pen or the like before thinning. Determination.

The thickness of the layered part is not less than 1 nm and not more than 50 nm. The thickness of the layered part is preferably from 2 nm to 45 nm, more preferably from 5 nm to 40 nm, still more preferably from 5 nm to 40 nm, still more preferably from 6 nm to 30 nm, especially preferably Above 6 nm and below 15 nm. In addition, the thickness of the layered portion may be set to be less than 15.0 nm. By setting the thickness of the layered part to 1 nm or more, not only water repellency but also durability such as wear resistance and scratch resistance are excellent, which is preferable in this point. In addition, it is preferable that the antibacterial activity on the surface of the laminate is not reduced (preferably, the antibacterial activity on the surface of the laminate can be further increased) by setting the thickness of the laminated part to 50 nm or less. Also, from the viewpoint of transparency, the thickness of the layered portion is preferably less than 40 nm, more preferably less than 30 nm. In addition, when the thickness of the laminated part is measured below the decimal point, the value obtained by rounding off the decimal point may satisfy the above-mentioned range.

The thickness of the laminated part can be obtained by STEM measurement in the cross-sectional direction or a probe-type film profiler, and the total thickness of each layer of the water-repellent layer (r) and layer (c), etc., and can be determined according to the material or thickness of each layer. Select the measurement method. In addition, when measuring the thickness of the laminated part by the STEM measurement of a cross-sectional direction, it may measure by the same method as measuring the thickness of the water-repellent layer (r) by the said STEM measurement.

1-4. Characteristics of laminates When measuring the surface of the water-repellent layer (r) of the laminate of the present invention (first aspect), when observing the situation of metal and fluorine atoms, the observed mass ratio of metal to fluorine atoms (metal/fluorine atoms) It is preferably at least 0.0001, more preferably at least 0.001, and more preferably at most 1, more preferably at most 0.5, still more preferably at most 0.1. The metal may, for example, be a metal derived from the aforementioned metal ion (K2). Moreover, as a fluorine atom, the fluorine atom derived from the said organosilicon compound (A) and the fluorine atom derived from the said organosilicon compound (B) are mentioned, for example. Therefore, by setting the material mass ratio (metal/fluorine atom) of the metal and the fluorine atom when measuring the surface of the water-repellent layer (r) to the above-mentioned range, better water-repellency and antibacterial properties can be simultaneously achieved. Furthermore, X-ray photoelectron spectroscopy (XPS) or STEM-EDS (Energy-dispersive X-ray spectroscopy, energy-dispersive X-ray analysis) can be used to measure the surface of the water-repellent layer (r).

The water contact angle (initial contact angle) on the surface of the water-repellent layer (r) of the laminate of the present invention (first aspect) is, for example, 105° or more, preferably 110° or more, more preferably 115° or more, and, For example, it is 125° or less.

Apply a load of 1000 g on a circle with a diameter of 6 mm as a unit, and rub the surface of the water-repellent layer (r) of the laminate of the present invention (first aspect) 1500 times (one reciprocation is one time) to perform the abrasion resistance The water contact angle (contact angle after 1500 times) of the surface of the water-repellent layer (r) after the test is, for example, 75° or more, preferably 100° or more, more preferably 105° or more, and more preferably 110° or more. , such as 120° or less. In the above abrasion resistance test, it is preferable to use an elastic body (preferably an eraser) for rubbing during rubbing. The stroke distance of the wear resistance test is, for example, 40 mm, the friction speed is set to 40 reciprocations/minute, and the contact angle can be measured in the approximate center of the stroke area. When loading a load, apply the same pressure as the area of a circle with a diameter of 6 mm to apply a load of 1000 g.

In addition, a load of 1000 g was applied in units of a circle with a diameter of 6 mm, and the surface of the water-repellent layer (r) of the laminate of the present invention (first aspect) was rubbed 3000 times (one reciprocation is one time), and the resistance was carried out. The water contact angle (contact angle after 3000 times) of the surface of the water-repellent layer (r) after the abrasion test is, for example, 73° or higher, preferably 100° or higher, more preferably 105° or higher, and more preferably 110° or higher , and, for example, 120° or less. In addition, the conditions of the above-mentioned abrasion resistance test are the same as the conditions for measuring the contact angle after 1500 times.

The kinetic friction coefficient of the surface of the water-repellent layer (r) of the present invention (first aspect) is preferably at most 0.1, more preferably at most 0.090, still more preferably at most 0.080, and may be at least 0.010.

Use an oil-based pen to draw 3 lines on the surface of the water-repellent layer (r), and then use Savina (registered trademark) to wipe the surface of the water-repellent layer (r) once, preferably to be able to wipe 2 or more of the above-mentioned lines, More preferably, all three can be wiped off. The above-mentioned line may be straight, curved, or triangular, square, or circular connecting the start point and the end point.

When performing an abrasion test in which a pressure of 250 g/ ^cm2 is applied and the surface of the water-repellent layer (r) of the above-mentioned laminate is rubbed with steel wool until peeling or damage is visually confirmed on the surface of the water-repellent layer (r), the steel wool The number of reciprocating times on the surface of the water layer (r) is, for example, more than 100 times, preferably more than 300 times, more preferably more than 500 times, more preferably more than 3000 times, especially preferably more than 4000 times, and, for example, 10000 times the following.

The haze of the laminate of the present invention (first aspect) when measured in accordance with JIS Z 8722 is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, still more preferably 2.5 or less, still more preferably Preferably it is 1.5 or less, especially preferably 1.0 or less, and, for example, 0.01 or more.

When the antibacterial activity test according to JIS Z 2801:2010 is carried out, the antibacterial activity value of the laminate of the present invention (first aspect) against Staphylococcus aureus exceeds 0, preferably 0.1 or above, more preferably 2.0 or above, and further Preferably it is 2.5 or more, especially preferably 3 or more, and, for example, 7 or less.

When the antibacterial activity test according to JIS Z 2801:2010 is carried out, the antibacterial activity value of the laminate of the present invention (first aspect) against Escherichia coli is, for example, more than 0, preferably 0.1 or more, more preferably 2.0 or more, and even more preferably It is 2.5 or more, preferably 3 or more, and, for example, 7 or less.

The antibacterial activity value of the laminate of the present invention (first aspect) against Staphylococcus epidermidis when the same test as the antibacterial activity test described in JIS Z 2801:2010 is performed except for the modified bacteria is, for example, more than 0, preferably 0.1 or more , more preferably 2.0 or more, still more preferably 2.5 or more, particularly preferably 3 or more, and, for example, 7 or less.

When the applied voltage was set to 500 V, and the surface resistivity measured on the surface of the water-repellent layer (r) was measured before and after a heat resistance test in which the laminate of the present invention (first aspect) was kept at 80°C for 36 hours, The surface resistivity after the heat resistance test is preferably less than 6.4 times, more preferably 4.0 times or less, further preferably 3.5 times or less, especially preferably 3.3 times or less, with respect to the surface resistivity before the heat resistance test. Especially limited, it may be 1.0 times or 1.5 times. Furthermore, the surface resistivity before the heat resistance test is preferably the surface resistivity measured in the laminated body of the present invention (first aspect) managed in the range of about 0°C to 35°C.

The laminate of the present invention (first aspect) preferably has at least one or more of the above properties, and more preferably has a combination of two or more of the above properties. In addition, the concrete method of evaluating each characteristic is demonstrated in detail in the column of an Example.

1-5. Manufacturing method of laminated body Next, the manufacturing method of the laminated body of this invention (1st aspect) is demonstrated.

1-5-1. Manufacturing method of laminate (1) When the laminated body of the present invention (first aspect) is the laminated body (1), the method for manufacturing the laminated body (1) includes: (i) coating the layer (c) on the substrate (s) for forming Step of composition; (ii) step of hardening the coating layer of the composition for forming the layer (c); (iii) coating the coating surface of the composition for forming the layer (c) for forming a water-repellent layer Composition (hereinafter, the composition for forming a water-repellent layer used in the production of the laminate (1) is referred to as the composition for forming a water-repellent layer (1)); and (iv) making the composition for forming a water-repellent layer (1) The step of hardening the coating layer, forming the above-mentioned layer (c) from the coating layer of the above-mentioned layer (c)-forming composition, forming the above-mentioned coating layer from the coating layer of the above-mentioned water-repellent layer-forming composition (1). Water-repellent layer (r).

The composition for forming the layer (c) is a mixed composition of the organosilicon compound (C). The mixed composition of organosilicon compound (C) can be obtained by mixing organosilicon compound (C), and in the case of mixing components other than organosilicon compound (C), it can be obtained by mixing organosilicon compound (C) with other Obtained by mixing ingredients. The layer (c) forming composition also includes those that react after mixing, for example, during storage. As an example of performing the reaction, the above-mentioned layer (c)-forming composition includes a compound bonded to the above-mentioned organosilicon compound (C). The hydrolyzable gene of the silicon atom is hydrolyzed to form a -SiOH group compound (hereinafter sometimes referred to as the hydrolyzate of the organosilicon compound (C)). In addition, as an example of carrying out the reaction, a condensate containing the above-mentioned organosilicon compound (C) in the composition for forming the layer (c) may be exemplified. As the condensate, - Dehydration condensation product formed by dehydration condensation of SiOH group or -SiOH group of organosilicon compound (C) generated by hydrolysis and -SiOH group derived from organosilicon compound (C) or -SiOH group derived from other compounds.

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

As an alcoholic solvent, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc. are mentioned. As a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned. The ether solvent may, for example, be diethyl ether, dipropyl ether, tetrahydrofuran or 1,4-dioxane. Examples of the hydrocarbon solvent 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. Ethyl acetate, propyl acetate, butyl acetate, etc. are mentioned as an ester type solvent.

The amount of the organosilicon compound (C) when the entire composition for forming the layer (c) is 100% by mass is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, still more preferably at least 0.1% by mass The above, and more preferably at most 5% by mass, more preferably at most 3% by mass, further preferably at most 1% by mass. The amount of the above organosilicon compound (C) can be adjusted during the preparation of the composition. In addition, the amount of the organosilicon compound (C) can also be calculated from the analysis results of the composition. As a specific method based on the analysis results of the composition, for example, the type of each compound contained in the composition can be analyzed by using gas chromatography-mass spectrometry or liquid chromatography-mass spectrometry, and the obtained The analysis results are identified by library search, and the amount of each compound contained in the composition can be calculated from the above analysis results using the calibration curve method. In addition, in this specification, when the range of the quantity of each component, mass ratio, or molar ratio is described, this range can be adjusted at the time of preparation of a composition.

The amount of the solvent (E) when the whole composition for forming the layer (c) is 100% by mass is preferably at least 80% by mass, more preferably at least 85% by mass, still more preferably at least 90% by mass, More preferably, it is at least 95% by mass, still more preferably at least 98% by mass, and may be at most 99.9% by mass.

In addition, the layer (c) forming composition may contain a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, Various additives such as antifungal agents, antibacterial agents, antiviral agents, antifouling agents, deodorants, pigments, flame retardants, and antistatic agents. The amount of the aforementioned additives is preferably at most 5 mass %, more preferably at most 1 mass %, based on 100 mass % of the layer (c) forming composition.

As a method of coating the composition for forming the layer (c), for example, a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, and a gravure coating method are mentioned. coating method, etc.

Before coating the layer (c)-forming composition, it is preferable to give an easy-adhesive treatment to the coated surface of the substrate (s). The easy-adhesive treatment includes, for example, hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment, and more preferably plasma treatment. OH groups (especially when the base material is epoxy resin) or COOH groups (especially when the base material is acrylic resin) can be formed on the surface of the substrate by easy-adhesive treatment such as plasma treatment When such functional groups are formed on the surface of the substrate, the adhesion between the layer (c) and the substrate (s) can be further improved.

After applying the composition for layer (c) formation, the coating layer of the composition for formation of layer (c) is dried by standing at room temperature and in the atmosphere, for example, for 10 seconds or more (usually less than 24 hours), Instead, the above-mentioned layer (c) can be formed from this coating layer. In the present invention (the first aspect), the normal temperature is in the range of 5 to 60°C, preferably 15 to 40°C. The humidity condition when standing at room temperature can be set to 50~90%RH. Also, after coating the layer (c) forming composition, it may be heated to a temperature exceeding 60°C (usually below 100°C, and may be below 80°C) and kept for 10 seconds to 60 minutes (preferably 20°C). minutes to 40 minutes).

Next, the water-repellent layer-forming composition (1) is applied to the coated surface of the above-mentioned layer (c)-forming composition, and dried, whereby the coating of the above-mentioned water-repellent layer-forming composition (1) can The cloth layer forms the above-mentioned water-repellent layer (r).

The composition (1) for forming a water-repellent layer is a mixed composition of an organosilicon compound (A), and can be obtained by mixing an organosilicon compound (A). Moreover, when mixing components other than an organosilicon compound (A), the composition (1) for water-repellent layer formation is obtained by mixing the said organosilicon compound (A) and other components. The composition (1) for water-repellent layer formation also includes what reacts after mixing, for example, in storage. As an example of the reaction, for example, hydrolyzable gene hydrolysis in which the above-mentioned composition for forming a water-repellent layer (1) contains a silicon atom (may also be bonded via a linking group) bonded to the above-mentioned organosilicon compound (A) A compound (hereinafter sometimes referred to as a hydrolyzate of an organosilicon compound (A)) that becomes a -SiOH group (Si and OH may also be bonded via a linking group). In addition, the above-mentioned composition (1) for forming a water-repellent layer may also include a condensate containing an organosilicon compound (A). As the condensate, for example, a -SiOH group or The -SiOH group of the organosilicon compound (A) produced by hydrolysis (Si and OH can also be bonded through the linking group) and the -SiOH group derived from the organosilicon compound (A) (Si and OH can also be bonded through the linking group) ), or the dehydration condensate formed from the dehydration condensation of -SiOH group of 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 preferably 0.5% by mass when the entire composition (1) for forming a water-repellent layer is 100% by mass. % or less, more preferably 0.3 mass % or less.

It is preferable that the said composition (1) for water-repellent layer formation mixes the said organosilicon compound (A) and organosilicon compound (B). Thereby, the water-repellent layer (r) can contain a structure derived from the organosilicon compound (B). The above-mentioned water-repellent layer-forming composition (1) is as described above, and also includes a mixture of the organosilicon compound (A) and the organosilicon compound (B) used if necessary, and then reacts. As an example of performing the reaction, The above-mentioned water-repellent layer-forming composition (1) contains a compound (hereinafter sometimes referred to as organosilicon compound (B)) that hydrolyzes the silicon atom bonded to the above-mentioned organosilicon compound (B) to form a -SiOH group. hydrolyzate). In addition, the above-mentioned water-repellent layer-forming composition (1) may also include a condensate containing an organosilicon compound (B), and the condensate may include -SiOH groups or hydrolyzed A dehydration condensate formed by the dehydration condensation of the -SiOH group of the organosilicon compound (B) and the -SiOH group derived from the organosilicon compound (B) or the -SiOH group derived from other compounds.

The amount of the organosilicon compound (B) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and preferably 0.3% by mass when the entire composition (1) for forming a water-repellent layer is 100% by mass % or less, more preferably 0.2 mass % or less.

The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) in the composition (1) for forming a water-repellent layer is preferably at least 0.2, more preferably at least 0.4, more preferably at most 3.0, and more preferably at least 0.4. Preferably below 1.5.

The said composition (1) for water-repellent layer formation may further mix an organosilicon compound (C). In this case, the water-repellent layer forming composition (1) can be obtained by mixing an organosilicon compound (A), an organosilicon compound (C), and other components used as needed. As mentioned above, the water-repellent layer-forming composition (1) also includes those that are mixed and then reacted. As an example of the reaction, the above-mentioned water-repellent layer-forming composition (1) includes the above-mentioned organosilicon compound (C ) hydrolyzate or dehydration condensate. The amount of the organosilicon compound (C) when the entire composition (1) for forming a water-repellent layer is 100% by mass is preferably at most 0.1% by mass, more preferably at most 0.01% by mass, and most preferably at most 0% by mass , that is, preferably not mixed with the organosilicon compound (C).

The above composition (1) for forming a water-repellent layer usually contains 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, a fluorinated alcohol-based solvent, etc., and a boiling point of 100° C. or higher is particularly preferable. . Fluorinated ether solvents are preferably hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl having 2 to 6 carbon atoms)-alkyl (especially methyl or ethyl) ethers, for example, ethyl Nonafluorobutyl ether or ethyl nonafluoroisobutyl ether. As ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether, for example, Novec (registered trademark) 7200 (manufactured by 3M Company, molecular weight about 264) may be mentioned. Fluorinated amine solvents are preferably amines in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, preferably all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (especially a perfluoroalkyl group) The tertiary amine specifically includes tris(heptafluoropropyl)amine, and Fluorinert (registered trademark) FC-3283 (manufactured by 3M Company, molecular weight about 521) corresponds to this. Examples of fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane and perfluorohexane, 1,3-bis(trifluoromethylbenzene ) and other fluorinated aromatic hydrocarbon solvents. As 1,1,1,3,3-pentafluorobutane, Solve 55 (made by Solvex Corporation) etc. are mentioned, for example. Examples of fluorinated alcohol-based solvents include: 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2 ,3,3,4,4,5,5-Octafluoro-1-pentanol, 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-1 -Heptanol, perfluorooctyl ethanol, 1H,1H,2H,2H-tridecafluoro-1-n-octanol, etc.

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

As the solvent (D), it is preferable to use at least an amine fluoride solvent. Also, as the solvent (D), it is preferable to use two or more kinds of fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (especially a fluorinated aliphatic hydrocarbon-based solvent).

The amount of the solvent (D) when the whole composition (1) for water-repellent layer formation is 100 mass % is preferably at least 80 mass %, more preferably at least 90 mass %, still more preferably at least 95 mass % , and more preferably at least 98% by mass, and may be at most 99.9% by mass.

In addition, the composition (1) for forming a water-repellent layer may contain a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a photostabilizing Agents, antifungal agents, antibacterial agents, antiviral agents, anti-fouling agents, deodorants, pigments, flame retardants, antistatic agents and other additives. The amount of the above-mentioned additive is preferably at most 5 mass %, more preferably at most 1 mass %, based on 100 mass % of the water-repellent layer-forming composition (1).

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

After applying the composition (1) for forming a water-repellent layer, the layered body (1) can be produced by allowing to stand at room temperature and in the atmosphere, for example, for 10 seconds or more (usually 24 hours or less). The humidity condition when standing at room temperature can be set to 50~90%RH. Also, after coating the composition (1) for forming a water-repellent layer, it may be heated to a temperature exceeding 60°C (usually below 100°C, and may be below 80°C) and kept for 10 seconds to 60 minutes (preferably 20 minutes to 40 minutes).

1-5-2. Manufacturing method of laminate (2) When the laminated body of the present invention (first aspect) is the laminated body (2), the method for manufacturing the laminated body (2) includes: (i) coating the combination for forming a water-repellent layer on the substrate (s) (hereinafter, the water-repellent layer-forming composition used to manufacture the laminate (2) is referred to as the water-repellent layer-forming composition (2)); and (ii) making the above-mentioned water-repellent layer-forming composition ( 2) The step of hardening.

The composition (2) for forming a water-repellent layer is a mixed composition of an organosilicon compound (A), preferably a mixed composition of an organosilicon compound (A) and an optionally used organosilicon compound (B), or an organosilicon compound (A) A mixed composition of compound (A), organosilicon compound (C) and optionally used organosilicon compound (B). The water-repellent layer-forming composition (2) can be obtained by mixing the organosilicon compound (A), and when mixing components other than the organosilicon compound (A), it can be obtained by mixing the above-mentioned organosilicon compound ( A) Obtained by mixing with other ingredients. The composition (2) for water-repellent layer formation also includes what reacts after mixing, for example, in storage. As an example of carrying out the reaction, for example, the above-mentioned water-repellent layer-forming composition (2) includes a hydrolyzate of the organosilicon compound (A), a dehydration condensate of the organosilicon compound (A), and a composition of the organosilicon compound (C). Hydrolyzate, or dehydration condensate of organosilicon compound (C), etc.

The amount of the organosilicon compound (A) is preferably at least 0.01% by mass, more preferably at least 0.02% by mass, and still more preferably at least 0.03% by mass, when the entire composition (2) for forming a water-repellent layer is 100% by mass % or more, and preferably at most 0.5% by mass, more preferably at most 0.3% by mass.

The amount of the organosilicon compound (C) is, for example, 0.005% by mass or more, preferably 0.01% by mass or more, more preferably 0.03% by mass or more when the entire composition (2) for forming a water-repellent layer is 100% by mass , and more preferably at least 0.05% by mass, and more preferably at most 1% by mass, more preferably at most 0.5% by mass, still more preferably at most 0.3% by mass.

Furthermore, the mass ratio of the organosilicon compound (C) to the organosilicon compound (A) is preferably at least 10% by mass, more preferably at least 15% by mass, further preferably at least 20% by mass, still more preferably at least 50% by mass The above is preferably at least 80% by mass, and is preferably at most 200% by mass, more preferably at most 150% by mass, may be at most 45% by mass, and may be at most 30% by mass.

The said composition (2) for water-repellent layer formation may further mix an organosilicon compound (B). The above-mentioned water-repellent layer-forming composition (2) is as described above, and is prepared by mixing the organosilicon compound (A), the organosilicon compound (C) if necessary, and the organosilicon compound (B) if necessary. For the reactant, as an example of performing the reaction, a hydrolyzate or a dehydration condensate containing the above-mentioned organosilicon compound (B) can be mentioned, for example, in the composition (2) for forming a water-repellent layer. In the case of using the organosilicon compound (B), the amount of the organosilicon compound (B) when the entire water-repellent layer-forming composition (2) is 100% by mass is, for example, 0.01% by mass or more, preferably 0.01% by mass or more. 0.03% by mass or more, and preferably at most 0.3% by mass, more preferably at most 0.2% by mass.

The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) in the composition (2) for forming a water-repellent layer is preferably at least 0.05, more preferably at least 0.08, still more preferably at least 0.10, and, Preferably it is 2.0 or less, more preferably 1.0 or less, still more preferably 0.6 or less.

The above composition (2) for forming a water-repellent layer usually contains a solvent (D). The solvent (D) is the same as described above, and its preferred aspects are also the same. The amount of the solvent (D) when the whole composition (2) for forming a water-repellent layer is 100% by mass is preferably at least 80% by mass, more preferably at least 90% by mass, still more preferably at least 95% by mass , and more preferably at least 98% by mass, and may be at most 99.9% by mass.

Also, when the composition for forming a water-repellent layer is a mixed composition of an organosilicon compound (A) and an organosilicon compound (C), the solvent (D) also preferably contains a fluorine-based solvent (D1) and a non-fluorine system solvent (D2).

The fluorine-based solvent (D1) may, for example, be the same as those described above as the fluorine-based solvent, and among them, it is preferable to use a fluorinated ether-based solvent. The amount of the fluorine-based solvent (D1) when the whole composition (2) for water-repellent layer formation is 100 mass % is preferably at least 50 mass %, more preferably at least 60 mass %, still more preferably at least 70 mass % % or more, and, for example, may be 99% by mass or less, or may be 95% by mass or less.

As the non-fluorine-based solvent (D2), water; alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol (isopropanol), and 1-butanol; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone; ether solvents such as diethyl ether, dipropyl ether, tetrahydrofuran, and 1,4-dioxane; aliphatic hydrocarbon solvents such as pentane and hexane; or aliphatic solvents such as cyclohexane Hydrocarbon-based solvents such as cyclic hydrocarbon-based solvents; ester-based solvents such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, and isoamyl acetate, etc. The amount of the non-fluorinated solvent (D2) when the whole composition (2) for water-repellent layer formation is 100 mass % is preferably at least 5 mass %, more preferably at least 10 mass %, still more preferably 13 mass % % or more by mass, the upper limit may be, for example, 30% by mass or 25% by mass.

In addition, the composition (2) for forming a water-repellent layer may contain a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a photostabilizing Agents, antifungal agents, antibacterial agents, antiviral agents, anti-fouling agents, deodorants, pigments, flame retardants, antistatic agents and other additives. The amount of the above-mentioned additive is preferably at most 5 mass %, more preferably at most 1 mass %, based on 100 mass % of the water-repellent layer-forming composition (2).

Before coating the above-mentioned water-repellent layer-forming composition (2), it is preferable to give an easy-adhesive treatment to the coated surface of the substrate (s). The above-mentioned easy-bonding treatment is the same as the above-mentioned easy-bonding treatment. The adhesiveness between the water-repellent layer (r) and the substrate (s) can be further improved by applying an easy-adhesive treatment to the coated surface of the substrate (s).

As a method of coating the composition (2) for water-repellent layer formation, the method similar to the method demonstrated as the method of coating the said composition (1) for water-repellent layer formation is mentioned. After applying the composition (2) for forming a water-repellent layer, the layered product of the present invention (first aspect) can be produced by allowing it to stand at room temperature and in the air for at least 10 seconds (usually less than 24 hours). . The humidity condition when standing at room temperature can be set to 50~90%RH. Also, after coating the composition (2) for forming a water-repellent layer, it may be heated to a temperature exceeding 60°C (usually below 100°C, and may be below 80°C) and kept for 10 seconds to 60 minutes (preferably 20 minutes to 40 minutes).

Furthermore, as described above, in the aspect of producing a laminate through the step of applying the composition for forming a water-repellent layer on the substrate (s) and the step of hardening the composition for forming a water-repellent layer, in When the composition for forming the water-repellent layer is a mixed composition of the organosilicon compound (A) and the organosilicon compound (C), the hardened layer formed on the substrate (s) may be derived from the mixed presence of the organosilicon compound The structure of (A) and the water-repellent layer (r) derived from the structure of organosilicon compound (C) can also be the water-repellent layer (r) comprising the structure derived from organosilicon compound (A) and the structure derived from organic silicon compound (C). The layer (c) of the structure of the silicon compound (C) is obtained by layer separation. The said layer separation is easy to generate|occur|produce by adjusting the volatilization rate of the solvent contained in the composition for water-repellent layer formation. As a method of adjusting the volatilization rate of the solvent, it is important to appropriately adjust the humidity conditions, for example, when the composition for forming a water-repellent layer is formed into a film or heated and dried, and the relative humidity is preferably set to 35% or more, more preferably 40% or more, and may be 60% or less, or may be 50% or less.

(Form for implementing the invention related to the second aspect) The laminate (second aspect) of the present invention is a laminate comprising a conductive substrate (s), a layer (c) containing nitrogen, and a layer (r) containing fluorine, and the layer (c) It is provided between the above-mentioned substrate (s) and the above-mentioned layer (r). Hereinafter, the substrate (s), the layer (r) containing fluorine element, and the layer (c) containing nitrogen element will be described respectively.

2-1. Substrate(s) The material and thickness of the base material (s) can all refer to the material and thickness of the base material (s) described in the above 1-1, and the preferred range is also included.

The substrate (s) may be a single layer or a multilayer of two or more layers. When the substrate (s) is multilayered, the substrate (s) preferably has a multilayer structure in which a surface layer (s2) different from the layer (s1) is provided on a matrix layer (s1). The surface layer (s2) is a layer present on the side closest to the layer (r) in the substrate (s). When the substrate (s) includes a layer (s1) and a surface layer (s2), the layered system of the present invention (second aspect) will layer (s1), surface layer (s2), layer (c) containing nitrogen The layers (r) containing fluorine element are sequentially laminated. Hereinafter, the surface layer (s2) is also simply referred to as "layer (s2)".

2-1-1. Layer (s1) The material of layer (s1) can be any one of the above-mentioned organic materials and inorganic materials, preferably an organic material, more preferably a resin, and the specific resin is the same as the resin exemplified in 1-1-1 above.

The thickness of the layer (s1) can refer to the thickness of the layer (s1) described in the above-mentioned 1-1-1, and a preferable range is also included.

2-1-2. Layer (s2) Regarding the layer (s2), you can refer to the description of the group (X1) and the group (X2) and the description of the thickness of the layer (s2) described in the above 1-1-2 of the first aspect, the preferred range or its effect You can also refer to them all.

In the case where the layer (s2) includes a layer formed of at least one layer selected from the above-mentioned group (X1), the layer (s2) can function as a hard coat layer (hc) having surface hardness. Regarding the hard coat layer The hardness, layer structure, specific resin and formation method of (hc) can all refer to the content related to the hard coating (hc) described in the above 1-1-2 of the first aspect, and the effect In the description, the "water-repellent layer (r)" of the first aspect in the description of 1-1-2 above can be renamed as "layer (r)" in the second aspect. Furthermore, when the antistatic agent (AS) described below is included in the layer (s2), a composition in which the antistatic agent (AS) is added to the composition containing the above-mentioned reactive material may be used.

When the layer (s2) includes a hard coat layer (hc), the hard coat layer (hc) may contain additives, and the descriptions related to the additives and the descriptions related to the thickness of the hard coat layer (hc) also include effects , all can refer to the content recorded in the layer (s2) of the above-mentioned 1-1-2 of the first aspect. Furthermore, in the description of the effects, the "water-repellent layer (r)" of the first aspect in the description of 1-1-2 above can be renamed as "layer (r)" in the second aspect.

When the layer (s2) includes a layer formed of at least one layer selected from the above group (X2), the layer (s2) can function as an anti-reflection layer (ar) that prevents reflection of incident light, All the descriptions related to the anti-reflection layer (ar) can refer to the content described in the above 1-1-2 of the first aspect.

The layer (s2) may comprise a hard coat (hc), may also comprise an anti-reflection layer (ar), may also comprise both a hard coat (hc) and an anti-reflection layer (ar), preferably at least comprises a hard coat Layer (hc), preferably layer (s2), is a hard coat layer. When the layer (s2) includes both the hard coat layer (hc) and the antireflection layer (ar), it is preferable to laminate the antireflection layer (ar) on the layer (r) side.

2-1-3. Conductivity of substrate(s) In the present invention (second aspect), the substrate (s) has conductivity, and it is preferable to exhibit conductivity by including an antistatic agent (AS) in the substrate (s). When the base material (s) contains the antistatic agent (AS) and the base material (s) is multi-layered with two or more layers, the antistatic agent (AS) may be included in any layer, or may be included in all layers . Especially when the substrate (s) is a multilayer structure in which a surface layer (s2) different from the layer (s1) is provided on the layer (s1) to be the matrix, the antistatic agent (AS) can be included in the layer (s1 ), may also be contained in the surface layer (s2), and is preferably contained in the surface layer (s2). When the antistatic agent (AS) is included in the surface layer (s2), it is preferred that the surface layer (s2) is a hard coat layer, more preferably the hard coat layer is selected from acrylic resins, polysiloxane resins and At least one of the group consisting of epoxy-based resins.

Examples of antistatic agents (AS) include: surfactants, conductive polymers, conductive particles, ionic compounds (i.e., salts), conjugated polymers with acceptors and/or donors introduced therein, etc. . One or more of these antistatic agents are used in combination.

The surfactant may, for example, be a hydrocarbon-based surfactant, a fluorine-based surfactant or a silicone-based surfactant.

The conductive polymer may, for example, be polyaniline, polypyrrole, polyacetylene or polythiophene.

Examples of conductive particles include metal oxides that may be doped with phosphorus or antimony, such as inorganic oxides such as indium-tin-composite oxide (ITO) and antimony-doped tin oxide (ATO). particle.

The ionic compound is preferably an ionic compound having a cationic organic group or an anionic organic group, for example, an alkali metal salt and/or an organic cation-anion salt. An organic cation-anion salt is a salt that includes a cation part and an anion part and the above-mentioned cation part is an organic substance, and the anion part can be organic or inorganic. Specifically, it can be exemplified: quaternary ammonium salt, pyridinium salt, Cationic compounds having various cationic organic groups, such as compounds with primary to tertiary amino groups. The anion portion of the organic cation-anion salt is preferably a halogen atom. Moreover, the anion part of an alkali metal salt may contain an organic substance, and may contain an inorganic substance, Preferably an anion part contains an organic substance. Examples of the alkali metal salt containing an organic substance in the anion portion include anionic compounds having anionic organic groups such as sulfonate groups, sulfate ester groups, phosphate ester groups, and phosphonate groups. As the ionic compound, a compound obtained by further increasing the molecular weight of the compounds exemplified above may be mentioned.

The antistatic agent is preferably an ionic compound, especially useful is an ionic compound that is easily affected by the external environment such as an alkali metal salt and/or a salt of an organic cation and anion, and is preferably a quaternary ammonium salt , pyridinium salt, and at least one of compounds having primary to tertiary amino groups, and more preferably a quaternary ammonium salt. The quaternary ammonium salt may be a salt of quaternary ammonium and an acid or a halogen, and the acid is preferably mainly a halogen acid such as sulfonic acid or hydrochloric acid. The quaternary ammonium salt is also preferably a compound represented by the following formula (as1).

The antistatic agent (AS) is more preferably a quaternary ammonium salt represented by formula (as1) (hereinafter sometimes referred to as a quaternary ammonium salt (as1)).

[chemical 20]

[R ^k1 to R ^k3 , R ^k4 and R ^k5 , Y ^k1 and Y ^k2 , A ^k1 and A ^k2 , Z ^k1 , k3, k4k5, n, X in formula (as1) and the above formula (k1) etc. have the same meaning, including the preferred range, and the items described in the above formula (k1) can be referred to. Furthermore, in the above-mentioned formula (k1), the formula (ki) can be changed to the formula (as-i).

[chem 21]

[In the formula (as-i), R ^k17 to R ^k19 independently represent a hydrocarbon group with 1 to 30 carbons, and * represents a bond with Y ^k2 ]]

The quaternary ammonium salt (as1) is more preferably a compound represented by formula (as1-1).

[chem 22]

In formula (as1-1), R ^k11 to R ^k16 , Y ^k11 and Y ^k12 , A ^k11 to A ^k14 , k13 and X have the same meanings as those in the above formula (k1-1), including preferred ones Within the range, the items described in the above formula (k1-1) can be referred to.

The quaternary ammonium salt (as1) is also more preferably a compound represented by the formula (as1-2).

[chem 23]

In formula (as1-2), R ^k21 ~ R ^k23 , R ^k24 , Y ^k21 , A ^k21 , k21 and X have the same meanings as those in formula (k1-2) above, including preferred ranges , you can refer to the items described in the above formula (k1-2).

As the quaternary ammonium salt (as1), it is preferable to use at least the compound represented by the formula (as1-1) and/or the compound represented by the formula (as1-2).

The content of the antistatic agent (AS) is preferably at least 0.001% by mass, more preferably at least 0.005% by mass, further preferably at least 0.01% by mass, and more preferably 50% by mass in 100% by mass of the substrate (s). Mass % or less, More preferably, it is 25 mass % or less, More preferably, it is 10 mass % or less. Also, when the substrate (s) is a multilayer structure in which a surface layer (s2) different from the layer (s1) is provided on the layer (s1) to be the matrix, the layer (s1) and the surface layer (s2) can be Include antistatic agent in two layers, and adjust the content of antistatic agent (AS) in two layers to the above-mentioned range, also can include antistatic agent in any one of them layer, will contain the antistatic agent in the layer of antistatic agent The content of the antistatic agent (AS) is adjusted to the above range, and it is more preferable to only include the antistatic agent in the surface layer (s2), and adjust the content of the antistatic agent (AS) in the surface layer (s2) to the above range.

In addition, in the substrate (s), in addition to the antistatic agent (AS), it is also preferred to disperse inorganic particles, organic particles, rubber particles, and may also contain coloring agents such as pigments or dyes, fluorescent whitening Agents, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents and other formulations. The content of the compounding agent other than the antistatic agent (AS) in the base material (s) is in 100 mass % of the base material (s), preferably 5 mass % or less, more preferably 3 mass % or less, still more preferably 1% by mass or less.

2-2. Layer containing fluorine element (r) The layer (r) containing fluorine usually has water repellency, and is preferably the outermost layer on the opposite side of the substrate (s) in the laminate.

The thickness of the layer (r) is preferably from 1 nm to 20 nm, more preferably from 1 nm to 15 nm, still more preferably from 2 nm to 10 nm, especially preferably from 3 nm to 8 nm. By setting the thickness of the layer (r) to a predetermined value or more, in addition to water repellency, it is also excellent in scratch resistance, which is preferable in this respect, and by making the above-mentioned thickness below a predetermined value, the laminated body The surface prevents electrification.

The thickness of the layer (r) can be adjusted by the concentration of the solid content in the layer (r) forming composition or the coating conditions of the layer (r) forming composition. The thickness of layer (r) can be measured by ellipsometer or X-ray reflection measurement, scanning transmission electron microscope (STEM) measurement of cross-sectional direction, X-ray photoelectron spectroscopy (XPS), probe type film profiler, etc. The measurement method can be appropriately selected according to the material or thickness of each layer.

In the STEM measurement of the cross-sectional direction, the laminate is sliced so as to include a surface parallel to the thickness direction of the substrate (s), and an ultrathin section is cut out, and the ultrathin section is observed with a scanning transmission electron microscope (STEM). Cross-section of a slice, whereby the thickness of layer (r) can be determined. As a method for thinning the laminate, any ultrathin sections with a thickness of 100 nm or less may be processed, and examples thereof include focused ion beam processing, ultramicrotome processing, and cryo-ultramicrotome processing. For example, when using the focused ion beam processing method, the ion source is preferably Ga, and the accelerating voltage is preferably set to about 30 kV. In the case of STEM observation, it is preferable to set the accelerating 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 STEM observation, in order to easily distinguish the interface between layer (r) and the outside world, the upper surface of layer (r) may be blackened with a felt pen or the like before thinning, and then measured.

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 substrate (s), as described in the Examples described below. Specifically, using glass as the material of the substrate (s), prepare a plurality of (preferably more than 3) laminate samples with the same thickness of the layer (c) and different thicknesses of the layer (r), and use an ellipsometer Resolution measures the thickness of layer (r). In addition, this sample was subjected to XPS measurement to find the ratio of the specific element amount derived from layer (r) to the specific element amount derived from layer (c), and to prepare the above-mentioned ratio with respect to the thickness of layer (r). Calibration curve. Then, by performing XPS measurement on the actually obtained laminate, the ratio of the specific element amount originating from layer (r) to the specific element amount originating from layer (c) can be obtained, and the layer (r) the thickness.

Furthermore, when the material of the substrate (s) is an organic material, the difference in refractive index between the substrate (s) and the layer (r) is small, so it may be difficult to measure the film thickness with an ellipsometer. In this case, STEM measurement in the cross-sectional direction or measurement using the above-mentioned calibration curve may be performed.

Furthermore, layer (r) is preferably a cured layer of organosilicon compound (A) containing fluorine element. When the layer (r) is a cured layer of the organosilicon compound (A), good water repellency can be imparted even as a thin film (the layer (r) may be referred to as a "water repellent layer" hereinafter). The above-mentioned organosilicon compound (A) is preferably an organosilicon compound (A) containing fluorine element and having a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded via a linking group or not. The hardened layer of the organosilicon compound (A) can usually be obtained by coating the mixed composition of the organosilicon compound (A) and curing it, that is, the layer (r) is a mixed composition of the organosilicon compound (A) hardened layer. Hereinafter, the mixed composition of the organosilicon compound (A) may be referred to as the composition for water-repellent layer formation.

When the layer (r) is a cured layer of a mixed composition of an organosilicon compound (A) containing fluorine and having a silicon atom bonded to a hydrolyzable group or a hydroxyl group via a linking group or not via a linking group, the layer (r) has a structure derived from the organosilicon compound (A). The organosilicon compound (A) has a hydrolyzable group or a hydroxyl group bonded to a silicon atom (it can also be bonded through a linking group). When hardening, the -SiOH group possessed by the organosilicon compound (A) or the organic The -SiOH group of the silicon compound (A) (Si and OH can also be bonded through a linking group) and the -SiOH group derived from the organosilicon compound (A) (Si and OH can also be bonded through a linking group), derived from other The -SiOH group of the compound, or the active hydrogen (hydroxyl group, etc.) on the surface (preferably layer (c)) forming the layer (r) in the laminate is dehydrated and condensed. Therefore, layer (r) preferably has a condensation structure derived from organosilicon compound (A).

2-2-1. Organosilicon compound (A) In a preferred aspect, the organosilicon compound (A) is a silicon atom having a hydrolyzable group or a hydroxyl group (hereinafter referred to as a reactive group (h3)) bonded via a linking group or not via a linking group compound. The above reactive group (h3) has the same meaning as the reactive group (h3) described in the above 1-2-1 of the first aspect.

The organosilicon compound (A) preferably contains a fluoropolyether structure in addition to the above-mentioned silicon atoms, and all the descriptions related to the fluoropolyether structure can refer to the description in the first aspect.

In the aspect where the organosilicon compound (A) includes a fluoropolyether structure, a silicon atom, and a reactive group (h3), it is preferable to have one of the valent groups of the oxygen atom of the fluoropolyether structure at the end of the bonding bond side ( Hereinafter referred to as FPE group) and the silicon atom are bonded via a linking group or not, and the silicon atom and the reactive group (h3) are bonded via a linking group or not. In the case where the above-mentioned FPE group and the silicon atom are bonded via a linking group, the silicon atom bonded to the above-mentioned reactive group (h3) via a linking group or not via a linking group may exist in a molecule of the organosilicon compound (A) 1 or plural, and the number is, for example, 1 or more and 10 or less.

The above-mentioned FPE group can also refer to the description of the FPE group of the first aspect, preferably, all the fluorine-containing groups contained in the above-mentioned FPE group can refer to the description of the first aspect of the fluorine-containing group.

The above-mentioned reactive group (h3) may be bonded to the silicon atom through a linking group, or may be directly bonded to the silicon atom without a linking group, and is preferably directly bonded to the silicon atom. The number of reactive groups (h3) bonded to one silicon atom may be at least one, and may be 2 or 3, preferably 2 or 3, and especially preferably 3. When the number of reactive groups (h3) bonded to one silicon atom is 2 or less, a valent group other than the reactive group (h3) may be bonded to the remaining bonds, for example, an alkane may be bonded group (especially an alkyl group with 1 to 4 carbon atoms), H, NCO, etc.

The above organosilicon compound (A) is preferably a compound represented by the above formula (a1) described in the first aspect.

The organosilicon compound (A) is preferably represented by the above formula (a2) described in the first aspect.

More specifically, the organosilicon compound (A) may, for example, be a compound represented by the above formula (a3) described in the first aspect, or a compound represented by the above formula (a4).

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

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

In layer (r), the structure derived from the organosilicon compound (A) preferably contains at least 50% by mass, more preferably at least 60% by mass, and may be 100% by mass, preferably at most 95% by mass, Furthermore, it is more preferable that it is 90 mass % or less. Here, the structure derived from the organosilicon compound (A) refers to the organosilicon compound (A) and the residue after dehydration condensation of the organosilicon compound (A).

2-2-2.Organosilicon compound (B) Layer (r) may have the above-mentioned structure derived from the organosilicon compound (A), and the structure described in the first aspect derived from the organosilicon compound (B) represented by the above formula (b1), and may also refer to the formula The preferred range of (b1). The layer (r) having a structure derived from the organosilicon compound (A) and a structure derived from the organosilicon compound (B) can be mixed with the organosilicon compound (B) by coating the composition for forming a water-repellent layer. ) and obtained by hardening the mixed composition.

The organosilicon compound (B), as described below, has a hydrolyzable group or a hydroxyl group bonded to a silicon atom. Generally, the -SiOH group of the organosilicon compound (B) or the -SiOH group of the organosilicon compound (B) produced by hydrolysis SiOH group and -SiOH group derived from organosilicon compound (B), -SiOH group derived from other compounds, or active hydrogen (hydroxyl group) on the surface of layer (r) (especially layer (c)) in the laminate etc.) dehydration condensation, so in a preferred aspect, the layer (r) has a dehydration condensation structure derived from the organosilicon compound (A) and a dehydration condensation structure derived from the organosilicon compound (B). Since the layer (r) has a dehydration condensation structure derived from the organosilicon compound (B), the sliding properties of water droplets and the like are further improved.

(C _j F _{2j + 1} -Si-(OCH ₃ ) ₃ , C _j F _{2j + 1} -Si-(OC ₂ H ₅ ) ₃ (j is Integers of 1 to 12), etc.) can also all refer to those exemplified in the first aspect.

Among the compounds represented by the above formula (b1), the compound represented by the above formula (b2) described in the first aspect is preferable.

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

When the layer (r) contains the structure derived from the organosilicon compound (B), the structure derived from the organosilicon compound (B) preferably contains 3% by mass or more in the layer (r), more preferably 5% by mass % or more, more preferably at least 10 mass %, and preferably at most 50 mass %, more preferably at most 40 mass %. Here, the structure derived from the organosilicon compound (B) refers to the organosilicon compound (B) and the residue after dehydration condensation of 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 at least 0.05, more preferably at least 0.08, further preferably at least 0.10, and , preferably 2.0 or less, more preferably 1.0 or less, further preferably 0.6 or less.

In addition, layer (r) may contain silanol condensation catalyst, antioxidant, antirust agent, ultraviolet absorber, light stabilizer, antifungal agent, antibacterial agent, antiviral agent, anti-fouling agent, deodorant, pigment, flame retardant, antistatic agent and other additives. The amount of the above-mentioned additives, that is, the amount of solid content other than the solid content derived from the organosilicon compounds (A) and (B), in layer (r) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less .

2-3. Layer (c) containing nitrogen element The layer (c) containing nitrogen element is arranged between the substrate (s) and the layer (r) containing fluorine element. By disposing the layer (c) between the substrate (s) and the layer (r), the adhesion of the layer (r) becomes good, the scratch resistance is improved, and the deterioration of the antistatic property after the heat resistance test can be suppressed . A layer other than the nitrogen element-containing layer (c) may also be provided between the substrate (s) and the fluorine element-containing layer (r), preferably the layer (c) and the layer (r) are not separated through other layers Direct lamination whereby layer (c) can function as an undercoat layer for layer (r). Moreover, it is more preferable that no other layers are present between the layer (c) and the layer (r), and between the layer (c) and the substrate (s), and they are directly laminated.

The thickness of layer (c) is preferably not more than 30 nm, more preferably not more than 25 nm, still more preferably not more than 20 nm. Scratch resistance can be further improved by making the thickness of a layer (c) into predetermined|prescribed or less. The lower limit of the thickness of the layer (c) is not particularly limited, for example, it is 3 nm.

The thickness of the layer (c) can be adjusted by the concentration of the solid content in the layer (c) forming composition or the coating conditions of the layer (c) forming composition. The thickness of layer (c) can be measured by ellipsometer or X-ray reflection measurement, X-ray photoelectron spectroscopy (XPS), STEM measurement of cross-sectional direction, probe-type film profiler, etc. It can be measured according to the material or thickness of each layer Choose the measurement method appropriately. In the case of measuring the thickness of the layer (c) by STEM measurement in the cross-sectional direction, it can be measured by including a layer parallel to the thickness direction of the substrate (s) in the same way as the measurement of the thickness of the layer (r) above. The layered body is thinned by the surface method, and the ultra-thin section is cut out, and the cross-section of the ultra-thin section is observed and measured by STEM. It is also possible to form the coating layer (r) by using the same method as above. The layered intermediate before the composition (that is, the state where only the layer (c) is provided on the substrate (s)) is thinned, and the cross-section is observed and measured by STEM. Furthermore, in the case of STEM observation of the cross-section of the laminated intermediate, in order to easily distinguish the interface between the layer (c) and the outside world, the upper surface of the layer (c) can be blackened with a felt pen before thinning and then To measure.

Also, the total thickness of layer (c) and layer (r) is preferably less than 50 nm, more preferably 40 nm or less, further preferably 30 nm or less, particularly preferably 25 nm or less. By making the total thickness of a layer (c) and a layer (r) into predetermined|prescribed or less, scratch resistance can be improved more, and an external appearance becomes favorable, so it is preferable. Also, the total thickness of layer (c) and layer (r) is preferably at least 5 nm, more preferably at least 8 nm.

2-3-1.Organosilicon compound (C) Layer (c) is preferably a hardened layer of organosilicon compound (C) containing nitrogen. In this case, layer (c) can usually be coated with a mixed composition of organosilicon compound (C) (hereinafter sometimes It is obtained by making it harden|cure called layer (c) composition for formation). The organosilicon compound (C) is preferably a compound containing nitrogen and having a silicon atom bonded to a hydrolyzable group or a hydroxyl group, because the -SiOH group possessed by the organosilicon compound (C) or the hydrolyzable silicon atom bonded The -SiOH group of the organosilicon compound (C) produced by the hydrolysis of the group is dehydrated from the -SiOH group of the organosilicon compound (C), or the active hydrogen (hydroxyl group, etc.) on the surface of the layer (c) in the laminate Condensation, so the layer (c) may contain the dehydration condensate of the organosilicon compound (C) (ie, derived from the condensation structure of the organosilicon compound (C)). Furthermore, all the organosilicon compounds (C) contained in the layer (c) may be dehydration condensates.

In a preferred aspect, the number of silicon atoms bonded to hydrolyzable groups or hydroxyl groups (hereinafter referred to as reactive groups (h1)) in the organosilicon compound (C) is greater than that of the organosilicon compound (C)1 The molecular weight is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 2 to 5. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetyloxy group, an isocyanate group, and the like, preferably an alkoxy group, and more preferably an alkoxy group having 1 to 4 carbon atoms. Preferably, an alkoxy group or a hydroxyl group is bonded to the above-mentioned silicon atom, and an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms is particularly preferable.

The number of reactive groups (h1) bonded to one silicon atom may be 1 or more, may be 2 or 3, and is preferably 2 or 3.

The organosilicon compound (C) contains nitrogen element in addition to the silicon atom to which the reactive group (h1) is bonded, and preferably contains nitrogen element by having an amine group or an amine skeleton. The organosilicon compound (C) may have any one of an amine group and an amine skeleton, and preferably has both an amine group and an amine skeleton. As an organosilicon compound (C), it is preferable to have one or more amine skeletons. Furthermore, the aforementioned amine skeleton is represented by -NR ¹⁰ -, and R ¹⁰ is a hydrogen atom or an alkyl group. R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbons. Moreover, when the organosilicon compound (C) contains a plurality of amine skeletons, the plural amine skeletons may be the same or different.

The organosilicon compound (C) is preferably a compound without a fluoropolyether structure, more preferably a compound without a fluorine element.

The organosilicon compound (C) is preferably a compound represented by the above formula (c1) or (c2) described in the first aspect (organosilicon compound (C1) or (C2)). That is, the layer (c) containing nitrogen is preferably a cured layer of the organosilicon compound (C) represented by the above formula (c1) or (c2).

As in the first aspect, the organosilicon compound (C1) is preferably represented by the above formula (c1-2).

As for the organosilicon compound (C2), similarly to the first aspect, a compound represented by the above formula (c2-2) is preferable.

The structure derived from the organosilicon compound (C) is preferably contained in layer (c) at least 80% by mass, more preferably at least 90% by mass, still more preferably at least 98% by mass, and may be 100% by mass %.

In addition, the layer (c) may contain a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, antiviral agent, anti-fouling agent, deodorant, pigment, flame retardant, antistatic agent and other additives. The amount of the aforementioned additives, that is, the amount of solids other than those derived from the organosilicon compound (C), is preferably 0.1% by mass or less, more preferably 0.01% by mass or less in layer (c).

2-4. Characteristics of laminates 2-4-1. Antistatic performance When the surface resistivity measured on the surface of the layer (r) was measured before and after the heat resistance test in which the laminate of the present invention (second aspect) was kept at 80°C for 36 hours with the applied voltage set to 500 V, the heat resistance test The surface resistivity after the heat resistance test is preferably not more than 6.4 times, more preferably not more than 4.0 times, more preferably not more than 3.5 times, and most preferably not more than 3.3 times the surface resistivity before the heat resistance test. The lower limit is not particularly limited. , can be 1.0 times or 1.5 times. Furthermore, the surface resistivity before the heat resistance test is preferably the surface resistivity measured in the laminated body of the present invention (second aspect) managed in the range of about 0°C to 35°C.

The surface resistivity before the heat resistance test is, for example, 1.0×10 ¹¹ Ω/□ or less, preferably 5.0×10 ¹⁰ Ω/□ or less. The lower limit is not particularly limited, for example, it may be 1.0×10 ⁸ Ω/□, or it may be 1.0×10 ⁹ Ω/□.

2-4-2. Scratch resistance When performing an abrasion test in which the surface of layer (r) of the laminate of the present invention (second aspect) is reciprocally rubbed 1,500 times by applying a pressure of 250 g/cm ² with steel wool, Preferably, no damage is observed on the surface of layer (r) under LED (Light Emitting Diode, light emitting diode) illumination.

2-4-3. Dynamic friction coefficient The dynamic friction coefficient of the layer (r) surface of the laminate of the present invention (second aspect) is preferably 0.1 or less, more preferably 0.090 or less, further preferably 0.080 or less, and may be 0.010 or more.

2-5. Manufacturing method of laminated body A preferred method of manufacturing the laminate of the present invention (second aspect) includes: (i) the step of coating the layer (c) forming composition on the substrate (s); (ii) making the above-mentioned layer (c) A step of hardening the coating layer of the composition for formation; (iii) a step of coating the composition for forming a water-repellent layer on the surface coated with the composition for formation of the layer (c); and (iv) making the above-mentioned water-repellent layer In the step of hardening the coating layer of the composition for forming the above layer (c), the above layer (c) is formed from the coating layer of the composition for forming the layer (c), and the above layer is formed by the coating layer of the composition for forming the water repellent layer ( r).

The composition for forming the layer (c) is a mixed composition of the organosilicon compound (C). The mixed composition of organosilicon compound (C) can be obtained by mixing organosilicon compound (C), and in the case of mixing components other than organosilicon compound (C), it can be obtained by mixing organosilicon compound (C) with other Obtained by mixing ingredients. The layer (c) forming composition also includes those that react after mixing, for example, during storage. As an example of performing the reaction, the above-mentioned layer (c) forming composition includes the above-mentioned organic compound bonded in a preferred form. The hydrolyzable gene of the silicon atom of the silicon compound (C) is hydrolyzed to form a -SiOH group compound (hereinafter sometimes referred to as the hydrolyzate of the organosilicon compound (C)). In addition, as an example of carrying out the reaction, a condensate containing the above-mentioned organosilicon compound (C) in the composition for forming the layer (c) may be exemplified. As the condensate, - Dehydration condensation product formed by dehydration condensation of SiOH group or -SiOH group of organosilicon compound (C) generated by hydrolysis and -SiOH group derived from organosilicon compound (C) or -SiOH group derived from other compounds.

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

As the alcohol solvent, ketone solvent, ether solvent, hydrocarbon solvent, and ester solvent, the same ones as those exemplified for the solvent (E) of the first aspect can be used.

The amount of the organosilicon compound (C) when the entire composition for forming the layer (c) is 100% by mass is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and preferably 5% by mass % or less, more preferably 3 mass % or less, further preferably 1 mass % or less. The amount of the above organosilicon compound (C) can be adjusted during the preparation of the composition. In addition, the amount of the organosilicon compound (C) can also be calculated from the analysis results of the composition. As a specific method based on the analysis results of the composition, for example, the type of each compound contained in the composition can be analyzed by using gas chromatography-mass spectrometry or liquid chromatography-mass spectrometry, and the obtained The analysis results are identified by library search, and the amount of each compound contained in the composition can be calculated from the above analysis results using the calibration curve method. In addition, in this specification, when the range of the quantity of each component, mass ratio, or molar ratio is described, this range can be adjusted at the time of preparation of a composition. Also, the amount of the organosilicon compound (C) in the solid content of 100% by mass in the layer (c) forming composition is preferably at least 85% by mass, more preferably at least 95% by mass.

The amount of the solvent (E) when the whole composition for forming the layer (c) is 100% by mass is preferably at least 80% by mass, more preferably at least 85% by mass, still more preferably at least 90% by mass, More preferably, it is at least 95% by mass, still more preferably at least 98% by mass, and may be at most 99.9% by mass.

In addition, the layer (c) forming composition may be mixed with a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, Various additives such as fungicides, antibacterial agents, antiviral agents, antifouling agents, deodorants, pigments, flame retardants, and antistatic agents. The amount of the above-mentioned additives, that is, the amount of substances other than the organosilicon compound (C) and the solvent (E), is preferably 5% by mass or less, more preferably 1% by mass, in 100% by mass of the layer (c) forming composition. Mass% or less.

As a method of coating the composition for forming the layer (c), for example, a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, and a gravure coating method are mentioned. coating method, etc.

Before coating the composition for forming layer (c) above, it is preferable to perform an easy-adhesive treatment on the coated surface of the substrate (s) in advance, and the preferred easy-adhesive treatment and its effects are the same as those described in the first aspect or the same.

After applying the composition for layer (c) formation, the coating layer of the composition for formation of layer (c) is dried by standing at room temperature and in the atmosphere, for example, for 10 seconds or more (usually less than 24 hours), Instead, the above-mentioned layer (c) can be formed from this coating layer. In the present invention (second aspect), normal temperature is 5-60°C, preferably 15-40°C. The humidity condition when standing at room temperature can be set to 50~90%RH. In addition, after coating the layer (c) forming composition, it may be heated to a temperature exceeding 60°C (usually 120°C or lower, may be 100°C or lower, or may be 80°C or lower) and keep it for 10 seconds to 60 minutes (Preferably 30 seconds to 40 minutes).

Next, the composition for forming a water-repellent layer is applied to the coated surface of the composition for forming the layer (c) and dried, whereby the layer (r ).

The composition for forming a water-repellent layer is a mixed composition of an organosilicon compound (A), and can be obtained by mixing an organosilicon compound (A). Moreover, when mixing components other than an organosilicon compound (A), the composition for water-repellent layer formation can be obtained by mixing the said organosilicon compound (A) and other components. The said composition for water-repellent layer formation also includes what reacted after mixing, for example, in storage. As an example of the reaction, for example, the composition for forming a water-repellent layer may be hydrolyzed by a hydrolyzable gene containing a silicon atom (may also be bonded via a linking group) bonded to the above-mentioned organosilicon compound (A) to become- A compound of SiOH group (Si and OH may be bonded via a linking group) (hereinafter sometimes referred to as a hydrolyzate of organosilicon compound (A)). In addition, the above-mentioned composition for forming a water-repellent layer may also include a condensate containing an organosilicon compound (A). As the condensate, for example, a -SiOH group contained in the organosilicon compound (A) or a condensate produced by hydrolysis may be exemplified. The -SiOH group of the organosilicon compound (A) (Si and OH may also be bonded via a linking group) and the -SiOH group derived from the organosilicon compound (A) (Si and OH may also be bonded via a linking group), or Dehydration condensate formed by dehydration condensation of -SiOH group derived from other compounds.

The amount of the organosilicon compound (A) when the whole composition for forming a water-repellent layer is 100% by mass is, for example, at least 0.01% by mass, preferably at least 0.05% by mass, and preferably at most 0.5% by mass, More preferably, it is 0.3 mass % or less.

It is preferable that the said composition for water-repellent layer formation mixes the said organosilicon compound (A) and organosilicon compound (B). Thereby, layer (r) can comprise a structure derived from organosilicon compound (B). The composition for forming a water-repellent layer is as described above, and also includes a mixture of an organosilicon compound (A) and an optionally used organosilicon compound (B) followed by a reaction. As an example of carrying out the reaction, the above-mentioned water-repellent The composition for layer formation contains the compound which hydrolyzed the silicon atom bonded to the said organosilicon compound (B) and became -SiOH group by hydrolysis (it may be called the hydrolyzate of organosilicon compound (B) hereafter). In addition, the above-mentioned composition for forming a water-repellent layer may also include a condensate containing an organosilicon compound (B), and the condensate may include -SiOH groups possessed by the organosilicon compound (B) or those produced by hydrolysis. A dehydration condensate formed by dehydration condensation of -SiOH group of organosilicon compound (B) and -SiOH group derived from organosilicon compound (B) or -SiOH group derived from other compounds.

The amount of the organosilicon compound (B) when the entire composition for forming a water-repellent layer is 100% by mass is, for example, at least 0.01% by mass, preferably at least 0.03% by mass, and preferably at most 0.3% by mass, More preferably, it is 0.2 mass % or less.

The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) in the composition for forming a water-repellent layer is preferably at least 0.2, more preferably at least 0.4, and preferably at most 3.0, more preferably at least 1.5 the following.

Also, the total amount of the organosilicon compounds (A) and (B) when the entire composition for forming a water-repellent layer is 100% by mass is preferably at least 0.05% by mass, more preferably at least 0.10% by mass. Preferably it is 0.7 mass % or less, More preferably, it is 0.5 mass % or less, More preferably, it is 0.3 mass % or less. The total amount of the organosilicon compounds (A) and (B) when the total of the solids in the composition for forming a water-repellent layer is 100% by mass is preferably at least 85% by mass, more preferably at least 90% by mass , and more preferably at least 95% by mass.

The above composition for forming a water-repellent layer usually contains 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., and it is particularly preferable to use a boiling point of 100° C. or higher. Examples of the fluorinated ether-based solvent, fluorinated amine-based solvent, and fluorinated hydrocarbon-based solvent include the same ones as those exemplified for the solvent (D) of the first aspect.

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

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

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

In addition, the composition for forming a water-repellent layer may be mixed with a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal Various additives such as antibacterial agent, antiviral agent, antifouling agent, deodorant, pigment, flame retardant, antistatic agent, etc. The amount of the above-mentioned additives, that is, the amount of substances other than the organosilicon compounds (A), (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, and more preferably Preferably, it is 1% by mass or less.

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

After applying the water-repellent layer-forming composition, the layered product of the present invention (second aspect) can be produced by allowing to stand at room temperature in the air for at least 10 seconds (usually less than 24 hours). The humidity condition when standing at room temperature can be set to 50~90%RH. Also, after coating the composition for forming a water-repellent layer, it may be heated to a temperature exceeding 60°C (usually below 120°C, may be below 100°C, or may be below 80°C) and kept for 10 seconds to 60 minutes ( Preferably, it is about 30 seconds to 40 minutes).

3. Display device The laminates of the present invention (the first aspect and the second aspect) can be suitably used for display devices, especially for flexible display devices. The laminate of the present invention (the first aspect and the second aspect) is preferably used as a front panel in a display device, and the front panel may be called a window film in some cases.

The above-mentioned display device preferably includes a laminate for a display device including a window film (that is, the laminate of the present invention (the first aspect and the second aspect)) and an organic EL (Electroluminescence, electroluminescent) display panel. The laminate for display devices is arranged on the viewing side of the organic EL display panel. In addition, in the flexible display device, it is preferable to include a laminate for a flexible display device including a window film having a flexible property, and an organic EL display panel, and arrange the laminate for a flexible display device in a visually recognizable position relative to the organic EL display panel. The side is configured in a bendable manner. The laminate for a display device (preferably a laminate for a flexible display device) may further include a polarizer (preferably a circular polarizer), a touch sensor, etc. to form a touch panel display, and the lamination sequence of these is arbitrary , preferably a window film, a polarizer, and a touch sensor are laminated sequentially from the viewing side, or a window film, a touch sensor, and a polarizer are laminated in sequence. If the polarizing plate is present on the viewing side of the touch sensor, it becomes difficult to recognize the pattern of the touch sensor and the visibility of the display image becomes good, which is preferable. Each member can be laminated using an adhesive, an adhesive, or the like. In addition, the display device (preferably a flexible display device) may be equipped with a light-shielding pattern formed on at least one side of any layer of the above-mentioned window film, polarizer, and touch sensor.

(window film) The window film is arranged on the viewing side of the display device (preferably a flexible image display device), and plays a role in protecting other components from external impacts or environmental changes such as temperature and humidity. As such a protective layer, glass can be used. In a flexible image display device, the window film is not rigid and hard like glass, and a material having soft properties can be used. Therefore, when using the laminate of the present invention (the first aspect and the second aspect) as a window film in a flexible display device, the substrate (s) preferably has a layer including a flexible transparent substrate, The substrate (s) may also have a multilayer structure with a hard coat layer on at least one area.

The visible light transmittance of the transparent substrate is, for example, above 70%, preferably above 80%. Any transparent base material can be used as long as it is a transparent polymer film. Specifically, it may be a film formed of an unstretched, uniaxially or biaxially stretched film having a monolayer containing polyethylene, polypropylene, polymethylpentene, norbornene, or cycloolefin. Polyolefins such as cycloolefin derivatives of body units; (modified) celluloses such as diacetyl cellulose, triacetyl cellulose, and acryl cellulose; methyl methacrylate (co) Acrylics such as polymers; polystyrenes such as styrene (co)polymers; acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers, Polyvinyl chloride, polyvinylidene chloride; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate and other polyesters; Nylon and other polyamides; Polymers such as urethanes and epoxy resins. These polymers can be used alone or in combination of two or more. Among the transparent substrates described above, polyamide films, polyamideimide films or polyimide films, polyester films, and olefin films having excellent transparency and heat resistance are preferred. , Acrylic film, cellulose film. It is also preferable to disperse inorganic particles such as silicon dioxide, organic fine particles, rubber particles, etc. in the polymer film. Furthermore, coloring agents such as pigments or dyes, fluorescent whitening agents, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricating agents, etc. Agents, solvents and other preparations. The thickness of the above-mentioned transparent substrate is not less than 5 μm and not more than 200 μm, preferably not less than 20 μm and not more than 100 μm. Especially when used in a flexible image display device, the thickness of the above-mentioned transparent substrate is preferably not less than 5 μm and not more than 60 μm.

When using the laminated body of this invention (1st aspect and 2nd aspect) as a window film, the hard-coat layer is also the same as said hard-coat layer (hc). As described above, the hard coat layer (hc) is preferably formed of an active energy ray-curable resin and a thermosetting resin that can be reactive by including irradiation of active energy ray or thermal energy to form a crosslinked structure. It is formed by the hardening of the hard coating composition of the material. The above-mentioned hard coat composition contains at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.

The above radical polymerizable compound is a compound having a radical polymerizable group. The radical polymerizable group contained in the above-mentioned radical polymerizable compound may be any functional group as long as it can undergo a radical polymerization reaction, and may, for example, be a group containing a carbon-carbon unsaturated double bond. Specifically, a vinyl group, a (meth)acryl group, etc. are mentioned. In addition, when the above-mentioned radical polymerizable compound has two or more radical polymerizable groups, these radical polymerizable groups may be respectively the same or different. It is preferable that the number of the radical polymerizable group which the said radical polymerizable compound has in 1 molecule is 2 or more from the point which raises the hardness of a hard-coat layer. As the above-mentioned radical polymerizable compound, a compound having a (meth)acryl group is preferable in terms of high or low reactivity, and a compound having 2 to 6 (methyl) groups in one molecule can be preferably used. Acryl-based compounds called polyfunctional acrylate monomers or molecules called epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates An oligomer with a molecular weight of several hundred to several thousand with several (meth)acryl groups in it. It is preferable to contain one or more types selected from epoxy (meth)acrylate, urethane (meth)acrylate, and polyester (meth)acrylate.

The above-mentioned 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 that the above-mentioned cationically polymerizable compound has in 1 molecule is preferably 2 or more, more preferably 3 or more, from the viewpoint of increasing the hardness of the hard coat layer. In addition, as the above-mentioned cationically polymerizable compound, a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable. Cyclic ether groups such as epoxy groups and oxetanyl groups are preferable in that the shrinkage accompanying the polymerization reaction is small. In addition, the compound having the epoxy group in the cyclic ether group has the following advantages: it is easy to obtain compounds of various structures, it does not adversely affect the durability of the obtained hard coat layer, and it is easy to control the chemical composition of the radical polymerizable compound. the compatibility. In addition, the oxetanyl group in the cyclic ether group has the following advantages: compared with the epoxy group, the degree of polymerization is easily increased, low toxicity, and the network obtained by the cationic polymerizable compound of the obtained hard coat is accelerated. The road formation speed is high, and even in the area where it is mixed with the radical polymerizable compound, unreacted monomers will not remain in the film, forming an independent network, etc.

Examples of cationic polymerizable compounds having epoxy groups include: polyglycidyl ethers of polyhydric alcohols having alicyclic rings; , cycloaliphatic epoxy resins obtained by epoxidizing cyclopentene ring compounds; polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, Aliphatic epoxy resins such as homopolymers and copolymers of glycidyl (meth)acrylate; addition of bisphenols such as bisphenol A, bisphenol F, or hydrogenated bisphenol A, or alkylene oxides thereof Glycidyl ethers produced by the reaction of derivatives such as caprolactone adducts and epichlorohydrin, and glycidyl ether-type epoxy resins derived from bisphenols as novolac epoxy resins, etc. A polymerization initiator may be further contained in the above-mentioned hard coat composition. As a polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, etc. can be selected suitably and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate free radicals or cations to carry out free radical polymerization and cationic polymerization.

The radical polymerization initiator is only required to release a substance that starts radical polymerization by at least any one of active energy ray irradiation and heating. For example, organic peroxides, such as hydrogen peroxide and perbenzoic acid, azo compounds, such as azobisbutyronitrile, etc. are mentioned as a thermal radical polymerization initiator. As active energy ray radical polymerization initiators, there are Type 1 free radical polymerization initiators that generate free radicals by molecular decomposition, and Type 2 free radicals that coexist with tertiary amines and generate free radicals through hydrogen abstraction reactions. The base polymerization initiators can be used alone or in combination.

The cationic polymerization initiator should just release a substance that starts cationic polymerization by at least any one of active energy ray irradiation and heating. As the cationic polymerization initiator, aromatic iodonium salts, aromatic permeic acid salts, cyclopentadienyl iron (II) complexes, and the like can be used. According to these structural differences, cationic polymerization can be initiated by either or both of active energy ray irradiation and heating.

The said polymerization initiator can contain 0.1-10 weight% with respect to 100 weight% of the said hard-coat composition wholes. When the content of the above-mentioned polymerization initiator is less than 0.1% by weight, the hardening cannot be performed sufficiently, and it is difficult to realize the mechanical properties or adhesion of the coating film finally obtained. When the content exceeds 10% by weight, there may be shrinkage caused by hardening Caused by poor adhesion or cracking phenomenon and curling phenomenon.

The above-mentioned hard coating composition may further contain one or more types selected from the group consisting of solvents and additives. Since the said solvent can dissolve or disperse the said polymeric compound and a polymerization initiator, if it is a solvent of the hard-coat composition of this technical field, it can use without limitation. The above-mentioned additives may further include: inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

(circular polarizer) As mentioned above, the display device (preferably a flexible display device) of the present invention (the first aspect and the second aspect) preferably includes a polarizing plate, and particularly preferably includes a circular polarizing plate. The circular polarizing plate is a functional layer having a function of transmitting only right or left circularly polarized light components by laminating a λ/4 retardation plate on a linear polarizing plate. For example, it is used to block the external light that converts the external light into right circularly polarized light and is reflected by the organic EL panel to become left circularly polarized light, and only transmits the light-emitting components of the organic EL, thereby suppressing the influence of reflected light and making the image easier observe. 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 need to be 45 degrees in theory, but it is 45±10 degrees in practice. The linear polarizer and the λ/4 retardation film do not have to be laminated adjacent to each other, as long as the relationship between the absorption axis and the retardation axis satisfies the above-mentioned range. It is preferable to achieve complete circular polarization at all wavelengths, but this is not necessarily the case in practice. Therefore, the circular polarizers in the present invention (the first aspect and the second aspect) also include elliptical polarizers. It is also preferable to laminate a λ/4 retardation film on the viewing side of the linear polarizing plate to make the outgoing light circularly polarized, thereby improving the visibility when wearing polarized sunglasses.

The linear polarizer is a functional layer having the function of passing light vibrating along the transmission axis, but blocking polarized light of a vibration component perpendicular to it. The above-mentioned linear polarizing plate may have only a linear polarizing element or a linear polarizing element and a protective film attached to at least one side thereof. The thickness of the above-mentioned linear polarizing plate may be less than 200 μm, preferably more than 0.5 μm and less than 100 μm. 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 mentioned above 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 to a PVA-based film aligned by stretching, or stretched while being adsorbed to PVA, and the dichroic dye is aligned to exhibit polarizing performance. In the manufacture of the above-mentioned film-type polarizing element, steps such as swelling, crosslinking with boric acid, washing with aqueous solution, and drying may be included in addition. The stretching or dyeing process may be performed only with the PVA-based film, or may be performed in a state of laminating with other films such as polyethylene terephthalate (resin base material for stretching). The thickness of the PVA-based film used is preferably 3-100 μm, and the above-mentioned elongation ratio is preferably 2-10 times. As a method of producing a laminate of the resin base material for stretching and the PVA-based resin layer, a method of coating a coating liquid containing a PVA-based resin on the surface of the resin base material for stretching and drying it is preferable.

In particular, if it is a manufacturing method including the step of stretching the PVA-based resin layer and the stretching resin base material in the state of the laminate, and the step of dyeing, even if the PVA-based resin layer is thin, the stretching resin base material can be Supported and stretched in the absence of defects such as breakage caused by stretching.

The thickness of the above-mentioned polarizer is 20 μm or less, preferably 12 μm or less, more preferably 9 μm or less, further preferably 1-8 μm, especially preferably 3-6 μm. If it is in the said range, there will be no hindrance to bending, and it will be a preferable aspect.

Furthermore, as another example of the above polarizing element, a liquid crystal coating type polarizing element formed by coating a liquid crystal polarizing composition may be mentioned. The above-mentioned liquid crystal polarizing composition may include a liquid crystal compound and a dichroic dye compound. The above-mentioned liquid crystal compound only needs to have the property of exhibiting a liquid crystal state. In particular, if it has a smectic high-order alignment state, it can exhibit high polarizing performance, so it is preferable. Also, the liquid crystal compound preferably has a polymerizable functional group. The above-mentioned dichroic dye compound is a dye that aligns with the above-mentioned liquid crystal compound to exhibit dichroism, and may have a polymerizable functional group, or the dichroic dye itself may have liquid crystallinity. Any one of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group. The above-mentioned liquid crystal polarizing composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The above-mentioned liquid crystal polarizing layer can be 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 thickness of the film-type polarizing element, and its thickness is preferably not less than 0.5 μm and not more than 10 μm, more preferably not less than 1 μm and not more than 5 μm.

The aforementioned alignment film can be produced by, for example, coating an alignment film-forming composition on a substrate and imparting alignment by rubbing, polarized light irradiation, or the like. The composition for forming an alignment film includes an alignment agent, and may further include a solvent, a crosslinking 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 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 above-mentioned alignment film is preferably from 5 nm to 10,000 nm, and more preferably from 10 nm to 500 nm in terms of sufficiently expressing the alignment restriction force. The above-mentioned liquid crystal polarizing layer may be peeled from the base material and transferred to be laminated, or the above-mentioned base material may be directly laminated. It is also preferable that the above-mentioned base material functions as a transparent base material for a protective film, a phase difference plate, or a window film.

As the protective film, any transparent polymer film may be used, and the same materials or additives as those used for the transparent substrate of the above-mentioned window film can be used. Preferable are cellulose-based films, olefin-based films, acrylic-based films, and polyester-based films. In addition, it may be a coating type protective film obtained by applying a cation-curing composition such as epoxy resin or a radical-curing composition such as acrylate and curing it. The protective film may contain plasticizers, ultraviolet absorbers, infrared absorbers, coloring agents such as pigments or dyes, fluorescent whitening agents, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, Lubricants, solvents, etc. The thickness of the protective film is preferably not more than 200 μm, more preferably not less than 1 μm and not more than 100 μm. When the thickness of a protective film exists in the said range, there exists a tendency for the flexibility of the said film to fall hard. The protective film can also serve as the transparent substrate of the window film.

The above-mentioned λ/4 retardation plate is a film that generates a retardation of λ/4 along the direction (in-plane direction of the film) that goes straight with the traveling direction of incident light. The aforementioned λ/4 phase difference plate may also be an extended type phase difference plate manufactured by stretching polymer films such as cellulose-based films, olefin-based films, and polycarbonate-based films. The above-mentioned λ/4 phase difference plate may contain phase difference adjusting agent, plasticizer, ultraviolet absorber, infrared absorber, coloring agent such as pigment or dye, fluorescent whitening agent, dispersant, heat stabilizer, light stabilizer, etc. Agents, antistatic agents, antioxidants, lubricants, solvents, etc. The thickness of the above-mentioned extended retardation plate is preferably less than 200 μm, more preferably not less than 1 μm and not more than 100 μm. When the thickness of the stretched retardation film is within the above range, the flexibility of the stretched retardation film tends to be less likely to decrease.

Furthermore, as another example of the aforementioned λ/4 retardation plate, a liquid crystal coating type retardation plate formed by coating a liquid crystal composition may be mentioned. The above-mentioned liquid crystal composition contains liquid crystal compounds exhibiting liquid crystal states such as nematic, cholesteric, and smectic. The above-mentioned liquid crystal compound has a polymerizable functional group. The above-mentioned liquid crystal composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The above-mentioned liquid crystal coating type retardation plate can be produced by applying a liquid crystal composition on a base layer and curing it to form a liquid crystal retardation layer similarly to the above-mentioned liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed thinner than that of the stretched type retardation plate. The thickness of the liquid crystal polarizing layer is preferably not less than 0.5 μm and not more than 10 μm, more preferably not less than 1 μm and not more than 5 μm. The above-mentioned liquid crystal coating type phase difference plate may be peeled from the base material and transferred to be laminated, or the above-mentioned base material may be directly laminated. It is also preferable that the above-mentioned base material functions as a transparent base material for a protective film, a phase difference plate, or a window film.

Generally, the shorter the wavelength is, the larger the birefringence is, and the longer the wavelength is, the smaller the birefringence is. In this case, since the phase difference of λ/4 cannot be achieved in the entire visible light region, the in-plane phase difference is preferably designed to be not less than 100 nm and not more than 180 nm, more preferably not less than 130 nm and not more than 150 nm, so that Near 560 nm, which is relatively high in visual sensitivity, becomes λ/4. The inverse dispersion λ/4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to that of ordinary ones is preferable in terms of good visibility. As such a material, for example, those described in Japanese Patent Laid-Open No. 2007-232873 and the like can be used, and those described in Japanese Patent Laid-Open No. 2010-30979 and the like can be used for liquid crystal coating type retardation plates. Also, as another method, a technique of obtaining a broadband λ/4 retarder by combining it with a λ/2 retarder is known (for example, Japanese Patent Application Laid-Open No. 10-90521, etc.). The λ/2 phase difference plate can also be manufactured by the same material method as the λ/4 phase difference plate. The combination of the stretched phase difference plate and the liquid crystal coating type phase difference plate is optional, and the thickness can be reduced by using the liquid crystal coating type phase difference plate. In order to improve visibility in oblique directions, there is known a method of laminating a positive C plate on the circular polarizing plate (for example, Japanese Patent Laid-Open No. 2014-224837, etc.). The positive C plate can be a liquid crystal coating type phase difference plate, or an extended type phase difference plate. The retardation in the thickness direction of the phase difference plate is preferably not less than -200 nm and not more than 20 nm, more preferably not less than -140 nm and not more than 40 nm.

(touch sensor) As mentioned above, the display device (preferably a flexible display device) including the laminate of the present invention (the first aspect and the second aspect) preferably includes a touch sensor. Touch sensors can be used as input mechanisms. As the touch sensor, various types such as a resistive film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and a capacitive type are exemplified, and a capacitive type is preferably exemplified. The capacitive touch sensor is divided into an active area and an inactive area located outside the active area. The active area is the area corresponding to the display area of the display panel (display portion), and is the area that senses the user’s touch, and the inactive area is the area corresponding to the area of the display device that does not display the image (non-display portion). The touch sensor preferably can include a substrate with soft properties, a sensing pattern formed on the active area of the substrate, and a non-active area formed on the substrate and connected to the outside through the sensing pattern and the pad. The sensing lines connected to the driving circuit. As the substrate having flexible properties, the same material as the transparent substrate of the above-mentioned window film can be used. Among the substrates of the touch sensor, those having a toughness of 2,000 MPa% or more are preferable in terms of crack suppression of the touch sensor. More preferably, the toughness is not less than 2,000 MPa% and not more than 30,000 MPa%. Here, the toughness is defined as the area under the curve up to the rupture point in the stress (MPa)-strain (%) curve (Stress-strain curve) obtained by the tensile test of the polymer material.

The sensing pattern may include a first pattern formed along the first direction and a second pattern formed along the second direction. The first pattern and the second pattern are arranged along mutually different directions. The first pattern and the second pattern are formed on the same layer, and in order to sense the touched part, the patterns must be electrically connected. The first pattern is a form in which a plurality of unit patterns are connected to each other through ferrules, and the second pattern is a structure in which a plurality of unit patterns are separated from each other in an island form. Therefore, in order to electrically connect the second patterns, additional bridge electrodes are required. As the electrodes used for the connection of the second pattern, known transparent electrodes can be used. As the material of the transparent electrode, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), indium gallium zinc oxide ( IGZO), cadmium tin oxide (CTO), PEDOT (poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)), carbon nanotubes (CNT), graphene, metal wire, etc. , preferably ITO. These can be used individually or in mixture of 2 or more types. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, telenium, chromium, and the like, which may be used alone or in combination of two or more. The bridge electrode can be formed on the upper part of the sensing pattern via an insulating layer, and the bridge electrode can be formed on the substrate, and the insulating layer and the sensing pattern can be formed thereon. The above bridging electrodes can also be formed of the same material as the sensing pattern, or can be formed of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium or alloys of two or more of these. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridging electrodes. The insulating layer may be formed only between the collar of the first pattern and the bridge electrodes, or may 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 be connected to the second pattern through a contact hole formed in the insulating layer.

The above-mentioned touch sensor may further include an optical adjustment layer between the substrate and the electrodes to properly compensate for the difference in transmittance between the pattern area where the sensory pattern is formed and the non-pattern area where the sensory pattern is not formed, specifically It is the mechanism for the difference in light transmittance induced by the difference in refractive index in these regions. The optical adjustment layer contains an inorganic insulating substance or an organic insulating substance. The optical adjustment layer can be formed by coating a photocurable composition including a photocurable organic adhesive and a solvent on the substrate. The above photocurable composition may further contain inorganic particles. The above-mentioned inorganic particles can increase the refractive index of the optical adjustment layer. The above-mentioned photocurable organic adhesive may contain, for example, acrylate monomers, styrene monomers, carboxylic acid monomers, etc. within the range that does not impair the effects of the present invention (the first aspect and the second aspect). Copolymers of various monomers. The photocurable organic adhesive may be, for example, a copolymer including repeating units different from each other such as epoxy group-containing repeating units, acrylate repeating units, and carboxylic acid repeating units. As said inorganic particle, a zirconia particle, a titania particle, an alumina particle etc. are mentioned, for example. The above-mentioned photocurable composition may further contain various additives such as a photopolymerization initiator, a polymerizable monomer, and a curing adjuvant.

(next layer) Each layer (window film, circular polarizing plate, touch sensor) forming the laminate for the above-mentioned display device (preferably a flexible image display device) and the film members (linear polarizing plate, λ/4 retardation plate) constituting each layer etc.) can be joined by an adhesive. As the adhesive, water-based adhesives, organic solvent-based, solvent-free adhesives, solid adhesives, solvent-evaporating adhesives, moisture-curing adhesives, heat-curing adhesives, anaerobic-curing adhesives, reactive Generally used adhesives such as energy ray-curing adhesives, hardener-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), remoistening adhesives, etc., preferably can be volatilized with water-based solvents type adhesive, active energy ray hardening type adhesive, adhesive. The thickness of the adhesive layer can be appropriately adjusted according to the required adhesive force, etc., preferably 0.01-500 μm, more preferably 0.1-300 μm. There are a plurality of adhesive layers in the above-mentioned laminate for a display device (preferably a flexible image display device), and the thickness or type of each layer may be the same or different.

As the above-mentioned water-based solvent-dispersing adhesive, water-dispersed polymers such as polyvinyl alcohol-based polymers, starch and other water-soluble polymers, ethylene-vinyl acetate-based emulsions, and styrene-butadiene-based emulsions can be used as main agents. agent polymer. In addition to the above-mentioned main ingredient polymer and water, cross-linking agents, silane compounds, ionic compounds, cross-linking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, etc. can also be formulated. In the case of bonding with the above-mentioned water-based solvent-evaporating adhesive, the above-mentioned water-based solvent-evaporating adhesive can be injected between the adhered layers to bond the adhered layers and then dried to impart adhesiveness. When using the above-mentioned water-based solvent-evaporating adhesive, the thickness of the adhesive layer is preferably 0.01-10 μm, more preferably 0.1-1 μm. When the above-mentioned water-based solvent-evaporating adhesive is used in multiple layers, the thickness or type of each layer may be the same or different.

The above-mentioned 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 by irradiating active energy rays. The active energy ray curing composition may contain at least one polymer of the same radical polymerizable compound and cation polymerizable compound as that contained in the hard coat composition. As the radical polymerizable compound, the same compound as the radical polymerizable compound in the hard coat composition can be used. As the above-mentioned cationically polymerizable compound, the same compound as the cationically polymerizable compound in the hard coat composition can be used. Epoxy compounds are particularly preferred as the cationically polymerizable compound used in the active energy ray-curable composition. In order to reduce the viscosity of the adhesive composition, it is also preferred to include a monofunctional compound as a reactive diluent.

In order to reduce the viscosity, the active energy ray composition may contain a monofunctional compound. As the monofunctional compound, an acrylate-based monomer having one (meth)acryl group in one molecule, or a compound having one epoxy group or oxetanyl group in one molecule, such as Glycidyl (meth)acrylate, etc. The active energy ray composition may further contain a polymerization initiator. As this polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, etc. are mentioned, and these can be selected suitably and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate free radicals or cations to carry out free radical polymerization and cationic polymerization. An initiator capable of starting at least any one of radical polymerization and cationic polymerization by active energy ray irradiation described in the description of the hard coat composition can be used. The above-mentioned active energy ray curing composition may further contain ion scavengers, antioxidants, chain transfer agents, adhesion imparting agents, thermoplastic resins, fillers, flow viscosity modifiers, plasticizers, defoaming agents, solvents, additives, and solvents. In the case of bonding two adhered layers with the above-mentioned active energy ray-curable adhesive, the above-mentioned active energy ray-curable composition is applied to either or both of the adhered layers and then pasted together. The adhered layer or both adhered layers can be adhered by irradiating active energy rays to harden them. When using the above-mentioned active energy ray-curable adhesive, the thickness of the adhesive layer is preferably from 0.01 to 20 μm, more preferably from 0.1 to 10 μm. When the above-mentioned active energy ray-curable adhesive is used to form a plurality of adhesive layers, the thickness or type of each layer may be the same or different.

As the adhesive, any one classified into an acrylic adhesive, a urethane adhesive, a rubber adhesive, a silicone adhesive, etc. may be used depending on the polymer of the main agent. In the adhesive, in addition to the main agent polymer, crosslinking agents, silane compounds, ionic compounds, crosslinking catalysts, antioxidants, adhesion imparting agents, plasticizers, dyes, pigments, inorganic fillers, etc. can also be formulated . The adhesive composition is obtained by dissolving and dispersing the components constituting the above adhesive in a solvent, and the adhesive composition is applied on a substrate and dried to form an adhesive layer. The adhesive layer can be formed directly, or it can be transferred to another one formed on the base material. In order to cover the adhesive surface before bonding, it is also preferable to use a release film. When using the above-mentioned active energy ray-curable adhesive, the thickness of the adhesive layer is preferably from 0.1 to 500 μm, more preferably from 1 to 300 μm. When the above-mentioned adhesive is used in multiple layers, the thickness or type of each layer may be the same or different.

(shading pattern) The above-mentioned light-shielding pattern can be used as at least a part of the frame or casing of the above-mentioned display device (preferably a flexible image display device). The light-shielding pattern hides the wiring arranged at the edge of the display device (preferably a flexible image display device) to make it difficult to see, thereby improving the visibility of the image. The above light-shielding pattern can be in the form of a single layer or a multi-layer. The color of the light-shielding pattern is not particularly limited, and it can be various colors such as black, white, and metallic. The light-shielding patterns can be formed by pigments used to realize colors and polymers such as acrylic resins, ester resins, epoxy resins, polyurethanes, and polysiloxanes. These may also be used alone or as a mixture of two or more. The above-mentioned light-shielding patterns 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. Moreover, it is also preferable to give shapes, such as an inclination, along the thickness direction of a light-shielding pattern.

The claims in this case are based on Japanese patent application No. 2021-017848 filed on February 5, 2021, Japanese patent application No. 2021-107125 filed on June 28, 2021, and Japanese patent application filed on January 7, 2022 Benefit of Priority of Application No. 2022-001911. Japanese Patent Application No. 2021-017848 filed on February 5, 2021, Japanese Patent Application No. 2021-107125 filed on June 28, 2021, and Japanese Patent Application No. 2022 filed on January 7, 2022 The entire contents of the specification No. 2022-001911 are cited in this case for reference. Example

(first form) Hereinafter, the present invention (first aspect) will be more specifically described by way of examples related to the first aspect. Of course, the present invention (first aspect) is not limited by the following examples, and can be implemented with appropriate changes within the scope of the above and the following gist, all of which are included in the present invention (first aspect) within the technical scope.

Example 1-1 N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chlorine A solution of 0.25% by mass of a reactant of propyltrimethoxysilane (trade name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99.75% by mass of butyl acetate as a solvent (E) at room temperature Stirring was carried out to obtain a composition for layer (c) formation. Also, a substrate (s) (Daicel Co., Ltd. manufactured by Daicel Co., Ltd.) was prepared in which a hard coat layer (s2) containing silver ions as an antibacterial component (K) was laminated on a polyethylene terephthalate substrate (s1). Antiviral hard coat S BV01, thickness: 50 μm), using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.) to activate the hard coat (s2) surface of the above substrate (s). Then, using OPTICOAT MS-A100 (rod coater) manufactured by MIKASA Co., Ltd., #2 rod, the layer (c) obtained above was combined under the conditions of 0.5 ml and 100 mm/sec. coated on the hard coat layer (s2) in the base material (s), and dried at 100° C. for 30 seconds to obtain a layered intermediate with the layer (c) formed thereon.

[chem 24]

Then, the compound (a10) satisfying the above formula (a3) as organosilicon compound (A) and FAS13E(C ₆ F ₁₃ -C ₂ H ₄ -Si(OC ₂ H ₅ ) as organosilicon compound (B) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.) and FC-3283 (C ₉ F ₂₁ N, manufactured by Fluorinert, 3M Company) as a solvent (D) were mixed, stirred at room temperature for a specified time, and a water-repellent layer was formed With composition 1-1. The ratio of the organosilicon compound (A) in the composition 1-1 for water repellent layer formation was 0.085 mass %, and the ratio of the organosilicon compound (B) was 0.05 mass %. The water-repellent layer-forming composition 1-1 was coated on the layer (c) in the laminated intermediate using a spray coater manufactured by API Corporation. The spraying conditions are scanning speed: 600 mm/sec, spacing: 5 mm, liquid volume: 6 cc/min, atomizing air: 350kPa, gap: 70 mm. Dry at 100° C. for 30 seconds to form a water-repellent layer. Furthermore, the compound (a10) used as the organosilicon compound (A) is a compound that satisfies the requirements of the above-mentioned compounds (a11) and (a21) and also satisfies the requirements of the formula (a3) including preferred aspects. Calculated by the measurement method of "(1-7) Thickness of layer (c)" described below, and the measurement method of "(1-8) Thickness of water-repellent layer (r)" described below The thickness of the layered part is within the range of not less than 5.0 nm and not more than 15.0 nm.

Example 1-2 Substrate (s) in which a hard coat (s2) containing silver ions as an antibacterial component (K) is laminated on a polyethylene terephthalate substrate (s1) (Daicel Antiviral manufactured by Daicel Co., Ltd. A laminate was produced in the same manner as in Example 1-1 except that the hard coat film S BV02, thickness: 50 μm). Layer (c) obtained by measuring "(1-7) Thickness of layer (c)" described below, and "(1-8) Thickness of water-repellent layer (r)" described below The thicknesses of the water-repellent layer (r) and the water-repellent layer (r) are 5.9 nm and 4.1 nm, respectively, and the thickness of the laminated part is 10.0 nm (5.9 nm+4.1 nm).

Example 1-3 Substrate made of polyethylene terephthalate U483 (s1) (thickness 50 μm) manufactured by Toray Co., Ltd. with an acrylic hard coat (s2) (thickness 5 μm) containing quaternary ammonium salt Except for the material (s), a laminate was produced in the same manner as in Example 1-1. Layer (c) obtained by measuring "(1-7) Thickness of layer (c)" described below, and "(1-8) Thickness of water-repellent layer (r)" described below and water-repellent layer (r) are 9.1 nm and 4.5 nm thick respectively, and the thickness of the laminated part is 13.6 nm (9.1 nm+4.5 nm).

Example 1-4 The layer (c) was formed by the same method as Example 1-1 except having used Daicel antiviral hard coat S BV02. Thereafter, a recess was formed inside by bending the end of the laminated intermediate, and 4 ml of the composition 1-1 for forming a water-repellent layer similar to Example 1-1 was poured into it. Furthermore, it dried at 100 degreeC for 15 minutes, and the water-repellent layer (r) was formed by this. The thickness of the laminated part was measured by the method described in "(1-9) Thickness of the laminated part" described below, and it was 40.0 nm.

Example 1-5 Other than 0.25% by mass of KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) as organosilicon compound (C) , A laminate was produced in the same manner as in Example 1-1. Layer (c) obtained by measuring "(1-7) Thickness of layer (c)" described below, and "(1-8) Thickness of water-repellent layer (r)" described below and water-repellent layer (r) are 12 nm and 4.5 nm thick respectively, and the thickness of the laminated part is 16.5 nm (12 nm + 4.5 nm).

Examples 1-6 A substrate (s) prepared by laminating a hard coat layer (s2) containing silver ions as an antibacterial component (K) on a polyethylene terephthalate substrate (s1) (Daicel Antivirus manufactured by Daicel Co., Ltd. The hard coat film S BV02, thickness: 50 μm), was activated on the hard coat (s2) surface of the substrate (s) using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.). Then, compound (a10) as organosilicon compound (A), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane as organosilicon compound (C) and chloropropyl trimethyl A reactant of oxysilane (trade name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.), Novec (registered trademark) 7300 as a solvent (D1), butyl acetate as a solvent (D2), and Solvent (D2) and isopropanol were mixed, and stirred at room temperature for a predetermined time to obtain composition 1-2 for forming a water-repellent layer. The ratio of the organosilicon compound (A) in the composition 1-2 for forming a water-repellent layer is 0.0701% by mass, the ratio of the organosilicon compound (C) is 0.0842% by mass, the ratio of the solvent (D1) is 79.93% by mass, acetic acid The ratio of butyl ester was 3.982% by mass, and the ratio of isopropanol was 15.93% by mass. Thereafter, using OPTICOAT MS-A100 (rod coater) manufactured by MIKASA Co., Ltd., a #9 rod, the composition 1-2 for forming a water-repellent layer was coated under the conditions of 0.5 ml and 100 mm/sec. Spread on the hard coat layer (s2) in the above-mentioned substrate (s), and dry at 100°C for 30 seconds to obtain a laminate with the layer (r) formed. The thickness of the laminated part was measured by the method described in "(1-9) Thickness of the laminated part" described below, and it was 15.0 nm.

Comparative example 1-1 The layer (c) was formed by the same method as Example 1-1 except having used Daicel antiviral hard coat S BV02. Thereafter, a water-repellent spray containing fluororesin (manufactured by AS ONE, product number: 62-3807-13) was sprayed, and left overnight at room temperature to form a water-repellent layer (r). The thickness of the laminated part was measured by the method described in "(1-9) Thickness of the laminated part" described below, and it was 110 nm.

Reference example 1-1 A substrate (s) prepared by laminating a hard coat layer (s2) containing silver ions as an antibacterial component (K) on a polyethylene terephthalate substrate (s1) (Daicel Antivirus manufactured by Daicel Co., Ltd. The hard coat film S BV02, thickness: 50 μm), was activated on the hard coat (s2) surface of the substrate (s) using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.). Next, compound (a10) which is organosilicon compound (A) and FAS13E which is organosilicon compound (B) were mixed, and stirred at room temperature for predetermined time, and the composition 1-3 for water-repellent layer formation was obtained. The ratio of the organosilicon compound (A) in the composition 1-3 for water-repellent layer formation was 0.085 mass %, and the ratio of the organosilicon compound (B) was 0.05 mass %. Thereafter, using a spray coater manufactured by API Corporation, under the same conditions as in Example 1-1, the composition 1-3 for forming a water-repellent layer was applied to the hard coat layer in the above-mentioned substrate (s) ( s2) on. The thickness of the laminated part was measured by the method described in "(1-9) Thickness of the laminated part" described below, and it was 4.2 nm.

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

(1-1) Initial contact angle 3 μL of water droplets were dropped on the surface of the water-repellent layer side of the obtained laminate, and water was measured by the droplet method (analysis method: θ/2 method) using a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM700). the contact angle. The results are shown in Table 1.

(1-2) Wear resistance test Using a scraping device equipped with a minoan eraser, apply a load of 1000 g to the water-repellent layer side surface of the obtained laminate with the eraser in contact with the laminate (contact surface: a circle with a diameter of 6 mm), and then apply a load of 40 The speed of r/min (the speed of reciprocating 40 times per minute), the stroke of 40 mm makes the eraser reciprocate on the laminated body, and the abrasion resistance test is carried out. The contact angles of water after the eraser reciprocated 1500 times and 3000 times on the laminate were respectively measured. The results are shown in Table 1.

(1-3) Dynamic friction coefficient The dynamic friction coefficient of the water-repellent layer (r) side surface was measured using Tribogear (surface property measuring machine TYPE: 38) manufactured by Shinto Scientific Co., Ltd. under a constant load, using artificial leather, and the measurement conditions were set to the following conditions. The results are shown in Table 1. Load converter: 1.961 mV/V Load: 200 g Moving distance: 50mm Moving speed: 100mm/min Number of samples: 3010

(1-4) Marking ink removal As an evaluation method for marking ink removal, three circles were drawn on the film using a marking ink (brush stroke oily Chinese characters manufactured by Sakura), and then wiped with a Savina (registered trademark) cloth. When all three marking ink traces were wiped off, it was rated as ◎, when two spots were wiped off, it was rated as ○, and when there was a spot that was not wiped off, it was rated as ×. The results are shown in Table 1.

(1-5) Scratch resistance Use a steel wool testing machine (manufactured by Daiei Seiki Co., Ltd.) equipped with steel wool #0000 (manufactured by Bonstar Co., Ltd.), and connect the steel wool to the surface of the laminate (water-repellent layer (r)) In this state, a wear test was carried out by applying a pressure of 250 g/cm ² , and the test was repeated until peeling and damage were visually confirmed, and the scratch resistance was evaluated by the number of tests when peeling and damage were confirmed. The number of tests was set to 1 reciprocation. In addition, the presence or absence of peeling and damage was confirmed under LED lighting. The results are shown in Table 1.

(1-6) Haze According to JIS Z 8722, using a colorimeter (CM-3700A, light source: D65) manufactured by Konica Minolta, the surface of the water-repellent layer (r) side of the laminate is facing the light source side, and the haze is measured. The obtained results are shown in Table 1.

(1-7) Thickness of layer (c) For the laminated intermediate product obtained by drying the coating layer (c) composition, the upper surface is blackened with a marker pen, and ultrathin sections are made by FIB-SEM (Focused Ion Beam Scanning Electron Microscopy) , observed from the cross-sectional direction with a scanning transmission electron microscope (STEM), thereby measuring the thickness of the layer (c). ＜FIB Processing Conditions＞ Device name: HeliosG4UX (manufactured by Japan FEI Corporation) Ion source: Ga Acceleration voltage: 30 kV Sample thickness: below 100 nm <STEM measurement conditions> Device name: HeliosG4UX (manufactured by Japan FEI Corporation) Acceleration voltage: 23 kV Current value: 50pA Magnification: 1 million times

(1-8) Thickness of water-repellent layer (r) The film thickness of the water-repellent layer (r) was measured using X-ray photoelectron spectroscopy (XPS) according to the following description. First, a layer (c) and a water-repellent layer (r) were fabricated on a glass substrate treated with atmospheric pressure plasma by the same method as in Example 1-1. At this time, the composition 1-1 for forming a water-repellent layer was applied while changing the coating amount in 4 places, and a total of 4 kinds of layers (c) had the same thickness and different thicknesses of the water-repellent layer (r) were produced. Then, the film thickness of each water-repellent layer (r) was measured using an ellipsometer. Also, for the same layer, use the XPS method to measure the amount of element F and the amount of element C other than elements bonded to F, calculate the ratio (F/C (other than C-F)), and make a water-repellent layer (r) The calibration curve of the film thickness. In this case, the amount of the F element comes from the water-repellent layer (r), and the amount of the C elements other than the C element bonded to the F element comes from the layer (c). Next, XPS measurement was performed on the laminates prepared in Examples 1-2 to 1-4, and the film thickness of the water-repellent layer (r) was calculated according to the calibration curve prepared above. <XPS measurement conditions> Device name: K-alpha manufactured by Thermofisher Scientific X-ray source: monochromatic Al Kα Power: 72W (12kV, 6mA) Spot size: 400 μm Pass energy: 50 eV Dwell time: 50 ms mode (element): narrow (F, C) Neutralizing gun: on Also, the calibration curve in Examples 1-5 was prepared by the same method, the laminate obtained in Examples 1-5 was subjected to XPS measurement, and the water-repellent layer (r) was calculated according to the calibration curve prepared above. Film thickness.

(1-9) Thickness of laminated part After sticking a tape on a part of the substrate for masking, form the layer (c) and the water-repellent layer (r), or only the water-repellent layer (r), and peel off the tape to form the film thickness of the laminated part quite a step difference. Thereafter, the film thickness of the laminated part was measured using a stylus thin film profiler. Device name: DektakXT (manufactured by Bruker Corporation) Range: 6.5 μm Probe type (stylus type): Radius 2 μm Probe pressure (stylus force): 3 mg Speed: 100 μm/s

(1-10) Antibacterial activity value 1 The antibacterial test of the laminates of Examples 1-1 and Examples 1-3 was conducted at BOKEN Quality Evaluation Institute (BOKEN QUALITY EVALUATION INSTITUTE). The test method was based on JIS Z 2801:2010 (film adhesion method). The test strains were Staphylococcus aureus and Escherichia coli, and the inoculated amount of the bacterial solution was set to 0.4 mL (the surface area of the coating film: 16 cm ² ). Also, as a standard sample, a polyethylene terephthalate substrate ("COSMOSHINE (registered trademark) A4360" manufactured by Toyobo Co., Ltd., thickness: 50 μm) was used. In Example 1-1, for the standard sample, the antibacterial activity value of Staphylococcus aureus was 2.7, and for the standard sample, the antibacterial activity value of Escherichia coli was 5.0, showing good antibacterial properties. Also, in Examples 1-3, the antibacterial activity value of Staphylococcus aureus was 3.2, which has a good antibacterial activity value.

(1-11) Antibacterial activity value 2 The antibacterial activity test in the laminates of Examples 1-2, 1-4, 1-5, 1-6, Comparative Example 1-1, and Reference Example 1-1 was except for the change bacteria Otherwise, it was carried out by the same method as JIS Z 2801:2010 (membrane adhesion method), the test strain was Staphylococcus epidermidis, and the inoculum amount was 0.4 mL (surface area of the coating film: 16 cm ² ). Also, as a standard sample, a polyethylene terephthalate substrate ("COSMOSHINE (registered trademark) A4360" manufactured by Toyobo Co., Ltd., thickness: 50 μm) was used. In embodiment 1-2, when only base material (s) (that is only Daicel antiviral hard coat S BV02) situation, for standard sample, antibacterial activity value is 2.2, contrast with this, embodiment 1-2 The antibacterial activity value of the laminate is 2.5, and even in the case of the laminate layer (c) and the water-repellent layer (r), it has the same or higher antibacterial activity. In Examples 1-4, the antibacterial activity value of the laminate was 2.3. In Examples 1-5, the antibacterial activity value of the laminate was 2.7. In Examples 1-6, the antibacterial activity value of the laminate was 3.1. In Reference Example 1-1, the antibacterial activity value of the laminate was 3.3. In Comparative Example 1-1, the antibacterial activity value of the laminate was 0.8, and the antibacterial activity value of the substrate (s) was suppressed due to the laminated water-repellent layer (r).

[Table 1] Example comparative example Reference example 1-1 1-2 1-3 1-4 1-5 1-6 1-1 1-1 initial contact angle ^o 118.0 113.1 115.3 114.0 116.4 114.1 111.2 115.6 wear resistance Contact angle after 1500 times ^o 113.4 109.6 115.4 103.6 112.7 114.3 69.5 44.3 Contact angle after 3000 times ^o 111.8 105.5 114.3 108.5 110.3 114.5 70.8 43.8 dynamic friction coefficient 0.076 0.032 0.04 0.083 0.032 0.048 0.328 0.075 Marking Ink Removal ◎ ◎ ◎ ◎ ◎ ◎ x x Scratch resistance Second-rate 500 3000 3000 3000 1500 1500 500 100 Haze 1.30 2.28 0.80 3.81 2.45 2.55 5.87 2.50

From the above results, it can be seen that the laminate of the present invention (first aspect) can achieve both good water repellency and antibacterial properties. Also, from the comparison of Examples 1-1 to 1-6 and Reference Example 1-1, it can be seen that the wear resistance, oil repellency, and improved scratch resistance.

(second form) Hereinafter, the present invention (second aspect) will be more specifically described by way of examples related to the second aspect. Of course, the present invention (second aspect) is not limited by the following examples, and can be implemented with appropriate changes within the scope of the above and the following gist, all of which are included in the present invention (second aspect) within the technical scope.

Example 2-1 N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chlorine A solution of 0.05% by mass of a reactant of propyltrimethoxysilane (trade name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99.95% by mass of isopropanol as a solvent (E) at room temperature Stirring was carried out to obtain a composition for layer (c) formation. Also, prepare the base material (s) formed by laminating the hard coat layer (s2) containing the quaternary ammonium salt as the antistatic agent (AS) on the polyethylene terephthalate base material (s1) (hard coat layer Thickness: 5 μm, thickness of the substrate (s): 50 μm), the hard coat (s2) surface of the above substrate (s) was activated using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.). Then, using OPTICOAT MS-A100 (rod coater) manufactured by MIKASA Co., Ltd., #2 rod, the layer (c) obtained above was combined under the conditions of 0.5 ml and 100 mm/sec. coated on the hard coat layer (s2) in the base material (s), and dried at 100° C. for 30 seconds to obtain a layered intermediate with the layer (c) formed thereon.

[chem 25]

Then, the compound (a10) satisfying the above formula (a1) as organosilicon compound (A) and FAS13E(C ₆ F ₁₃ -C ₂ H ₄ -Si(OC ₂ H ₅ ) as organosilicon compound (B) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.), FC-3283 (C ₉ F ₂₁ N, manufactured by Fluorinert, 3M Company) as a solvent (D) were mixed, and stirred at room temperature for a specified time to obtain a water-repellent layer. combination. The ratio of the organosilicon compound (A) in the composition for water-repellent layer formation was 0.085 mass %, and the ratio of the organosilicon compound (B) was 0.05 mass %. Using OPTICOAT MS-A100 (rod coater) manufactured by MIKASA Co., Ltd., #2 rod, apply the water-repellent layer-forming composition to the laminated intermediate under the conditions of 0.5 ml and 100 mm/sec The layer (c) was dried at 100° C. for 30 seconds to obtain a laminate with the layer (r) formed thereon. Furthermore, the compound (a10) used as the organosilicon compound (A) is a compound that satisfies the requirements of the above-mentioned compounds (a11) and (a21) and also satisfies the requirements of the formula (a3) including preferred aspects. Each thickness obtained by the measurement method of "(2-4) Thickness of layer (c)" described below, and the measurement method of "(2-3) Thickness of layer (r)" described below 6.6 nm and 4.3 nm, and their total thickness is 10.9 nm.

Example 2-2 A laminate was produced in the same manner as in Example 2-1 except that the bar of the layer (C) forming method was set to #18. The layer (c) and The thicknesses of layer (r) are 18.1 nm and 3.7 nm respectively, and their total thickness is 21.8 nm (18.1 nm+3.7 nm).

Example 2-3 The organosilicon compound of layer (C) was set as KBM603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), except that, by the same method as in Example 2-1 way to make laminates. The layer (c) and The thicknesses of layer (r) are 5.6 nm and 4.3 nm respectively, and the total thickness thereof is 9.9 nm (5.6 nm+4.3 nm).

Comparative example 2-1 Prepare a substrate (s) formed by laminating a hard coat (s2) containing a quaternary ammonium salt as an antistatic agent (AS) on a polyethylene terephthalate substrate (s1) (thickness of the hard coat: 5 μm, the thickness of the substrate (s): 50 μm). Since neither layer (c) nor layer (r) was formed, the thickness of either layer was 0 nm, and the total thickness was also 0 nm.

Comparative example 2-2 A laminate was produced in the same manner as in Example 2-1 except that the layer (C) was not formed. The layer (c) and The thicknesses of layer (r) are 0 nm and 4.5 nm respectively, and their total thickness is 4.5 nm (0 nm+4.5 nm).

Comparative example 2-3 A laminate was produced in the same manner as in Example 2-1 except that the organosilicon compound of the layer (C) was TEOS (tetraethoxysilane) and the bar of the formation method was #18. The layer (c) and The thicknesses of layer (r) are 31.4 nm and 4.2 nm respectively, and their total thickness is 35.6 nm (31.4 nm+4.2 nm).

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

(2-1) Calculation method of surface resistance increase rate Using Hiresta-UP (MCP-HT450 manufactured by Mitsubishi ANALYTECH Co., Ltd.), in the state of being in contact with the surface of the laminate, the applied voltage: 500 V is used for measurement, and the heat resistance test of the laminate (80°C, 36 hours) ) were also measured. In addition, the surface resistance increase rate was calculated by the following calculation method. Surface resistivity after heat resistance test/surface resistivity before test

(2-2) Scratch resistance Using a steel wool testing machine (manufactured by Daiei Seiki Co., Ltd.) equipped with steel wool #0000 (manufactured by Bonstar Co., Ltd.), the steel wool is in contact with the surface (layer (r)) of the laminate. Under the pressure of 250 g/cm ² , wear test was carried out, reciprocating 1500 times. Check for damage after abrasion. Furthermore, the confirmation of the presence or absence of damage was performed under LED lighting.

(2-3) Thickness of layer (r) The film thickness of layer (r) was measured using X-ray photoelectron spectroscopy (XPS) according to the following description. First, layer (c) and layer (r) were fabricated on a glass substrate treated with atmospheric pressure plasma by the same method as in Example 1. At this time, the composition for forming a water-repellent layer was applied while changing the coating amount in four places, and a total of four types of laminates having the same thickness of the layer (c) and different film thicknesses of the layer (r) were produced. Next, the film thickness of each layer (r) was measured using an ellipsometer. Also, for the same layer, the amount of element F and the amount of element C other than elements bonded to F are measured by XPS method, and the ratio (F/C (other than C-F)) is calculated to prepare a film for layer (r) Thick calibration curve. In this case, the amount of the F element comes from the layer (r), and the amount of the C elements other than the C element bonded to the F element comes from the layer (c). Next, XPS measurement was carried out on the laminate produced in the example, and the film thickness of the layer (r) was calculated according to the calibration curve prepared above. <XPS measurement conditions> Device name: K-alpha manufactured by Thermofisher Scientific X-ray source: Monochromatic Al Kα Power: 72W (12kV, 6mA) Spot size: 400 μm Pass energy: 50 eV Dwell time: 50 ms mode (element): narrow (F, C) Neutralizing gun: on

(2-4) Thickness of layer (c) For the laminate coated with layer (c) and layer (r), ultra-thin sections were made by FIB-SEM, and the thickness of layer (c) was measured by observing with scanning transmission electron microscope (STEM) from the cross-sectional direction. ＜FIB Processing Conditions＞ Device name: HeliosG4UX (manufactured by Japan FEI Corporation) Ion source: Ga Acceleration voltage: 30 kV Sample thickness: below 100 nm <STEM measurement conditions> Device name: HeliosG4UX (manufactured by Japan FEI Corporation) Acceleration voltage: 23 kV Current value: 50pA Magnification: 1 million times

(2-5) Dynamic friction coefficient The dynamic friction coefficient of the water-repellent layer (r) side surface was measured using Tribogear (surface property measuring machine TYPE: 38) manufactured by Shinto Scientific Co., Ltd. under a constant load, using artificial leather, and the measurement conditions were set to the following conditions. Load converter: 1.961 mV/V Load: 200 g Moving distance: 50mm Moving speed: 100mm/min Number of samples: 3010

Table 2 shows the evaluation results of the above-mentioned (2-1) to (2-5) about Examples and Comparative Examples.

[Table 2] layer (c) Layer (r) thickness (nm) Anti-static performance Scratch resistance test dynamic friction test Organosilicon compound (C) Thickness (nm) Surface resistivity before heat resistance test (Ω/□) Surface resistivity after heat resistance test (Ω/□) Surface resistivity increase rate before and after heat resistance test Example 2-1 X-12-5263HP 6.6 4.3 1.1×10 ¹⁰ 3.8×10 ¹⁰ 3.5 times no scratches 0.041 Example 2-2 X-12-5263HP 18.1 3.7 9.8×10 ⁹ 3.2×10 ¹⁰ 3.3 times no scratches 0.042 Example 2-3 KBM603 5.6 4.3 1.4×10 ¹⁰ 3.7×10 ¹⁰ 2.6 times no scratches 0.045 Comparative example 2-1 - 0 0 9.7×10 ⁹ 6.3×10 ¹⁰ 6.5 times have scratches -(※) Comparative example 2-2 - 0 4.5 9.8×10 ⁹ 8.9×10 ¹⁰ 9.1 times have scratches 0.052 Comparative example 2-3 TEOS 31.4 4.2 9.9×10 ⁹ 4.2×10 ¹⁰ 4.2 times have scratches 0.051 ※The value is too high to measure

According to Table 2, the surface resistivity after the heat resistance test of the laminates of Examples 1 to 3 in which the layer (c) containing nitrogen element is provided between the conductive substrate (s) and the above-mentioned layer (r) The rise of the carbon dioxide is suppressed, and the scratch resistance is also excellent. Industrial availability

The laminates of the present invention (the first aspect and the second aspect) can be suitably used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, automobiles, and buildings Window glass, metal products such as cooking utensils, ceramic products such as tableware, and auto parts made of plastic are useful in industry. In addition, it can also be preferably used in kitchens, bathrooms, washbasins, mirrors, and various components around the toilet.

Claims (29)

A laminate comprising a substrate (s) containing an antibacterial component (K) and a water-repellent layer (r), and The above laminate contains an organosilicon compound (C) having a silicon atom bonded to a hydrolyzable group or a hydroxyl group, The above-mentioned water-repellent layer (r) is a hardened layer of an organosilicon compound (A) having a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded via a linking group or not via a linking group, The thickness of the layered part including the water-repellent layer (r) provided on the substrate (s) is not less than 1 nm and not more than 50 nm. The laminate according to claim 1, wherein a layer (c) is provided between the water-repellent layer (r) and the substrate (s), Layer (c) contains organosilicon compound (C). The laminate according to claim 2, wherein the thickness of the above-mentioned layer (c) is less than 30 nm. Such as the laminated body of claim 1, wherein the substrate (s) and the water-repellent layer (r) are directly laminated, The water-repellent layer (r) contains organosilicon compound (C). The laminate according to any one of claims 1 to 4, wherein the organosilicon compound (C) is a compound having an amine group or an amine skeleton. The laminate according to any one of claims 1 to 5, wherein the organosilicon compound (C) is a compound represented by any one of formulas (c1) to (c3), or two or more compounds represented by formula (c3) The compound formed by the condensation of at least any one of the following X ³¹ to X ³⁴ is bonded, [Chem. 1]

In the above formula (c1), R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x11 , the multiple R ^x11 can be respectively Different, when there is a plurality of R ^x12 , the plurality of R ^x12 can be different, when there is a plurality of R ^x13 , the plurality of R ^x13 can be different, and when there is a plurality of R ^x14 , the plurality of R x14 R ^x14 can be different respectively, Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group with 1 to 20 carbons or fluorine atoms in which one or more hydrogen atoms are replaced by fluorine atoms, and there are multiple Rf ^x11 In the case of multiple Rf x11, the plurality of Rf ^x11 can be different. In the case of multiple Rf ^x12 , the plurality of Rf ^x12 can be different. In the case of multiple Rf ^x13 , the plurality of Rf ^x13 can be different. In the case of a plurality of Rf ^x14 , the plurality of Rf ^x14 can be different, and R ^x15 is an alkyl group with 1 to 20 carbons. In the case of a plurality of R ^x15 , the plurality of R ^x15 can be different, and X ¹¹ is hydrolyzed In the case of a neutral group or a hydroxyl group, when there are a plurality of X ¹¹ , the plurality of X ¹¹ can be different, Y ¹¹ is -NH-, or -S-, when there is a plurality of Y ¹¹ , the plurality of Y ¹¹ can be are different, Z ¹¹ is vinyl, α-methylvinyl, styrene, methacryl, acryl, amine, isocyanate, isocyanurate, epoxy, urea, or mercapto, 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 of 1 to 3, and when Z ¹¹ is not an amino group , has at least one Y ¹¹ that is -NH-, and when all Y ¹¹ are -S- or p5 is 0, Z ¹¹ is an amino group, and Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _{3 - p6} , p1-{C(R ^x11 )(R ^x12 )}-unit (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 )}-unit (U _c14 ), p5-Y ¹¹ -unit ( U _c15 ), Z ¹¹ - is one terminal of the compound represented by formula (c1), -Si(X ¹¹ ) _p6 (R ^x15 ) _{3 - p6} is the other terminal, as long as -O- is not continuous with -O-, Then each unit (U _c11 )～unit (U _c15 ) is arranged in any order and bonded ; [Chem 2]

In the above formula (c2), R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x20 , the multiple R ^x20 can be different. In the case of R ^x21 , the plurality of R ^x21 may be different, and Rf ^x20 and Rf ^x21 are each independently an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms. In the case of Rf ^x20 , a plurality of Rf ^x20 may be different, and in the case of a plurality of Rf ^x21 , a plurality of Rf ^x21 may be different, R ^x22 and R ^x23 are independently an alkyl group with 1 to 20 carbon atoms, and When there are multiple R ^x22 and R ^x23 , ^the multiple R ^x22 and R ^x23 can be different respectively, X20 and ^X21 are independently hydrolyzable groups or hydroxyl groups, and when there are multiple ^X20 and ^X21 , A plurality of X ²⁰ and X ²¹ can be different, p20 is independently an integer of 1 to 30, p21 is an integer of 0 to 30, respectively, and at least one of the repeating units marked p20 or p21 and enclosed in parentheses is replaced by Amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ in the above amine skeleton is a hydrogen atom or an alkyl group, p22 and p23 are independently an integer of 1 to 3, p20 -{C(R ^x20 )(R ^x21 )}-units ( U _c21 ), p21-{C(Rf ^x20 )(Rf ^x21 )}-units (U _c22 ) do not need to be p20 units (U _c21 ) or p21 units (U _c22 ) continuous, each unit (U _c21 ) and Units (U _c22 ) are arranged in any order and bonded. One end of the compound represented by formula (c2) is -Si(X ²⁰ ) _p22 (R ^x22 ) _{3 － p22} , and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _{3 - p23} ; [chemical 3]

In the above formula (c3), Z ³¹ and Z ³² are independently hydrolyzable groups and reactive functional groups other than hydroxyl groups, and R ^x31 , R ^x32 , R ^x33 , and R ^x34 are independently hydrogen atoms or carbon numbers of 1 to 4 The alkyl group, when there are multiple R ^x31 , the multiple R ^x31 can be different, when there are multiple R ^x32 , the multiple R ^x32 can be different, when there are multiple R ^x33 , Plural R ^x33 may be different, and when there are multiple R ^x34 , multiple R ^x34 may be different, Rf ^x31 , Rf ^x32 , Rf ^x33 , Rf ^x34 are each independently one or more hydrogen atoms replaced by fluorine For an alkyl or fluorine atom with 1 to 20 carbon atoms, when there are multiple Rf ^x31 , the multiple Rf ^x31 may be different, and when there are multiple Rf ^x32 , the multiple Rf ^x32 may be different, When there are multiple Rf ^x33 , the multiple Rf ^x33 can be different, and when there are multiple Rf ^x34 , the multiple Rf ^x34 can be different, Y ³¹ is -NH-, -N(CH ₃ )- Or -O-, when there are multiple Y ^31s , the multiple Y ^31s can be different, and X ³¹ , X ³² , X ³³ , and X ³⁴ are independently -OR ^c (R ^c is a hydrogen atom with a carbon number of 1 ~4 alkyl groups, or amino C _1-3 alkyl _{diC 1-3} alkoxysilyl groups), when there are multiple X ^31s , the multiple X ^31s can be different, and when there are multiple X In the case of ³² , the plurality of X ³² can be different, and in the case of a plurality of X ³³ , the plurality of X ³³ can be different, and in the case of a plurality of X ³⁴ , the plurality of X ³⁴ can be different, p31 is an integer of 0 to 20, p32, p33, and p34 are independently an integer of 0 to 10, p35 is an integer of 0 to 5, p36 is an integer of 1 to 10, p37 is 0 or 1, and satisfies the requirements of Z ³¹ and Z ³² At least one of them is an amino group, or at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and one terminal of the compound represented by formula (c3) is Z ³¹ -, and the other terminal is Z ³² -, as long as -O- is not continuous with -O-, then p31-{C(R ^x31 )(R ^x32 )}-unit (U _c31 ), p32-{C(Rf ^x31 )(Rf ^x32 ) }-unit(U _c32 ), p33-{Si(R ^x33 )(R ^x34 )}-unit(U _c33 ), p34-{Si(Rf ^x33 )(Rf ^x34 )}-unit(U _c34 ), p35-Y ³¹ -unit (U _c35 ), p36-{Si(X ^{3 1} )(X ³² )-O}-unit (U _c36 ), and p37-{Si(X ³³ )(X ³⁴ )}-unit (U _c37 ) are respectively arranged in an arbitrary order to form a bond. The laminate according to any one of claims 1 to 6, wherein the antibacterial component (K) contains metal ions. The laminate according to any one of claims 1 to 7, wherein the antibacterial component (K) contains a quaternary ammonium salt. As the laminate of claim item 8, wherein the quaternary ammonium salt is a compound represented by formula (k1), [Chemical 4]

[In formula (k1), R ^k1 to R ^k3 independently represent a hydrocarbon group with 1 to 30 carbons, R ^k4 and R ^k5 independently represent an alkyl group with 1 to 4 carbons, and where there are a plurality of R ^k5 In this case, a plurality of R ^k5 may be different, Y ^k1 and Y ^k2 independently represent a single bond or a divalent hydrocarbon group with 1 to 10 carbons, A ^k1 and A ^k2 independently represent a hydrolyzable group or a hydroxyl group, in presence In the case of a plurality of A ^k1 , the plurality of A ^k1 may be different, and in the case of a plurality of A ^k2 , the plurality of A ^k2 may be different respectively, and Z ^k1 is a hydrolyzable group, a hydroxyl group, or an alkane having 1 to 4 carbon atoms group, or a group represented by formula (ki), k3 represents 1 or 2, k4 represents an integer of 0 to 2, k5 represents an integer of 0 to 10, and Z ^k1 is a hydrolyzable group, a hydroxyl group, or a carbon number of 1 to 4 In the case of an alkyl group, n represents 1, and in the case where Z ^k1 is a group represented by formula (ki), n represents 2, and X represents a halogen atom; [Chemical 5]

[In formula (ki), R ^k17 to R ^k19 each independently represent a hydrocarbon group having 1 to 30 carbon atoms, and * represents a bonding bond]]. The laminate according to any one of claims 1 to 9, wherein the water contact angle on the surface of the water-repellent layer (r) is 105° or more, and satisfies the group selected from the following requirements (α) and (β) At least one of the elements: (α) The antibacterial activity value against Staphylococcus aureus in the antibacterial activity test according to JIS Z 2801:2010 is 0.1 or more; (β) When the antibacterial activity test according to JIS Z 2801:2010 is carried out, the antibacterial activity value against Escherichia coli is 0.1 or more. The laminated body according to any one of claims 1 to 10, wherein a load of 1000 g is applied on a circle with a diameter of 6 mm, and the surface of the water-repellent layer (r) of the laminated body is reciprocally rubbed 1500 times to perform the abrasion resistance The water contact angle on the surface of the water-repellent layer (r) after the test is above 75°. The laminate according to any one of Claims 1 to 11, wherein the wear test is carried out by applying a pressure of 250 g/cm ² and utilizing steel wool to rub the surface of the water-repellent layer (r) of the above-mentioned laminate until the surface of the water-repellent layer ( r) When peeling or damage is visually confirmed on the surface, the number of times the steel wool reciprocates on the surface of the water-repellent layer (r) is 100 or more. A laminate comprising a conductive substrate (s), a layer (c) containing nitrogen, and a layer (r) containing fluorine, wherein the layer (c) is provided on the substrate (s) and the layer (r) above. The laminate according to claim 13, wherein the thickness of the above-mentioned layer (c) is less than 30 nm. The laminate according to claim 13 or 14, wherein the substrate (s) is a substrate containing an antistatic agent, or a substrate containing a surface layer containing an antistatic agent. The laminate according to claim 15, wherein the substrate (s) includes a resin substrate and the surface layer containing an antistatic agent, and the surface layer is a hard coat layer. The laminate according to claim 16, wherein the hard coat layer is at least one selected from the group consisting of acrylic resins, polysiloxane resins, and epoxy resins. The laminate according to any one of claims 15 to 17, wherein the surface layer has a thickness of 10 μm or less. The laminate according to any one of claims 15 to 18, wherein the antistatic agent is an ionic compound. The laminate according to any one of claims 15 to 19, wherein the antistatic agent is an ionic compound having a cationic organic group or an anionic organic group. The laminate according to any one of claims 15 to 20, wherein the antistatic agent is at least one selected from the group consisting of quaternary ammonium salts, pyridinium salts, and compounds having primary to tertiary amine groups. The laminate according to any one of claims 13 to 21, wherein the total thickness of the layer (c) and the layer (r) is less than 50 nm. The laminate according to any one of claims 13 to 22, wherein the layer (c) is a hardened layer of an organosilicon compound (C) represented by the following formula (c1) or (c2); [Chemical 6]

In the above formula (c1), R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x11 , the multiple R ^x11 can be respectively Different, when there is a plurality of R ^x12 , the plurality of R ^x12 can be different, when there is a plurality of R ^x13 , the plurality of R ^x13 can be different, and when there is a plurality of R ^x14 , the plurality of R x14 R ^x14 can be different respectively, Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group with 1 to 20 carbons or fluorine atoms in which one or more hydrogen atoms are replaced by fluorine atoms, and there are multiple Rf ^x11 In the case of multiple Rf x11, the plurality of Rf ^x11 can be different. In the case of multiple Rf ^x12 , the plurality of Rf ^x12 can be different. In the case of multiple Rf ^x13 , the plurality of Rf ^x13 can be different. In the case of a plurality of Rf ^x14 , the plurality of Rf ^x14 can be different, and R ^x15 is an alkyl group with 1 to 20 carbons. In the case of a plurality of R ^x15 , the plurality of R ^x15 can be different, and X ¹¹ is hydrolyzed In the case of a neutral group or a hydroxyl group, when there are a plurality of X ¹¹ , the plurality of X ¹¹ can be different, Y ¹¹ is -NH-, or -S-, when there is a plurality of Y ¹¹ , the plurality of Y ¹¹ can be are different, Z ¹¹ is vinyl, α-methylvinyl, styrene, methacryl, acryl, amine, isocyanate, isocyanurate, epoxy, urea, or mercapto, 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 of 1 to 3, and when Z ¹¹ is not an amino group , has at least one Y ¹¹ that is -NH-, and when all Y ¹¹ are -S- or p5 is 0, Z ¹¹ is an amino group, and Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _{3 - p6} , p1-{C(R ^x11 )(R ^x12 )}-unit (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 )}-unit (U _c14 ), p5-Y ¹¹ -unit ( U _c15 ), Z ¹¹ - is one terminal of the compound represented by formula (c1), -Si(X ¹¹ ) _p6 (R ^x15 ) _{3 - p6} is the other terminal, as long as -O- is not continuous with -O-, Then each unit (U _c11 )～unit (U _c15 ) is arranged in any order and bonded , [C7]

In the above formula (c2), R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple R ^x20 , the multiple R ^x20 can be different. In the case of R ^x21 , the plurality of R ^x21 may be different, and Rf ^x20 and Rf ^x21 are each independently an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms. In the case of Rf ^x20 , a plurality of Rf ^x20 may be different, and in the case of a plurality of Rf ^x21 , a plurality of Rf ^x21 may be different, R ^x22 and R ^x23 are independently an alkyl group with 1 to 20 carbon atoms, and When there are multiple R ^x22 and R ^x23 , ^the multiple R ^x22 and R ^x23 can be different respectively, X20 and ^X21 are independently hydrolyzable groups or hydroxyl groups, and when there are multiple ^X20 and ^X21 , A plurality of X ²⁰ and X ²¹ can be different respectively, p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, at least one of the repeating units marked with p20 or p21 and enclosed in brackets is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ in the above-mentioned amine skeleton is a hydrogen atom or an alkyl group, p22 and p23 are independently an integer of 1 to 3, p20 -{C(R ^x20 )(R ^x21 )}-units (U _c21 ), p21-{C(Rf ^x20 )(Rf ^x21 )}-units (U _c22 ) need not be continuous for p20 units (U _c21 ) or p21 units (U _c22 ), each unit (U _c21 ) and unit (U _c22 ) are arranged in any order and bonded, one end of the compound represented by formula (c2) is -Si(X ²⁰ ) _p22 (R ^x22 ) _{3 － p22} , and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _{3 - p23} . The laminate according to any one of Claims 1 to 23, wherein the water-repellent layer (r) has a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded via a linking group or not, and contains fluorine. The hardened layer of organosilicon compound (A), The above layer (r) is a cured layer of organosilicon compound (A) containing fluorine element. The laminate according to claim 24, wherein the organosilicon compound (A) is a compound having a fluoropolyether structure. The laminate as claimed in item 25, wherein the organosilicon compound (A) is a compound represented by formula (a1); [Chemical 8]

In the above formula (a1), Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by fluorine atoms. When there is a plurality of Rf ^a26 , the plurality of Rf ^a26 can be different, and when there is a plurality of Rf ^a27 , the plurality of Rf ^a27 can be different, and when there is a plurality of Rf ^a28 , the plurality of Rf ^a28 can be different. They are different. When there are multiple Rf ^a29s , the multiple Rf ^a29s can be different. R ²⁵ and R ²⁶ are independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbon atoms, or one or more hydrogen atoms A halogenated alkyl group with 1 to 4 carbon atoms whose atom is replaced by a halogen atom. At least one of ^R25 and ^R26 bonded to a carbon atom is a hydrogen atom. When there are multiple R25s, the multiple ^{R25 25} can be different respectively. When there are multiple R ²⁶ , the multiple R ²⁶ can be different respectively. R ²⁷ and R ²⁸ are independently a hydrogen atom, an alkyl group with 1 to 4 carbons, or a single bond. In the case of one R ²⁷ , the plurality of R ²⁷ may be different, and in the case of a plurality of R ²⁸ , the plurality of R ²⁸ may be different, R ²⁹ and R ³⁰ are independently an alkyl group with 1 to 20 carbons, When there are a plurality of R ²⁹ , the plurality of R ²⁹ may be different, and in the case of a plurality of R ³⁰ , the plurality of R ³⁰ may be different, M ⁷ is -O-, -C(=O)- O-, -OC(=O)-, -NR-, -NRC(=O)-, -C(=O)NR-, -CH=CH-, or -C ₆ H ₄ -, the above R is hydrogen atom, an alkyl group with 1 to 4 carbons, or a fluorine-containing alkyl group with 1 to 4 carbons, when there are multiple ^M7s , the multiple ^M7s can be different, and ^M5 is a hydrogen atom, a fluorine atom or a carbon For an alkyl group with a number of 1 to 4, when there are multiple ^M5s , the multiple ^M5s can be different, ^M10 is a hydrogen atom or a halogen atom, ^M8 and ^M9 are independently hydrolyzable groups, hydroxyl groups, Or -(CH ₂ ) _e7 -Si(OR ¹⁴ ) ₃ , where e7 is 1 to 5, R ¹⁴ is methyl or ethyl, and when there are multiple M ⁸ , the multiple M ⁸ can be different, and when there are ^In the case of multiple M9s, the multiple ^M9s can be different, f21, f22, f23, f24, and f25 are independently integers from 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 Above, f26 is an integer of 0 to 20, f27 is an integer of 0 to 2 independently, g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, and g21+g22≦3, g31 is an integer of 1 to 3, g32 is an integer from 0 to 2, and g31+g32≦3, about M ¹⁰ -, -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _{3 － g31 － g32} , f21-{C(R ²⁵ )(R ²⁶ )}-unit (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 -unit (U _a5 ), and f26-[C(M ⁵ ){(CH ₂ ) _f27 -Si(M ⁸ ) _g21 (H) _g22 (R ²⁹ ) _{3 - g21 - g22} }]-unit (U _a6 ), M ¹⁰ - is one terminal in formula (a1), -Si(M ⁹ ) _g31 (H) _g32 (R ³⁰ ) _{3 - g31 - g32} is the other Terminals are arranged in the order forming at least a part of the fluoropolyether structure, and as long as -O- and -O- are not continuous, each unit can be arranged in any order and bonded. The laminate according to any one of claims 1 to 26, wherein the coefficient of dynamic friction of the surface of the water-repellent layer (r) or the surface of the layer (r) is 0.1 or less. The laminate according to any one of Claims 1 to 27, wherein the surface resistivity after the heat resistance test of the laminate at 80°C for 36 hours is less than 6.4 times the surface resistivity before the heat resistance test. A window film or a touch panel display, comprising the laminate according to any one of claims 1 to 28.