JP2012240266A - Hard coat film, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high function hard coat layer having antifouling properties, receiving no scratch damage even after rubbed many times by steel wool and having surface abrasion durability of high antifouling properties, good surface finger slip properties, high water repellency and low interference fringe properties.SOLUTION: This hard coat film 1 includes a base material sheet 12 and the hard coat layer 11 formed at least on one side of the base material sheet 12. The hard coat layer 11 comprises cured matter obtained by curing a hard coat layer forming composition, which contains a fluoric compound having a (meth)acryloyl group at its terminal, a polysiloxane compound having a (meth)acryloyl group, a polyfunctional (meth)acryl monomer and a photopolymerization initiator. When the peak strengths of Kα rays of a fluorine atom and a silicon atom obtained by the fluorescence X-ray analysis of the hard coat film are respectively set to a and b, the hard coat film satisfies formula (1):0.01≤a/b≤0.5.

Description

  The present invention is a hard coat film whose surface is excellent in scratch resistance, antifouling property, fingerprint resistance, slipperiness, water and oil repellency, abrasion durability and the like. More specifically, the present invention relates to a protective sheet that is attached to a display product to protect the display.

  In recent years, there are various display products such as a flat panel display such as a liquid crystal system, a plasma display system and an organic EL system, a guidance display display such as a signboard and a road sign, and a display such as a showcase for product display. In order to protect these display products, a protective sheet is attached to the surface.

A thin glass plate may be used on the surface of a flat panel display that has recently attracted attention, and a protective sheet is attached to the display surface in order to prevent the glass from scattering. Since the protective sheet uses a plastic sheet, it is more likely to be scratched than glass, so that many have a hard coat layer having excellent scratch resistance and scratch resistance on the surface. Anti-static function, electromagnetic wave shielding function, low reflection function, anti-glare function, UV blocking function, anti-blocking function, anti-Newton ring function, anti-smudge function, water repellency function, oil repellency function, super hydrophilic function on this hard coat layer Protective sheets with improved functionality are widely used by providing various functions such as lipophilic function, anti-fogging function, and flaw repair function.

  A large number of products in which a touch panel is attached to a flat panel display such as a personal computer, a mobile phone, a portable game device, and an ATM are beginning to be commercialized. Initially, a resistive touch panel with a single touch function was mounted on a display such as a portable game machine or ATM, but with the advent of smartphones and tablet PCs, a capacitive touch panel with a multi-touch function was mounted at once. The number is growing.

A capacitive touch panel display can be operated only with a human finger instead of a touch pen, and when used as a telephone, the display surface touches the face. As a problem peculiar to such usage, it is mentioned that the touch panel display surface is likely to be contaminated with cosmetic oils such as fingerprints, sebum and foundation. Therefore, a protective sheet made of a water- and oil-repellent antifouling hard coat film that hardly adheres to dirt and a protective sheet made of an oleophilic antifouling hard coat film that hardly sees even if dirt is attached are often used. Yes.

JP 2007-77188 A JP 2009-263600 A WO2008 / 108153

In the hard coat layer method proposed in Patent Document 1 and Patent Document 2, the water and oil repellent antifouling hard coat film, which does not easily adhere to dirt, has a strong ability to repel water and oil stains, so that dirt is not removed. It has the characteristics that it is difficult to adhere and it is easy to wipe off the adhered dirt. However, there is a problem that the attached dirt is noticeable white. On the other hand, an oleophilic hard coat film that is difficult to see even if dirt is attached has a problem that the attached dirt is not noticeable, but the dirt is easily attached and the attached dirt is difficult to wipe off.
In addition, with the hard coat layer method proposed in Patent Document 3, not only simple antifouling performance but also scratching even after many rubbing with a finger or cloth while smartphones and tablet PCs show a large spread. There is a need for high wear durability that maintains antifouling performance, high surface finger slipperiness that makes it easy to operate the touch panel, hard coat performance that shows high water repellency that makes it easy for water droplets attached to the surface to flow and not remain, Low interference fringe hard coat that does not show rainbow patterns or interference fringes caused by interference between surface reflected light on hard coat layer surface and reflected light on hard coat layer / base sheet interface as touch panel display size increases However, it was difficult to satisfy all of these requirements.

As a result of intensive studies, the present inventors have found that the above problems can be solved by adopting the following configurations [1] to [2].

[1] A hard coat film comprising a base sheet and a hard coat layer formed on at least one surface of the base sheet, wherein the hard coat layer has a (meth) acryloyl group at a terminal. It is a cured product obtained by curing a hard coat layer forming composition containing a fluorine compound, a polysiloxane compound having a (meth) acryloyl group at the terminal, a polyfunctional (meth) acrylic monomer, and a photopolymerization initiator with active energy rays. And
When the peak intensity of the Kα ray of fluorine atoms and silicon atoms obtained by fluorescent X-ray (XRF) analysis of the hard coat film is a and b, respectively.
0.01 ≦ a / b ≦ 0.5 Equation (1)
Meet hard coat film.
[2] The hard coat film according to the above [1], wherein the thickness of the hard coat layer is 1 to 15 μm, and the surface roughness of the hard coat layer is 0.5 μm or less.
[3] A laminate having the hard coat film according to [1] or [2], wherein the laminate includes at least an adhesive layer on the surface of the base sheet opposite to the hard coat layer.

  In the present invention, dirt such as fingerprints, sebum, and foundation is difficult to adhere, easy to wipe, and not easily noticeable, and has high antifouling performance without scratching even after being rubbed many times with steel wool. A high-functional hard coat layer having surface wear durability, good surface finger slipperiness, high water repellency, and low interference fringe properties can be obtained.

Schematic sectional view showing an example of the hard coat film of the present invention Schematic sectional view showing an example of the laminate of the present invention Schematic sectional view showing another example of the laminate of the present invention

An example of the embodiment will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a hard coat film according to the present invention, FIG. 2 is a schematic cross-sectional view showing an example of a laminate according to the present invention, and FIG. 3 is another view of the laminate according to the present invention. It is a schematic cross section which shows an example.

(Hard coat film)
First, the hard coat film 1 of the present invention shown in FIG. 1 will be described. The hard coat film 1 of the present invention includes a base sheet 12 and a hard coat layer 11 formed on at least one surface of the base sheet 12. If necessary, the hard coat layer 11 may be a single layer or a multilayer structure. In addition, hard coat layers may be formed on both surfaces of the substrate 12. The hard coat film 1 of the present invention preferably has a configuration in which a single-layer hard coat layer 11 is formed on one surface of a base sheet 12 because of its functional effects and manufacturing simplicity.

(Substrate sheet)
Examples of the base sheet 12 include resin sheets such as polypropylene resin, polyethylene resin, polyolefin resin, polyamide resin, polyester resin, polyacrylic resin, polyvinyl chloride resin, nylon resin, and urethane resin. Metal foils such as aluminum foil and copper foil, glassine paper, coated paper, cellulose-based sheets such as triacetylcellulose, or composites of the above respective sheets can be used.
Since the hard coat layer provided on the base sheet is often formed by applying a solvent paint, the base sheet has solvent resistance, and when used in a flat panel display or the like, the base sheet is optically transparent. Since the property is good, the substrate sheet 1 is preferably a PET film, a triacetyl cellulose film or the like. A biaxially stretched PET film is more preferable because it is excellent in optical transparency and advantageous in terms of cost. The same applies to the base material sheets 22 and 32 used in FIGS.

(Hard coat layer)
The hard coat layer 12 is a layer formed on at least one surface of the base sheet 12 and having scratch resistance and scratch resistance as basic performance. Furthermore, the hard coat layer of the present invention has stain resistance such as fingerprints, sebum, foundation, etc., which is difficult to adhere, easy to wipe off and is not noticeable, and does not get scratched even after rubbing many times with steel wool. It is a high-functional hard coat layer having high surface wear durability, antifouling performance unchanged, good surface finger slipperiness, high water repellency, and low interference fringe properties.
In order to develop the high functionality, the hard coat layer 12 includes a fluorine-based compound having a (meth) acryloyl group at a terminal, a polysiloxane compound having a (meth) acryloyl group at a terminal, and a polyfunctional (meth) acrylic monomer. The hard coat layer-forming composition containing a photopolymerization initiator is preferably a cured product obtained by curing with an active energy ray. More preferably, a cured product obtained by curing a composition obtained by removing the fluorine compound and the polysiloxane compound (hereinafter referred to as a hard coat base material) from the hard coat layer forming composition with active energy rays is used. It is a cured product that does not have scratches after the wool abrasion test.

  In general, when a fluorine-based compound that does not have a (meth) acryloyl group at the end is added, water and oil repellency can be imparted, and the hard coat has an antifouling effect that makes it difficult for dirt to adhere and easily wipe off dirt. Although it can be applied to the surface of the layer, if it is wiped off with a finger or cloth, it easily peels off from the surface and has the disadvantage that the antifouling effect cannot be sustained.

In the present invention, it is preferable to use a fluorine-based compound having a (meth) acryloyl group at the terminal. The reason is that, when the fluorine-based compound does not have a polymerizable functional group such as a (meth) acryloyl group, the added fluorine-based compound is in a state where it is not immobilized in a state of floating on the surface of the hard coat layer. This is presumed. On the other hand, when the fluorine-based compound has a polymerizable functional group, the added fluorine-based compound can react with the hard coat base material on the surface of the hard coat layer and can be fixed, so that the antifouling effect can be maintained even after wiping. I understood that I have it.

The polymerizable functional group of the fluorine-based compound used in the present invention was introduced at the end in order to cure the composition for forming a hard coat layer using a polyfunctional (meth) acrylic monomer as a hard coat base material with active energy rays. A (meth) acryloyl group is preferred. Furthermore, in order to increase the durability of the antifouling effect, it is more preferably a fluorine-based compound having a bifunctional or higher (meth) acryloyl group at the terminal and an acryloyl group at one terminal.

Examples of the fluorine-based compound having a (meth) acryloyl group at the end of the present invention include SUA1900L series (manufactured by Shin-Nakamura Kagaku Co., Ltd.), UT-3971 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), MegaFuck RS series and Defensa TF3000 series (manufactured by DIC Corporation), Light Procoat AFC3000 (manufactured by Kyoeisha Chemical Co., Ltd.), OPTOOL DAC-HP (manufactured by Daikin Industries, Ltd.) KSN5300 (manufactured by Shin-Etsu Chemical Co., Ltd.), UVHC series (GE) Toshiba Silicone Co., Ltd.).
The compounding quantity of the fluorine-type compound which has a (meth) acryloyl group at the terminal of this invention is 0.01-10 mass solid of the whole hard-coat layer formation composition solid (the whole composition except a solvent when a solvent is included). % Is preferred. When the amount is less than 0.01% by weight, a sufficient antifouling effect is not exhibited. When the amount exceeds 10% by weight, the antifouling effect is saturated and the cost is increased. May become cloudy and reduce transparency, or may have a foreign matter defect such as a precipitate.

In addition, it is generally known that water repellency and antifouling properties can be imparted by adding a polysiloxane compound, and the hard coat layer surface has an antifouling effect that makes it difficult for dirt to adhere and makes it easy to wipe off dirt. Can be granted.

In the present invention, it is preferable to use a polysiloxane compound having a (meth) acryloyl group at the terminal. The reason is that the use of a polysiloxane compound having a (meth) acryloyl group at the terminal has the advantage that the antifouling effect can be maintained even after the hard coat layer surface is wiped or rubbed with a cloth or the like. . Furthermore, in order to increase the durability of the antifouling effect, a polysiloxane compound having a bifunctional or higher (meth) acryloyl group at the terminal and an acryloyl group at one terminal is more preferable.
Examples of the polysiloxane compound having a (meth) acryloyl group at the terminal of the present invention include TSL9700 series (manufactured by GE Toshiba Silicone), Silaplane FM series (manufactured by Chisso), BYK-UV3500 series (BIC Chemie). -Japan Co., Ltd.).
The compounding quantity of the polysiloxane type compound which has a (meth) acryloyl group at the terminal of this invention is 0.01-20 mass solids of the hard-coat layer formation composition whole solid (the whole composition except a solvent when a solvent is included). % Is preferred. When the amount is less than 0.01% by mass, sufficient antifouling effect is not exhibited. When the amount exceeds 20% by mass, the antifouling effect is saturated and the cost is increased, or the hard coat forming composition or the hard coat layer 12 is used. May become cloudy and reduce transparency, or may have a foreign matter defect such as a precipitate.

Moreover, in order to provide the hard coat layer of the present invention with a function of expressing antifouling properties, it is also possible to add an acrylate monomer having a long chain aliphatic structure that is not a polysiloxane compound. Examples of acrylate monomers having a long-chain aliphatic structure include amyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, tetracosyl And TA37 series (manufactured by Hitachi Chemical Polymer Co., Ltd.) such as (meth) acrylate, octacosyl (meth) acrylate, and UV curable urethane acrylate TA37-227A having a long-chain aliphatic pendant structure.
The expression of the antifouling effect is attributed to the fluorinated hydrocarbon structure of the fluorine-based compound, the polysiloxane-based compound, and the hydrocarbon structure of the compound having a long-chain aliphatic structure. Fluorohydrocarbon structures and hydrocarbon structures have very low polarizabilities of carbon-fluorine bonds and carbon-hydrogen bonds, so that the cohesive force of molecules can be reduced and surfaces with low surface free energy can be obtained. . The critical surface tension γ _c value of the surface on which the CH ₃ chain is oriented, which is the hydrocarbon structure of the polysiloxane compound and the compound having a long-chain aliphatic structure, is 20 to 22 dyn / cm. On the other hand, the γ _c value of the surface with the (CF ₂ ) ₂ chain oriented fluorinated hydrocarbon structure of the fluorine-based compound is 18 dyn / cm, and in particular, the γ _c value of the surface with the CF ₃ chain oriented is 6 dyn / cm. It becomes. The surface tension of water is about 72 dyn / cm, and the surface tension of many oils exceeds 20 dyn / cm. The solid surface repels the liquid better as the γ _c value of the solid surface is smaller than the surface tension of the liquid (water and oil). Therefore, since the antifouling effect on oil is particularly superior to polysiloxane compounds and compounds having a long-chain aliphatic structure, the fluorine-based compound is less likely to get dirty against both water and oil stains, and is easy to wipe off. In order to obtain an antifouling effect with high oil repellency, a fluorine-based compound is excellent.

  As a result of intensive studies by the present inventors, the surface on which the polysiloxane compound and the compound having a long-chain aliphatic structure are oriented has better water slidability and finger slipperiness than the surface on which the fluorine compound is oriented. In particular, by using a polysiloxane compound having a (meth) acryloyl group at the terminal and a fluorine compound having a (meth) acryloyl group at the terminal, the water and oil repellency is highly resistant to dirt and easy to wipe off. It has been found that a hard coat layer showing an effect and having excellent water sliding and finger sliding properties can be obtained.

  As a polysiloxane compound having a (meth) acryloyl group at the end that is excellent in water sliding and finger slipping, the portion having a polysiloxane chain occupies 1 to 80% by mass and has a (meth) acryloyl group at the end. The polysiloxane compound is a polymer having a molecular weight of 1000 to 100000, more preferably 3000 to 50000, and is preferably a polysiloxane compound having a bifunctional or higher (meth) acryloyl group only at one end.

When the peak intensities of the Kα rays of fluorine atoms and silicon atoms obtained by fluorescent X-ray (XRF) analysis of the hard coat film 1 of the present invention are a and b, respectively.
0.01 ≦ a / b ≦ 0.5 ... Formula (1)
In the case of satisfying the above, it has been found that the surface of the hard coat layer 11 which is difficult to be soiled, easily wiped off, hardly sees attached dirt, and has excellent water sliding and finger slipping properties can be obtained.

That is, when the ratio of fluorine atoms is large and exceeds 0.5, the antifouling effect is sufficient, but the water sliding property and finger sliding property are inferior. Further, when the ratio of silicon atoms is large and becomes smaller than 0.01, the antifouling effect is not sufficient.
Excellent antifouling effect by controlling the blending amount of fluorine compound having (meth) acryloyl group at the terminal and polysiloxane compound having (meth) acryloyl group at the terminal, contained in the hard coat layer, water Both sliding property and finger sliding property can be satisfied.

The polyfunctional (meth) acrylic monomer used for the hard coat layer 11 of the present invention includes 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth). ) Acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di ( (Meth) acrylate, EO-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide Iido-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate , Tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta (meth) acrylate propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include caprolactone-modified dipentaerythritol hexa (meth) acrylate. One of these active energy ray-curable monomers may be used alone, or two or more thereof may be used in combination.
It is preferable that the compounding quantity of a polyfunctional (meth) acryl monomer is 70 mass% or more with respect to the hard-coat layer formation composition whole solid (when the solvent is included, the whole composition except a solvent). It is because sufficient hard coat performance cannot be obtained as it is less than 70 mass%.

Examples of the photopolymerization initiator used in the hard coat layer 11 of the present invention include benzoin, 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-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzoph Non, 4,4′-diethylaminobenzophenone, propiophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2 -Chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate and the like. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.
It is preferable that the compounding quantity of a photoinitiator is 0.2-10 mass% with respect to the hard-coat layer forming composition solid whole (the whole composition except a solvent when a solvent is included). When the blending amount of the photopolymerization initiator is less than 0.2% by mass, curing failure may occur. When it exceeds 10% by mass, curing cannot be accelerated according to the blending amount, and it remains. The photoinitiator has an adverse effect on yellowing or bleeding out. Further, the cost is increased, which is not preferable.

In addition to the photopolymerization initiator, a photosensitizer can be further contained. Examples of the photosensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.

The active energy rays used for curing the composition for forming a hard coat layer of the present invention include ionizing radiation such as electron beams, ultraviolet rays, visible rays, and γ rays. Among these, it is preferable to use ultraviolet rays. When irradiating with ultraviolet rays, an ultraviolet lamp generally used in the semiconductor / photoresist field, the ultraviolet curing field, or the like can be used. Typical UV lamps include, for example, halogen lamps, halogen heater lamps, xenon short arc lamps, xenon flash lamps, ultra high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, medium pressure mercury lamps, deep UV lamps, metal halide lamps. There are noble gas fluorescent lamps, krypton arc lamps, excimer lamps, etc., and there are also Y-ray lamps that emit an extremely short wavelength (peak at 214 nm). Some of these lamps are ozone-less types that generate less ozone. Various lasers such as an ArF excimer laser, a KrF excimer laser, a YAG laser via a harmonic unit including a nonlinear optical crystal, and an ultraviolet light emitting diode can also be used. The emission wavelength of the ultraviolet lamp, laser, or ultraviolet light emitting diode is not limited as long as it does not interfere with the curing reaction, but preferably the emission wavelength that overlaps the photosensitive wavelength region of the photopolymerization initiator. Furthermore, a light emission wavelength that overlaps the maximum absorption wavelength or the maximum absorption wavelength in the photosensitive wavelength region of these generators is more preferable because the generation efficiency increases.
These ultraviolet rays may be scattered light or parallel light with high straightness. Although it depends on the photopolymerization initiator, it is preferable to use a high-pressure mercury lamp and a metal halide lamp in terms of price and running cost.
The energy irradiation intensity of ultraviolet rays is appropriately determined depending on the active energy ray curable resin or the photopolymerization initiator. When using an ultraviolet lamp with high irradiation intensity typified by various mercury lamps and metal halide lamps, productivity can be improved, and the irradiation intensity (lamp output) is 30 W / cm or more, and 80 W / cm or more. Is preferred. The cumulative amount of UV irradiation (J / cm ² ) is in the range of 1 mJ / cm ^{2 to 2} J / cm ² and more preferably 10 mJ / cm ^{2 in order} to stably and continuously produce a cured product having sufficient curability. ˜1 J / cm ² is preferred.
In addition, if the curing of the cured product surface does not proceed sufficiently due to oxygen inhibition, unreacted acryloyl groups and allyl groups remain on the surface, which peels off due to reaction with the protective layer resin during active energy ray curing of the protective layer May decrease. In that case, it is preferable to reduce the oxygen concentration by, for example, making the irradiated portion a nitrogen atmosphere. Although depending on the active energy ray-curable resin and the photopolymerization initiator, the preferable oxygen concentration is 10,000 ppm or less, more preferably 5000 ppm or less, and still more preferably 2000 ppm or less.

Examples of the method for forming the hard coat layer 12 include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a comma coating method, and other printing methods, a gravure printing method, and a screen printing method.

As a result of intensive studies by the present inventors, in order to further enhance the durability and durability of the excellent antifouling effect of the hard coat layer 12, the composition for forming the hard coat layer is a polysiloxane having a (meth) acryloyl group at the end. In addition to containing a compound and a fluorine compound having a (meth) acryloyl group at the end, a composition obtained by removing the fluorine compound and the polysiloxane compound from the hard coat layer forming composition, that is, a polyfunctional (meta ) It has been found that a cured product obtained by curing a composition comprising an acrylic monomer and a photopolymerization initiator with an active energy ray is preferably a cured product that does not cause scratches after a steel wool scratch test.
The steel wool scratch test of the present invention is a test in which # 0000 steel wool is placed on the hard coat layer at a load of 200 g / cm ² and the steel wool is reciprocated 150 times over a distance of 5 to 10 cm on the hard coat layer. Sure. # 0000 steel wool is made by entanglement of hard fine metal fibers, so the surface when the hard coat layer surface is rubbed with fingers or cloth for a long time is simulated in a short time as an accelerated test. Can be reproduced. Since the conventional accelerated scratch test on the surface of the hard coat layer is often performed at about 10 reciprocations, the 150 reciprocation test can be said to be a very severe test.

If a hardened surface of a hardened base material, which is composed of a polyfunctional (meth) acrylic monomer and a photopolymerization initiator, is cured with active energy rays, the surface of the cured product is fixed on the surface with a steel wool test. Further, the polysiloxane compound having a (meth) acryloyl group at the terminal and the fluorine compound having a (meth) acryloyl group at the terminal are scraped together with the hard coat base material, so that the antifouling effect cannot be maintained. Therefore, a cured product obtained by curing a composition composed of a polyfunctional (meth) acrylic monomer and a photopolymerization initiator with an active energy ray is a cured product that does not get scratched after a steel wool scratch test. The durability of the antifouling effect of the hard coat layer containing a polysiloxane compound having an acryloyl group and a fluorine compound having a (meth) acryloyl group at the terminal can be dramatically increased.
From the viewpoint that a cured product obtained by curing a composition composed of a polyfunctional (meth) acrylic monomer and a photopolymerization initiator with an active energy ray becomes a cured product that is not damaged after a steel wool abrasion test, the present inventors have earnestly As a result of the investigation, the polyfunctional (meth) acrylate monomer is composed of at least a tetrafunctional or higher (meth) acrylic monomer, preferably a pentafunctional or higher (meth) acrylic monomer as a main component, and a bifunctional and trifunctional (meth) acrylate monomer. It was found that the desired cured product can be obtained by using as a subcomponent.

Examples of the bicomponent and trifunctional (meth) acrylate monomers as tricomponents are ethylene oxide-modified trimethylolpropane tri (meth) acrylate and a trifunctional (meth) acrylate monomer having 2 to 3 repeating units of ethylene oxide, Alternatively, a polyethylene glycol di (meth) acrylate having a secondary component of a bifunctional (meth) acrylate monomer having 2 to 3 repeating units of polyethylene glycol is preferable. When the number of repeating units of ethylene oxide and polyethylene glycol is within this range, a cured product having excellent scratch resistance can be obtained when the following composition is used.
The blending amount of the subcomponent with respect to the entire polyfunctional (meth) acrylic monomer solid is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When blended at less than 5% by weight, the composition comprising a polyfunctional (meth) acrylic monomer and a photopolymerization initiator has high hardness but tends to be brittle, and the abrasion resistance to steel wool is poor. On the other hand, when it exceeds 50 mass%, the composition comprising the polyfunctional (meth) acrylic monomer and the photopolymerization initiator is reduced in hardness and inferior in scratch resistance to steel wool. .

  As a result, it is difficult to get dirty, easy to wipe off, and has an antifouling effect that makes it difficult to see adhered dirt, and has surface performance that is excellent in both water-sliding and finger-sliding properties. However, the very excellent hard coat film 1 which can maintain the surface performance and which has never been obtained can be obtained.

The hard coat layer 12 of the present invention is formed to a thickness of 1 to 15 μm, preferably 3 to 10 μm. If it is less than 1 μm, sufficient hard coat performance cannot be obtained, and if it exceeds 15 μm, the cost becomes high. Furthermore, the hard coat layer 12 of the present invention preferably has a surface irregularity of 0.5 μm or less. If the surface unevenness is 0.5 μm or more, the rainbow pattern generated by the interference between the surface reflected light on the hard coat layer surface and the interface reflected light at the hard coat layer / substrate sheet interface becomes a conspicuous appearance problem. .
The hard coat layer 12 of the present invention has a surface energy measured by a wet tension test mixed solution (manufactured by Wako Pure Chemical Industries, Ltd.) in order to obtain a stable antifouling property, preferably 25.4 mN or less. / M or less.
In the composition for forming a hard coat layer of the present invention, various materials can be added as needed within a range not impairing the intended function. For example, ultraviolet absorbers, light stabilizers, inorganic and organic particles, hollow particles, antistatic agents and the like can be added.
The above can be applied not only to the hard coat layer 12 of FIG. 1 but also to the hard coat layers 22 and 23 of FIGS. 2 and 3 of the present invention.

(Laminate)
An example of the laminated body of this invention and another example are shown in FIG. 2 and FIG.
The hard coat film 1 can be formed into a laminate that can protect the surface by being attached to a touch panel display or the like by forming the adhesive layers 23 and 33 on the back surface thereof.
The adhesive layers 23 and 33 are, for example, natural rubber adhesives, synthetic rubber adhesives, acrylic adhesives, urethane adhesives, silicone adhesives, polyester adhesives, ethylene-acrylic copolymer adhesives, ethylene -Vinyl acetate copolymer pressure sensitive adhesive. Moreover, any of solvent system, emulsion system, and water system may be sufficient. In particular, when used for optical applications such as a touch panel display, an acrylic solvent-based pressure-sensitive adhesive is particularly preferable from the viewpoints of transparency, light resistance, durability, cost, and the like.
Other auxiliary agents may be added to the adhesive as necessary. Other auxiliaries include thickeners, pH adjusters, tackifiers, binders, crosslinking agents, adhesive fine particles, antifoaming agents, preservatives, pigments, inorganic fillers, stabilizers, wetting agents, wetting agents, etc. Can be mentioned.

Examples of the method for forming the adhesive layers 23 and 32 include a coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing method.
The thickness of the adhesive layer is preferably about 5 to 30 μm. If the pressure-sensitive adhesive layer is thin, sufficient adhesion to the adherend cannot be obtained, and if it is thick, there is a concern that the surface hardness of the entire protective sheet / adhered body attached to the adherend may be reduced.

  Since the hard coat layer 21 in FIG. 2 alone can function as a release layer for the adhesive layer, it is wound up without a separate film, and the laminate 2 is subsequently pulled out from the winding and pasted on a touch panel display or the like. Is possible.

Unlike the structure shown in FIG. 2, the laminate shown in FIG. 3 has a configuration in which a separate film 34 is further laminated on the adhesive layer 33. Thereby, even when the hard coat layer 31 does not have a sufficient function as a release layer for the adhesive layer, the laminate 3 having the separate film 34 is pulled out and peeled off, and the separate film 34 is peeled off. It becomes possible to affix to. Examples of the separate film 34 include a known film in which a release layer such as silicone is formed on various plastic films, and a polyolefin film alone such as a polypropylene film.
The protective sheet of the present invention may be provided with functional layers such as a hard coat protective layer, an easy adhesion layer, a printing layer, a transparent conductive layer, an antistatic layer, and an ultraviolet shielding layer between protective sheet constituents as necessary. Is possible. For example, as the hard coat protective layer, a hard coat protective sheet having a pressure-sensitive adhesive may be laminated on a plastic sheet such as polyester, polyethylene, or polypropylene. A printed layer or a transparent conductive layer may be provided between the substrate and the adhesive layer.

  The present invention has antifouling performance in which dirt such as fingerprints, sebum, foundations, etc. is difficult to adhere, easy to wipe off, and is not noticeable. And a highly functional hard coat layer having high surface wear durability, good surface finger slipperiness, high water repellency, and low interference fringe properties. Therefore, it can utilize for a wide laminated body, such as surface protection sheets, such as a touchscreen display, and surface protection sheets, such as a signboard.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited by these Examples. Unless otherwise specified, “parts” and “%” in the examples represent “parts by mass” and “mass%”, respectively.

<Example 1>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as the base sheet, and the hard coat layer forming composition (A) was bar-coated on the base sheet. The hard coat layer forming composition (A) has 1 part by mass of a fluorine-based compound having a (meth) acryloyl group at the end (trade name Optool DAC, manufactured by Daikin Industries, Ltd.) and a (meth) acryloyl group at the end. 0.2 parts by mass of the silicone compound (A) having polyfunctional (meth) acrylate, 64.1 parts by mass of hexafunctional acrylate (trade name DPHA, manufactured by Daicel Cytec Co., Ltd.), diethylene glycol diacrylate (trade name) SR230, manufactured by Sartomer) 27.5 parts by mass, photopolymerization initiator (trade name IRGACURE184, manufactured by BASF) 4 parts by mass, light stabilizer (TINUVIN152, manufactured by BASF) 4 parts by mass, as dilution solvent , MIBK 50.8 parts by mass and cyclohexanone 50.8 parts by mass. Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer.
The silicone compound (A) was obtained as follows. 230 parts of isophorone diisocyanate is heated to 80 ° C., 120 parts of 2-hydroxyethyl acrylate and 0.135 part of hydroquinone are added in an air atmosphere over 2 hours, and then reacted at 80 ° C. for 3 hours to give isocyanate groups in the molecule. And a compound (I) having an acryloyl group.
Next, 15 parts of a polysiloxane compound having a (meth) acryloyl group at one end (trade name: Silaplane FM-0721, manufactured by Chisso Corporation), 70 parts of 2-hydroxyethyl methacrylate, 15 parts of butyl methacrylate, 200 parts of methyl ethyl ketone, The mixture was heated to 80 ° C. with stirring in an atmosphere, 3 parts of azobisisobutyronitrile was added, and the mixture was reacted at 80 ° C. for 2 hours for polymerization. A solution prepared by dissolving 205 parts of the compound (I) and 1 part of tin octylate in 20 parts of MEK was added dropwise to the polymerization solution over about 10 minutes, and reacted for 2 hours after the addition to obtain a compound (II). Cyclohexanone was added to compound (II), and MIBK having the same mass as cyclohexanone was added to give a solid content of 20% to obtain silicone compound (A). The mass average molecular weight by GPC (polystyrene conversion) of the obtained silicone compound (A) was 20,000.
Each of the obtained hard coat films was evaluated by the following methods.

(Steel wool scratch resistance of hard coat base material (abbreviated as base metal scratch resistance))
The hard coat film of the present invention is obtained by removing from the composition for forming a hard coat layer a composition obtained by removing a fluorine compound having a (meth) acryloyl group at the terminal and a silicone compound having a (meth) acryloyl group at the terminal. In the same manner as above, coating and curing were carried out (this cured product is referred to as a hard coat base material).
Separate the non-carrier double-sided pressure-sensitive adhesive film (trade name CCL / D1 / T3T3, Shin Tac Kasei Co., Ltd.), and transfer the pressure-sensitive adhesive layer to the resulting hard coat base material film. Attached to a glossy black acrylic board. A # 0000 steel wool was placed on the hard coat base material and rubbed back and forth 150 times at a load of 200 g / cm ² and a distance of 9 cm. After rubbing, it was held over a lamp such as a fluorescent lamp to observe whether the rubbed portion was scratched. The case where there was no flaw was marked with ○, and the case where there was a flaw was marked with ×.

(XRF analysis a / b value)
The X-ray fluorescence intensity of fluorine and silicone of the obtained hard coat film was measured using a fluorescent X-ray analyzer (trade name PW-2404, manufactured by Nippon Philips Co., Ltd.). The value of a / b was determined by setting the Kα-ray peak intensities (kcps) of the obtained fluorine and silicon as a and b, respectively.

(Surface energy evaluation)
The surface energy of the obtained hard coat film was measured using a mixed solution for wetting tension test (manufactured by Wako Pure Chemical Industries, Ltd.), and it was rated as ○ when it was 25.4 dyn / cm or less.

(Anti-fingerprint, finger-slip, interference fringes)
To the obtained hard coat film, peel off the separate film of the non-carrier double-sided pressure-sensitive adhesive film (trade name CCL / D1 / T3T3, New Tac Kasei Co., Ltd.), transfer the pressure-sensitive adhesive layer, and give the mirror gloss through the pressure-sensitive adhesive layer. Affixed to a black acrylic board.
The appearance immediately after the fingerprint was applied to the hard coat surface was observed to see if the fingerprint was noticeable white. The score was 0 when the white fingerprint was conspicuous, and 1 when the fingerprint was not conspicuous.
The fingerprint on the hard coat surface was wiped 10 times with Kimwipe. After wiping, the white fingerprint was conspicuous with 0 points, and the fingerprint was not conspicuous with 1 point. Five points were evaluated as Δ, and four points or less as X.
Rub the surface of the hard coat with a finger to operate the touch panel, 1 point when finger slippery is good, 0 point when finger slippery is bad, and 10 people gave a score of 8 points or more, 6 points The above 7 points or less were evaluated as ◯, 5 points as Δ, and 4 points or less as x.
The result is a score of 10 people, holding a hard coat film affixed to the blackboard over a three-wavelength fluorescent lamp, giving 0 points when the rainbow pattern or interference fringes appearing on the hard coat layer is conspicuous, and 1 point when the interference fringes are not conspicuous , 6 points or more were evaluated as ◯, 5 points as △, and 4 points or less as ×.

(Contact angle, sliding angle)
Using a contact angle measuring device (model number CA-X) manufactured by Kyowa Interface Science Co., Ltd., a drop of 2 μl of pure water is dropped on the surface of the hard coat film to be measured. The contact angle was determined by image processing of a water droplet shape. As for the drop angle, a drop of 100 μl of pure water was dropped on the surface of the hard coat film to be measured in the same manner as the contact angle measurement, the measurement sample was tilted, and the tilt angle when the receding contact angle portion of the droplet started to move was determined. The hard coat film adhered to the black acrylic plate by the above-mentioned method was used as a measurement sample, and the measurement was performed after the static electricity of the measurement sample was sufficiently removed with a static elimination blower before the measurement. When the contact angle is 100 ° or more, the water-repellent performance is high, and when the falling angle is 10 ° or less, the water on the surface easily flows and cuts, so that it can be said that the surface has excellent waterproof performance.

(Scratch property, contact angle after scratch treatment)
The scratch property of the hard coat film was evaluated in the same manner as the base material scratch property evaluation method. Further, the contact angle after the scratch treatment was measured by the aforementioned contact angle measurement method. Abrasion is an indicator of the ease of surface scratches. The fact that the contact angle after scratches is not changed from that before scratches can be said to be high in antifouling performance of the antifouling performance of the surface.

(Optical properties)
The applicator was applied to the base material surface opposite to the hard coat layer of the obtained hard coat film so that the film thickness became 10 μm after drying the adhesive. The pressure-sensitive adhesive is 100 parts by mass of an acrylic adhesive (trade name KP2514, manufactured by Nippon Carbide Industry Co., Ltd.), and 1 part by mass of an isocyanate-based crosslinking agent (trade name CK-117, manufactured by Nippon Carbide Industry Co., Ltd.). It is a paint composed of 67.4 parts by mass of ethyl acetate as a diluent solvent. Then, it was heated and dried at 100 ° C. for 120 seconds, bonded to a separate film (trade name 38RL-07 (2), manufactured by Oji Specialty Paper Co., Ltd.), and subjected to a crosslinking reaction aging for 1 week in an environment of 23 ° C. and 50%. A protective film was obtained. The protective film was peeled off, and the hard coat film was affixed to the inspection glass plate through the adhesive layer so that air and dust would not enter. The total light transmittance and haze of the hard coat film affixed to the glass were measured using NDH5000 manufactured by Nippon Denshoku Co., Ltd. in accordance with JIS K7361-1 and JIS K7136, respectively. If the total light transmittance exceeds 90% and the haze is less than 1%, it is a hard coat film and laminate applicable to optical applications.

(Measurement of hard coat layer surface irregularities)
A film thickness distribution measuring device FiDiCa manufactured by JFE Techno-Research Co., Ltd. was used as a sample by peeling off a separate film of the obtained laminate and attaching a hard coat film to a black acrylic plate having a specular gloss through an adhesive layer. Was used to measure the thickness distribution of the hard coat layer having a surface of 10 cm × 9 cm, and the difference between the maximum thickness and the minimum thickness was determined as surface irregularities.
The evaluation results are shown in Table 1.

<Example 2>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as the base sheet, and the hard coat layer forming composition (B) was bar-coated on the base sheet. The hard coat layer forming composition (B) has 1 part by mass of a fluorine compound having a (meth) acryloyl group at the end (trade name Optool DAC, manufactured by Daikin Industries, Ltd.) and a (meth) acryloyl group at the end. 65. Silicone compound (trade name: Silaplane FM-0711, manufactured by Chisso Corp.), 0.1 part by mass, polyfunctional (meth) acrylate, hexafunctional acrylate (trade name: DPHA, manufactured by Daicel Cytec Co., Ltd.) 2 parts by weight, diethylene glycol diacrylate (trade name SR230, manufactured by Sartomer) 27.5 parts by weight, photopolymerization initiator (trade name IRGACURE184, manufactured by BASF) 4 parts by weight, light stabilizer (TINUVIN152, BASF) 4) parts by mass, 50.4 parts by mass of MIBK and 50.4 parts by mass of cyclohexanone as a diluent solvent. Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer.
An adhesive was applied to the base material surface opposite to the hard coat layer of the obtained hard coat film. The pressure-sensitive adhesive is 100 parts by mass of an acrylic adhesive (trade name KP2514, manufactured by Nippon Carbide Industry Co., Ltd.), and 1 part by mass of an isocyanate-based crosslinking agent (trade name CK-117, manufactured by Nippon Carbide Industry Co., Ltd.). It is a paint composed of 67.4 parts by mass of ethyl acetate as a diluent solvent. Then, it is heated and dried at 100 ° C. for 120 seconds, bonded to a separate film (trade name 38RL-07 (2), manufactured by Oji Specialty Paper Co., Ltd.), and subjected to a crosslinking reaction aging for 1 week in an environment of 23 ° C. and 50%. As a result, a laminate was obtained. The thickness of the adhesive layer was 10 μm.

(Base material scratch)
The base material scratch resistance was evaluated by the same method as in Example 1.

(XRF analysis a / b value)
The XRF analysis a / b value was determined by the same method as in Example 1.

(Surface energy evaluation)
The surface energy of the hard coat surface of the obtained protective sheet was evaluated by the same method as in Example 1.

(Anti-fingerprint, finger-slip, interference fringes)
The obtained laminate was stuck on a black acrylic plate having a specular gloss through an adhesive layer.
The appearance immediately after the fingerprint was applied to the hard coat surface was observed to see if the fingerprint was noticeable white. The score was 0 when the white fingerprint was conspicuous, and 1 when the fingerprint was not conspicuous.
The fingerprint on the hard coat surface was wiped 10 times with Kimwipe. After wiping, the white fingerprint was conspicuous with 0 points, and the fingerprint was not conspicuous with 1 point. Five points were evaluated as Δ, and four points or less as X.
Rub the surface of the hard coat with a finger to operate the touch panel, 1 point when finger slippery is good, 0 point when finger slippery is bad, and 10 people gave a score of 8 points or more, 6 points The above 7 points or less were evaluated as ◯, 5 points as Δ, and 4 points or less as x.
The result is a score of 10 people, holding a hard coat film affixed to the blackboard over a three-wavelength fluorescent lamp, giving 0 points when the rainbow pattern or interference fringes appearing on the hard coat layer is conspicuous, and 1 point when the interference fringes are not conspicuous , 6 points or more were evaluated as ◯, 5 points as △, and 4 points or less as ×.

(Contact angle, sliding angle)
The contact angle and sliding angle on the hard coat surface of the obtained laminate were evaluated in the same manner as in Example 1.

(Scratch property, contact angle after scratch treatment)
The separated film of the obtained laminate is peeled off, the hard coat film is attached to a black acrylic plate having a specular gloss through an adhesive layer, and the same steel wool as the base material scratching property of Example 1 is placed on the hard coat surface. Then, the evaluation was made in the same manner as the evaluation of the scratch resistance of the base material in Example 1. Further, the contact angle after the scratch treatment was evaluated by the same method as in Example 1.

(Optical properties)
The separated film of the obtained laminate was peeled off, and the hard coat film was affixed to the inspection glass plate through the adhesive layer so that air and dust would not enter. The total light transmittance and haze of the hard coat film affixed to the glass were measured using NDH5000 manufactured by Nippon Denshoku Co., Ltd. in accordance with JIS K7361-1 and JIS K7136, respectively.
The evaluation results are shown in Table 1.

(Measurement of hard coat layer surface irregularities)
The surface roughness of the hard coat layer was measured in the same manner as in Example 1.
The evaluation results are shown in Table 1.

<Example 3>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as the base sheet, and the hard coat layer forming composition (C) was bar-coated on the base sheet. The hard coat layer-forming composition (C) is composed of 0.5 parts by mass of a fluorine compound having a (meth) acryloyl group at the end (trade name: Megafuck RS-75-K, manufactured by DIC Corporation) at the end ( 0.5 parts by mass of a silicone compound having a (meth) acryloyl group (trade name: Silaplane FM-0721, manufactured by Chisso Corporation) as a polyfunctional (meth) acrylate, hexafunctional acrylate (trade name DPHA, Daicel Cytec ( 66.4 parts by mass, trimethylolpropane ethylene oxide modified triacrylate (trade name Aronix M-370, manufactured by Toagosei Co., Ltd.), photopolymerization initiator (trade name IRGACURE184, BASF) Manufactured) is 4.5 parts by mass, MIBK is 50.2 parts by mass, and cyclohexanone is 50.2 parts by mass. Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer.
An adhesive was applied to the base material surface opposite to the hard coat layer of the obtained hard coat film. The pressure-sensitive adhesive is 100 parts by mass of an acrylic adhesive (trade name KP2514, manufactured by Nippon Carbide Industry Co., Ltd.), and 1 part by mass of an isocyanate-based crosslinking agent (trade name CK-117, manufactured by Nippon Carbide Industry Co., Ltd.). It is a paint composed of 67.4 parts by mass of ethyl acetate as a diluent solvent. Then, it is heated and dried at 100 ° C. for 120 seconds, bonded to a separate film (trade name 38RL-07 (2), manufactured by Oji Specialty Paper Co., Ltd.), and subjected to a crosslinking reaction aging for 1 week in an environment of 23 ° C. and 50%. As a result, a laminate was obtained. The thickness of the adhesive layer was 10 μm.
The obtained hard coat film and protective sheet were evaluated in the same manner as in Example 2. The evaluation results are shown in Table 1.

<Comparative Example 1>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as the base sheet, and the hard coat layer forming composition (D) was bar-coated on the base sheet. The hard coat layer-forming composition (D) is composed of 1.25 parts by mass of a fluorine compound having a (meth) acryloyl group at the end (trade name: Megafax RS-75-K, manufactured by DIC Corporation) at the end ( A silicone compound having a meth) acryloyl group is not blended, and 66.5 parts by mass of a polyfunctional (meth) acrylate (trade name DPHA, manufactured by Daicel Cytec Co., Ltd.), diethylene glycol diacrylate (trade name SR230) , Sartomer Co., Ltd.) 28.5 parts by mass, photopolymerization initiator (trade name IRGACURE184, manufactured by BASF) 4.5 parts by mass, MIBK 50.4 parts by mass, cyclohexanone 50.4 parts by mass It is. Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer. Except for this, a laminate was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative example 2>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as a base sheet, and a hard coat layer forming composition (E) (Aikatron Z883-3, Aika Industry Co., Ltd.) was used on the base sheet. Bar Co., Ltd.) was applied. The hard coat layer-forming composition (E) is a hard coat layer-forming coating composition that does not contain a fluorine compound having a (meth) acryloyl group at the terminal and contains a silicone compound having a (meth) acryloyl group at the terminal. . Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer. Except for this, a laminate was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 3>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as the base sheet, and the hard coat layer forming composition (F) was bar-coated on the base sheet. The hard coat layer-forming composition (F) has 0.5 parts by mass of a fluorine compound having no (meth) acryloyl group at the end (trade name: Megafac F-555, manufactured by DIC Corporation) and (meta) ) 0.2 parts by mass of a silicone compound having no acryloyl group (trade name: Silaplane FM-0411, manufactured by Chisso Corporation), polyfunctional (meth) acrylate, hexafunctional acrylate (trade name DPHA, Daicel Cytec ( Co., Ltd.) 66.5 parts by mass, trimethylolpropane ethylene oxide modified triacrylate (trade name Aronix M-370, manufactured by Toagosei Co., Ltd.), 28.5 parts by weight, photopolymerization initiator (trade names IRGACURE184, BASF) Co., Ltd.) 4.5 parts by mass, MIBK 50.2 parts by mass, and cyclohexanone 50.2 parts by mass. Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer. Except for this, a laminate was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative example 4>
A PET film (trade name: TA010, manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm was used as the base sheet, and the hard coat layer forming composition (G) was bar-coated on the base sheet. The hard coat layer forming composition (G) has 1 part by mass of a fluorine compound having a (meth) acryloyl group at the end (trade name Optool DAC, manufactured by Daikin Industries, Ltd.) and a (meth) acryloyl group at the end. 0.2 parts by mass of a silicone compound (trade name: Silaplane FM-0211, manufactured by Chisso Corporation), and an organic-inorganic hybrid hard coat layer-forming coating material (trade names: KZ-6406, JSR) containing no fluorine and silicone additives Co., Ltd.) and 90.8 parts by mass of MIBK. Then, it was heated and dried at 80 ° C. for 60 seconds, and UV irradiation was performed using a high pressure mercury lamp UV irradiation machine (made by Eye Graphics Co., Ltd.) at 160 W / cm, lamp height 13 cm, belt speed 10 m / min, 2 pass, under a nitrogen atmosphere. Then, a hard coat film was obtained by curing and forming a 10 μm thick hard coat layer. Except for this, a laminate was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  As shown in Table 1, the examples using the hard coat film of the present invention provide a hard coat layer that exhibits an antifouling effect that is difficult to get dirty and easy to wipe, and has excellent water sliding properties (falling angle) and finger slipping properties. It was. On the other hand, since Comparative Example 1 did not contain a silicone-based additive, finger slipping and water slipping were particularly poor. In Comparative Example 2, since a fluorine-based additive was not included, the contact angle was low and a sufficient antifouling effect could not be exhibited. In Comparative Example 3, since a fluorine-based additive having no (meth) acryloyl group and a silicone-based additive having no (meth) acryloyl group at the terminal were used, the antifouling durability was lacking. Comparative Example 4 lacked antifouling durability due to poor scratch resistance of the base material. Therefore, none of the comparative examples could satisfy both the antifouling effect and the slipperiness.

DESCRIPTION OF SYMBOLS 1 ... Hard coat film 2 ... Example of laminated body 3 ... Other examples of laminated body 11, 21, 31 ... Hard coat layer 12, 22, 32 ... Base material sheet 13, 23 33 ... Adhesive layer 34 ... Separate film

Claims (3)

A hard coat film comprising a base sheet and a hard coat layer formed on at least one surface of the base sheet,
The hard coat layer includes a fluorine-based compound having a (meth) acryloyl group at a terminal, a polysiloxane compound having a (meth) acryloyl group at a terminal, a polyfunctional (meth) acryl monomer, and a photopolymerization initiator. A cured product obtained by curing the forming composition with active energy rays,
When the peak intensity of the Kα ray of fluorine atoms and silicon atoms obtained by fluorescent X-ray (XRF) analysis of the hard coat film is a and b, respectively.
0.01 ≦ a / b ≦ 0.5 (1)
Meet hard coat film. 2. The hard coat film according to claim 1, wherein the thickness of the hard coat layer is 1 to 15 μm, and the surface roughness of the hard coat layer is 0.5 μm or less. It is a laminated body which has a hard coat film of Claim 1 or 2, Comprising: The laminated body which contains an adhesion layer at least on the base material sheet surface on the opposite side to a hard coat layer.

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