TWI811737B - 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 full amplitude at half maximum of the peaks originating from the periodic arrangement of the perfluoropolyether groups in the in-plane direction of the antifouling layer measured by in-plane diffraction measurement in the grazing angle incident X-ray diffraction method is: 0.4 Å ^-1 or more.

Description

laminated body

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

It is known that an antifouling layer has been formed on the surface of a film base material or on the surface of optical components such as optical films in order to prevent the adhesion of stains such as hand stains and fingerprints.

As such an optical film provided with an antifouling layer, for example, an antireflective film including a film base material, an antireflective layer, and an antifouling layer is proposed 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 adhering to the antifouling layer are wiped off, the antifouling properties of the antifouling layer may be adversely affected.

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

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 formed by grazing The full amplitude at half maximum of the peaks originating from the periodic arrangement of the perfluoropolyether groups in the in-plane direction of the antifouling layer measured by the in-plane diffraction measurement using the angle-incidence X-ray diffraction method is 0.4Å. ^-1 or more.

The present invention [2] includes the laminated body 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 laminated body as described in the above [3], wherein the antifouling layer is an alkoxysilane compound having a perfluoropolyether group formed on the undercoat layer via a siloxane bond.

The present invention [5] includes the laminated body according to the above [1], further including an adhesive 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 laminated body 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 of the laminate of the present invention contains an alkoxysilane compound having a perfluoropolyether group. Furthermore, in the antifouling layer, the periodic arrangement of the perfluoropolyether groups in the in-plane direction measured by in-plane diffraction measurement in the grazing angle incident X-ray diffraction method The full amplitude of the half peak of the wave peak is more than 0.4Å ^-1 . Therefore, even after the stains attached to the antifouling layer are wiped off, 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 vertically aligned with respect to substrate layer 2

20B: Alkoxysilane compound tiltedly aligned with respect to base material layer 2

20C: Alkoxysilane compound aligned parallel to base material layer 2

21:Group

21A: A group of a plurality of alkoxysilane compounds 20A that are vertically aligned with respect to the base material layer 2

21B: A group of a plurality of alkoxysilane compounds 20B that are obliquely aligned with respect to the base material layer 2

21C: A group of a plurality of alkoxysilane compounds 20C aligned in parallel with respect to the base material layer 2

22:Area

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 to 3G illustrate illustrations of an alkoxysilane compound having a perfluoropolyether group deposited on a substrate layer. FIG. 3A shows an illustration of an alkoxysilane compound having a single perfluoropolyether group deposited on a substrate layer. Figure 3B shows a layer with multiple perfluoropolyether groups deposited on the substrate layer. Illustration of an alkoxysilane compound. 3C shows an explanatory diagram of an alkoxysilane compound having a perfluoropolyether group deposited on the base material layer when the half-maximum full-width value of the antifouling layer is small. 3D shows an explanatory diagram of an alkoxysilane compound having a perfluoropolyether group deposited on the base material layer when the half-maximum full-width value of the antifouling layer is large. 3E shows an explanatory diagram of an alkoxysilane compound having a perfluoropolyether group deposited on the base material layer when the integrated intensity of the antifouling layer is relatively small. 3F shows an explanatory diagram of an alkoxysilane compound having a perfluoropolyether group deposited on the base material layer when the integrated intensity of the antifouling layer is relatively large. Figure 3G shows an alkoxysilane compound having a perfluoropolyether group deposited on the base material layer when the half-maximum full-width value of the antifouling layer is above a specific range and the integrated intensity ratio of the antifouling layer is below a specific range. illustrative diagram.

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 step 3. FIG. 5B shows the step of arranging a hard coat layer (functional layer) on the substrate 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 measurement in Example 2.

FIG. 8 shows the fitting results of the in-plane diffraction measurement in 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 of the paper is the upper side (one side in the thickness direction), and the lower side of 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 surface are the surface directions orthogonal to the up-down direction. Please refer to the direction arrows in each figure for details.

<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 includes 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 so as to be 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 be in contact with the lower surface of the functional layer 5 .

Examples of the base material 4 include 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, polyamide resin, Imide 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 preferably used, and triacetyl cellulose is more preferably used.

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, and more preferably 100 μm or less.

The thickness of the base material 4 can be measured using a dial gauge (manufactured 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 suppress damage to the base material 4 .

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

The hard coating composition contains resin, and optionally particles. That is, the hard coat layer includes resin, visual Particles needed.

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

Examples of the curable resin include an active energy ray curable resin that is cured by irradiation of active energy rays (such as ultraviolet rays and electron beams) and a thermosetting resin that is cured by heating. As the curable resin, a preferred example is an active energy ray curable resin.

Examples of the active energy ray-curable resin include: (meth)acrylic ultraviolet curable resin, urethane resin, melamine resin, alkyd resin, siloxane-based polymer, and organosilane condensate . As the active energy ray curable resin, a preferred example is a (meth)acrylic ultraviolet curable resin.

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 the particles include metal oxide fine particles and organic fine particles. Examples of materials for the metal oxide fine particles include silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Examples of materials for organic fine particles include: polymethyl methacrylate, polysiloxane, polystyrene, polyurethane, Acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate. As the organic fine particles, a preferred example is polymethylmethacrylate.

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 (such as organoclay), a photopolymerization initiator, a filler, and a leveling agent may be blended in an appropriate ratio in the hard coating composition if necessary. In addition, the hard coating composition can be diluted with a known solvent.

When forming the hard coat layer, a diluted solution of the hard coat composition is applied to one side of the base material 4 in the thickness direction, and is heated and dried if necessary. Details will be described later. 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 used to prevent dirt, fingerprints and other contaminants from adhering to one side in the thickness direction of the base material layer 2 stain layer.

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 in contact with 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 composed 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 fluorinated alkyl group (carbon number, for example, 1 to 20) in which one or more hydrogen atoms in the alkyl group are substituted with a fluorine atom, Preferably, it represents 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. As a repeating structure of a linear PFPE group, for example, 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; the same applies to the following ). 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 - structure. The repeating structure of the PFPE group is preferably a repeating structure of a linear PFPE group, and more preferably -(OCF ₂ ) _p - and -(OC ₂ F ₄ ) _p -.

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, and preferably represents an ether group.

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

Among such alkoxysilane compounds having a perfluoropolyether group, a compound represented by the following general formula (2) is 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.

As the alkoxysilane compound having a perfluoropolyether group, commercially available products can be used. Specifically, OPTOOL UD509 (an alkoxysilane compound having a perfluoropolyether group represented by the above general formula (2)) can be used. , manufactured by DAIKIN INDUSTRIES Co., Ltd.), OPTOOL UD120 (manufactured by DAIKIN INDUSTRIES Co., Ltd.), 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.

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 antifouling layer 3 has periodic wave peaks originating from the perfluoropolyether groups in the in-plane direction measured by in-plane diffraction measurement in the grazing-angle incident X-ray diffraction method as described below. The full amplitude at half peak is 0.4Å ^-1 or more, preferably 0.45Å ^-1 or more, more preferably 0.5Å ^-1 or more, further preferably 0.55Å ^-1 or more, and, for example, 0.8Å ^-1 or less .

In addition, the above-mentioned peak originating from the periodic arrangement of the perfluoropolyether groups in the in-plane direction (peak A4 (detailed in the examples described below)) was observed at a wave number between 1.5~2.0Å ^-1 arrive.

In addition, the integrated intensity ratio measured by the test described below is preferably 0.78 or less, preferably 0.60 or less, more preferably 0.50 or less, further preferably 0.40 or less, especially 0.35 or less, and most preferably 0.35 or less. The best value is below 0.30.

The above half-peak full amplitude and the above integrated intensity ratio can be determined by 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, it is the type of gas used in plasma treatment), and when the surface treatment method is plasma treatment, the output power of the plasma treatment is adjusted, and the adjustment It is more than the above-mentioned specific value or below the above-mentioned specific value.

Furthermore, the half-peak full amplitude value of the wave peak indicating the layered laminated structure measured by in-plane diffraction measurement in the grazing angle incident X-ray diffraction method described below is, for example, 0.0Å ^-1 or more, and, For example, it is 1.0Å ^-1 or less.

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

The peaks indicating the layered laminated structure measured by in-plane diffraction measurement in the grazing angle incident X-ray diffraction method described below are relatively different from those in the grazing angle incident X-ray diffraction method described below. The intensity ratio of the wave peaks originating from the periodic arrangement of the perfluoropolyether groups in the in-plane direction measured by in-plane diffraction measurement (in-plane diffraction by grazing angle incident X-ray diffraction method described below) The wave peak indicating the layered laminated structure measured by radiometry/the in-plane direction derived from the perfluoropolyether group measured by the in-plane diffraction measurement in the grazing angle incident X-ray diffraction method described below The periodic peaks above) are, for example, 0 or more, and are, for example, 1.0 or less.

Furthermore, regarding the measurement method of in-plane diffraction (full amplitude at half maximum and integrated intensity) The method is described in detail in the examples described below.

Moreover, the water contact angle of the antifouling layer 3 is, for example, 100° or more, preferably 105° or more, and, for example, 130° or less.

As long as 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 described below.

<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, each layer is sequentially arranged in a roll-to-roll manner, for example.

<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 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 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, for example, surface treatment is performed on the surface of the base material layer 2 to improve the adhesion between the base material layer 2 and the antifouling layer 3 . 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, or, for example, 150W or less.

In addition, 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 integrated intensity ratio to a specific value or less, it is relatively convenient. A good example is the dry coating method. Examples of dry coating methods include vacuum evaporation, sputtering, and CVD (Chemical Vapor Deposition), and a preferred example is vacuum evaporation.

The vacuum evaporation method combines the evaporation source (alkoxysilane compound with perfluoropolyether group) and the substrate Layer 2 (functional layer 5) is arranged in a vacuum chamber facing each other, and the evaporation source is heated to evaporate or sublime, so that the evaporated or sublimated evaporation source is deposited on the surface of 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, and, for example, 300°C or lower.

Thereby, the antifouling layer 3 is disposed on one side of the base material layer 2 in the thickness direction, thereby producing a laminated body 1 including the base material layer 2 and the antifouling layer 3 in order toward the thickness direction side.

<Effect>

In the laminate 1, the antifouling layer 3 has a periodic arrangement in the in-plane direction of the perfluoropolyether groups measured by in-plane diffraction measurement using the grazing-angle incident X-ray diffraction method. The full amplitude of the half peak of the wave peak is more than 0.4Å ^-1 .

As long as the half-peak full width value is equal to or higher than the lower limit, even after the stains attached to the antifouling layer 3 are wiped off, the antifouling property of the antifouling layer 3 can be suppressed from being reduced (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 with respect to the base material layer 2 . Specifically, the alkoxysilane compound 20A is aligned perpendicularly with respect to the base material layer 2 , the alkoxysilane compound 20B is aligned obliquely with respect to the base material layer 2 , and the alkoxysilane compound 20B is aligned in parallel with respect to the base material layer 2 . Aligned alkoxysilane compound 20C.

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

Furthermore, the above-mentioned half-peak full amplitude value represents the inverse of the correlation length. That is, it is an index indicating the size of the region 22 of each group 21 (in other words, the amount of periodic arrangement of the fluoroalkyl groups of the alkoxysilane compound having a perfluoropolyether group).

Therefore, if the half-maximum full-width value becomes smaller, as shown in FIG. 3C , it means that the size of the region 22 of each group 21 becomes larger. On the other hand, if the half-maximum full-width value becomes larger, as shown in FIG. 3D , it means that the size of the region 22 of each group 21 becomes smaller.

Furthermore, the half-peak full amplitude value of the antifouling layer 3 is 0.4Å ^-1 or more. That is, as shown in FIG. 3C , the size of the area 22 of each group 21 is relatively small. In this way, even after the stains adhering to the antifouling layer 3 are wiped off, the antifouling property of the antifouling layer 3 can be suppressed from decreasing (excellent antifouling durability).

Moreover, in the laminated body 1, it is preferable that the integrated strength ratio of the antifouling layer 3 measured by the test mentioned below is 0.78 or less.

Specifically, in the experiment, through the in-plane diffraction measurement in the grazing angle incident parallel The integrated intensity of the wave peak (the first in-plane diffraction integrated intensity) of the ground-aligned structure). In addition, by in-plane diffraction measurement in the grazing angle incident X-ray diffraction method, the integrated intensity of the peaks originating from the periodic arrangement of the perfluoropolyether groups in the in-plane direction was measured for the antifouling layer (second surface Internal diffraction integrated intensity). Based on the obtained first in-plane diffraction integrated intensity and the second in-plane diffraction integrated intensity, the integrated intensity ratio of the first in-plane diffraction integrated intensity to the second in-plane diffraction integrated intensity is calculated (the first in-plane diffraction integrated intensity Diffraction integrated intensity/second in-plane diffraction integrated intensity).

The integrated intensity ratio is an index of the amount (hereinafter, sometimes referred to as the amount of arrangement) that the fluoroalkyl groups of the alkoxysilane compound having a perfluoropolyether group are periodically arranged in the in-plane direction in the antifouling layer 3 . If the integrated intensity ratio becomes smaller, as shown in FIG. 3E , it means that the amount of arrangement becomes larger. On the other hand, if the integrated intensity ratio becomes larger, as shown in FIG. 3F , it means that the amount of arrangement becomes smaller.

And, as mentioned above, this integrated intensity ratio is calculated by dividing the first in-plane diffraction integrated intensity by the second in-plane diffraction integrated intensity.

The second in-plane diffraction integrated intensity is the integrated intensity derived from the periodically arranged wave peaks in the in-plane direction of the perfluoropolyether group of the alkoxysilane compound having a perfluoropolyether group. If the second in-plane diffraction integrated intensity increases, this means that the amount of arrangement increases. In this way, studies have also been conducted on using the second in-plane diffraction integrated intensity directly as an index of the alignment amount.

However, in grazing angle incident X-ray diffraction measurement, the background value will change each time due to subtle differences in the sample, so the integrated intensity of the second in-plane diffraction will also change each time it is measured. Therefore, if the absolute value of the integrated intensity of diffraction in the second plane is directly used as an index, then there is no The method can be used to find the permutation quantity uniformly.

Therefore, by dividing the first in-plane diffraction integrated intensity by the second in-plane diffraction integrated intensity, the second in-plane diffraction integrated intensity is expressed as a relative value to the first in-plane diffraction integrated intensity, that is, an integrated intensity ratio. Integrated radiation intensity. This makes it possible to obtain the amount of arrangement uniformly.

As long as the integrated intensity ratio is below the above upper limit, the amount of arrangement increases. In this way, even after the stains adhering to the antifouling layer 3 are wiped off, the antifouling property of the antifouling layer 3 can be suppressed from decreasing (excellent antifouling durability).

Based on the above situation, the half-peak full amplitude value of the antifouling layer 3 is 0.4Å ^-1 or more, and preferably the integrated intensity ratio is 0.78 or less. That is, as shown in FIG. 3G , it is preferable that the size of the area 22 of the group 21 is small and the amount of the area 22 of the group 21 is large.

In addition, the antifouling durability can be evaluated by the antifouling durability test described in detail in the Examples described below. Specifically, as long as 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, the antifouling durability of the antifouling layer 3 Excellent.

2. Second embodiment

A second embodiment of the laminated body of the present invention will be described with reference to FIG. 4 .

Furthermore, in the second embodiment, the same components and steps as those in the first embodiment are appended. The same reference symbols are used, and detailed descriptions thereof are omitted. In addition, unless otherwise stated, the second embodiment can exhibit the same functions and effects as those of the first embodiment. 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 the thickness direction side. More specifically, the laminated body 1 includes a base material layer 2, an adhesion layer 6 directly disposed on the upper surface of the base material layer 2 (one surface in the thickness direction), and an optical fiber layer directly disposed on the upper surface (one surface in the thickness direction) of the adhesion layer 6. The functional layer 7 and the antifouling layer 3 are directly arranged 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 be in contact with the lower surface of the optical functional layer 7 .

The base material layer 2 is the same as the base material layer 2 of the first embodiment, and includes a base material 4 and a functional layer 5 .

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 be in contact with the lower surface of the functional layer 5 .

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

The thickness of the base material 4 is the same as the thickness of the base material 4 of 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 includes 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 layer 2 (functional layer 5) in contact with the upper surface of the base layer 2 (functional layer 5).

As a material of the adhesion 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, examples of the material of the adhesion layer 6 include alloys of two or more of the above-mentioned metals and oxides of the above-mentioned metals.

As a material for the adhesive layer 6, from the viewpoint of adhesiveness and transparency, preferred examples include silicon oxide (SiOx) and indium tin oxide (ITO). When silicon oxide is used as the material of the adhesive layer 6, it is preferable to use SiOx with an oxygen content less than the stoichiometric composition, and more preferably to use SiOx with x being 1.2 or more and 1.9 or less. As the material of the contact layer 6, a more preferred example is: indium tin oxide (ITO).

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

<Optical functional layer>

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

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 includes two or more layers having mutually different refractive indexes. Specifically, the anti-reflection 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. The interference between the reflected light in the multiple interfaces of the multiple thin layers (high refractive index layer, low refractive index layer) included in the anti-reflective layer will attenuate the net reflected light intensity. In addition, in the anti-reflection layer, the interference effect of attenuating the intensity of reflected light can be expressed 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, it includes one selected from the group consisting of 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 materials used in the anti-reflective layer can be chosen depending on 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 balancing high refractive index with 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), preferably niobium oxide, 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 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 balancing low refractive index and low absorption of visible light, examples of the low refractive index material include silicon dioxide (SiO ₂ ) and magnesium fluoride, and a preferred example is silicon dioxide. 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.

Especially 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 difference between the second low refractive index layer 14 and the antifouling layer 3 Excellent adhesion between them.

In addition, 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, for example, 50 nm. 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, 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, preferably 0.5 or more. It is 0.7 or more, and 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, preferably It is 7 or more, and for example, it is 15 or less, 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, preferably It is 3 or more, and for example, it is 10 or less, Preferably it is 8 or less.

The anti-reflective 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, and, 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 (Transmission Electron Microscopy, transmission electron microscope) observation and determination.

<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) in contact with the upper surface of the optical functional layer 7 (anti-reflective layer).

The antifouling layer 3 is formed of the above-described 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 composed of an alkoxysilane compound having a perfluoropolyether group.

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

The thickness, full width at half maximum, integrated intensity ratio, and water contact angle of the antifouling layer 3 are the same as those of the antifouling layer 3 in the first embodiment.

Regarding the half-peak full amplitude and integrated intensity, the type of alkoxysilane compound having a perfluoropolyether group and the surface of the optical functional layer 7 (anti-reflection layer) in the fifth step described below can be determined. The treatment method (when the surface treatment method is plasma treatment, the type of gas used in the plasma treatment), and the output power of the plasma treatment when the surface treatment method is plasma treatment are adjusted. Adjust to be above the above specific value or 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 the optical functional layer 7 ( Anti-reflective layer) Step 5 of configuring the anti-fouling layer 3. 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-reflection 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, the adhesive 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 low refractive index layer are sequentially arranged on the side of the base material layer 2 facing the thickness direction. Refractive index layer 14.

That is, in this method, the fourth step includes: a step of arranging the adhesion layer 6 on the base material layer 2, a step of arranging the first high refractive index layer 11 on the adhesion layer 6, and a step of arranging the first high refractive index layer 11 on the adhesion layer 6. 1. The first low refractive index layer arranging step of arranging the first low refractive index layer 12 on the high refractive index layer 11, the second high refractive index layer arranging step of arranging the second high refractive index layer 13 on the first low refractive index layer 12, and a second low refractive index layer arranging step of arranging the second low refractive index layer 14 on the second high refractive index layer 13 . Furthermore, in this manufacturing method, each layer is sequentially arranged by a vacuum evaporation method, a sputtering method, a lamination method, a plating method, or an ion plating method, and a sputtering method is preferable.

Hereinafter, the method of arranging each layer sequentially by sputtering will be 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 , the surface of the base material layer 2 is subjected to surface treatment, for example. As the surface treatment, the surface treatment exemplified in the above-mentioned second step can be exemplified, and a preferred example is plasma treatment.

Moreover, the sputtering method is to use the target (material of 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 14) ) and the base material layer 2 are arranged facing each other in the vacuum chamber. While supplying gas, a voltage is applied from the power source, thereby accelerating the gas ions and irradiating them to the target, causing the target material to eject from the target surface, thereby causing the target material to be ejected from the target surface. Each layer is deposited sequentially on the surface of material layer 2.

Examples of the gas include inert gases (for example, argon gas). In addition, reactive gases such as oxygen may be used together if necessary. When reactive gases are used together, the flow ratio of the reactive gases (sccm) is not particularly limited, but the ratio to the total flow rate of the sputtering gas and the reactive gas is, for example, 0.1 flow % or more and 100 flow % or less.

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

For example, the power supply may be any one of DC (Direct Current) power supply, AC (Alternating Current) power supply, MF (Medium frequency, intermediate frequency) power supply, and RF (Radio Frequency, radio frequency) power supply. Alternatively, it may be It is a combination of these.

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, the surface of the optical functional layer 7 (anti-reflective layer) is subjected to surface treatment, for example. As the surface treatment, the surface treatment exemplified in the above-mentioned second step can be exemplified. Preferably, it is plasma treatment, and more preferably, it is plasma treatment using oxygen.

As a method of arranging the antifouling layer 3 on the optical functional layer 7 (anti-reflection layer), the above-mentioned method can be exemplified. The method of arranging the antifouling layer 3 on the base material layer 2 in the second step is the same as the method exemplified. From the viewpoint of adjusting the above-mentioned integrated intensity ratio to a specific value or less, dry coating is preferably exemplified. Method, preferably a vacuum evaporation method.

The vacuum evaporation method is to arrange the evaporation source (an alkoxysilane compound with a 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 make it Evaporate or sublimate, and the evaporated or sublimated evaporation source is deposited on the surface of the optical functional layer 7 (anti-reflective 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, and, for example, 300°C or lower.

In this way, the antifouling layer 3 is disposed on one side of the optical function layer 7 (anti-reflection layer) in the thickness direction, and the substrate layer 2, the adhesion layer 6, and the optical function layer 7 (anti-reflection 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.

Furthermore, when one side in the thickness direction of the optical functional layer 7 (antireflection layer) is a layer containing silicon dioxide, in other words, a layer containing silicon dioxide (for example, containing silicon dioxide) is directly disposed on the surface below the antifouling layer 3 In the case of the second low refractive index layer 14 of silicon dioxide, 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 will undergo a dehydration condensation reaction with the silicon in silica dioxide. In other words, the antifouling layer 3 is formed of an alkoxysilane compound having a perfluoropolyether group on the optical functional layer 7 (anti-reflective layer) via a siloxane bond. This can further improve antifouling durability.

3.Examples of changes

In the modification 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 stated, the modified examples can exhibit 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 appropriately combined.

In the first embodiment, the laminated body 1 includes the base material layer 2 and the antifouling layer 3. As shown in FIG. 6, the laminated body 1 may further include a primer layer 15 between the base material layer 2 and the antifouling layer 3. Specifically, the laminated body 1 may have 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 primer layer 15 is a layer closely connected with the antifouling layer 3 .

As a material of the undercoat layer 15, a preferred example is silicon dioxide (SiO ₂ ). More preferably, the undercoat layer 15 contains silicon dioxide (SiO ₂ ).

As long as 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 will undergo a dehydration condensation reaction with the silicon in the silica dioxide. In other words, the antifouling layer 3 is an alkoxysilane compound having a perfluoropolyether group formed on the base coat layer 15 via a siloxane bond. This can further improve antifouling durability.

The undercoat layer 15 is formed by, for example, sputtering, plasma CVD, vacuum evaporation, or the like.

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 may also be composed 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 further explain the present invention in detail. 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 recorded upper limit value (a value defined as "below" or "under") or the lower limit value (a value defined as "above" or "exceeds").

1. Manufacturing of laminated body Example 1 <Step 3>

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

Then, a hard coat layer is disposed on one side of the base material (TAC film) in the thickness direction. Specifically, first, 100 parts by mass of silica particles were added 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) based on 100 parts by mass of the resin component. Organosilica sol ("MEK-ST-L" manufactured by Nissan Chemical Co., Ltd.) was added so that the amount became 25 parts by mass. The average primary particle diameter of the silica particles (inorganic filler): 50 nm. The particle size distribution of the silica particles. : 30nm~130nm, solid content 30% by weight) and mixed 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 became 6 μm, and dried at 80° C. for 3 minutes. Thereafter, ultraviolet rays with a cumulative light intensity of 200 mJ/cm ² were irradiated using a high-pressure mercury lamp to harden the coating layer to form a hard coat layer. Thereby, the base material layer is prepared.

<Step 4>

Plasma treatment is performed on one side of the substrate layer (hard coating) in the thickness direction using a roll-to-roll plasma treatment device in a vacuum environment of 1.0Pa. In this plasma treatment, argon gas was used as an inert gas, and the discharge power was set to 100W.

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) the thickness of the adhesive layer on the HC layer of the TAC film with the HC (Hard Coating) layer after plasma treatment. An indium tin oxide (ITO) layer of 2.0 nm, a Nb ₂ O ₅ layer with a thickness of 12 nm as the first high refractive index layer, a SiO ₂ layer with a thickness of 28 nm as the first low refractive index layer, and a second high refractive index layer. The Nb ₂ O ₅ layer with a thickness of 100 nm, and the 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 was used, argon as an inert gas, and oxygen as a reactive gas in an amount of 10 parts by volume relative to 100 parts by volume of argon, and the discharge voltage was set to 350V. The air pressure (film forming pressure) is set to 0.4Pa, and the ITO layer is formed by MFAC (medium frequency alternating current Model Free Adaptive Control, medium frequency alternating current) sputtering.

In the formation of the first high refractive index layer, an Nb target is used. 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, the film-forming gas pressure was set to 0.42 Pa, 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, the film-forming gas pressure was set to 0.3 Pa, and a SiO ₂ layer was formed by MFAC sputtering.

In the formation of the second high refractive index layer, an Nb target is used. 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 0.5 Pa, and an Nb ₂ O ₅ layer was formed by MFAC sputtering.

In the formation of the second 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 340V and the film-forming gas pressure was set to 0.25 Pa, and a SiO ₂ layer was formed by MFAC sputtering.

In the above manner, the adhesive layer and the anti-reflective 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 as surface treatment is performed 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 vapor deposition source is a solid component obtained by drying OPTOOL UD120 (manufactured by DAIKIN INDUSTRIES Co., Ltd.). In addition, the heating temperature of the vapor deposition source (crucible) of the vacuum vapor deposition method was set to 260°C. In this way, a layered body is obtained.

Example 2

A laminated body was produced based on the same procedure as Example 1.

However, in the fifth step, for one side of the anti-reflection layer in the thickness direction, the surface treatment is changed to plasma treatment with oxygen instead of plasma treatment with argon.

Example 3

A laminated body was produced based on the same procedure as in Example 2.

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

Comparative example 1

A laminated body was produced based on the same procedure as Example 1.

However, change step 5 as follows.

<Step 5>

On one side of the anti-reflective layer in the thickness direction, apply OPTOOL UD509 using a gravure coater so that the coating thickness becomes 8 μm. Thereafter, 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

A laminated body was produced based on the same procedure as Example 1.

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

2.Evaluation (grazing angle incident X-ray diffraction measurement)

For the antifouling layer of the laminated body of each Example and each Comparative Example, in-plane diffraction (in plane) measurement was performed by the grazing angle incident X-ray diffraction method under the following conditions.

The results of in-plane diffraction measurement in Example 2 are shown in FIG. 7 .

<Measurement conditions>

Experimental facility: Aichi Synchrotron Radiation Center

Experiment station: 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: Use thinly applied grease to fix it on the flat sample table

Hereinafter, the full amplitude at half maximum value is calculated based on the obtained in-plane diffraction (in plane) measurement results. The calculation method uses the fitting method to uniformly calculate the half-peak full amplitude value. This method will be described in detail using Example 2 as an example.

First, the results obtained by 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, it is assumed that the actual measurement data (in-plane diffraction (in plane) measurement) is the sum of the background and the peaks A1 to A4 (see Figure 8), and fitting is performed. Furthermore, standardization was performed so that the background at high wavelength 24 nm ^-1 was consistent among all samples.

(In formula (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 wave 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 center of gravity position of A1; q _A2 represents the center of gravity position of wave peak A2; q _A3 represents the center of gravity position of wave peak A3; q _A4 represents the center of gravity position of wave peak A4); △q _An represents the half-peak full amplitude value (△q _A1 represents the center of gravity position of wave peak A1 The 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 is a peak indicating a layered 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 groups in the in-plane direction, and the center of gravity position is 1.5Å ^-1 or more and 2.0Å ^-1 or less.

The fitting results are shown in Figure 8 (Example 2).

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 fully consistent with the fitting results.

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

In addition, the half-peak full amplitude of the wave peak A4 derived from the periodic arrangement of the perfluoropolyether groups in the in-plane direction obtained by fitting, the intensity of the wave peak, the peak position, the integrated intensity and the normalized integrated intensity, Table 1 shows the peak intensity, peak position, half-peak full amplitude value, integrated intensity and normalized integrated intensity of the peak A1 representing the layered laminated structure.

(anti-fouling durability)

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

<Measurement conditions>

Drop volume: 2μl

Temperature: 25℃

Humidity: 40%

Next, with respect to the antifouling layer of the laminate of each Example and each Comparative Example, an eraser sliding test was performed based on the following conditions, and then the water contact angle was measured in the same procedure as the above method (sometimes referred to as the post-erasing eraser sliding test). the contact angle). The results are shown in Table 1.

Next, the change amount of the contact angle is calculated based on the following equation (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 manufactured by Minoan Company (Φ6mm)

Sliding distance: 100mm one way

Sliding speed: 100mm/second

Load: 1kg/6mmΦ

Number of slides: 3000 times

In addition, the above-mentioned invention is provided as an exemplary embodiment of the present invention, and it is only an example and should not be interpreted in a restrictive manner. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the patent application described below.

[Industrial availability]

The laminate of the present invention is suitably used 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. According to the grazing angle incident X-ray diffraction method, The half-peak full amplitude of the wave peaks originating from the periodic arrangement of perfluoropolyether groups in the in-plane direction of the above-mentioned antifouling layer measured by in-plane diffraction measurement is more than 0.4Å ^-1 . In the above-mentioned anti-fouling layer, The other side of the dirt layer in the thickness direction is provided with a primer layer, and the primer layer is a layer containing 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. According to the grazing angle incident X-ray diffraction method, The half-peak full amplitude of the wave peaks originating from the periodic arrangement of the perfluoropolyether groups in the in-plane direction of the above-mentioned antifouling layer measured by in-plane diffraction measurement is more than 0.4Å ^-1 , and the above-mentioned base A close contact layer and an anti-reflective layer are further provided between the material layer and the anti-fouling layer, and one side of the anti-reflective layer in the thickness direction is a layer containing silicon dioxide. The laminate according to claim 1, wherein the antifouling layer is an alkoxysilane compound having a perfluoropolyether group formed on the undercoat layer via a siloxane bond. The laminated body of claim 2, wherein the anti-reflection layer includes two or more layers having mutually different refractive indexes. The laminated body of claim 4, wherein the anti-reflection layer includes one selected from the group consisting of metal, metal oxide, and metal nitride.