JP2015096877A - Hard coat film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which prevents blocking of hard coat films and offers superior abrasion resistance and adhesion, and to provide a manufacturing method for the same.SOLUTION: A hard coat film has a hard coat layer formed on at least one surface of a base material film, where the hard coat layer comprises a cured product of a hard coat layer-forming material containing at least (A) an energy ray-curable resin and (B) hydrophobic silica sol, the (A) energy ray-curable resin containing specific compounds in predetermined proportions and a (B) hydrophobic silica sol content being in a range of 0.3-55 pts.wt. per 100 pts.wt. of the (A) energy ray-curable resin in terms of solid content. The (B) hydrophobic silica sol is segregated to a surface of the hard coat layer opposite to the base material film after the hard coat layer-forming material is cured.

Description

  The present invention relates to a hard coat film and a method for producing a hard coat film, and more particularly to a hard coat film having blocking resistance and a method for producing such a hard coat film.

Conventionally, the image display surface of the display and the surface of the printed material have been required to have scratch resistance and appropriate hardness so as not to be damaged during handling. For this reason, a hard coat film is often provided on such a surface.
As such a hard coat film, one having a hard coat layer on the surface of a substrate is known.

For example, a hard coat film for a display in which a slippery adhesive layer, a hard coat layer, and an antireflection layer are laminated in this order on one or both sides of a transparent polyester film is disclosed (for example, see Patent Document 1).
That is, Patent Document 1 discloses a hard coat film for display having a predetermined surface hardness and a predetermined thickness as a hard coat layer, a surface water contact angle of 40 to 80 °, and containing inorganic fine particles. It is disclosed.

Further, a printed surface protection film having excellent scratch resistance on the surface of a printed material such as a guide plate or a poster and having anti-light reflection performance is disclosed (for example, see Patent Document 2).
That is, Patent Document 2 discloses a printed surface protective film in which a hard coat layer has a high refractive index by dispersing high refractive index ultrafine particles in a binder resin.

On the other hand, from the viewpoint of productivity and handleability, a film having hard coat properties may be wound into a roll after being applied with a hard coat layer and stored in a roll for several days. There were problems that the surfaces were stuck together (blocking), the surface of the hard coat layer was scratched, or the surface was uneven when using a hard coat film with blocking.
Therefore, for example, in the production process, when the hard coat film is wound up with a roll, the light transmissive group is prevented in order to prevent the hard coat films from sticking to each other or becoming difficult to peel off. An optical laminate having a predetermined hard coat layer on both surfaces of a material, a transparent conductive film, and a capacitive touch panel have been proposed (see, for example, Patent Document 3).
More specifically, the hard coat layer is a layer formed using a composition for a hard coat layer containing a binder resin, a leveling agent, and a lubricant, and the lubricant is from the group consisting of silica particles and silicone particles. An optical laminate that is at least one selected is disclosed.

Also disclosed is a method for producing a hard coat film with high productivity, which has high transparency, improved scratch resistance, and can impart a function conventionally formed by a plurality of layers in a single layer. (For example, refer to Patent Document 4).
More specifically, a method for producing a hard coat film in which a hard coat film is provided on at least one side of a transparent substrate film, wherein the coating composition of the hard coat layer comprises predetermined metal oxide fine particles, ionizing radiation curable properties. There has been proposed a method for producing a hard coat film, which contains a resin and an organic solvent containing ketones and alcohols, and in which the metal oxide fine particles contained in the hard coat layer form a localized phase.

JP 2001-109388 A (Claims and specification) Japanese Patent Application Laid-Open No. 11-77874 (Claims and Specifications) JP 2012-66409 A (Claims, specification) JP 2013-60481 A (Claims and specification)

However, since the hard coat film for display disclosed in Patent Document 1 has a predetermined pencil hardness because the surface of the hard coat layer is hydrophilic, the slipperiness is not sufficient. There was a problem that adhesion could not be effectively prevented.
In addition, it is essential to use ultra-fine particles of high refractive index for the hard coat layer described in Patent Document 2, and in particular, it is described that zinc oxide or titanium oxide is used. Has a problem in that antireflection performance may not be obtained.
In addition, the optical laminate described in Patent Document 3 prevents the optical laminates from sticking to each other by using relatively large silica particles as a lubricant, but can prevent adhesion between films to some extent. Since the lubricant is a relatively large particle, there has been a problem that the transparency of the optical laminate may be insufficient.
In addition, the method for producing a hard coat film described in Patent Document 4 localizes metal oxide fine particles on the surface by utilizing the difference in evaporation rate of two kinds of solvents and the attraction and binding action of cross-linking components on the fine particle surface. Therefore, there has been a problem that the manufacturing method is complicated and it is difficult to manufacture stably.

Therefore, as a result of intensive studies on such problems, the present inventors have provided a hard coat layer on at least one surface of the base film, and a predetermined hydrophobized silica sol as a hard coat layer forming material for forming the hard coat layer. By blending a predetermined amount and using a predetermined energy ray curable resin, it is possible to effectively prevent pressure bonding between the hard coat films and to obtain a hard coat film having excellent scratch resistance. The title and the present invention have been completed.
That is, the present invention can effectively prevent blocking (sticking) between hard coat films (anti-blocking property) and has excellent scratch resistance. An object is to provide a manufacturing method.

According to the present invention, a hard coat film having a hard coat layer on at least one surface of a base film, the hard coat layer comprising at least (A) an energy ray curable resin and (B) a hydrophobized silica sol. (A) an energy ray curable resin comprising (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth) An acrylate compound, and the content weight ratio of (a1) polyfunctional (meth) acrylate compound to (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is 100: 0 to 20 Is a value within the range of 80, and the blending amount of (B) hydrophobized silica sol is based on (A) 100 parts by weight of energy ray curable resin. The value is within the range of 0.3 to 55 parts by weight in terms of solid content, and (B) the hydrophobized silica sol is opposite to the base film of the hard coat layer after the hard coat layer forming material is cured. A hard coat film characterized by being segregated on the surface on the side is provided, and the above-described problems can be solved.
That is, by using a hydrophobized silica sol as the hard coat layer forming material, the hydrophobized silica sol is phase-separated on the surface opposite to the base film of the hard coat layer after curing the hard coat layer forming material. Since it exists, a fine unevenness | corrugation arises on the hard coat film surface, and sticking of hard coat films can be prevented.
In addition, the energy ray curable resin contains a polyfunctional (meth) acrylate compound and an ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound in a predetermined amount range, whereby the hardness of the hard coat film. Can be suitably adjusted.

Moreover, when comprising the hard coat film of this invention, it is preferable that the average particle diameter of (B) hydrophobic silica sol is a value within the range of 10-100 nm.
By comprising in this way, the optical characteristic of a hard coat film can be maintained or improved effectively, and sufficient light transmittance can be obtained.

Moreover, when comprising the hard coat film of this invention, it is preferable to make the contact angle of the water with respect to the coating film at the time of making (B) hydrophobic silica sol into a coating film the value of 100 degrees or more.
By comprising in this way, blocking of hard coat films can be prevented effectively.

In constituting the hard coat film of the present invention, it is preferable that the hard coat layer forming material further contains (C) a leveling agent.
By constituting in this way, in the process of forming a hard coat layer on the base film, the leveling agent is oriented on the outermost surface of the coating film, and it is prevented that floating, mottle, etc. occur on the coating film surface. be able to.

Further, in constituting the hard coat film of the present invention, the arithmetic average roughness Ra measured in accordance with JIS B 0601-1994 on the surface of the hard coat layer is a value in the range of 1.5 to 15 nm. It is preferable.
By comprising in this way, a fine unevenness | corrugation can be obtained on the surface of the obtained hard coat film, and blocking of hard coat films can be prevented suitably.
Moreover, if the arithmetic mean roughness in the surface of a hard-coat layer is a value within such a range, the hard-coat film which has the outstanding optical characteristic can be obtained.

Moreover, another aspect of the present invention is a hard coat film for protecting a printed material surface, in which the above-described hard coat film is used on the outermost surface of the printed material.
That is, by using a hard coat film excellent in adhesion and scratch resistance on the outermost surface of the printed material, even when used for a large printed material, the surface is suitably protected by preventing peeling from the printed material. be able to.

Still another embodiment of the present invention is an image display device in which the above-described hard coat film is used on the outermost surface of the image display device.
That is, when the hard coat film excellent in adhesion and scratch resistance is provided, for example, on the outermost surface of the capacitive touch panel, the outermost surface of the image display device can be suitably protected.

Another aspect of the present invention is a method for producing a hard coat film comprising a hard coat layer on at least one side of a substrate film,
It is a manufacturing method of the hard coat film characterized by including following process (1)-(3).
(1) At least (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound, and (a1) a polyfunctional (meth) acrylate compound And (a2) an energy ray-curable resin in which the content weight ratio of (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is in the range of 100: 0 to 20:80 And (A) (B) a hydrophobized silica sol having a value in the range of 0.3 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of the energy ray curable resin, a hard coat layer forming material is prepared. Step (2) A step of applying a hard coat layer forming material to at least one surface of the base film (3) Curing the hard coat layer forming material, and (B) Hydrophobized silica gel A step of forming a hard coat film having a hard coat layer segregated on the surface of the hard coat layer opposite to the base film. It is possible to efficiently produce a hard coat film that is segregated on the surface on the opposite side.
Therefore, even when the hard coat film is manufactured by Roll To Roll, it is possible to effectively prevent the hard coat films from sticking to each other and improve productivity.

Fig.1 (a)-(b) is a figure provided in order to demonstrate the aspect in the hard coat film of this invention. FIG. 2 (a) is a photograph showing segregation of the hydrophobized silica sol of the present invention, and FIG. 2 (b) is a diagram for conceptually explaining the segregation state of the hydrophobized silica sol. FIG. 3 is a diagram for explaining an embodiment of the hard coat film for protecting a printed material surface of the present invention. FIG. 4 is a diagram provided for explaining an embodiment in an image display device provided with the hard coat film of the present invention on the outermost surface. FIG. 5 is a diagram for explaining a hard coat film containing a silica sol having a hydrophilic surface.

[First embodiment]
The first embodiment is a hard coat film including a hard coat layer on at least one surface of a base film, and the hard coat layer includes at least (A) an energy ray curable resin, and (B) a hydrophobized silica sol. (A) an energy ray curable resin comprising (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meta ) Acrylate compound, and the content weight ratio of (a1) polyfunctional (meth) acrylate compound to (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is 100: 0 to 20:80, and the blending amount of (B) hydrophobized silica sol is (A) 100 parts by weight of energy ray curable resin. On the other hand, it is a value within the range of 0.3 to 55 parts by weight in terms of solid content, and (B) the hard coat layer after curing the hard coat layer forming material is opposite to the base film. The hard coat film is segregated on the side surface.
Hereinafter, the conductive film of the first embodiment will be specifically described with reference to the drawings as appropriate.

1. Type of base film (1) The resin used for the base film 10 illustrated in FIGS. 1A to 1B is not particularly limited as long as it is excellent in flexibility and transparency. Polyester film such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, Polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polymethylpentene film, polysulfone film, polyetheretherketone fill , Polyether sulfone film, polyether imide film, a polyimide film, a fluororesin film, a polyamide film, an acrylic resin film, polyurethane resin film, norbornene resin film, other plastic films such as cycloolefin resin film.
Among these, since it is excellent in transparency and has versatility, it is preferable to use a transparent resin film made of polyethylene terephthalate or polycarbonate.

(2) Thickness Moreover, it is preferable to make the thickness of the base film 10 illustrated to FIG. 1 (a)-(b) into the value within the range of 25-188 micrometers.
The reason for this is that when the thickness of the substrate film is less than 25 μm, the handling property is remarkably reduced, for example, wrinkles are likely to occur. This is because it may be lowered, and in particular, it may be difficult to form a roll.
Therefore, since the balance between mechanical strength and light transmittance becomes better, the thickness of the base film is more preferably set to a value within the range of 25 to 125 μm.

(3) Primer layer Although not shown, by providing a primer layer on the surface of the base film, the adhesion between the base film and the cured material of the hard coat layer forming material is improved and the hard coat layer is scratch-resistant. The property can be further improved.
Here, examples of the constituent material of the primer layer include one kind of urethane resin, acrylic resin, epoxy resin, polyester resin, and silicone resin, or a combination of two or more kinds.

Moreover, it is preferable to make the thickness of a primer layer into the value within the range of 0.01-20 micrometers.
This is because the primer effect may not be exhibited when the thickness of the primer layer is less than 0.01 μm. On the other hand, when the thickness of the primer layer exceeds 20 μm, the light transmittance may be lowered when a hard coat film is formed.
Therefore, since the balance between the primer effect and the light transmittance becomes better, it is more preferable to set the thickness of the primer layer to a value within the range of 0.1 to 15 μm.

2. Hard coat layer forming material (1) (A) Energy beam curable resin (1) -1. Type As a type of the (A) energy ray curable resin constituting the hard coat layer forming material, polyfunctional (meth) acrylate is included.
More specifically, as polyfunctional (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (Meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol Dipentaerythritol polyfunctional (meth) acrylates such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate Risuritoru polyfunctional (meth) acrylate, glycerol tri (meth) acrylate, triallyl (meth) acrylate.
Among these, pentaerythritol polyfunctional (meth) acrylate or dipentaerythritol polyfunctional (meth) acrylate is more preferable because moderate hardness can be imparted to the hard coat layer.
Further, as other energy ray curable resins, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, silicone (meth) acrylate, or the like may be included.

Further, the polyfunctional (meth) acrylate includes EO (ethylene oxide) or PO (propylene oxide) addition type polyfunctional (meth) acrylate.
The EO (ethylene oxide) or PO (propylene oxide) addition type polyfunctional (meth) acrylate is a compound obtained by esterifying an EO or PO addition type polyhydric alcohol with acrylic acid, and more specifically. EO or PO modified glycerol triacrylate, EO or PO modified trimethylolpropane acrylate, EO or PO modified pentaerythritol tetraacrylate, EO or PO modified dipentaerythritol hexaacrylate, and the like.
Among these, it is EO or PO-modified dipentaerythritol hexaacrylate, EO or PO-modified trimethylolpropane tetraacrylate because cracking and cracking of the hard coat layer can be prevented by imparting appropriate flexibility to the hard coat layer. It is more preferable.

  In addition, in the EO or PO addition type polyfunctional (meth) acrylate, the EO or PO addition amount is preferably a value within the range of 6 to 18 mol in order to impart appropriate flexibility to the hard coat layer. More preferably, it is 8 to 16 mol.

(1) -2. Compounding amount The (A) energy ray-curable resin constituting the hard coat layer forming material is composed of (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth). An acrylate compound, and the content weight ratio of (a1) polyfunctional (meth) acrylate compound to (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is 100: 0 to 20 : A value in the range of 80.
The reason for this is that the hard coat layer forming material is a polyfunctional (meth) acrylate compound that has a relatively high hardness when irradiated with energy rays, and an ethylene oxide or propylene oxide addition type that has relatively high flexibility even when irradiated with energy rays. This is because the hardness of the hard coat layer can be easily adjusted by including the polyfunctional compound at a predetermined content.
That is, (a1) when the content weight ratio of the polyfunctional (meth) acrylate compound is less than 20, the scratch resistance of the hard coat layer after curing may be lowered.
Therefore, the content weight ratio of (a1) polyfunctional (meth) acrylate compound to (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is within the range of 95: 5 to 30:70. It is more preferable that the value is within the range of 90:10 to 50:50.

(1) -3. (D) Photopolymerization initiator In addition, in the hard coat layer forming material of the present invention, it is preferable to contain (D) a photopolymerization initiator as desired.
This is because a hard coat layer can be efficiently formed by irradiating the hard coat layer forming material with active energy rays by containing a photopolymerization initiator.
Here, the photopolymerization initiator refers to a compound that generates radical species by irradiation with active energy rays such as ultraviolet rays.
Examples of the photopolymerization initiator 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-morpholinopropan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzene Zophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane] and the like Of these, one kind may be used alone, or two or more kinds may be used in combination.
In addition, as content when (D) a photoinitiator is contained, it is preferable to set it as the value within the range of 0.2-20 weight part with respect to 100 weight part of (A) energy-beam curable resin. More preferably, the value is in the range of 0.5 to 15 parts by weight, and even more preferably in the range of 1 to 13 parts by weight.

(2) (B) Hydrophobized silica sol (2) -1. Type Further, the hard coat layer forming material includes (B) a hydrophobized silica sol.
Here, examples of the silica sol include sols of silica fine particles such as alkoxysilane compounds and chlorosilane compounds.
As an alkoxysilane compound, if it is a silicon compound which has a hydrolyzable alkoxyl group, it will not specifically limit, For example, the compound represented by General formula (1) can be mentioned.
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein R ¹ is a hydrogen atom or a non-hydrolyzable group, specifically, an alkyl group, a substituted alkyl group (substituent: halogen atom, epoxy atom, (meth) acryloyloxy group, etc.), alkenyl group, An aryl group or an aralkyl group, R ² represents a lower alkyl group, n is an integer of 0 to 2, and when R ¹ and OR ² are plural, plural R ¹ are the same or different And the plurality of OR ² may be the same or different.)

  Here, as the alkoxysilane compound represented by the general formula (1), tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, Tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane hydride, triethoxysilane hydride, tripropoxysilane hydride, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxy One or more of propyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, etc. The combination of is preferable.

In this case, as an alkoxysilane compound, an inorganic silica-based cured product can be obtained by completely hydrolyzing a compound in which n is 0 or n is 1 to 2 and R ¹ is a hydrogen atom. A siloxane-based cured product or a mixed cured product of inorganic silica and polyorganosiloxane is obtained.
On the other hand, a compound in which n is 1 to 2 and R ¹ is a non-hydrolyzable group has a non-hydrolyzable group, so that a polyorganosiloxane-based cured product is obtained by partial or complete hydrolysis.
Examples of the chlorosilane compound include ethyldichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, trichlorosilane, trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane.

Silica sol is a dispersion of silica fine particles in a sol state in water or an organic solvent.
The organic solvent is not particularly limited, and examples include methanol, ethanol, isopropanol, ethylene glycol, n-propyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, propylene glycol monomethyl ether, cyclohexane, benzene, toluene, and the like. Methyl isobutyl ketone and propylene glycol monomethyl ether having a high boiling point are particularly preferred.

The silica sol of the present invention is a hydrophobic silica sol in which a part or all of silanol groups on the surface of silica particles is treated with a surface modifier having a hydrophobic group.
Here, examples of the surface modifier include a silane coupling agent having both a functional group capable of reacting with a silanol group on the surface of the silica particle and a hydrophobic group.
More specifically, examples of the hydrophobized silica sol include SIRPGM15WT% -E26 manufactured by CIK Nanotech.

(2) -2. Hydrophobic degree The degree of hydrophobicity of the silica sol was determined by coating the silica sol on a PET film, removing the solvent to form a silica sol coating film, and measuring the contact angle of water with the coating film.
More specifically, the contact angle of water with respect to the coating film when the silica sol is used as the coating film is preferably set to a value of 100 ° or more.
That is, if the contact angle of water with the silica sol coating film is 100 ° or more, it can be determined that the surface of the silica sol is hydrophobic.
Here, FIG. 2 (a) shows an SEM photograph of the hard coat layer of the present invention, and FIG. 2 (b) shows a schematic diagram for explaining the presence state of silica sol.
More specifically, the hydrophobized silica sol 16 of the present invention is present in a large amount on the surface opposite to the PET surface 10 in the hard coat layer 12, and the ratio existing in the vicinity of the PET surface and in the hard coat layer is low. It is understood. In the SEM photograph of FIG. 2A, the upper part of the hard coat layer is an adhesive layer 11 used for sample preparation.
Therefore, the addition of the hydrophobized silica sol can impart an appropriate surface roughness to the surface on the opposite side of the substrate from the vicinity of the substrate surface in the hard coat layer as compared with the center portion. Even in the case where time elapses due to overlapping each other, blocking (crimping) between films can be prevented.
That is, it is understood that the effect of predetermined blocking resistance (sometimes referred to as anti-blocking property) can be exhibited even with a relatively small amount of addition.
If the contact angle of water with the hydrophobized silica sol coating film is excessively high, adhesion may be reduced when a transparent conductive layer or the like is further laminated on the hard coat film. The contact angle of water is more preferably set to a value within the range of 100 to 130 °.
On the other hand, when the contact angle of water with respect to the silica sol coating film is less than 100 ° and the hydrophilicity increases, the silica sol 18 does not segregate only on the surface opposite to the base film as shown in FIG. It has been confirmed that it exists in a dispersed state throughout the hard coat layer.
Therefore, it is understood that a relatively large amount needs to be blended in order to impart a predetermined surface roughness to the hard coat layer.
In addition, in Example 1, the measuring method of the contact angle of water with respect to the coating film of a silica sol is demonstrated concretely.

(2) -3. Average particle diameter Moreover, it is preferable that the average particle diameter of the hydrophobized silica sol of this invention is a value within the range of 10-100 nm.
The reason for this is that when the average particle size of the hydrophobized silica sol is less than 10 nm, it is difficult to obtain a predetermined surface roughness, especially when it is difficult to prevent blocking with a small amount of compounding. Because there is.
On the other hand, when the average particle size of the hydrophobized silica sol exceeds 100 nm, the optical properties of the hard coat film may be excessively deteriorated.
Therefore, the average particle diameter of the hydrophobized silica sol is more preferably in the range of 10 to 50 nm, and still more preferably in the range of 15 to 40 nm.
The average particle size of the silica sol is a particle size (median diameter D50) at an integrated value of 50% in the particle size distribution obtained using a laser diffraction / confusion type particle size distribution measuring device.

(2) -4. Compounding quantity Moreover, the compounding quantity of the hydrophobized silica sol of this invention is a value within the range of 0.3-55 weight part in conversion of solid content with respect to 100 weight part of (A) energy beam curable resin. Features.
The reason for this is that when the blended amount of the hydrophobized silica sol is less than 0.3 parts by weight, it may be difficult to develop the effect of preventing blocking of the hard coat films.
On the other hand, when the amount of the hydrophobized silica sol exceeds 55 parts by weight, the adhesion and scratch resistance of the hard coat film may be excessively lowered.
Further, as described above, since the hydrophobic silica sol tends to segregate on the surface opposite to the substrate surface in the hard coat layer, the amount of the hydrophobized silica sol is (A) the energy beam curable resin. In the case of 0.3 to 25.0 parts by weight in terms of solid content with respect to 100 parts by weight, even if the blending amount of the hydrophobized silica sol is a relatively small amount of addition, the anti-blocking effect is effectively expressed. Therefore, it can be suitably used as a hard coat film for a transparent conductive film requiring transparency.
When the blending amount of the hydrophobized silica sol is a value in the range of 25 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of the (A) energy beam curable resin, the hydrophobized silica sol is based on Since more segregation occurs on the surface opposite to the material surface, as described later, although haze value increases, not only blocking resistance but also scratch resistance can be suitably obtained. It can be used for the outermost surface.
Therefore, when used for the outermost surface of the image display device or the printed material, the blended amount of the hydrophobized silica sol is 25 to 53 parts by weight in terms of solid content with respect to 100 parts by weight of the (A) energy beam curable resin. A value within the range is more preferred, a value within the range of 28 to 50 parts by weight is further preferred, and a value within the range of 28 to 30 parts by weight is particularly preferred.

(3) (C) Leveling agent It is preferable that the hard coat layer forming material further includes (C) a leveling agent.
This is because the leveling agent is oriented to the outermost surface of the coating film during the drying process of the hard coat layer forming material by containing the leveling agent, uniformizing the surface tension of the coating film, and preventing floating, mottle, repelling, etc. This is because wetting of the object to be coated can be improved.
That is, when forming a transparent conductive layer on a hard-coat layer, adhesiveness with this transparent conductive layer can be improved.
Here, the type of the leveling agent is not particularly limited, and examples thereof include fluorine-based and silicone-based ones.
In addition, it is more preferable that it is a silicone type leveling agent which is comparatively cheap and fully exhibits leveling property.

Moreover, it is preferable to mix | blend (C) leveling agent with the value within the range of 0.01-5 weight part with respect to 100 weight part of (A) energy-beam curable resin.
This is because, when the leveling agent is set to a value within such a range, when an antireflection film or the like is formed on the hard coat layer, adhesion with the antireflection film can be improved. .
More specifically, when the amount of the leveling agent is less than 0.01 parts by weight, it may be difficult to make the hard coat layer surface uniform.
On the other hand, when the amount of the leveling agent exceeds 5 parts by weight, the scratch resistance may be insufficient or the antiblocking property may be lowered.
Therefore, the blending amount of the leveling agent (D) is more preferably set to a value within the range of 0.02 to 3 parts by weight, and further preferably set to a value within the range of 0.05 to 2 parts by weight.

(4) Other additives In addition, other additives can be appropriately contained within a range not impairing the effects of the present invention.
Examples of other additives include an antioxidant, an ultraviolet absorber, an antistatic agent, a polymerization accelerator, a polymerization inhibitor, an infrared absorber, a plasticizer, and a diluent solvent.
In addition, it is preferable to make content of other additives into the value within the range of 0.01-5 weight part with respect to 100 weight part of (A) energy beam curable resin generally, and 0.02-3 weight The value is more preferably in the range of parts by weight, and more preferably in the range of 0.05 to 2 parts by weight.

(5) Thickness Moreover, it is preferable to make thickness of the hard-coat layer 12 illustrated by FIG. 1 into the value within the range of 1-10 micrometers.
The reason for this is that if the thickness of the hard coat layer is a value within such a range, a hard coat film having excellent scratch resistance can be obtained and suitable optical characteristics of the hard coat film can be maintained. Can do.
Further, if the thickness of the hard coat layer is less than 1 μm, the scratch resistance may be remarkably lowered.
On the other hand, when the thickness of the hard coat layer exceeds 10 μm, curling may increase.
Accordingly, the thickness of the hard coat layer is more preferably set to a value within the range of 1 to 5 μm, and further preferably within the range of 1.5 to 4 μm.

3. Characteristics of Hard Coat Film (1) Surface Roughness of Hard Coat Layer Also, in accordance with JIS B 0601-1994 on the surface of hard coat layers 12 and 12 ′ exemplified in FIGS. It is preferable that the arithmetic average roughness (Ra) measured in this manner is a value in the range of 1.5 to 15 nm.
This is because when the arithmetic average roughness (Ra) is less than 1.5 nm, it may be difficult to prevent so-called blocking, in which hard coat films adhere to each other.
On the other hand, when the arithmetic average roughness (Ra) is a value exceeding 15 nm, the light transmittance may be remarkably lowered.
Accordingly, the arithmetic average roughness (Ra) on the surface of the hard coat layer is more preferably a value within the range of 2.0 to 10 nm, and further preferably a value within the range of 2.5 to 8 nm. .

(2) Pencil Hardness of Hard Coat Layer The pencil hardness measured according to JIS K 5600-5-4 on the surface of the hard coat layer exemplified in FIGS. 1A to 1B is HB or more. It is preferable.
The reason for this is that when the pencil hardness is less than HB, the scratch resistance may be insufficient when the hard coat film is provided on the outermost surface of the image display device or the outermost surface of the printed material. Because there is.

(3) Haze value of hard coat film Moreover, the haze value measured based on JISK7105 of the hard coat film 20 illustrated by Fig.1 (a)-(b) is a value of 25.0% or less. It is characterized by being.
The reason for this is that when the haze value exceeds 25.0%, when the hard coat film is provided on the outermost surface of the image display device or the outermost surface of the printed material, the visibility is excessively lowered. It is because there is a case to do.
Moreover, when the haze value of a hard coat film is 1.0% or less, it can utilize as transparent conductive films, such as a capacitive touch panel. On the other hand, if the haze value is in the range of 1.0 to 25.0%, by providing it on the outermost surface of the image display device or the printed material, dirt (such as fingerprints) can be made inconspicuous or reflected. It is possible to demonstrate the function of preventing jamming.

[Second Embodiment]
2nd Embodiment is a manufacturing method of the hard coat film provided with the hard coat layer on the at least single side | surface of the base film, Comprising: The following process (1)-(3) is included, The hard coat film characterized by the above-mentioned. It is a manufacturing method.
(1) At least (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound, and (a1) a polyfunctional (meth) acrylate compound And (a2) an energy ray-curable resin in which the content weight ratio of (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is in the range of 100: 0 to 20:80 And (A) (B) a hydrophobized silica sol having a value in the range of 0.3 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of the energy ray curable resin, a hard coat layer forming material is prepared. Step (2) A step of applying a hard coat layer forming material to at least one surface of the base film (3) Curing the hard coat layer forming material, and (B) Hydrophobized silica gel The step of forming a hard coat film comprising a hard coat layer segregated on the surface of the hard coat layer opposite to the base film is hereinafter referred to as the first about the base film and hard coat layer to be used. Since it can be set as the content similar to embodiment of this, it demonstrates centering on the matter regarding the manufacturing method of a hard coat film.

(1) Step 1: Preparation step of hard coat layer forming material Step (1) is 0 in terms of solid content with respect to at least (A) energy beam curable resin and (A) 100 parts by weight of energy beam curable resin. A step of preparing a hard coat layer forming material containing (B) a hydrophobized silica sol having a value within the range of 3 to 55 parts by weight.
More specifically, this is a step of uniformly mixing the above-mentioned hard coat layer forming material and the diluting solvent.
Examples of the solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, pentyl alcohol, ethyl cellosolve, benzene, toluene, xylene, ethylbenzene, cyclohexane, ethylcyclohexane, ethyl acetate, Examples include butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, propylene monomethyl ether, and water, and two or more solvents may be combined.
In particular, since energy ray curable resins such as acrylic monomers can be easily dissolved, propylene monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, n-butyl acetate, cyclohexanone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, It is preferable to use n-butyl alcohol, isobutyl alcohol, pentyl alcohol or the like.
In addition, about the structure of a predetermined | prescribed hard-coat layer forming material, since it is as having already described, it abbreviate | omits.

(2) Step 2: Step of applying hard coat layer forming material to base film Step (2) is a step of applying the hard coat layer forming material to at least one side of the base film.
More specifically, the base film 10 is prepared, and the hard coat layer forming material adjusted in the step (1) is prepared on the hard coat layer having a thickness of 1 to 10 μm after curing. It is the process of coating so that it becomes.
The coating method of the hard coat layer forming material is not particularly limited, and known methods such as a bar coating method, a gravure coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, etc. Can be used.

(3) Step 3: curing step In step (3), the hard coat layer forming material is cured, and (B) the hydrophobized silica sol segregates on the surface of the hard coat layer opposite to the base film. Forming a hard coat film having a hard coat layer.
More specifically, it is preferable to cure the coated material of the hard coat layer forming material from which the solvent has been evaporated through a drying process by irradiating it with an energy beam, for example, an ultraviolet ray or an electron beam.
By carrying out in this way, the hard coat layer can be formed quickly and can be firmly adhered to the base film, and the hydrophobized silica sol can be applied to the surface of the hard coat layer opposite to the base film. This is because segregation can be effectively performed.
Therefore, it is possible to improve the mechanical strength of the hard coat layer and to effectively prevent the hard coat films from being pressed against each other.

In forming the hard coat layer, for example, when ultraviolet rays are irradiated, it is preferable to set the irradiation amount (integrated light amount) to the hard coat layer forming material to a value within the range of 100 to 1000 mJ / cm ² .
The reason for this is that the hard coat layer may be insufficiently cured when the ultraviolet irradiation amount is less than 100 mJ / cm ² .
On the other hand, when the ultraviolet irradiation amount exceeds 1000 mJ / cm ² , the hard coat layer and the substrate film may be deteriorated by the ultraviolet rays.
In addition, there is no restriction | limiting in particular about the kind of energy beam irradiation apparatus to be used, For example, the ultraviolet irradiation apparatus using a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fusion H lamp etc. can be used.
(4) Step 4: Step of forming a hard coat layer on the other surface of the base film In step (4), the hard coat layer 12 is applied to one surface of the base film 10 as shown in FIG. After the formation, the hard coat layer 12 'is formed on the other surface of the base film.
That is, after forming a hard coat layer on one surface of the above-mentioned base film, the hard coat layer forming material is applied to the other side of the base film in the same manner, and cured to form both sides of the base film. Is a step of forming a hard coat layer.
In addition, since the application process and the curing process are the same as described above, the details are omitted.

[Third embodiment]
3rd Embodiment is a hard coat film for printed matter surface protection in which the hard coat film mentioned above is used for the outermost surface of printed matter.
Hereinafter, the hard coat film for protecting a printed matter surface will be specifically described with reference to the drawings, focusing on differences from the contents described in the first and second embodiments.
That is, as shown in FIG. 3, the printed matter surface-protecting hard coat film includes the hard coat film 20 having the hard coat layer 12 on at least one side through the pressure-sensitive adhesive layer 40 on the outermost surface of the printed matter 30. .

  The hard coat film for protecting the surface of the printed material of the present embodiment is easy to segregate on the surface of the hydrophobized silica sol contained in the hard coat film. Reflection can be prevented by utilizing internal confusion due to the difference in refractive index between the resin and the hydrophobized silica sol particles.

Here, the printed matter 30 includes general printed matter, ink jet, electrostatic recording, PPC (plain paper copier), or those formed by thermal transfer, paintings, photographs, panels, and the like.
Moreover, there is no restriction | limiting in particular as an adhesive used for the adhesive layer 40, An acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, etc. are preferable. Moreover, what added the ultraviolet absorber and the light stabilizer may be used. Moreover, it is preferable that the thickness of an adhesive layer is a value within the range of 5-50 micrometers. Moreover, in order to improve the adhesiveness between the pressure-sensitive adhesive layer and the hard coat film, the hard coat film may be subjected to corona treatment or the like.

[Fourth Embodiment]
The fourth embodiment is an image display device in which the above-described hard coat film is used on the outermost surface of the image display device.
Hereinafter, an image display device provided with a hard coat film on the outermost surface will be specifically described with reference to the drawings, focusing on differences from the contents described in the first and second embodiments.

  Examples of the image display device include a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, electronic paper, and the like. Is mentioned.

As an image forming apparatus, for example, as shown in FIG. 4, the liquid crystal display 100 has a protective film 102 and a polarizing element 104 from the light source side (the figure, the lower side) toward the observer side (the figure, the upper side). The retardation film 106, the adhesive layer 108, the liquid crystal cell 110, the adhesive layer 108 ', the retardation film 106', the polarizing element 104 ', and the hard coat film 20 are laminated in this order. Further, although not shown, another layer such as an antireflection layer may be further laminated on the hard coat film.
The liquid crystal cell is provided with a liquid crystal layer, an alignment film, an electrode layer, a color filter, and the like between two glass substrates.

  Here, examples of the protective film 102 include a triacetyl cellulose film (TAC film), and examples of the retardation films 106 and 106 ′ include a triacetyl cellulose film or a cycloolefin polymer film. Examples of the adhesive constituting the adhesive layers 108 and 108 ′ include a pressure sensitive adhesive.

  Examples of the polarizing elements 104 and 104 ′ include a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, and an ethylene-vinyl acetate copolymer saponified film. When laminating the base material of the hard coat film and the polarizing element, it is preferable to saponify the base material in advance in order to obtain adhesion and an antistatic effect.

  The hard coat film mounted on the image display device according to the present embodiment is easily segregated on the surface of the hydrophobized silica sol contained in the hard coat film. Reflection can be prevented by utilizing internal confusion caused by the difference in refractive index between the resin constituting the resin and the hydrophobized silica sol particles.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.

[Example 1]
1. Preparation of hard coat film (1) Preparation step of hard coat layer forming material As shown in Table 1, (A) energy ray curable resin as component, (B) hydrophobized silica sol as component, (D) The hard coat layer forming material of Example 1 was prepared from a photopolymerization initiator as a component and a leveling agent as a component (C).
More specifically, as the component (A), (a1) pentaerythritol triacrylate (NK ester, Shin-Nakamura Chemical Co., Ltd., A-TMM-3L) 200 parts by weight, (D) photopolymerization initiator ( Ciba Specialty Chemicals, Irgacure 184) 10 parts by weight, (B) Hydrophobized silica sol A (CIK Nanotech, SIRPGGM15WT% -E26, average particle size 30 nm) 0.8 parts by weight, (C) Diluted with 0.1 part by weight of leveling agent (SH-28 manufactured by Toray Dow Corning Co., Ltd.) as an ingredient and 492.1 parts by weight of propylene monomethyl ether as a diluent solvent, a hard coat layer forming material (solid content concentration 30 weight) %) Was adjusted.

(2) Hard coat layer forming material coating step Next, the hard coat layer forming material is used as a base film, and a PET film with an easy adhesion layer on both surfaces subjected to an easy adhesion treatment (Toray Industries, Lumirror U48, film) The film was applied to one side having a thickness of 100 μm using a Meyer bar so that the film thickness after drying was 3 μm.

(3) Drying step Next, the diluent solvent contained in the hard coat layer forming material applied to the base film was removed.
That is, using a hot air drying apparatus, it was heated and dried at 70 ° C. for 1 minute to sufficiently remove the diluted solvent.

(4) Curing Step Next, using a high-pressure mercury lamp, ultraviolet rays were irradiated at 300 mJ / cm ² to photocur the hard coat layer forming material to obtain a hard coat film.
Although not shown, the cross section of the hard coat film produced in Example 1 was accelerating voltage 10 kV and magnification 20,000 times using a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd., S-4700 type). As a result, it was confirmed that the hydrophobized silica sol was segregated on the surface of the hard coat layer opposite to the base film.

2. Evaluation of Hard Coat Film (1) Hydrophobic Degree Measurement Hydrophobized silica sol A (solid content concentration 15%) dispersed in methyl isobutyl ketone is applied to a Meyer bar # on PET film (Toray Industries, Lumirror U48, film thickness 100 μm). 8 was applied.
Subsequently, it was dried in an oven at 90 ° C. for 1 minute to obtain a silica sol coating film having a thickness of 1 μm after drying.
Next, the contact angle of water with the silica sol coating film was measured to evaluate the degree of hydrophobicity.
That is, a PET film on which a silica sol coating film is formed on a flat glass substrate is allowed to stand, and when the inclination of the glass substrate is 0 degree, 2 μL of a water droplet is dropped, and when the droplet is stationary, Young's formula The water contact angle was determined. The obtained results are shown in Table 1.

(2) Pencil hardness evaluation The pencil hardness of the obtained hard coat film was measured using a pencil scratch hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) according to JIS K 5600-5-4. The scratching speed was 1 mm / second. The obtained results are shown in Table 1.

(3) Evaluation of blocking resistance The obtained hard coat film was cut into a size of 100 × 100 mm, and two hard coat films were superposed (this state is assumed to be initial).
Then, after applying the load of 10 kg / m ² for 5 days in the initial storage environment at 23 ° C. and 50% RH (this state is assumed to be after the lapse of time), the stacked films were placed under a fluorescent lamp. And the state was visually observed, and the presence or absence of blocking was evaluated according to the following criteria. The obtained results are shown in Table 1.
○: Even at the initial stage and after the passage of time, no blocking occurred and no sticking between the film surfaces occurred. Δ: Although no blocking occurred at the beginning, the blocking occurred after the passage of time ( The sticking area between the film surfaces is 30% or more.)
X: Blocking has occurred from the beginning (the sticking area between the film surfaces is 30% or more).

(4) Haze value The haze value of the obtained hard coat film was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7105. The obtained results are shown in Table 1.

(5) Adhesiveness A cross-cut peel test was performed as an adhesive evaluation of the obtained hard coat film.
That is, using a cutter knife on the surface of the hard coat layer of the hard coat film, cut 11 squares and 11 horizontal cuts in a grid pattern at intervals of 1 mm, and carve an adhesive tape ( Made of Nichiban Co., “cello tape (registered trademark)” was pasted, and in accordance with JIS K 5600-5-6 (cross-cut method) cross-cut tape method, a cello tape (registered trademark) peel test was performed, and the following criteria were used. The adhesion of the hard coat layer was evaluated, and the results obtained are shown in Table 1.
A: No peeling at all O: Although peeling occurred slightly, the peeled area was less than 10%.
Δ: Peeling occurs, and the peeled area is 10% or more and less than 50%.
X: An area of 50% or more was peeled off.

(6) scratch resistance resulting hard coat layer surface of the hard coat film, a # 0000 steel wool under a load of 100 g / cm ² and 200 g / cm ^2, a 10cm length of the wound when the 10 reciprocally The presence or absence was evaluated according to the following criteria. The obtained results are shown in Table 1.
A: No damage even after 10 reciprocations at a load of 200 g / cm ² .
○: No damage even after 10 reciprocations at a load of 100 g / cm ² .
×: Scratched after 10 reciprocations with a load of 100 g / cm ² .

[Example 2]
In Example 2, a hard coat film was prepared and evaluated in the same manner as in Example 1 except that the amount of (B) the hydrophobized silica sol A was 2.7 parts by weight. The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 2 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a substrate of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Example 3]
In Example 3, as (A) energy beam curable resin, (a1) 100 parts by weight of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester, A-TMM-3L) and (a2) dipentaerythritol Hexaacrylate (EO 12 mol adduct) (Shin Nakamura Chemical Co., Ltd., A-DPH-12E) 100 parts by weight, and (B) component, Hydrophobized Silica Sol B (CIK Nanotech Co., SIRMIBK 15WT%- E83, average particle size 30 nm) A hard coat film was prepared and evaluated in the same manner as in Example 1 except that 2.7 parts by weight were blended. The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 3 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a substrate of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Example 4]
In Example 4, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 22.5 parts by weight of hydrophobized silica sol A was blended as the component (B). The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 4 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a base material of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Example 5]
In Example 5, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 50 parts by weight of hydrophobized silica sol A was blended as the component (B). The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 5 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a base material of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Example 6]
In Example 6, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 60 parts by weight of hydrophobized silica sol A was blended as the component (B). The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 6 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a substrate of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Example 7]
In Example 7, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 80 parts by weight of the hydrophobized silica sol A was blended as the component (B). The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 7 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a substrate of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Example 8]
In Example 8, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 100 parts by weight of the hydrophobized silica sol A was blended as the component (B). The obtained results are shown in Table 1.
Although not shown, when the cross section of the hard coat film produced in Example 8 was photographed with a scanning electron microscope (SEM) in the same manner as in Example 1, the hydrophobized silica sol was a base material of the hard coat layer. It was confirmed that segregation occurred on the surface opposite to the film.

[Comparative Example 1]
In Comparative Example 1, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 120 parts by weight of hydrophobic silica sol A was added as the component (B). The obtained results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 2, a hard coat film was prepared and evaluated in the same manner as in Example 3 except that 180 parts by weight of hydrophobic silica sol A was added as the component (B). The obtained results are shown in Table 1.

[Comparative Example 3]
In Comparative Example 3, as (A) energy beam curable resin, (a1) 25 parts by weight of pentaerythritol triacrylate (A-TMM-3L) and (a2) dipentaerythritol hexaacrylate (EO 12 mol adduct) (A- A hard coat film was prepared and evaluated by the same method as in Example 6 except that 175 parts by weight of DPH-12E) was blended. The obtained results are shown in Table 1.

[Comparative Example 4]
In Comparative Example 4, as the component (B), except that 5.4 parts by weight of silica sol I (manufactured by CIK Nanotech, SIRMIBK15WT% -K18, average particle size 100 nm) was blended, the same method as in Example 3, A hard coat film was created and evaluated. The obtained results are shown in Table 1.

[Comparative Example 5]
In Comparative Example 5, a hard coat film was prepared by the same method as Comparative Example 4 except that silica sol J (manufactured by JGC Catalysts, OSCAL-1632, average particle size 30 nm) was used as the component (B). ,evaluated. The obtained results are shown in Table 1.

[Comparative Example 6]
In Comparative Example 6, a hard coat film was prepared by the same method as Comparative Example 4 except that silica sol K (manufactured by Nissan Chemical Industries, MIBK-ST, average particle size 15 nm) was used as the component (B). And evaluated. The obtained results are shown in Table 1.

[Comparative Example 7]
In Comparative Example 7, a hard coat film was prepared in the same manner as in Comparative Example 4 except that silica sol D (CIR Nanotech, SIRMIBK-E65, average particle size 100 nm) was used as the component (B). ,evaluated. The obtained results are shown in Table 1.

Examples 1 to 5 using a relatively small amount of a predetermined hydrophobized silica sol do not cause blocking between films, have a haze value of 1.0% or less, and also have scratch resistance. Could get.
Further, in Examples 6 to 8 using a relatively large amount of a predetermined hydrophobized silica sol, the haze value was 1.0% or more, but the blocking resistance and adhesion were good. A hard coat film having excellent properties could be obtained.
On the other hand, Comparative Examples 1 and 2 in which the hydrophobized silica sol was excessively blended were able to prevent blocking between the films, but the results were inferior in transparency and inferior in adhesion and scratch resistance. It was.
Moreover, the comparative example 3 which made the compounding quantity of (a2) excessive was inferior in blocking resistance, adhesiveness, and abrasion resistance, and predetermined | prescribed hardness was not obtained.
In Comparative Examples 4 to 7 using a silica sol having no predetermined contact angle, that is, having a hydrophilic surface, it was difficult to prevent blocking between films with a small addition amount.

As described above in detail, according to the hard coat film of the present invention, the hard coat film includes a hard coat layer on at least one surface of the base film, and the hard coat layer includes a predetermined energy curable resin and It consists of a cured product of a hard coat layer forming material containing a predetermined hydrophobized silica sol, etc., and the hydrophobized silica sol is segregated on the surface on the opposite side of the base film in the hard coat layer. Thus, a hard coat film excellent in adhesion and scratch resistance can be obtained.
In addition, a hard coat film containing a relatively small amount of a predetermined hydrophobized silica sol is particularly excellent in transparency, so that it can be used as a transparent conductive film and can be effectively mounted on a capacitive touch panel or the like.
In addition, a hard coat film containing a relatively large amount of a predetermined hydrophobized silica sol is particularly excellent in scratch resistance, and therefore is expected to be suitably used for the outermost surface of a printed matter or an image display device.

10: Base film 11: Adhesive layer (for measurement)
12, 12 'hard coat layer 16: hydrophobized silica sol 18: hydrophilic silica sol 20: hard coat film 30: printed matter 40: adhesive layer 50: printed matter provided with a hard coat film 100: image display device 102: protective film 104, 104 ': Polarizing elements 106, 106': Retardation films 108, 108 ': Adhesive layer 110: Liquid crystal cell

Claims (8)

A hard coat film provided with a hard coat layer on at least one side of a base film,
The hard coat layer comprises a cured product of a hard coat layer forming material containing at least (A) an energy ray curable resin and (B) a hydrophobized silica sol,
The (A) energy beam curable resin contains (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound, The weight ratio of the polyfunctional (meth) acrylate compound and the (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is a value within the range of 100: 0 to 20:80. ,
The blending amount of the (B) hydrophobized silica sol is a value in the range of 0.3 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of the (A) energy beam curable resin,
The hard coat film, wherein the (B) hydrophobized silica sol is segregated on the surface of the hard coat layer after the hard coat layer forming material is cured, on the side opposite to the base film.   2. The hard coat film according to claim 1, wherein the average particle diameter of the (B) hydrophobized silica sol is a value within a range of 10 to 100 nm.   The hard coat film according to claim 1 or 2, wherein a contact angle of water with respect to the coating film when the (B) hydrophobized silica sol is used as a coating film is set to a value of 100 ° or more.   The hard coat film according to any one of claims 1 to 3, wherein the hard coat layer forming material further comprises (C) a leveling agent.   The arithmetic average roughness Ra measured in accordance with JIS B 0601-1994 on the surface of the hard coat layer is a value in the range of 1.5 to 15 nm, any one of claims 1 to 4 The hard coat film according to claim 1.   A hard coat film for surface protection of printed matter, wherein the hard coat film according to any one of claims 1 to 5 is used on the outermost surface of the printed matter.   An image display device, wherein the hard coat film according to any one of claims 1 to 5 is used on an outermost surface of the image display device. A method for producing a hard coat film comprising a hard coat layer on at least one side of a base film,
The manufacturing method of the hard coat film characterized by including following process (1)-(3).
(1) at least (a1) a polyfunctional (meth) acrylate compound and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound, The content weight ratio of the compound to the (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound is a value within the range of 100: 0 to 20:80. Hard coat layer forming material comprising resin and (B) hydrophobized silica sol having a value in the range of 0.3 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of (A) energy ray curable resin (2) applying the hard coat layer forming material to at least one side of the base film (3) curing the hard coat layer forming material And (B) a step of forming a hard coat film comprising the hard coat layer in which the hydrophobized silica sol is segregated on the surface of the hard coat layer opposite to the base film.