TWI811738B - laminate - Google Patents

Abstract

The laminated body of the present invention includes a base material layer and an antifouling layer in order toward one side in the thickness direction. The antifouling layer contains an alkoxysilane compound having a perfluoropolyether group. The center of gravity position of the periodic arrangement of the wave peaks based on the in-plane direction of the perfluoropolyether derived from the above-mentioned antifouling layer measured by in-plane diffraction measurement in the micro-angle incident X-ray diffraction method is 1.8Å ^-1 the following.

Description

laminated body

The present invention relates to a laminated body, and specifically to a laminated body provided with an antifouling layer.

Previously, it has been known to form an antifouling layer on the surface of a film base material or on the surface of optical components such as optical films from the viewpoint of preventing the adhesion of stains such as fingerprints and fingerprints.

As such an optical film provided with an antifouling layer, for example, an antireflection film has been proposed that includes a film base material, an antireflection layer, and an antifouling layer in this order (see, for example, Patent Document 1).

[Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2020-52221

On the other hand, if stains adhered to the antifouling layer are wiped off, the antifouling properties of the antifouling layer are adversely affected.

The present invention provides a laminate that can suppress the deterioration of the antifouling properties of the antifouling layer even after wiping off stains attached to the antifouling layer.

The present invention [1] is a laminated body, which has a base material layer and an antifouling layer in order toward one side in the thickness direction. The antifouling layer contains an alkoxysilane compound having a perfluoropolyether group and is incident through a small angle. The position of the center of gravity of the periodic arrangement of the wave peaks based on the in-plane direction of the perfluoropolyether derived from the above-mentioned antifouling layer measured by in-plane diffraction measurement using the X-ray diffraction method is 1.8 Å ^-1 or less.

The present invention [2] includes the laminate according to the above [1], which is provided with a primer layer on the other surface in the thickness direction of the antifouling layer.

The present invention [3] includes the laminated body according to the above [2], wherein the undercoat layer is a layer containing silica.

The present invention [4] includes the laminate according to the above [3], wherein the antifouling layer is formed on the undercoat layer by using an alkoxysilane compound having a perfluoropolyether group via a siloxane bond.

The present invention [5] includes the laminated body according to the above [1], further comprising an adhesion layer and an anti-reflection layer between the base material layer and the antifouling layer.

The present invention [6] includes the laminated body according to the above [5], wherein the anti-reflection layer includes two or more layers having mutually different refractive indexes.

The present invention [7] includes the laminate according to the above [6], wherein the antireflection layer contains one selected from the group consisting of metal, metal oxide, and metal nitride.

The present invention [8] includes the laminate according to the above [6] or [7], wherein one side of the antireflection layer in the thickness direction is a layer containing silicon dioxide.

The antifouling layer in the laminate of the present invention contains an alkoxysilane compound having a perfluoropolyether group. Furthermore, in the antifouling layer, the periodic arrangement of wave peaks derived from the perfluoropolyether in the antifouling layer based on the in-plane direction measured by in-plane diffraction measurement in the micro-angle incident X-ray diffraction method The center of gravity position is below 1.8Å ^-1 . Therefore, even after wiping off the stains attached to the antifouling layer, the antifouling properties of the antifouling layer can be suppressed from decreasing.

1: Laminated body

2: Base material layer

3: Antifouling layer

4:Substrate

5: Functional layer

6: Adhesive layer

7: Optical functional layer

11: 1st high refractive index layer

12: 1st low refractive index layer

13: 2nd high refractive index layer

14: 2nd low refractive index layer

15: Base coat

20: Alkoxysilane compound with perfluoropolyether group

20A: Alkoxysilane compound

20B:Alkoxysilane compound

20C: Alkoxysilane compound

21:Group

21A:Group

21B:Group

21C:Group

FIG. 1 shows a cross-sectional view of the first embodiment of the laminated body of the present invention.

2A to 2C illustrate an embodiment of the manufacturing method of the first embodiment of the laminated body of the present invention. Figure 2A shows the step of preparing the substrate in the first step. FIG. 2B shows the step of arranging a hard coat layer (functional layer) on the base material in the first step. Figure 2C shows the second step of arranging the antifouling layer on the base material layer.

3A and 3B are explanatory views of an alkoxysilane compound having a perfluoropolyether group deposited on the base material layer. FIG. 3A is an explanatory diagram of an alkoxysilane compound having a singular perfluoropolyether group deposited on the base material layer. FIG. 3B is an explanatory diagram of an alkoxysilane compound having a plurality of perfluoropolyether groups deposited on the base material layer.

FIG. 4 shows a cross-sectional view of the second embodiment of the laminated body of the present invention.

5A to 5D illustrate an embodiment of a manufacturing method of the second embodiment of the laminated body of the present invention. Figure 5A shows the step of preparing the substrate in the third step. FIG. 5B shows the step of arranging a hard coat layer (functional layer) on the base material in the third step. Figure 5C shows the fourth step of sequentially arranging the adhesive layer and the optical functional layer (anti-reflective layer) on the base material layer. Figure 5D shows the fifth step of arranging the antifouling layer on the optical functional layer (anti-reflection layer).

FIG. 6 shows a cross-sectional view of a variation of the first embodiment of the laminate of the present invention (a laminate further provided with a primer layer between the base material layer and the antifouling layer).

FIG. 7 shows the results of in-plane diffraction (In-Plane) measurement in Example 2.

FIG. 8 shows the fitting results in the in-plane diffraction (In-Plane) measurement of Example 2.

1. First Embodiment

The first embodiment of the laminated body of the present invention will be described with reference to FIG. 1 .

In FIG. 1 , the upper and lower directions on the paper are the up and down directions (thickness direction), the upper side on the paper is the upper side (one side in the thickness direction), and the lower side on the paper is the lower side (the other side in the thickness direction). In addition, the left-right direction and the depth direction of the paper are orthogonal to the up-down direction. Specifically, it is based on the direction arrow of each figure.

<Laminated body>

The laminated body 1 has a film shape (including a sheet shape) having a specific thickness. The laminated body 1 extends in the plane direction orthogonal to the thickness direction. The laminated body 1 has a flat upper surface and a flat lower surface.

As shown in FIG. 1 , the laminated body 1 has a base material layer 2 and an antifouling layer 3 in order toward one side in the thickness direction. More specifically, the laminated body 1 includes a base material layer 2 and an antifouling layer 3 disposed directly on the upper surface (one surface in the thickness direction) of the base material layer 2 .

The total light transmittance (JIS K 7375-2008) of the laminated body 1 is, for example, 80% or more, preferably 85% or more.

The thickness of the laminated body 1 is, for example, 300 μm or less, preferably 200 μm or less, and, for example, 10 μm or more, preferably 30 μm or more.

<Substrate layer>

The base material layer 2 is a base material for ensuring the mechanical strength of the laminated body 1 .

The base material layer 2 has a film shape. The base material layer 2 is disposed on the entire lower surface of the antifouling layer 3 in contact with the lower surface of the antifouling layer 3 .

The base material layer 2 includes a base material 4 and a functional layer 5 . Specifically, the base material layer 2 includes a base material 4 and a functional layer 5 in order toward one side in the thickness direction.

The total light transmittance (JIS K 7375-2008) of the base material layer 2 is, for example, 80% or more, preferably 85% or more.

<Substrate>

The base material 4 is an object to be treated that is provided with antifouling properties by the antifouling layer 3 .

The base material 4 has a film shape. The base material 4 is preferably flexible. The base material 4 is disposed on the entire lower surface of the functional layer 5 so as to contact the lower surface of the functional layer 5 .

An example of the base material 4 is a polymer film. Examples of materials for the polymer film include polyester resin, (meth)acrylic resin, olefin resin, polycarbonate resin, polyether resin, polyarylate resin, melamine resin, polyamide resin, and polyamide resin. Imine resin, cellulose resin, and polystyrene resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the (meth)acrylic resin include polymethacrylate. Examples of the olefin resin include polyethylene, polypropylene, and cycloolefin polymers. Examples of the cellulose resin include triacetyl cellulose. As the material of the polymer membrane, cellulose resin is preferred, and triacetyl cellulose is more preferred.

The thickness of the base material 4 is, for example, 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and, for example, 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less.

The thickness of the base material 4 can be measured using a dial gauge (made by PEACOCK, "DG-205").

<Functional layer>

Functional layer 5 has a film shape. The functional layer 5 is arranged on one side of the base material 4 in the thickness direction.

Examples of the functional layer 5 include a hard coat layer.

In this case, the base material layer 2 includes the base material 4 and the hard coat layer in order toward the thickness direction side.

In the following description, the case where the functional layer 5 is a hard coat layer will be described.

The hard coat layer is a protective layer used to prevent damage to the base material 4 .

The hard coat layer is formed of, for example, a hard coat composition.

The hard coat composition contains a resin and optionally particles. That is, the hard coat layer contains resin and optionally particles.

Examples of the resin include thermoplastic resin and curable resin. Examples of the thermoplastic resin include polyolefin resin.

Examples of the curable resin include active energy ray-curable resins that are cured by irradiation with active energy rays (such as ultraviolet rays and electron beams) and thermosetting resins that are cured by heating. As the curable resin, an active energy ray curable resin is preferably used.

Examples of active energy ray-curable resins include (meth)acrylic ultraviolet curable resins, urethane resins, melamine resins, alkyd resins, siloxane-based polymers, and organosilane condensates. As the active energy ray curable resin, a (meth)acrylic ultraviolet curable resin is preferably used.

Moreover, the resin may contain the reactive diluent described in Japanese Patent Application Laid-Open No. 2008-88309, for example. Specifically, the resin may include polyfunctional (meth)acrylates.

The resin can be used alone or in combination of two or more types.

Examples of particles include metal oxide fine particles and organic fine particles. Examples of the material of the metal oxide fine particles include silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Examples of materials for organic fine particles include polymethylmethacrylate, polysiloxane, polyethylene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate. As the organic fine particles, polymethyl methacrylate is preferably exemplified.

The purpose of including particles in the hard coat layer is, for example, to provide anti-glare properties, improve adhesion, increase hardness, and adjust refractive index.

Particles can be used individually or in combination of 2 or more types.

In addition, a thixotropy imparting agent (for example, organoclay), a photopolymerization initiator, a filler, and a leveling agent may be added to the hard coating composition in an appropriate ratio as necessary. In addition, the hard coating composition can be diluted with a well-known solvent.

In addition, the method of forming the hard coat layer will be described in detail later. The method is to apply a diluted solution of the hard coat composition on one side of the substrate 4 in the thickness direction, and dry it by heating if necessary. After drying, the hard coat composition is hardened by, for example, active energy ray irradiation or heating.

Thereby, a hard coat layer is formed.

The thickness of the hard coat layer is 1 μm or more and 50 μm or less, preferably 30 μm or less.

<Antifouling layer>

The antifouling layer 3 is a layer used to prevent stains such as dirt and fingerprints from adhering to one side in the thickness direction of the base material layer 2 .

The antifouling layer 3 has a film shape. The antifouling layer 3 is disposed on the entire upper surface of the base material layer 2 so as to contact the upper surface of the base material layer 2 .

The antifouling layer 3 is formed of an alkoxysilane compound having a perfluoropolyether group. In other words, the antifouling layer 3 includes an alkoxysilane compound having a perfluoropolyether group, and is preferably formed of an alkoxysilane compound having a perfluoropolyether group.

Examples of the alkoxysilane compound having a perfluoropolyether group include compounds represented by the following general formula (1).

R ¹ -R ² -X-(CH ₂ ) _m -Si(OR ³ ) ₃ (1)

In the general formula (1), R ¹ represents a linear or branched fluoroalkyl group (for example, the number of carbon atoms is from 1 to 20) in which more than one hydrogen atom in the alkyl group is replaced by a fluorine atom, preferably A perfluoroalkyl group in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms.

R ² represents a structure containing a repeating structure of at least one perfluoropolyether (PFPE) group, preferably a structure containing a repeating structure of two PFPE groups. Examples of the repeating structure of the PFPE group include a repeating structure of a linear PFPE group and a repeating structure of a branched PFPE group. Examples of the repeating structure of the linear PFPE group include a structure represented by -(OC _n F _2n ) _p - (n represents an integer from 1 to 20, p represents an integer from 1 to 50, and the same applies below). Examples of the repeating structure of the branched PFPE group include a structure represented by -(OC(CF ₃ ) ₂ ) _p - and a structure represented by -(OCF ₂ CF(CF ₃ )CF ₂ ) _p -. As the repeating structure of the PFPE group, a repeating structure of a linear PFPE group is preferably exemplified, and -(OCF ₂ ) _p - and -(OC ₂ F ₄ ) _p - are more preferably exemplified.

R ³ represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

X represents an ether group, a carbonyl group, an amine group, or an amide group, preferably an ether group.

m represents an integer above 1. Moreover, m is preferably an integer of 20 or less, more preferably 10 or less, and still more preferably 5 or less.

Among the alkoxysilane compounds having such perfluoropolyether groups, compounds represented by the following general formula (2) are preferably used.

CF ₃ -(OCF ₂ ) _q -(OC ₂ F ₄ ) _r -O-(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ (2)

In the general formula (2), q represents an integer ranging from 1 to 50, and r represents an integer ranging from 1 to 50.

Commercially available alkoxysilane compounds having a perfluoropolyether group can also be used. Specific examples include OPTOOL UD509 (an alkoxysilane compound having a perfluoropolyether group represented by the above general formula (2), Daikin Industrial Co., Ltd.), OPTOOL UD120 (Daikin Industrial Co., Ltd. Corporation), and KY1903-1 (manufactured by Shin-Etsu Chemical).

The alkoxysilane compound having a perfluoropolyether group can be used alone or in combination of two or more types.

The antifouling layer 3 is formed by the method described below.

The thickness of the antifouling layer 3 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less, more preferably 15 nm or less, further preferably 10 nm or less.

The thickness of the antifouling layer 3 can be measured by fluorescent X-ray (ZXS PrimusII manufactured by Rigaku).

Furthermore, the position of the center of gravity of the wave peak derived from the periodic arrangement of the perfluoropolyether in the in-plane direction measured by in-plane diffraction measurement in the small-angle incident X-ray diffraction method described below in the antifouling layer 3 is 1.8 Å ^-1 or less, preferably 1.7Å ^-1 or less, and for example, 1.4Å ^-1 or more, preferably 1.5Å ^-1 or more, more preferably 1.6Å ^-1 or more, further preferably 1.65Å ^-1 or more , especially preferably 1.67Å ^-1 or more, and most preferably 1.68Å ^-1 or more.

The center of gravity position can be adjusted by adjusting the type of alkoxysilane compound having a perfluoropolyether group and the surface treatment method of the base material layer 2 in the second step described below (when the surface treatment method is plasma treatment, adjust The type of gas used in plasma treatment), and the output power of plasma treatment when the surface treatment method is plasma treatment, are adjusted to be below the above specific value.

In addition, the full width at half maximum of the peak derived from the periodic arrangement of the perfluoropolyether in the in-plane direction measured by in-plane diffraction measurement in the small-angle incident X-ray diffraction method described below is, for example, 0.1 Å. ^-1 or more, and for example, 1.0Å ^-1 or less.

In addition, the half-peak full width value of the wave peak indicating the laminated structure of the sheet measured by in-plane diffraction measurement in the small-angle incident X-ray diffraction method described later is, for example, 0.0Å ^-1 or more, for example, 1.0Å ^-1 the following.

In addition, the above-mentioned peak indicating the layered structure (wave peak A1 (described in detail in the examples below)) is observed at a wave number between 0.2 and 1.0Å ^-1 .

The peak indicating the laminated structure of the lamellae is measured by in-plane diffraction measurement using the micro-angle incident X-ray diffraction method described later, compared to the in-plane diffraction measurement using the micro-angle incident X-ray diffraction method described later. The measured intensity ratio of the wave peaks derived from the periodic arrangement of the perfluoropolyether based on the in-plane direction (measured by the in-plane diffraction measurement in the micro-angle incident X-ray diffraction method described later) represents the laminated structure of the sheet The peak/the peak derived from the periodic arrangement of the perfluoropolyether based on the in-plane direction measured by in-plane diffraction measurement in the micro-angle incident X-ray diffraction method described later) is, for example, 0 or more, for example, 1.0 the following.

Furthermore, the measurement method of in-plane diffraction (In-Plane) measurement (full amplitude at half maximum, center of gravity position, and integrated intensity) will be described in detail in the Examples to be described later.

In addition, the water contact angle of the antifouling layer 3 is, for example, 100° or more, preferably 105° or more, for example, 120° or less.

If the water contact angle of the antifouling layer 3 is above the above-mentioned lower limit, the antifouling property of the antifouling layer 3 can be improved.

Furthermore, the method for measuring the water contact angle of the antifouling layer 3 will be described in detail in the Examples to be described later.

<Manufacturing method of laminated body>

The manufacturing method of the laminated body 1 is demonstrated with reference to FIG. 2A-FIG. 2C.

The manufacturing method of the laminated body 1 includes the first step of preparing the base material layer 2 and the second step of arranging the antifouling layer 3 on the base material layer 2 . Furthermore, in this manufacturing method, for example, roll-to-roll Configure each layer in sequence.

<Step 1>

In the first step, as shown in FIG. 2A , the base material 4 is first prepared.

Next, as shown in FIG. 2B , a diluted solution of the hard coating composition is applied to one side of the substrate 4 in the thickness direction, and after drying, the hard coating composition is hardened by ultraviolet irradiation or heating.

Thereby, the hard coat layer (functional layer 5) is arranged (formed) on one side of the base material 4 in the thickness direction. Thereby, the base material layer 2 is prepared.

<Step 2>

In the second step, as shown in FIG. 2C , the antifouling layer 3 is disposed on the base material layer 2 . Specifically, the antifouling layer 3 is disposed on one side of the base material layer 2 in the thickness direction.

When disposing the antifouling layer 3 on the base material layer 2 , first, from the viewpoint of improving the adhesion between the base material layer 2 and the antifouling layer 3 , surface treatment is performed on the surface of the base material layer 2 . Examples of the surface treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment, and a preferred example is plasma treatment.

Examples of the plasma treatment include plasma treatment using argon gas and plasma treatment using oxygen gas. Preferably, plasma treatment using oxygen gas is used. In addition, the output power of the plasma treatment is, for example, 80W or more, for example, 150W or less.

Moreover, as a method of arranging the antifouling layer 3 on the base material layer 2, for example, a dry coating method and a wet coating method can be mentioned, from the viewpoint of adjusting the above-mentioned first integrated intensity ratio to a specific value or less. , a dry coating method is preferred. Examples of dry coating methods include vacuum evaporation, sputtering, and CVD, and preferably, vacuum evaporation is used.

The vacuum evaporation method is to arrange the evaporation source (alkoxysilane compound with perfluoropolyether group) and the substrate layer 2 (functional layer 5) in a vacuum chamber to face each other, and heat the evaporation source to evaporate or Sublimation causes the evaporated or sublimated vapor deposition source to be deposited on the surface of the base material layer 2 (functional layer 5).

In the vacuum evaporation method, the temperature of the evaporation source (crucible) is, for example, 200°C or higher, preferably 250°C or higher, for example, 300°C or lower. Thereby, the laminated body 1 which has the antifouling layer 3 disposed on one side of the base material layer 2 in the thickness direction, and which has the base material layer 2 and the antifouling layer 3 in order toward one side in the thickness direction is produced.

<Effect>

In the laminated body 1, the antifouling layer 3 has periodic wave peaks derived from the in-plane direction of the perfluoropolyether as measured by in-plane diffraction measurement using the micro-angle incident X-ray diffraction method. The center of gravity position is, for example, 1.8Å ^-1 or less.

If the center of gravity position is below the above upper limit, even after wiping off stains adhering to the antifouling layer 3 , the antifouling property of the antifouling layer 3 can be suppressed from decreasing (excellent antifouling durability).

Specifically, in the above second step, as shown in FIG. 3A , the alkoxysilane compound 20 having a perfluoropolyether group is deposited on one side of the base material layer 2 in the thickness direction. The alkoxysilane compound 20 having a perfluoropolyether group is aligned relative to the base material layer 2 . Specifically, the alkoxysilane compound 20A is vertically aligned with the base material layer 2 , the alkoxysilane compound 20B is obliquely aligned with the base material layer 2 , and the alkoxysilane compound 20B is aligned parallel with the base material layer 2 . Oxysilane compound 20C.

Furthermore, as shown in FIG. 3B , a plurality of alkoxysilane compounds 20 having perfluoropolyether groups aligned in the same direction are stacked to form a group 21 . Specifically, a group 21A including a plurality of alkoxysilane compounds 20A aligned perpendicularly with respect to the base material layer 2 and a group 21B having a plurality of alkoxysilane compounds 20B oriented obliquely with respect to the base material layer 2 are exemplified. , and having a plurality of alkoxysilane compounds 20C aligned in parallel with respect to the base material layer 2 .

Moreover, the center of gravity in group 21 is the stacked alkoxylate having a perfluoropolyether group. The distance between the silane compounds 20 is an indicator.

Therefore, the smaller the center of gravity position means the above-mentioned distance is larger. On the other hand, a larger position of the center of gravity means that the above-mentioned distance is smaller.

Moreover, the center of gravity of the antifouling layer 3 is preferably 1.8Å ^-1 or less. That is, the distance between the stacked alkoxysilane compounds 20 having a perfluoropolyether group in the group 21 is relatively large. Therefore, even after wiping off stains adhering to the antifouling layer 3, the antifouling property of the antifouling layer 3 can be suppressed from decreasing (excellent antifouling durability).

In addition, the antifouling durability can be evaluated by the antifouling durability test described in detail in the examples below. Specifically, the change amount of the contact angle obtained by the antifouling durability test is, for example, 30° or less, preferably 23° or less, more preferably 15° or less. In this case, the antifouling layer 3 has excellent antifouling durability. .

2. Second embodiment

Referring to FIG. 4 , a second embodiment of the laminated body of the present invention will be described.

In addition, in the second embodiment, the same components and steps as those in the first embodiment are assigned the same reference numerals, and detailed descriptions thereof are omitted. In addition, the second embodiment can achieve the same functions and effects as those of the first embodiment unless otherwise specified. Furthermore, the first embodiment and the second embodiment can be combined appropriately.

<Laminated body>

As shown in FIG. 4 , the laminated body 1 includes a base material layer 2 , an adhesive layer 6 , an optical functional layer 7 , and an antifouling layer 3 in this order toward one side in the thickness direction. More specifically, the laminated body 1 has a base material layer 2, an adhesive layer 6 directly disposed on the upper surface of the base layer 2 (one surface in the thickness direction), and an optical function of being directly disposed on the upper surface (one surface in the thickness direction) of the adhesion layer 6. layer 7, and the antifouling layer 3 directly disposed on the upper surface (one side in the thickness direction) of the optical functional layer 7.

The total light transmittance (JIS K 7375-2008) of the laminated body 1 is, for example, 80% or more, preferably 85% or more.

The thickness of the laminated body 1 is, for example, 250 μm or less, preferably 200 μm or less, and, for example, 10 μm or more, preferably 20 μm or more.

<Substrate layer>

The base material layer 2 is a base material for ensuring the mechanical strength of the laminated body 1 .

The base material layer 2 has a film shape. The base material layer 2 is disposed on the entire lower surface of the optical functional layer 7 so as to contact the lower surface of the optical functional layer 7 .

The base material layer 2 includes a base material 4 and a functional layer 5 like the base material layer 2 in the first embodiment.

The total light transmittance (JIS K 7375-2008) of the base material layer 2 is, for example, 80% or more, preferably 85% or more.

<Substrate>

The base material 4 has a film shape. The base material 4 is preferably flexible. The base material 4 is disposed on the entire lower surface of the functional layer 5 so as to contact the lower surface of the functional layer 5 .

Examples of the base material 4 include the same base material as the base material 4 in the first embodiment, preferably a cellulose resin, and more preferably a triacetyl cellulose.

The thickness of the base material 4 is the same as the thickness of the base material 4 in the first embodiment.

<Functional layer>

Functional layer 5 has a film shape. The functional layer 5 is arranged on one side of the base material 4 in the thickness direction.

Examples of the functional layer 5 include the same hard coat layer as in the first embodiment.

In this case, the base material layer 2 is provided with the base material 4 and the hard coat layer in order toward the thickness direction side.

The thickness of the hard coat layer is the same as the thickness of the hard coat layer in the first embodiment.

<Adhesive layer>

The adhesive layer 6 is a layer for ensuring the adhesive force between the base material layer 2 and the optical functional layer 7 .

The adhesive layer 6 has a film shape. The adhesive layer 6 is disposed on the entire upper surface of the base material layer 2 (functional layer 5) so as to contact the upper surface of the base material layer 2 (functional layer 5).

As a material of the close contact layer 6, metal can be mentioned, for example. Examples of the metal include indium, silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium. In addition, as the material of the close contact layer 6, alloys of two or more kinds of the above-mentioned metals and oxides of the above-mentioned metals can also be exemplified.

As a material of the adhesive layer 6, from the viewpoint of adhesiveness and transparency, silicon oxide (SiOx) and indium tin oxide (ITO) are preferably exemplified. When silicon oxide is used as the material of the adhesion layer 6, it is preferable to use SiOx whose oxygen content is less than the stoichiometric composition, and more preferably to use SiOx whose x is 1.2 or more and 1.9 or less.

As a material of the adhesion layer 6, indium tin oxide (ITO) is more preferably exemplified.

From the viewpoint of ensuring the adhesion between the base material layer 2 and the optical functional layer 7 and achieving the transparency of the adhesion layer 6 , the thickness of the adhesion layer 6 is, for example, 1 nm or more, for example, 10 nm or less.

<Optical functional layer>

In the second embodiment, the optical functional layer 7 is an anti-reflection layer used to suppress the reflection intensity of external light.

In the following description, the case where the optical functional layer 7 is an anti-reflection layer will be described in detail.

The anti-reflection layer has two or more layers with mutually different refractive indexes. specific and In other words, the anti-reflective layer alternately has a high refractive index layer with a relatively large refractive index and a low refractive index layer with a relatively small refractive index in the thickness direction. In the anti-reflective layer, the net reflected light intensity is attenuated by the interference between the reflected light at the multiple interfaces in the multiple thin layers (high refractive index layer, low refractive index layer) contained therein. In addition, in the anti-reflection layer, the interference effect of attenuating the intensity of reflected light can be demonstrated by adjusting the optical film thickness (product of refractive index and thickness) of each thin layer. This anti-reflection layer includes a first high refractive index layer 11, a first low refractive index layer 12, a second high refractive index layer 13, and a second low refractive index layer 14 in order toward the thickness direction side.

The anti-reflection layer (specifically, the high refractive index layer and the low refractive index layer) preferably contains one selected from the group consisting of metals, alloys, metal oxides, metal nitrides, and metal fluorides, and more preferably contains selected materials. A member of the group consisting of free metals, metal oxides, and metal nitrides. Thereby, the anti-reflection layer can suppress the reflection intensity of external light.

Examples of the metal include silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, niobium, and palladium. Examples of the alloy include alloys of the above metals. Examples of metal oxides include metal oxides of the above metals. Examples of the metal nitride include metal nitrides of the above metals. Examples of the metal fluoride include metal nitrides of metal fluorides of the above metals.

In particular, the material used for the antireflection layer can be selected according to the required refractive index.

Specifically, the first high refractive index layer 11 and the second high refractive index layer 13 each include a high refractive index material whose refractive index at a wavelength of 550 nm is preferably 1.9 or more. From the viewpoint of achieving both high refractive index and low absorption of visible light, examples of high refractive index materials include niobium oxide (Nb ₂ O ₅ ), titanium oxide, zirconium oxide, indium tin oxide (ITO), and Antimony-doped tin oxide (ATO) is preferably niobium oxide. That is, it is preferable that the material of the first low refractive index layer 12 and the material of the second low refractive index layer 14 are both niobium oxide.

The first low refractive index layer 12 and the second low refractive index layer 14 each include a low refractive index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm. From the viewpoint of achieving both low refractive index and low visible light absorption, examples of the low refractive index material include silicon dioxide (SiO ₂ ) and magnesium fluoride, and preferably, silicon dioxide is used. That is, it is preferable that the material of the first low refractive index layer 12 and the material of the second low refractive index layer 14 are both silicon dioxide.

In particular, if the material of the second low refractive index layer 14 is silicon dioxide (in other words, if one side of the anti-reflective layer in the thickness direction is a layer containing silicon dioxide), then the second low refractive index layer 14 and the antifouling layer 3 The adhesion between them is excellent.

Moreover, in the anti-reflection layer, the thickness of the first high refractive index layer 11 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less. The thickness of the first low refractive index layer 12 is, for example, 10 nm or more, preferably 20 nm or more, and is, for example, 50 nm or less, preferably 30 nm or less. The thickness of the second high refractive index layer 13 is, for example, 50 nm or more, preferably 80 nm or more, and is, for example, 200 nm or less, preferably 150 nm or less. The thickness of the second low refractive index layer 14 is, for example, 60 nm or more, preferably 80 nm or more, and, for example, 150 nm or less, preferably 100 nm or less.

The ratio of the thickness of the second low refractive index layer 14 to the thickness of the second high refractive index layer 13 (thickness of the second low refractive index layer 14/thickness of the second high refractive index layer 13) is, for example, 0.5 or more, which is greater than Preferably it is 0.7 or more, for example, it is 0.9 or less.

The ratio of the thickness of the second high refractive index layer 13 to the thickness of the first high refractive index layer 11 (thickness of the second high refractive index layer 13/thickness of the first high refractive index layer 11) is, for example, 5 or more, which is greater than Preferably it is 7 or more, for example, it is 15 or less, More preferably, it is 10 or less.

The ratio of the thickness of the second low refractive index layer 14 to the thickness of the first low refractive index layer 12 (thickness of the second low refractive index layer 14/thickness of the first low refractive index layer 12) is, for example, 1 or more, which is greater than 1. Preferably it is 3 or more, for example, it is 10 or less, More preferably, it is 8 or less.

The anti-reflection layer is formed by the method described below.

The thickness of the anti-reflection layer is, for example, 100 nm or more, preferably 150 nm or more, for example, 300 nm or less, preferably 250 nm or less.

The thickness of the anti-reflective layer can be measured by cross-sectional TEM observation.

<Antifouling layer>

The antifouling layer 3 has a film shape. The antifouling layer 3 is disposed on the entire upper surface of the optical functional layer 7 (anti-reflective layer) so as to contact the upper surface of the optical functional layer 7 (anti-reflective layer).

The antifouling layer 3 is formed of the above-mentioned alkoxysilane compound having a perfluoropolyether group (preferably the alkoxysilane compound having a perfluoropolyether group represented by the above general formula (2)). In other words, the antifouling layer 3 includes an alkoxysilane compound having a perfluoropolyether group, and is preferably formed of an alkoxysilane compound having a perfluoropolyether group.

The antifouling layer 3 is formed by the method described below.

The thickness, center of gravity position, intensity ratio, full amplitude at half maximum and water contact angle of the antifouling layer 3 are the same as the thickness, center of gravity position, intensity ratio, full amplitude at half maximum and water of the antifouling layer 3 in the first embodiment. The contact angles are the same.

The center of gravity position can be determined by adjusting the type of alkoxysilane compound having a perfluoropolyether group and the surface treatment method of the optical functional layer 7 (anti-reflection layer) in step 5 described below (the surface treatment method is plasma treatment In this case, the type of gas used for plasma treatment is adjusted), and when the surface treatment method is plasma treatment, the output power of the plasma treatment is adjusted to be below the above specific value.

<Manufacturing method of laminated body>

The manufacturing method of the laminated body 1 is demonstrated with reference to FIG. 5A - FIG. 5D.

The manufacturing method of the laminated body 1 includes: the third step of preparing the base material layer 2; the fourth step of sequentially arranging the adhesive layer 6 and the optical functional layer 7 (anti-reflection layer) on the base material layer 2; and placing the optical functional layer 7 on the base material layer 2. Step 5 of arranging the antifouling layer 3 on the (anti-reflective layer). Furthermore, in this manufacturing method, each layer is sequentially arranged in a roll-to-roll manner, for example.

<Step 3>

In the third step, as shown in FIG. 5A , the base material 4 is first prepared.

Next, as shown in FIG. 5B , a diluted solution of the hard coating composition is applied to one surface in the thickness direction of the base material 4 , and after drying, the hard coating composition is hardened by ultraviolet irradiation or heating.

Thereby, the hard coat layer (functional layer 5) is arranged (formed) on one side of the base material 4 in the thickness direction. Thereby, the base material layer 2 is prepared.

<Step 4>

In the fourth step, as shown in FIG. 5C , the adhesive layer 6 and the optical functional layer 7 (anti-reflective layer) are sequentially arranged on the base material layer 2 . Specifically, the adhesive layer 6 and the optical functional layer 7 (anti-reflection layer) are sequentially arranged on one side of the base material layer 2 in the thickness direction.

More specifically, on the base material layer 2 , the adhesion layer 6 , the first high refractive index layer 11 , the first low refractive index layer 12 , the second high refractive index layer 13 , and the second high refractive index layer 13 are arranged in this order toward one side in the thickness direction. Low refractive index layer 14.

That is, in this method, the fourth step includes: a step of arranging the adhesive layer of arranging the adhesive layer 6 on the base material layer 2; and a step of arranging the first high refractive index layer of arranging the first high refractive index layer 11 on the adhesive layer 6. ; The first low refractive index layer arranging step of arranging the first low refractive index layer 12 on the first high refractive index layer 11 ; The second high refractive index layer arranging the second high refractive index layer 13 on the first low refractive index layer 12 the second low refractive index layer arranging step; and the second low refractive index layer arranging step of arranging the second low refractive index layer 14 on the second high refractive index layer 13 . Moreover, in this manufacturing method, for example, vacuum evaporation method, sputtering method, layer Pressing method, plating method, ion plating method, preferably sputtering method are used to arrange each layer in sequence.

Below, the method of arranging each layer sequentially by sputtering is described in detail.

In this method, first, from the viewpoint of improving the adhesion between the base material layer 2 and the adhesion layer 6 , for example, the surface of the base material layer 2 is subjected to surface treatment. As a surface treatment, the surface treatment mentioned in the said 2nd step can be mentioned, Preferably, plasma treatment can be mentioned.

Furthermore, in the sputtering method, the target (each layer (adhesive layer 6, first high refractive index layer 11, first low refractive index layer 12, second high refractive index layer 13, and second low refractive index layer 13) is placed in a vacuum chamber). The material of the rate layer 14)) and the base material layer 2 are arranged facing each other, supplying gas and applying voltage from the power source to accelerate the gas ions and irradiate them to the target, and eject the target material from the target surface, and the target material is in the base material layer 2 are accumulated on the surface to form each layer in sequence.

An example of the gas is an inert gas (for example, argon gas). In addition, a reactive gas such as oxygen may be used in combination if necessary. When a reactive gas is used together, the flow rate ratio (sccm) of the reactive gas is not particularly limited, but it is, for example, 0.1 flow % or more and 100 flow % or less relative to the total flow rate of the sputtering gas and the reactive gas.

The gas pressure during sputtering is, for example, 0.1 Pa or more, and is, for example, 1.0 Pa or less, preferably 0.7 Pa or less.

The power supply may be, for example, any one of DC power supply, AC power supply, MF power supply, and RF power supply, or a combination thereof.

Thereby, the adhesive layer 6 and the optical functional layer 7 (anti-reflection layer) are sequentially arranged on one side of the base material layer 2 in the thickness direction.

<Step 5>

In the fifth step, as shown in FIG. 5D , the antifouling layer 3 is disposed on the optical functional layer 7 (anti-reflection layer). Specifically, the antifouling layer 3 is disposed on one side of the optical functional layer 7 (antireflection layer) in the thickness direction.

In this method, first, from the viewpoint of improving the adhesion between the optical functional layer 7 (anti-reflective layer) and the anti-fouling layer 3, for example, the surface of the optical functional layer 7 (anti-reflective layer) is subjected to surface treatment. Examples of the surface treatment include the surface treatments exemplified in the second step, preferably plasma treatment, more preferably plasma treatment using oxygen.

As a method of arranging the antifouling layer 3 on the optical functional layer 7 (antireflection layer), the same method as the method of arranging the antifouling layer 3 on the base material layer 2 in the second step can be used. , from the viewpoint of adjusting the integrated intensity ratio to a specific value or less, a dry coating method is preferred, and a vacuum evaporation method is more preferred.

The vacuum evaporation method is to arrange the evaporation source (alkoxysilane compound with perfluoropolyether group) and the optical functional layer 7 (anti-reflection layer) in a vacuum chamber to face each other, and heat the evaporation source to evaporate or Sublimation, so that the evaporated or sublimated evaporation source is deposited on the surface of the optical functional layer 7 (anti-reflection layer).

In the vacuum evaporation method, the temperature of the evaporation source (crucible) is, for example, 200°C or higher, preferably 250°C or higher, for example, 300°C or lower.

Thereby, the antifouling layer 3 is disposed on the thickness direction side of the optical functional layer 7 (anti-reflective layer), and the base material layer 2, the adhesion layer 6, and the optical functional layer 7 (anti-reflective layer) are sequentially provided toward the thickness direction side. , and the laminate 1 of the antifouling layer 3.

<Effect>

The laminated body 1 has an optical functional layer 7 (antireflection layer) between the base material layer 2 and the antifouling layer 3 .

Therefore, reflection of external light can be suppressed.

In addition, when one side of the optical function layer 7 (anti-reflection layer) in the thickness direction is a layer containing silicon dioxide, in other words, a layer containing silicon dioxide (for example, a layer containing silicon dioxide) is directly disposed on the lower surface of the antifouling layer 3 In the case of the second low refractive index layer 14 of silicon, the hydrolyzable group (-(OR ₃ ) in the above formula (1)) in the alkoxysilane compound having a perfluoropolyether group in the antifouling layer 3 is The silanol group generated during the hydrolysis process undergoes dehydration and condensation reaction with the silicon in silicon dioxide. In other words, the antifouling layer 3 is formed on the optical functional layer 7 (anti-reflective layer) from an alkoxysilane compound having a perfluoropolyether group via a siloxane bond. This can further improve antifouling durability.

3.Examples of changes

In the modified example, the same components and steps as those in the first embodiment and the second embodiment are assigned the same reference numerals, and detailed descriptions thereof are omitted. In addition, unless otherwise specified, the modified examples can achieve the same functions and effects as those of the first embodiment and the second embodiment. Furthermore, the first embodiment, the second embodiment and their modifications can be combined appropriately.

In the first embodiment, the laminated body 1 includes the base material layer 2 and the antifouling layer 3. However, as shown in FIG. 6 , a primer layer 15 may be further provided between the base material layer 2 and the antifouling layer 3. Specifically, the laminated body 1 may be provided with the primer layer 15 on the other surface in the thickness direction of the antifouling layer 3 .

That is, in this case, the laminated body 1 has the base material layer 2, the primer layer 15, and the antifouling layer 3 in order toward the thickness direction side.

The base coat 15 is a layer closely connected with the antifouling layer 3 .

As a material of the undercoat layer 15, silicon dioxide ( _SiO2 ) is preferably exemplified. A more preferred example of the undercoat layer 15 is silicon dioxide (SiO ₂ ).

If the material of the primer layer 15 is silicon dioxide (SiO ₂ ), the hydrolyzable group (-(OR 3) in the above formula (1) in the alkoxysilane compound having a perfluoropolyether group in the antifouling layer ₃ )) The silanol group generated during the hydrolysis process undergoes a dehydration condensation reaction with the silicon in the silicon dioxide. In other words, the antifouling layer 3 is formed on the undercoat layer 15 from an alkoxysilane compound having a perfluoropolyether group via a siloxane bond. This can further improve antifouling durability.

The primer layer 15 can be formed by, for example, sputtering, plasma CVD, vacuum evaporation, etc. form.

In the first embodiment and the second embodiment, the base material layer 2 includes the base material 4 and the functional layer 5 in order toward one side in the thickness direction. However, the base material layer 2 can also be formed of the base material 4 without the functional layer 5 .

In the second embodiment, the anti-reflection layer includes two high refractive index layers with a relatively high refractive index, and two low refractive index layers with a relatively low refractive index. However, the number of high refractive index layers and low refractive index layers is not particularly limited.

[Example]

Examples and comparative examples are shown below to explain the present invention more specifically. In addition, the present invention is not limited at all by the Examples and Comparative Examples. In addition, specific numerical values such as blending ratios (content ratios), physical property values, and parameters used in the following description may be replaced by corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Embodiments." The corresponding recorded upper limit value (defined as a value "below" or "under") or lower limit value (defined as a value "above" or "exceeded").

1. Manufacturing of laminated body

Example 1

<Step 3>

As a base material, a triacetyl cellulose (TAC) film (thickness: 80 μm) was prepared.

Next, a hard coat layer is placed on one side of the base material (TAC film) in the thickness direction. Specifically, first, to an ultraviolet curable acrylic resin composition (manufactured by DIC, trade name "GRANDIC PC-1070", refractive index at a wavelength of 405 nm: 1.55), 100 parts by mass of silica was added to the resin component. Organic silica sol ("MEK-ST-L" manufactured by Nissan Chemical Co., Ltd., manufactured by Nissan Chemical Co., Ltd.) was added so that the amount of particles would be 25 parts by mass. The average primary particle diameter of the silica particles (inorganic filler) was: 50 nm. The particle size of the silica particles diameter distribution: 30 nm to 130 nm, solid content 30% by weight) to prepare a hard coating composition. The hard coating composition was applied to one side in the thickness direction of the base material (TAC film) so that the thickness after drying was 6 μm, and dried at 80° C. for 3 minutes. Then, a high-pressure mercury lamp is used to irradiate ultraviolet rays with a cumulative light intensity of 200 mJ/cm ² to harden the coating layer to form a hard coat layer. Thereby, the base material layer is prepared.

<Step 4>

Using a roll-to-roll plasma treatment device, plasma treatment is performed on one side of the substrate layer (hard coating) in the thickness direction under a vacuum atmosphere of 1.0 Pa. In this plasma treatment, argon gas was used as an inert gas, and the discharge power was set to 2400W.

Then, an adhesive layer and an anti-reflection layer (optical functional layer) are sequentially arranged (formed) on one side of the base material layer in the thickness direction.

Specifically, a roll-to-roll sputtering film forming device is used to sequentially arrange (form) an indium tin oxide with a thickness of 2.0 nm as an adhesive layer on the HC layer of the TAC film with the HC layer after plasma treatment. material (ITO) layer, a 12 nm thick Nb ₂ O ₅ layer as the first high refractive index layer, a 28 nm thick SiO ₂ layer as the first low refractive index layer, and a 100 nm thick Nb 2 layer as the second high refractive index layer. ₂ O ₅ layer and a SiO ₂ layer with a thickness of 85 nm as the second low refractive index layer.

In the formation of the adhesion layer, an ITO target, argon as an inert gas, and oxygen as a reactive gas were used in an amount of 10 parts by volume relative to 100 parts by volume of argon. The discharge voltage was set to 350V, and the air pressure in the film-forming chamber was adjusted. (Film formation pressure) was set to 0.4 Pa, and an ITO layer was formed by MFAC sputtering.

An Nb target is used for forming the first high refractive index layer. Moreover, 100 parts by volume of argon gas and 5 parts by volume of oxygen gas were used. Furthermore, the discharge voltage was set to 415V and the film-forming gas pressure was set to 0.42Pa, and an Nb ₂ O ₅ layer was formed by MFAC sputtering.

In the formation of the first low refractive index layer, a Si target is used. Moreover, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used. Furthermore, the discharge voltage was set to 350V and the film-forming gas pressure was set to 0.3 Pa, and a SiO ₂ layer was formed by MFAC sputtering.

An Nb target is used for forming the second high refractive index layer. Moreover, 100 parts by volume of argon gas and 13 parts by volume of oxygen gas were used. Furthermore, the discharge voltage was set to 460V and the film-forming gas pressure was set to 0.5Pa, and an Nb ₂ O ₅ layer was formed by MFAC sputtering.

A Si target is used for forming the second low refractive index layer. Moreover, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used. Furthermore, the discharge voltage was set to 340V and the film-forming gas pressure was set to 0.25Pa, and an Nb ₂ O ₅ layer was formed by MFAC sputtering.

As mentioned above, the adhesive layer and the anti-reflection layer are sequentially arranged (formed) on one side of the base material layer in the thickness direction.

<Step 5>

An antifouling layer is disposed on one side of the anti-reflective layer in the thickness direction.

Specifically, first, plasma treatment using argon gas is performed as surface treatment on one side of the antireflective layer in the thickness direction. The output power of plasma treatment is 100W. Then, an antifouling layer with a thickness of 7 nm was placed on one side of the antireflection layer in the thickness direction by a vacuum evaporation method using an alkoxysilane compound containing a perfluoropolyether group as the evaporation source.

The evaporation source is a solid component obtained by drying OPTOOL UD120 (manufactured by Daikin Industries, Ltd.). In addition, the heating temperature of the vapor deposition source (crucible) in the vacuum evaporation method was set to 260°C. Thereby, a laminated body is obtained.

Example 2

Based on the same procedure as Example 1, a laminated body was produced.

However, in step 5, the thickness direction of the anti-reflective layer is The surface treatment was changed to plasma treatment using oxygen instead of plasma treatment using argon gas.

Example 3

Based on the same procedure as Example 2, a laminated body was produced.

However, in the fifth step, the vapor deposition source was changed to KY1903-1 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Comparative example 1

Based on the same procedure as Example 1, a laminated body was produced.

However, change step 5 as follows.

<Step 5>

On one side of the anti-reflective layer in the thickness direction, OPTOOL UD509 is coated with a coating thickness of 8 μm using a gravure coater. Then, heat treatment was performed at a drying temperature of 60°C for 60 seconds. Thereby, an antifouling layer with a thickness of 7 nm is disposed on one side of the antireflection layer in the thickness direction.

Comparative example 2

Based on the same procedure as Example 1, a laminated body was produced.

However, in step 5, the output power of the plasma treatment is changed to 4500W.

2.Evaluation

(Small angle incident X-ray diffraction measurement)

Based on the following conditions, in-plane diffraction (In-Plane) measurement was performed on the antifouling layer of the laminated body of each Example and each Comparative Example using a small-angle incident X-ray diffraction method.

The results of the in-plane diffraction (In-Plane) measurement of Example 2 are shown in FIG. 7 .

<Measurement conditions>

Experimental facility: Aichi Synchrotron Radiation Center

Experimental platform: BL8S1

Incident energy: 14.4keV

Beam size: 500μm (width) × 40μm (vertical)

Sample angle: 0.1 degrees relative to incident light

Detector: 2D detector PILATAS

Sample setting method: Fix it on the flat sample table by applying a thin layer of grease

Hereinafter, the center of gravity position is calculated based on the obtained in-plane diffraction (In-Plane) measurement results. From the viewpoint of uniformly calculating the position of the center of gravity, the fitting method is used as the calculation method. This method will be described in detail taking Embodiment 2 as an example.

First, the results obtained by the in-plane diffraction (In-Plane) measurement (hereinafter referred to as actual measurement data (in-plane diffraction (In-Plane) measurement)) are fitted based on the following equation (3). Specifically, fitting is performed assuming that the actual measured data (in-plane diffraction (In-Plane) measurement) is the sum of the background and peaks A1 to A4 (see Figure 8). Furthermore, the background normalized to a high wavelength of 24 nm ^-1 was consistent among all samples.

In (Equation (3)), q represents the scattering vector (wave number) (=4πsinΘ/λ)/nm ^-1 (Θ represents the Bragg angle. λ represents the wavelength of X-rays). An represents the peak intensity (n is 1~4 is an integer. _{A 1} represents the peak intensity of wave peak A1. _{A 2} represents the peak intensity of wave peak A2. _{A 3} represents the peak intensity of wave peak A3. _{A 4} represents the peak intensity of wave peak A4). _{q An} represents the center of gravity position (q _A1 represents the wave peak The position of the center of gravity of A1. q _A2 represents the position of the center of gravity of the wave peak A2. q _A3 represents the position of the center of gravity of the wave peak A3. q _A4 represents the position of the center of gravity of the wave peak A4). △q _An represents the half-peak full amplitude value (△q _A1 represents the position of the center of gravity of the wave peak A1 Full amplitude at half peak. △q _A2 represents the full amplitude at half peak of peak A2. △q _A3 represents the full amplitude at half peak of peak A3. △q _A4 represents the full amplitude at half peak of peak A4).

In addition, the peak A1 represents the peak of the laminated structure, and the center of gravity position is 0.2Å ^-1 or more and 1.0Å ^-1 or less. In addition, the peak A4 is a peak derived from the periodic arrangement of perfluoropolyether based on the in-plane direction, and the center of gravity position is 1.8Å ^-1 or less.

Figure 8 (Example 2) shows the fitting results.

In addition, the fitting results are shown in Figure 7 together with the actual measurement data (in-plane diffraction (In-Plane) measurement).

According to Figure 7, it can be seen that the measured data (in-plane diffraction (In-Plane) measurement) are consistent with the fitting results.

From this, it can be seen that the actual measured data (in-plane diffraction (In-Plane) measurement) can be expressed as the sum of the background and the peaks A1 to A4, as assumed.

Furthermore, the center of gravity position, intensity, half-peak full amplitude, integrated intensity and normalized integrated intensity of the peak A4 derived from the periodic arrangement in the in-plane direction of the perfluoropolyether group obtained by fitting represent the laminated structure of the sheet. The peak intensity, peak position, half-peak full amplitude, integrated intensity and standardized integrated intensity of the wave peak A1 are shown in Table 1.

(anti-fouling durability)

Using DMo-501 manufactured by Kyowa Interface Science Co., Ltd., the contact angle (sometimes referred to as the initial contact angle) of the antifouling layer with respect to pure water was measured for the antifouling layer of the laminate of each example and each comparative example based on the following conditions. The results are shown in Table 1.

<Measurement conditions>

Drop volume: 2μl

Temperature: 25℃

Humidity: 40%

Next, based on the following conditions, after performing an eraser sliding test on the antifouling layer of the laminate of each example and each comparative example, the water contact angle was measured by the same procedure as the above method (sometimes referred to as an eraser sliding test). the contact angle). The results are shown in Table 1.

Furthermore, the change amount of the contact angle was calculated based on the following formula (4). The results are shown in Table 1.

The smaller the change amount of the contact angle, the more excellent the antifouling durability is evaluated.

Change in contact angle = initial contact angle – contact angle after eraser sliding test (4)

(Eraser sliding test)

Eraser made by Minoan Company (Φ 6mm)

Sliding distance: single channel 100mm

Sliding speed: 100mm/second

Load: 1kg/6mm Φ

Number of slides: 3000 times

[Table 1]

In addition, the above-mentioned invention is provided as an exemplary embodiment of the present invention, and is only for illustration and is not to be construed in a limiting manner. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the claims described below.

[Industrial availability]

The laminate of the present invention is suitable for, for example, an antireflective film with an antifouling layer, a transparent conductive film with an antifouling layer, and an electromagnetic wave shielding film with an antifouling layer.

1: Laminated body

2: Base material layer

3: Antifouling layer

4:Substrate

5: Functional layer

Claims (5)

A laminated body having a base material layer and an antifouling layer in sequence toward one side in the thickness direction. The antifouling layer contains an alkoxysilane compound having a perfluoropolyether group and is detected by micro-angle incident X-ray diffraction. According to the in-plane diffraction measurement, the center of gravity of the periodic peaks of the perfluoropolyether derived from the above-mentioned anti-fouling layer based on the in-plane direction is 1.8Å ^-1 or less, and in the thickness direction of the above-mentioned anti-fouling layer. One side is provided with a primer layer, and the primer layer includes a layer of silicon dioxide. A laminated body having a base material layer and an antifouling layer in sequence toward one side in the thickness direction. The antifouling layer contains an alkoxysilane compound having a perfluoropolyether group and is detected by micro-angle incident X-ray diffraction. The center of gravity position of the periodically arranged wave peaks based on the in-plane direction of the perfluoropolyether derived from the above-mentioned antifouling layer measured by in-plane diffraction measurement is 1.8Å ^-1 or less, between the above-mentioned base material layer and the above-mentioned antifouling layer A close contact layer and an anti-reflective layer are further provided between the layers, and one surface in the thickness direction of the anti-reflective layer is a layer containing silicon dioxide. The laminated body according to claim 1, wherein the antifouling layer is formed on the undercoat layer via a siloxane bond from an alkoxysilane compound having a perfluoropolyether group. The laminated body of Claim 2, wherein the anti-reflection layer includes two or more layers with mutually different refractive indexes. The laminated body of claim 4, wherein the anti-reflection layer contains one selected from the group consisting of metal, metal oxide, and metal nitride.