JP2023171767A - Evaluating method of fingerprint resistance, method of producing optical member, and optical member - Google Patents

Abstract

To provide an evaluation method of fingerprint resistance capable of evaluating fingerprint resistance quantitatively and with high reproducibility, a method for producing an optical member using the evaluation method, and an optical members with excellent fingerprint resistance.SOLUTION: The evaluation method of fingerprint resistance for evaluating the fingerprint resistance of the surface of an evaluation object using the lightness L* before and after application of the oleic acid diluent as an index, includes the steps of: measuring the lightness L* defined by CIE1976 L*a*b* color system on the surface of the evaluation object; applying oleic acid diluent over the surface of the evaluation object; and after drying the oleic acid diluent, measuring the lightness L* defined by CIE1976 L*a*b* color system; and evaluating lightness L* before and after applying oleic acid diluent as the index.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for evaluating fingerprint resistance, a method for producing an optical member using the evaluation method, and an optical member, particularly an optical member having excellent fingerprint resistance.

2. Description of the Related Art In recent years, touch panels that serve as display devices and input means have been widely used in various electronic devices. A hard coat film having a hard coat layer is usually provided on the surface of the touch panel to prevent scratches.

Since such a touch panel is often operated with a finger, fingerprints due to finger oil are usually attached to the surface of the touch panel. When fingerprints adhere to the surface of the touch panel in this way, the appearance deteriorates and the displayed image becomes difficult to see. Therefore, the above-mentioned hard coat film is required to have fingerprint resistance so that attached fingerprints are difficult to see.

Until now, there has been no clear indicator for evaluating fingerprint resistance, and the only methods available have been to measure the contact angle of water or oleic acid as a reference, or to perform a sensory evaluation of how it looks when a fingerprint is actually attached. Ta. However, there was a problem that the correlation between the measured contact angle and the sensory evaluation was low, and the reproducibility of visual sensory evaluation alone was low.

Therefore, Patent Document 1 proposes a contamination evaluation method in which a test body is irradiated with light and scattered light reflected or transmitted by the test body is detected to evaluate the degree of contamination on the surface of the test body. Specifically, we use ΔE*ab in the L*a*b* color model specified by the International Commission on Illumination (CIE), and calculate ΔE*ab after the surface is artificially contaminated and the subsequent cleaning treatment. The degree of contamination is evaluated based on the difference from ΔE*ab after applying.

International Publication No. 2008/029946

However, when ΔE*ab is used as in Patent Document 1, the difference between ΔE*ab after the surface is artificially contaminated and ΔE*ab after subsequent cleaning treatment is absolutely small. It was difficult to tell the extent of the fingerprints. Therefore, it was not a sufficient index for evaluating fingerprint resistance.

The present invention has been made in view of the above circumstances, and provides a fingerprint resistance evaluation method that can quantitatively and highly reproducibly evaluate fingerprint resistance, and an optical member using the evaluation method. The purpose of the present invention is to provide a production method for the same, and an optical member having excellent fingerprint resistance.

In order to achieve the above object, the present invention first measures the lightness L* defined by the CIE1976L*a*b* color system of the surface of the object to be evaluated, and then measures the lightness L* of the surface of the object to be evaluated. After applying a diluted oleic acid solution and drying it, the lightness L* defined by the CIE1976L*a*b* color system is measured, and the lightness L* before and after applying the diluted oleic acid solution is used as an index. Accordingly, a method for evaluating fingerprint resistance is provided, which is characterized in that the fingerprint resistance of the surface of the object to be evaluated is evaluated (Invention 1).

In addition, "fingerprint resistance" in the present invention refers to a property in which attached fingerprints are difficult to see visually.

According to the above invention (invention 1), fingerprint resistance can be evaluated quantitatively and with high reproducibility. Furthermore, there is a high correlation with visual evaluation.

In the above invention (invention 1), the oleic acid diluted solution is preferably a solution obtained by diluting oleic acid with a volatile solvent. Further, the volatile solvent is preferably an alcohol solvent, and the alcohol solvent is preferably ethanol. The concentration of oleic acid in the oleic acid diluted solution is preferably 0.12% by mass or more and 12% by mass or less. The diluted oleic acid solution is preferably applied to the surface of the object to be evaluated using a bar coater.

In the above invention (invention 1), the lightness L* before application of the oleic acid diluted solution is defined as the pre-coating lightness L*, and the lightness L* after the application of the oleic acid diluted solution is defined as the post-coating lightness L*. , the fingerprint resistance of the surface of the object to be evaluated is evaluated based on the amount of change ΔL* obtained by subtracting the lightness L* before application from the lightness L* after application, or the lightness L before application of the diluted oleic acid solution is evaluated. * is the lightness before coating L*, the lightness L* after coating the oleic acid diluted liquid is the lightness after coating L*, and the change rate (%) calculated by the following formula is used to determine the surface of the object to be evaluated. It is preferable to evaluate fingerprint resistance (Inventions 2 and 3). Alternatively, evaluation may be performed using both.
Rate of change = {(Lightness after application L*-Lightness before application L*)/Lightness before application L*}×100

In the above inventions (Inventions 1 to 3), it is preferable that a hard coat layer is present on the surface of the evaluation target to which the oleic acid diluted solution is applied (Invention 4).

In the above inventions (Inventions 1 to 4), it is preferable that the object to be evaluated is an optical member (Invention 5).

Second, the present invention comprises a step of obtaining an optical member, and an evaluation step of evaluating fingerprint resistance using the optical member as an evaluation object by the fingerprint resistance evaluation method (inventions 1 to 5). A method for producing an optical member is provided (invention 6).

Thirdly, in the present invention, the lightness L* defined by the CIE1976L*a*b* color system before application of the diluted oleic acid solution is taken as the brightness L* before application, and the brightness L* defined by the CIE1976L*a*b* color system before application of the diluted oleic acid solution is defined as the lightness L* before application. When the lightness L* defined by the *a*b* color system is the lightness L* after coating, the amount of change ΔL* obtained by subtracting the lightness L* before coating from the lightness L* after coating is 0. Provided is an optical member characterized in that the number is less than 3 (Invention 7).

Fourthly, in the present invention, the lightness L* defined by the CIE1976L*a*b* color system before application of the diluted oleic acid solution is defined as the lightness L* before application, and the lightness L* defined by the CIE1976L*a*b* color system before application of the diluted oleic acid solution is defined as the lightness L* before application. Provided is an optical member characterized in that, when the lightness L* defined by the *a*b* color system is the lightness L* after coating, the rate of change calculated by the following formula is 6% or less. (Invention 8).
Rate of change = {(Lightness after application L*-Lightness before application L*)/Lightness before application L*}×100

In the above inventions (Inventions 7 and 8), it is preferable that a hard coat layer exists on the surface of the optical member to which the oleic acid diluted solution is applied (Invention 9).

According to the method for evaluating fingerprint resistance according to the present invention, fingerprint resistance can be evaluated quantitatively and with high reproducibility. Moreover, according to the method for producing an optical member according to the present invention, it is possible to produce an optical member after evaluating fingerprint resistance quantitatively and with high reproducibility. Furthermore, the optical member according to the present invention has excellent fingerprint resistance.

FIG. 1 is a cross-sectional view of an optical member according to an embodiment of the present invention.

Embodiments of the present invention will be described below.
[Evaluation method of fingerprint resistance]
A fingerprint resistance evaluation method according to an embodiment of the present invention measures the lightness L* defined by the CIE1976L*a*b* color system of the surface of the object to be evaluated, and then measures the lightness L* of the surface of the object to be evaluated. After applying the oleic acid diluted solution and drying it, the lightness L* specified by the CIE1976L*a*b* color system was measured, and the lightness L* before and after applying the oleic acid diluted solution was used as an index. , evaluate the fingerprint resistance of the surface of the object to be evaluated.

According to the above evaluation method, fingerprint resistance can be evaluated quantitatively and with high reproducibility. Furthermore, there is a high correlation with visual evaluation.

The type of object to be evaluated is not particularly limited, and according to the fingerprint resistance evaluation method described above, the fingerprint resistance of various objects to be evaluated can be evaluated. As such an object to be evaluated, an object to which fingerprints are easily attached or an object to which fingerprints are easily attached is preferably mentioned, and an object having a smooth surface is particularly preferably mentioned. In addition, the object to be evaluated may be transparent, opaque, colorless, or colored; among others, A transparent material is preferred, and a colorless and transparent material is particularly preferred. Examples of specific objects to be evaluated include optical members, optical discs, casings, and the like. Optical members include, for example, plastic films, plastic plates, and glass plates; various functional layers (transparent conductive film, metal layer, silica layer, hard coat layer, anti-glare layer, etc.) provided on one or both sides thereof. Objects; examples include displays, touch panels, and parts thereof. Among the above, particularly preferred are plastic films, plastic plates, glass plates, displays, touch panels, etc. that have a hard coat layer on the outermost surface (the surface that comes into contact with a finger).

The details of the method for measuring the lightness L* will be described later, but when the object to be evaluated is a transparent member (particularly a transparent film), it is preferable to attach the object to a black board and then measure. Thereby, the fingerprint attached to the object to be evaluated can be more accurately measured as the lightness L*.

The color of the black board used in this case is defined by the CIE1976L*a*b* color system, with a lightness L* of 0.1 to 60 and a chromaticity a* of -40 to 40. , chromaticity b* is preferably -40 to 40, particularly lightness L* is 1 to 30, chromaticity a* is -20 to 20, and chromaticity b* is -20 to 20. More preferably, the lightness L* is 2 to 15, the chromaticity a* is -10 to 10, and the chromaticity b* is -10 to 10.

The material of the black plate is not particularly limited, and for example, a plastic plate, a metal plate, a ceramic plate, etc. can be used, and among them, a plastic plate that easily produces the above-mentioned black color is preferable. Examples of the plastic board include an acrylic board, a polycarbonate board, a polyethylene terephthalate board, a vinyl chloride resin board, and among these, the acrylic board is preferred because it easily produces the above-mentioned black color.

The method for attaching the evaluation target to the black board is not particularly limited, but it is preferable to use a pressure-sensitive adhesive sheet with high transparency and a pressure-sensitive adhesive layer with a refractive index close to 1. The haze value (measured according to JIS K7136:2000) of the adhesive layer is preferably 10% or less, particularly preferably 5% or less, and more preferably 1% or less. . Further, the refractive index of the adhesive layer (method B according to JIS K7142) is preferably 1.2 to 1.8, particularly preferably 1.3 to 1.6, and more preferably 1.4. It is preferably 1.55 to 1.55.

The diluted oleic acid solution applied to the surface of the object to be evaluated is preferably a solution obtained by diluting oleic acid with a volatile solvent. The volatile solvent preferably has a boiling point of 35 to 110°C. Examples of such volatile solvents include alcohols such as methanol, ethanol, butanol, and isopropyl alcohol; ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone; esters such as ethyl acetate; aliphatic hydrocarbons such as hexane; benzene; Examples include aromatic hydrocarbons such as toluene, and halogenated hydrocarbons such as methylene chloride and trichloroethane. These can be used alone or in combination of two or more.

Among the above, alcohol solvents are preferred, and ethanol is particularly preferred, from the viewpoint of increasing the brightness L* after application of the oleic acid diluted solution and making it easier to evaluate fingerprint resistance.

The lower limit of the concentration of oleic acid in the oleic acid diluted solution is preferably 0.12% by mass or more, particularly preferably 0.15% by mass or more, and more preferably 0.18% by mass or more. It is preferable. This approximates the ease with which fingerprints actually adhere. The upper limit of the concentration of oleic acid in the oleic acid diluted solution is preferably 12% by mass or less, more preferably 6% by mass or less, particularly preferably 2% by mass or less, and is preferably 0.5% by mass or less. This makes it close to the ease of wiping off actual fingerprints.

As a method for applying the diluted oleic acid solution to the surface of the object to be evaluated, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, etc. can be used. Among the above, it is preferable to apply by a bar coating method, that is, by a bar coater. According to the bar coater, the diluted oleic acid solution can be uniformly applied to the flat surface of the object to be evaluated, thereby forming an oleic acid layer uniformly on the surface of the object to be evaluated. It becomes possible to accurately measure the lightness L* after coating. As the bar coater, a wire bar is particularly preferred.

After applying the diluted oleic acid solution to the surface of the object to be evaluated, the diluted oleic acid solution is dried to form an oleic acid layer on the surface of the object to be evaluated. The drying conditions may be determined as appropriate depending on the diluting solvent used, but from the viewpoint of uniformly forming an oleic acid layer on the surface of the object to be evaluated, the drying conditions are preferably 5°C to 80°C, especially 20°C to 40°C. Preferably, it is dried. In particular, when ethanol is used as the diluent solvent, it is preferable to air dry at normal temperature and pressure (mainly 23° C., 50% RH).

After drying the oleic acid diluted solution as described above, the lightness L* of the surface of the object to be evaluated (the surface on which the oleic acid layer is formed) is measured again by the same method as described above.

Here, the lightness L* measured before application of the diluted oleic acid solution is referred to as "lightness L* before application," and the lightness L* measured after application of the diluted oleic acid solution is referred to as "lightness L* after application." do. In this embodiment, the fingerprint resistance of the surface of the object to be evaluated is evaluated using the pre-coating lightness L* and the post-coating lightness L* as indicators.

Specifically, first, the fingerprint resistance of the surface of the object to be evaluated can be evaluated based on the amount of change ΔL* obtained by subtracting the lightness L* before application from the lightness L* after application. In this case, it can be said that the smaller the amount of change ΔL* is, the better the fingerprint resistance is. In order to have excellent fingerprint resistance, the amount of change ΔL* is preferably less than 0.3, more preferably 0.2 or less, particularly preferably 0.12 or less, Furthermore, it is preferably 0.04 or less. The lower limit value of the amount of change ΔL* is most preferably 0, but it is usually preferably 0.01 or more, and particularly preferably 0.02 or more.

Second, the fingerprint resistance of the surface of the object to be evaluated can be evaluated based on the rate of change (%) in the lightness L* calculated by the following formula.
Rate of change = {(Lightness after application L*-Lightness before application L*)/Lightness before application L*}×100
In this case, it can be said that the smaller the rate of change, the better the fingerprint resistance. In order to have excellent fingerprint resistance, the rate of change in lightness L* is preferably 6% or less, more preferably 4% or less, particularly preferably 2% or less, and is preferably 1.0% or less, most preferably 0.9% or less. The lower limit of the rate of change is most preferably 0%, but usually it is preferably 0.01% or more, particularly preferably 0.1% or more.

Note that the method for evaluating fingerprint resistance using the pre-coating lightness L* and post-coating lightness L* as indicators in the present invention is not limited to the above. For example, the value of (lightness L* after coating) ² - (lightness L* before coating) ² or the square root of the value can be used as an index.

[Production method of optical components]
A method for producing an optical member according to an embodiment of the present invention includes a step of obtaining an optical member, and an evaluation step of evaluating fingerprint resistance using the above-described fingerprint resistance evaluation method using the optical member as an evaluation object. It is equipped with According to this method for producing an optical member, it is possible to produce an optical member after evaluating fingerprint resistance quantitatively and with high reproducibility in the evaluation step. Therefore, optical members with excellent fingerprint resistance can be produced at a high yield.

More specifically, an optical member as a sample is manufactured (step of obtaining an optical member), and the fingerprint resistance is evaluated using the optical member as an evaluation object using the above-mentioned fingerprint resistance evaluation method (evaluation Step), it is preferable that the optical member be manufactured by the same manufacturing method as that of the sample determined to have excellent fingerprint resistance (step of obtaining the optical member).

Examples of the types of optical members include those described above. Among these, particularly preferred are plastic films, plastic plates, glass plates, displays, touch panels, etc. that have a hard coat layer on the outermost surface (the surface that comes into contact with fingers).

The optical member itself can be manufactured by a conventionally known method. However, for optical members with excellent fingerprint resistance, it is preferable to manufacture them by the method described below.

[Optical member]
The optical member according to the first embodiment of the present invention is an optical member in which the amount of change ΔL* obtained by subtracting the lightness L* before coating from the lightness L* after coating described above is less than 0.3. Further, the optical member according to the second embodiment of the present invention is an optical member in which the rate of change calculated by the following formula based on the above-mentioned lightness L* after coating and lightness L* before coating is 6% or less. be.
Rate of change = {(Lightness after application L*-Lightness before application L*)/Lightness before application L*}×100

The optical member according to the first embodiment and the optical member according to the second embodiment have excellent fingerprint resistance, that is, excellent performance in making attached fingerprints difficult to see. This excellent anti-fingerprint property was evaluated quantitatively and with high reproducibility.

From the viewpoint of fingerprint resistance, the amount of change ΔL* in the optical member according to the first embodiment is preferably 0.2 or less, particularly preferably 0.12 or less, and more preferably 0.04. It is preferable that it is below. Furthermore, from the viewpoint of anti-fingerprint properties, the rate of change in the optical member according to the second embodiment is preferably 4% or less, particularly preferably 2% or less, and further preferably 1.0% or less. It is preferably 0.9% or less, and most preferably 0.9% or less. The lower limit of the amount of change ΔL* is most preferably 0, but is usually preferably 0.01 or more, particularly preferably 0.02 or more. Further, the lower limit of the rate of change is most preferably 0%, but usually it is preferably 0.01% or more, particularly preferably 0.1% or more.

Examples of the types of optical members according to this embodiment include those described above. Among these, particularly preferred are plastic films, plastic plates, glass plates, displays, touch panels, etc. that have a hard coat layer on the outermost surface (the surface that comes into contact with fingers).

The optical member according to this embodiment will be explained with reference to FIG. 1.
As shown in FIG. 1, the optical member 1 according to the present embodiment includes a base material 11 and a hard coat layer 12 formed on one surface of the base material 11.

1. Each member 1-1. Substrate The substrate 11 of the optical member 1 according to the present embodiment is not particularly limited, but preferably includes a plastic film, a plastic plate, and a glass plate. Various functional layers such as a transparent conductive film, a metal layer, a silica layer, a hard coat layer, an anti-glare layer, etc. may be provided on the surface of the base material 11 opposite to the hard coat layer 12. Further, various functional layers such as a transparent conductive film, a metal layer, a silica layer, an anti-glare layer, etc. may be provided between the base material 11 and the hard coat layer 12.

Examples of plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyolefin films such as polyethylene film and polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, and polyester film. Vinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyether Imide film, fluororesin film, polyamide film, acrylic resin film, polyurethane resin film, norbornene polymer film, cyclic olefin polymer film, cyclic conjugated diene polymer film, vinyl alicyclic hydrocarbon polymer film, etc. Examples include plastic films and laminated films thereof. Among these, polyethylene terephthalate film, polycarbonate film, norbornene polymer film, etc. are preferred from the viewpoint of mechanical strength and the like.

In addition, in order to improve the adhesion with layers provided on the surface of the plastic film (hard coat layer 12, adhesive layer, etc.), one or both sides of the plastic film may be treated with a primer, oxidized, or roughened, if desired. Surface treatment can be performed by a method or the like. Examples of the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone/ultraviolet treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, etc. These surface treatment methods are appropriately selected depending on the type of plastic film, but in general, corona discharge treatment is preferably used in terms of effectiveness and operability.

The thickness of the plastic film is usually about 15 to 300 μm, preferably about 30 to 200 μm.

The plastic plate is not particularly limited, and examples thereof include an acrylic plate, a polycarbonate plate, and the like. The thickness of the plastic plate is not particularly limited, but is usually 0.3 to 5 mm, preferably 0.5 to 3 mm.

The glass plate is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium/strontium containing glass, aluminosilicate glass, lead glass, borosilicate glass, and barium borosilicate glass. etc. The thickness of the glass plate is not particularly limited, but is usually 0.1 to 5 mm, preferably 0.2 to 3 mm.

1-2. Hard Coat Layer The hard coat layer 12 of the optical member 1 in this embodiment is such that the amount of change ΔL* or the rate of change using the lightness L* after coating and the lightness L* before coating satisfy the above-mentioned value. Although it may be formed from any material, it is preferably formed by curing the coating composition C described below. According to coating composition C, it is easy to form the hard coat layer 12 that satisfies the above-mentioned values.

Coating composition C in this embodiment contains an active energy ray-curable component, fine particles, and a predetermined surface conditioner.

(1) Each component (1-1) Active energy ray curable component Since the coating composition C contains an active energy ray curable component, a hard coat obtained by curing the coating composition C with active energy rays. The layer 12 has desired hardness and scratch resistance.

Examples of active energy ray-curable components include polyfunctional (meth)acrylate monomers, (meth)acrylate prepolymers, active energy ray-curable polymers, and the like. As the active energy ray-curable component, it is preferable to use at least a polyfunctional (meth)acrylate monomer, and it is particularly preferable to use a polyfunctional (meth)acrylate monomer and a (meth)acrylate prepolymer together. . In addition, in this specification, (meth)acrylate means both acrylate and methacrylate. The same applies to other similar terms.

Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. (meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated Cyclohexyl di(meth)acrylate, Isocyanurate di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Dipentaerythritol tri(meth)acrylate, Propionic acid modified dipentaerythritol tri(meth)acrylate, Pentaerythritol tri(meth)acrylate ) acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol Examples include polyfunctional (meth)acrylates such as hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among the above, dipentaerythritol-based (meth)acrylates are preferred, dipentaerythritol hexa(meth)acrylate is particularly preferred, and dipentaerythritol hexaacrylate is even more preferred. These may be used alone or in combination of two or more.

On the other hand, examples of (meth)acrylate prepolymers include prepolymers such as polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These prepolymers may be used alone or in combination of two or more.

As a polyester acrylate prepolymer, for example, a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol may be prepared by esterifying the hydroxyl groups with (meth)acrylic acid, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth)acrylic acid.

The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolac-type epoxy resin to esterify it.

The urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth)acrylic acid.

A polyol acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid.

Among the above, urethane acrylate prepolymers (polyfunctional urethane (meth)acrylate) are preferred, and polyfunctional urethane acrylate is particularly preferred. Moreover, it is preferable to use polyfunctional urethane (meth)acrylate in combination with a polyfunctional (meth)acrylate monomer, and in particular, it is preferable to use it in combination with dipentaerythritol hexa(meth)acrylate.

When a polyfunctional urethane (meth)acrylate and a polyfunctional (meth)acrylate monomer (especially dipentaerythritol hexa(meth)acrylate) are used together, the polyfunctional The amount of urethane (meth)acrylate blended is preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and even more preferably 95 parts by mass or more. Further, the blending amount is preferably 150 parts by mass or less, particularly preferably 120 parts by mass or less, and further preferably 105 parts by mass or less.

(1-2) Fine Particles The fine particles may be either inorganic fine particles or organic fine particles, but inorganic fine particles are preferred because the amount and rate of change in brightness L* before and after coating tends to be the above-mentioned values. Further, the shape of the fine particles, particularly the inorganic fine particles, is preferably non-spherical, and particularly preferably amorphous. The term "irregular shape" as used herein refers to a shape that is not a regular shape such as a spherical shape or an elliptical shape, but has a large number of irregular corners or surfaces. In addition, one type of fine particles can be used alone or two or more types can be used in combination.

Examples of inorganic fine particles include metal oxides such as silica, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide; Examples include fine particles made of metal fluorides such as magnesium fluoride and sodium fluoride. Among the above, silica and aluminum oxide are preferred, silica is particularly preferred, and amorphous silica is even more preferred. Note that the surface of the inorganic fine particles may be chemically modified with an organic compound or the like.

The average particle diameter of the fine particles is preferably 0.1 μm or more, particularly preferably 0.4 μm or more, and even more preferably 0.6 μm or more. Further, the average particle diameter of the fine particles is preferably 20 μm or less, more preferably 10 μm or less, particularly preferably 4 μm or less, and even more preferably 2 μm or less. Note that the average particle diameter of the fine particles in this specification is a value measured by a laser diffraction scattering particle size distribution analyzer (manufactured by Horiba, Ltd., product name "LA-920").

Regarding the particle size distribution of the above-mentioned fine particles, the coefficient of variation (CV value) of the particle size expressed by the following formula is preferably 10% or more, particularly preferably 50% or more, and more preferably 80% or more. It is preferable that there be. Further, the CV value is preferably 300% or less, more preferably 200% or less, particularly preferably 150% or less, and even more preferably 100% or less.
Particle size variation coefficient (CV value) (%) = (standard deviation particle size/average particle size) x 100
The coefficient of variation (CV value) of the particle size is a value measured using a laser diffraction scattering particle size distribution analyzer (manufactured by Horiba, Ltd., product name "LA-920").

The blending ratio of the fine particles to 100 parts by mass of the active energy ray-curable component is preferably 1 part by mass or more, particularly preferably 6 parts by mass or more, and even more preferably 12 parts by mass or more. Further, the above-mentioned blending ratio is preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, and further preferably 20 parts by mass or less. When the blending ratio of the fine particles is within the above range, the amount and rate of change in lightness L* before and after application tend to be the values described above.

(1-3) Surface Conditioning Agent The surface conditioning agent contained in coating composition C is preferably a fluorine-based compound in order to obtain an optical member with excellent fingerprint resistance. Examples of the fluorine-based compound include fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkylsulfonates, fluoroalkylammonium salts, fluoroalkylethylene oxide derivatives, fluoroalkenyl oligomer derivatives, fluoroadamantane derivatives, and the like. Among them, fluorine-based compounds having an adamantane skeleton are particularly preferred from the viewpoint of anti-fingerprint properties.

Further, from the viewpoint of fingerprint resistance, the fluorine-based compound is preferably one having a polymerizable functional group, that is, a fluorine-based compound containing a polymerizable functional group. Among these, from the viewpoint of anti-fingerprint properties, it is particularly preferable to use a fluorine-based compound containing a polymerizable functional group having an adamantane skeleton, that is, a fluorine-containing adamantane derivative containing a polymerizable group. In addition, one type of surface conditioner may be used alone, or two or more types may be used in combination.

The above polymerizable group-containing fluorine-containing adamantane derivative is preferably represented by the following general formula (I).

In the above general formula (I), s is an integer of 1 to 15, preferably 1 to 12, t is an integer of 1 to 15, preferably 4 to 15, and u is an integer of 0 to 14, preferably 0 to 4. Yes, and s+t+u=16. Moreover, in the above general formula (I), F represents a fluorine atom.

In the above general formula (I), Y represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a hydroxyl group, a carboxyl group, and the same carbon group. Indicates a group selected from C═O formed by two Y atoms bonded to a carbon atom.

Examples of the hydrocarbon group represented by Y include an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, and butyl groups. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the halogen-substituted hydrocarbon group include a group in which one or more hydrogen atoms of the above hydrocarbon group are substituted with a halogen atom, such as a trifluoromethyl group. Note that halogen atoms include fluorine, chlorine, bromine, and iodine (the same applies hereinafter).

Examples of the cyclic hydrocarbon group represented by Y include a cycloalkyl group having 5 to 10 carbon atoms, specifically a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, and the like. In addition, the halogen-substituted cyclic hydrocarbon group includes a group in which one or more hydrogen atoms of the above-mentioned cyclic hydrocarbon group are substituted with a halogen atom, such as a fluorocyclopentyl group, a fluorocyclohexyl group, a trifluoromethylcyclopentyl group, and a trifluorocyclopentyl group. Examples include methylcyclohexyl group.

In the above general formula (I), Z ¹ represents a group represented by the following general formula (II) or (III).

In the above general formula (II) or (III), R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, or a C1 to C20, preferably C1 to C15 fatty acid which may contain a hetero atom. Indicates a group hydrocarbon group. n and m are integers of 0 or more.

Among the aliphatic hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, represented by R ¹ to R ⁴ , those that do not contain a hetero atom include methyl, ethyl, n-propyl, isopropyl, and n-butyl. , isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eicosyl, etc. having 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms Examples include 15 straight-chain or branched alkyl groups.

Of the aliphatic hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, represented by R ¹ to R ⁴ , those containing a hetero atom include -O- (having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms); -S- (straight chain or branched alkyl group having 1 to 15 carbon atoms), -S- (straight chain or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms), -CO- (straight chain or branched alkyl group having 1 to 15 carbon atoms) 19, preferably a straight chain or branched alkyl group having 1 to 14 carbon atoms), -NH- (a straight chain or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms), -N (A linear or branched alkyl group having 1 to 19 carbon atoms, preferably 1 to 7 carbon atoms ₎ .

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, containing a hetero atom include methoxy group, ethoxy group, butoxy group, hydroxymethyl group, hydroxyethyl group, methylthio group, and ethylthio group. group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, etc.

In the above general formula (II), n is an integer of 0 or more, for example an integer of 0 to 20, preferably an integer of 0 to 10, more preferably 0, 1, 2, 3, 4 or 5.

In the above general formula (III), m is an integer of 0 or more, for example an integer of 0 to 20, preferably an integer of 0 to 10, more preferably 0, 1, 2, 3, 4 or 5, particularly preferably 0. Or 1.

In the above general formula (I), X ¹ represents a polymerizable group represented by the following general formula (IV), the following formula (V), or the following general formula (VI).

In the above general formula (IV), R ⁵ represents a hydrogen atom, a methyl group or a trifluoromethyl group. Furthermore, in the above general formula (VI), R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms. Examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group and an alkoxy group. The alkyl group may be linear, branched, or cyclic, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and sec-butyl group. group, tert-butyl group, pentyl group, etc. Examples of the alkoxy group include a methoxy group and an ethoxy group.

As the polymerizable group-containing fluorine-containing adamantane derivative, 1-perfluoroadamantyl methacrylate, perfluoro-1,3-bis(acryloxyethoxy)adamantane and perfluoro-1,3-adamantanediol dimethacrylate are particularly preferred.

Since the above-mentioned polymerizable group-containing fluorine-containing adamantane derivative has X ¹ polymerizable group, for example, a reactive (meth)acrylate group in the molecule, it can be cured by active energy rays as a main ingredient by irradiation with active energy rays. The hard coat layer 12 is formed by reacting with the chemical component and forming an integrated hard coat layer 12. According to this hard coat layer 12, the amount and rate of change in the lightness L* before and after coating easily reach the above-mentioned values, and the durability of the physical properties is high.

Commercially available products as fluorine-based surface conditioners include, for example, the Megafac F series, Megafac R series, and Megafac RS series manufactured by DIC Corporation; the Ftergent series manufactured by Neos Corporation; and the 3M Japan Corporation. FC-4430 and FC-4432 manufactured by AGC Seimi Chemical Co., Ltd.; Surflon series manufactured by AGC Seimi Chemical Co., Ltd., and the like.

The blending ratio of the surface conditioning agent to 100 parts by mass of the active energy ray-curable component is preferably 0.01 parts by mass or more, particularly preferably 0.08 parts by mass or more, and more preferably 0.12 parts by mass. It is preferable that it is more than 1 part. Further, the above-mentioned blending ratio is preferably 1 part by mass or less, particularly preferably 0.6 part by mass or less, and even more preferably 0.2 part by mass or less. When the content of the surface conditioner is within the above range, the amount and rate of change in lightness L* before and after coating tends to be the above-mentioned values.

(1-4) Photopolymerization initiator When ultraviolet rays are used as active energy rays to cure the active energy ray-curable component, coating composition C preferably contains a photopolymerization initiator. By containing a photopolymerization initiator in this manner, the active energy ray-curable component can be efficiently polymerized, and the polymerization curing time and the amount of ultraviolet ray irradiation can be reduced.

Examples of such photopolymerization initiators include bensoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio) phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichloro Benzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo[2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]propanone], 2,4,6- Examples include trimethylbenzoyl-diphenyl-phosphine oxide. These may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator to 100 parts by mass of the active energy ray-curable component is preferably 0.01 parts by mass or more, particularly preferably 0.1 parts by mass or more, and more preferably 1 part by mass. It is preferable that it is above. Further, the above blending ratio is preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.

(1-5) Other components Coating composition C may contain various additives in addition to the above-mentioned components. Various additives include, for example, ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, silane coupling agents, antiaging agents, thermal polymerization inhibitors, colorants, surfactants, storage stabilizers, and plasticizers. agent, lubricant, antifoaming agent, wettability improver, coating surface improver, etc.

(2) Thickness of hard coat layer The thickness of the hard coat layer 12 is preferably 1 μm or more, particularly preferably 2 μm or more, and even more preferably 3 μm or more. When the lower limit of the thickness of the hard coat layer 12 is the above value, the hard coat layer has desired scratch resistance and pencil hardness. Further, the thickness of the hard coat layer 12 is preferably 20 μm or less, particularly preferably 15 μm or less, and even more preferably 10 μm or less. By setting the upper limit of the thickness of the hard coat layer 12 to the above value, the amount and rate of change in the lightness L* before and after coating tend to reach the above-mentioned values. Furthermore, from the viewpoint of achieving a more preferable value for the amount and rate of change in lightness L* before and after coating, the thickness of the hard coat layer 12 is preferably 8 μm or less, particularly preferably 5 μm or less, and is preferably 4 μm or less.

2. Method for manufacturing optical member Optical member 1 according to the present embodiment is produced by applying a coating liquid containing a coating composition for forming hard coat layer 12, preferably coating composition C, and optionally a solvent to base material 11. The hard coat layer 12 can be manufactured by coating and curing the hard coat layer 12.

Solvents can be used to improve coating properties, adjust viscosity, adjust solid content concentration, etc., and can be used without particular limitations as long as they dissolve curable components and disperse fine particles. .

Specific examples of solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and esters such as ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. Ethers such as ethylene glycol monomethyl ether (methyl cellosolove), ethylene glycol monoethyl ether (ethyl cellosolove), diethylene glycol monobutyl ether (butyl cellosolove), propylene glycol monomethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene; dimethylformamide , dimethylacetamide, N-methylpyrrolidone, and other amides. Among the above, ethers are preferred from the viewpoint of dispersibility of components in the coating liquid and coatability, and propylene glycol monomethyl ether is particularly preferred.

The concentration (solid content concentration) of the coating liquid is preferably 10% by mass or more, particularly preferably 20% by mass or more, and even more preferably 25% by mass or more. Further, the concentration is preferably 60% by mass or less, particularly preferably 48% by mass or less, and further preferably 42% by mass or less. When the concentration of the coating liquid is within the above range, the in-plane uniformity of the coated surface (coating layer surface) is improved, and the reproducibility of the lightness L* is further improved.

The coating solution of the coating composition may be applied by a conventional method, such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. After applying the coating solution of the coating composition, it is preferable to dry the coating film at 40 to 120°C for about 30 seconds to 5 minutes.

When the coating composition is active energy ray curable like coating composition C, the coating composition is cured by irradiating the coating film of the coating composition with active energy rays such as ultraviolet rays and electron beams. . The ultraviolet irradiation can be carried out using a high-pressure mercury lamp, Fusion H lamp, xenon lamp, etc., and the amount of ultraviolet irradiation is preferably about 50 to 1000 mW/cm ² in illuminance and 50 to 1000 mJ/cm ² in light amount. In particular, from the perspective of improving the in-plane uniformity of the coated surface, and improving the reproducibility of lightness L* due to improved in-plane uniformity, it becomes easier to set the amount and rate of change in L* before and after coating to desired values. From this point of view, illuminance of 200 to 500 mW/cm ² and light amount of 200 to 500 mJ/cm ² are preferable. On the other hand, electron beam irradiation can be performed using an electron beam accelerator or the like, and the amount of electron beam irradiation is preferably about 10 to 1000 krad.

3. Physical Properties of Optical Member (1) Haze Value The haze value of the optical member 1 according to the present embodiment is preferably 30% or less, more preferably 20% or less, and particularly preferably 15% or less. . When the haze value is 30% or less, it becomes suitable for use as a display body. On the other hand, when imparting anti-glare properties to the optical member 1 or the hard coat layer 12, the haze value is preferably 3% or more, more preferably 4.5% or more, and 5.4%. It is particularly preferable that it is above. Note that the haze value is a value measured in accordance with JIS K7136-2000.

(2) Total light transmittance The total light transmittance of the optical member 1 according to the present embodiment is preferably 70% or more, particularly preferably 80% or more, and more preferably 90% or more. preferable. When the total light transmittance is 70% or more, it becomes suitable for use in displays. Further, the upper limit value of the total light transmittance is not particularly limited, but is usually preferably 100%, more preferably 96% or less, and particularly preferably 92% or less. Note that the total light transmittance is a value measured in accordance with JIS K7361-1:1997.

(3) Arithmetic mean surface roughness (Ra)
The arithmetic mean surface roughness (Ra) of the surface of the hard coat layer 12 of the optical member 1 according to the present embodiment is preferably 0.6 μm or less, particularly preferably 0.3 μm or less, and more preferably 0.6 μm or less. It is preferable that it is .15 μm or less. When the arithmetic mean surface roughness (Ra) is 0.6 μm or less, it becomes suitable for use in displays. On the other hand, when imparting anti-glare properties to the hard coat layer 12, the arithmetic mean surface roughness (Ra) is preferably 0.01 μm or more, particularly preferably 0.03 μm or more, and It is preferable that it is 0.08 μm or more. Note that the arithmetic mean surface roughness (Ra) in this specification is determined from a roughness curve measured using a contact roughness meter in accordance with JIS B0601-1994.

(4) Image clarity The total value of the image clarity (%) of the optical combs of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm and 2.0 mm measured for the optical member 1 according to the present embodiment is , is preferably 200 or more, particularly preferably 250 or more, and even more preferably 300 or more. Thereby, the image visibility as a display body becomes good. On the other hand, when imparting anti-glare properties to the optical member 1 or the hard coat layer 12, the total value of image clarity is preferably 450 or less, particularly preferably 405 or less, and more preferably 360 or less. It is preferable that

Here, image clarity is measured by measuring the amount of parallel light rays transmitted through a test specimen through an optical comb having a transmitting part and a light blocking part. The smaller the width (comb width) between the transmitting part and the light shielding part in the optical comb, the higher the image clarity. Image clarity is measured according to the transmission method of JIS K7374:2007.

(5) Contact angle (5-1) Contact angle with water (water contact angle)
The water contact angle on the surface of the hard coat layer 12 of the optical member 1 according to the present embodiment is preferably 45° or more as a lower limit, particularly preferably 55° or more, and more preferably 65° or more. It is preferable. This makes it difficult for fingerprints to adhere to the hard coat layer 12, and makes it easy to wipe off the attached fingerprints. On the other hand, the upper limit of the water contact angle is not particularly limited, but is preferably 90° or less, more preferably 85° or less, particularly preferably 80° or less, and even more preferably 75° or less. It is preferable.

Note that the water contact angle is defined as the tangent line of the droplet at the grounding part of the surface of the hard coat layer and the surface of the hard coat layer when a droplet of water is left standing on the surface of the hard coat layer. This is the angle on the side that includes the droplet. Details of the method for measuring the water contact angle are as shown in the test examples described below.

(5-2) Contact angle with oleic acid (oleic acid contact angle)
The lower limit of the oleic acid contact angle on the surface of the hard coat layer 12 of the optical member 1 according to the present embodiment is preferably 10° or more, particularly preferably 15° or more, and more preferably 20° or more. It is preferable that there be. This makes it difficult for fingerprints to adhere to the hard coat layer 12, and makes it easy to wipe off the attached fingerprints. On the other hand, the upper limit of the oleic acid contact angle is not particularly limited, but is preferably 50° or less, particularly preferably 40° or less, and even more preferably 30° or less.

In addition, the oleic acid contact angle is defined as the tangent line of the droplet at the grounding part of the surface of the hard coat layer and the contact angle of the droplet when the droplet of oleic acid is left standing on the surface of the hard coat layer. Among the angles formed by the layer surface, this refers to the angle on the side that includes the droplet. Details of the method for measuring the oleic acid contact angle are as shown in the test examples described below.

(6) Scratch Resistance The hard coat layer 12 of the optical member 1 according to the present embodiment is scratched by rubbing the hard coat layer 12 back and forth for 10 cm with a load of 250 g/cm ² 10 times using #0000 steel wool. It is preferable that this does not occur. By having such scratch resistance as determined by steel wool hardness evaluation, it is possible to suppress scratches on the hard coat layer 12 when the optical member 1 is used on the surface of a touch panel.

(7) Pencil Hardness The pencil hardness of the hard coat layer 12 of the optical member 1 according to the present embodiment is preferably 2H or more. Since the hard coat layer 12 has such pencil hardness, the surface of the optical member 1 has sufficient hardness, so when the optical member 1 is used on the surface of a touch panel, for example, it has excellent surface protection properties. can demonstrate.

The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

For example, the surface of the optical member 1 to which the oleic acid diluted solution is applied does not have to be planar. However, it is preferable to uniformly apply the oleic acid diluted solution.

Hereinafter, the present invention will be explained in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

Hard coat films as evaluation objects were manufactured according to the following Manufacturing Examples 1 to 6.
[Manufacture example 1]
50 parts by mass of dipentaerythritol hexaacrylate (expressed in terms of solid content. The same applies to other components hereinafter) and 50 parts of polyfunctional urethane acrylate (manufactured by Arakawa Chemical Industry Co., Ltd., product name "Beam Set 575CB") parts by mass, 17 parts by mass of silica fine particles (average particle size 0.8 μm, CV value 93%, refractive index 1.46, amorphous), 3 parts by mass of α-hydroxyphenyl ketone as a photopolymerization initiator, and the surface A coating composition was obtained by mixing with 0.15 parts by mass of a polymerizable group-containing fluorine-containing adamantane derivative (manufactured by NEOS, product name "Ftergent 602A") as a regulator. The coating composition was diluted with propylene glycol monomethyl ether to prepare a coating liquid with a solid content concentration of 30% by mass.

The coating liquid obtained above was applied to a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name: "Lumirror U48", thickness: 125 μm), which had been treated with easy adhesion on both sides, as a base film using a wire bar #12. It was applied and dried at 70°C for 1 minute. Next, in a nitrogen atmosphere, ultraviolet rays were irradiated with an ultraviolet irradiation device (manufactured by Eye Graphics, product name "Eye Grantage ECS-401GX type") under the following conditions to form a hard coat layer with a thickness of 4 μm, A hard coat film was obtained.
<Ultraviolet irradiation conditions>
・Light source: High pressure mercury lamp ・Lamp power: 2kW
・Conveyor speed: 4.23m/min
・Illuminance: 240mW/ ^cm2
・Light intensity: 307mJ/ ^cm2

[Production example 2]
100 parts by mass of dipentaerythritol hexaacrylate, 14 parts by mass of silica fine particles (average particle size 1.5 μm, CV value 83%, refractive index 1.46, amorphous), and α-hydroxyphenyl ketone as a photopolymerization initiator. 3 parts by mass and 0.15 parts by mass of a polymerizable group-containing fluorine-containing adamantane derivative (manufactured by NEOS, product name "Ftergent 602A") as a surface conditioner were mixed to obtain a coating composition. The coating composition was diluted with propylene glycol monomethyl ether to prepare a coating liquid with a solid content concentration of 30% by mass. A hard coat film was produced in the same manner as in Production Example 1 using the obtained coating liquid.

[Manufacture example 3]
A coating composition obtained in the same manner as in Production Example 1 was diluted with propylene glycol monomethyl ether to prepare a coating liquid with a solid content concentration of 40% by mass. Using the obtained coating liquid, a hard coat film was produced in the same manner as in Production Example 1 except that the thickness of the hard coat layer was 6 μm.

[Manufacture example 4]
A coating composition obtained in the same manner as in Production Example 1 was diluted with propylene glycol monomethyl ether to prepare a coating liquid with a solid content concentration of 35% by mass. Using the obtained coating liquid, a hard coat film was produced in the same manner as in Production Example 1 except that the thickness of the hard coat layer was 5 μm.

[Manufacture example 5]
40 parts by mass of dipentaerythritol hexaacrylate, 60 parts by mass of reactive silica fine particles (silica fine particles having an acryloyl group on the surface, the average particle size of the silica fine particles before surface modification being 40 nm), and crosslinked polyester. 4 parts by mass of methyl methacrylate fine particles (average particle size 1.5 μm, CV value 23%, refractive index 1.49, spherical) and a modified carboxyl group-containing polymer as a dispersant (manufactured by Kyoeisha Kagaku Co., Ltd., product name ``Floren'') G-700") 0.2 parts by mass, 3 parts by mass of α-hydroxyphenylketone as a photopolymerization initiator, and acrylic-modified polydimethylsiloxane as a surface conditioner (manufactured by BYK Chemie, product name "BYK-3550") ) and 0.2 parts by mass to obtain a coating composition. The coating composition was diluted with propylene glycol monomethyl ether to prepare a coating liquid with a solid content concentration of 30% by mass. A hard coat film was produced in the same manner as in Production Example 1 using the obtained coating liquid.

[Production example 6]
50 parts by mass of dipentaerythritol hexaacrylate, 50 parts by mass of polyfunctional urethane acrylate (manufactured by Arakawa Chemical Co., Ltd., product name "Beam Set 575CB"), and silica fine particles (average particle size 0.8 μm, CV value 93%, refraction 15 parts by mass of α-hydroxyphenylketone as a photopolymerization initiator, and acrylic-modified polydimethylsiloxane as a surface conditioner (manufactured by BYK Chemie, product name: BYK-3550). '') to obtain a coating composition. The coating composition was diluted with propylene glycol monomethyl ether to prepare a coating liquid with a solid content concentration of 30% by mass. A hard coat film was produced in the same manner as in Production Example 1 using the obtained coating liquid.

[Reference example] (Selection of oleic acid concentration)
Oleic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.; the same applies hereinafter) itself was used as Sample 1 (oleic acid concentration: 100% by mass).
A diluted oleic acid solution obtained by adding 4 g of ethanol to 1 g of oleic acid and completely dissolving it was designated as Sample 2 (oleic acid concentration: 20% by mass).
A diluted oleic acid solution obtained by adding 99 g of ethanol to 1 g of oleic acid and completely dissolving it was designated as Sample 3 (oleic acid concentration: 1% by mass).
A diluted oleic acid solution obtained by adding 99.8 g of ethanol to 0.2 g of oleic acid and completely dissolving it was designated as Sample 4 (oleic acid concentration: 0.2% by mass).
A diluted oleic acid solution obtained by adding 99.9 g of ethanol to 0.1 g of oleic acid and completely dissolving it was designated as Sample 5 (oleic acid concentration: 0.1% by mass).

Each of Samples 1 to 5 was attached to the surface of the hard coat layer of the hard coat film obtained in Production Example 1 using a finger cot. On the other hand, an actual fingerprint was attached to the surface of the hard coat layer of the hard coat film obtained in Production Example 1.

The hard coat film to which Samples 1 to 5 were attached was visually compared with the hard coat film to which actual fingerprints were attached. In addition, from the hard coat film to which each sample 1 to 5 was attached and the hard coat film to which the actual fingerprint was attached, each sample was 1-5 and the actual fingerprints were wiped off. The ease of wiping was compared between samples 1 to 5 and actual fingerprints. The results are shown in Table 1.

From the results in Table 1, it can be seen that the oleic acid diluted solution with an oleic acid concentration of 0.2% by mass was superior to the actual fingerprint in terms of the degree of adhesion to the hard coat film (adhesiveness) and the ease of wiping it off from the hard coat film (wipeability). It was found to be equivalent to

[Test Example 1] (Measurement of haze value and total light transmittance)
The haze value (%) and total light transmittance (%) of the hard coat film manufactured in each manufacturing example were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH-5000") according to JIS K7136: 2000 and JIS K7361-1:1997. The results are shown in Table 2.

[Test Example 2] (Measurement of surface roughness)
The arithmetic mean surface roughness (Ra; unit: μm) of the hard coat layer surface of the hard coat film produced in each production example was measured using a contact roughness meter (manufactured by Mitutoyo Co., Ltd., product name: The roughness was determined from the roughness curve measured using SV3000S4. The results are shown in Table 2.

[Test Example 3] (Measurement of image clarity)
The hard coat film produced in each production example was measured using an image clarity measuring device (manufactured by Suga Test Instruments Co., Ltd., product name "ICM-10P"), and 5 types of optical measurements were performed in accordance with the transmission method of JIS K7374:2007 The image definition (%) of the combs (comb widths: 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm) was measured, and the total value was calculated as the image definition. The results are shown in Table 2.

[Test Example 4] (Measurement of contact angle)
(1) Measurement of water contact angle The water contact angle on the hard coat layer surface of the hard coat film produced in each manufacturing example was measured using a fully automatic contact angle measuring meter (manufactured by Kyowa Kaimen Kagaku Co., Ltd., product name "DM-701"). Measurements were made using the following conditions. Note that pure water was used as water. The results are shown in Table 2.
・Environmental temperature: 23℃
・Water droplet volume: 2μl
・Measurement time: 3 seconds after dropping ・Image analysis method: θ/2 method

(2) Measurement of oleic acid contact angle The oleic acid contact angle on the hard coat layer surface of the hard coat film produced in each production example was measured using a fully automatic contact angle measuring meter (manufactured by Kyowa Kaimen Kagaku Co., Ltd., product name: DM-701). ) under the following conditions. As the oleic acid, oleic acid manufactured by Tokyo Kasei Kogyo Co., Ltd. was used. The results are shown in Table 2.
・Environmental temperature: 23℃
・Droplet volume of oleic acid: 2μl
・Measurement time: 3 seconds after dropping ・Image analysis method: θ/2 method

[Test Example 5] (Evaluation of scratch resistance)
The surface of the hard coat layer of the hard coat films produced in Examples and Comparative Examples was rubbed 10 times back and forth for 10 cm at a load of 250 g/cm ² using #0000 steel wool. The surface of the hard coat layer was visually confirmed under a three-wavelength fluorescent lamp, and the scratch resistance was evaluated based on the following criteria. The results are shown in Table 2.
A: No scratches were observed.
B: Scratches were confirmed.

[Test Example 6] (Measurement of pencil hardness)
The pencil hardness of the hard coat layer surface of the hard coat films produced in Examples and Comparative Examples was measured according to JIS K5600 using an electric pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., product name "No. 553-M1"). Measured according to the following. The results are shown in Table 2.

[Test Example 7] (Evaluation of fingerprint resistance)
(1) Preparation of evaluation samples Using an acrylic transparent double-sided adhesive sheet (manufactured by Lintec, product name "OPTERIA MO-3006C", refractive index: 1.49, haze: <1.0%), each production example was The surface of the produced hard coat film on the base film side was bonded to a black acrylic plate (L*3.42, a*-0.17, b*0.40), and this was used as an evaluation sample.

(2) Sensory evaluation A fingerprint was attached to the surface of the hard coat layer of the evaluation sample obtained above. Then, the attached fingerprints were visually observed under a three-wavelength fluorescent lamp (1000 lux.), and the visibility of the fingerprints was evaluated according to the following criteria. Note that an evaluation of 3 or higher is considered good. The results are shown in Table 2.
5: The attached fingerprint is very difficult to stand out. 4: The attached fingerprint is difficult to stand out. 3: The attached fingerprint is slightly noticeable. 2: The attached fingerprint is noticeable. 1: The attached fingerprint is very noticeable.

(3) Evaluation using the lightness L* as an index before and after applying the diluted oleic acid solution First, the surface of the hard coat layer in the evaluation sample obtained above was measured using a simultaneous photometric spectrophotometer The lightness L* (lightness L* before application) defined by the CIE1976L*a*b* color system was measured under the following conditions. The results are shown in Table 2.
<Measurement conditions>
Light source: C light source Measurement method: Reflection measurement Measurement area: φ30mm (circle with a diameter of 30mm)

On the other hand, 99.8 g of ethanol was added to 0.2 g of oleic acid to completely dissolve it, and this was used as an oleic acid diluted solution. The obtained oleic acid diluted solution was applied to the surface of the hard coat layer in the evaluation sample obtained above using wire bar #2, and air-dried at 23° C. and 50% RH to form an oleic acid layer.

The lightness L* (lightness L* before and after application) of the surface on which the oleic acid layer was formed in the evaluation sample was measured in the same manner as above. The results are shown in Table 2.

Next, the amount of change ΔL* was calculated by subtracting the lightness L* before application from the lightness L* after application. Further, the rate of change (%) in lightness L* was calculated according to the following formula. The results are shown in Table 2.
Rate of change = {(Lightness after application L*-Lightness before application L*)/Lightness before application L*}×100

As can be seen from Table 2, by using the lightness L* before application and the lightness L* after application as indicators, there is a high correlation with sensory evaluation, and fingerprint resistance can be quantitatively evaluated. Furthermore, the hard coat films according to Production Examples 1 to 4 had excellent fingerprint resistance.

[Test Example 8] (Reproducibility test of fingerprint resistance evaluation)
Two hard coat films were separately produced in the same manner as in Production Example 1. Note that the three hard coat films were manufactured on different days. Each hard coat film obtained was evaluated for fingerprint resistance according to Test Example 7, and its reproducibility was confirmed. The results are shown in Table 3, where N=1 for the hard coat film of Production Example 1, N=2 for the second hard coat film, and N=3 for the third hard coat film.

As can be seen from Table 3, for all hard coat films, the amount of change ΔL* in lightness L* and the rate of change in lightness L* are within a certain range, and the sensory evaluation and the amount of change ΔL in lightness L* are within a certain range. * and the rate of change in brightness L*. That is, according to the above method for evaluating fingerprint resistance, fingerprint resistance could be evaluated quantitatively and with high reproducibility.

The method for evaluating fingerprint resistance according to the present invention is suitable, for example, for evaluating the fingerprint resistance of a touch panel, particularly a hard coat film located at the outermost layer of a touch panel. Further, the optical member according to the present invention is suitable as, for example, a hard coat film located at the outermost layer of a touch panel.

1... Optical member 11... Base material 12... Hard coat layer

Claims (6)

A hard coat film comprising a base material and a hard coat layer on the outermost surface,
The hard coat film is arranged such that the hard coat layer is located on the outermost surface of the article to which fingerprints can be attached, and
The hard coat layer is a cured product of a coating composition containing an active energy ray-curable component, fine particles, and a surface conditioner that is a fluorine-based compound,
A hard coat film characterized in that a blending ratio of the surface conditioning agent to 100 parts by mass of the active energy ray-curable component is 0.01 part by mass or more and 0.2 parts by mass or less. The hard coat film according to claim 1, wherein the surface conditioning agent is a fluorine-based compound having an adamantane skeleton. The hard coat film according to claim 1 or 2, wherein a blending ratio of the fine particles to 100 parts by mass of the active energy ray-curable component is 1 part by mass or more and 30 parts by mass or less. The hard coat film according to any one of claims 1 to 3, wherein the fine particles have an average particle size of 0.1 μm or more and 20 μm or less. The hard coat film according to any one of claims 1 to 4, wherein the article is a touch panel. A touch panel comprising the hard coat film according to claim 5,
The hard coat layer is arranged so as to be located on the outermost surface of the touch panel where fingerprints can be attached.
touch panel.

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