CN104822522B

CN104822522B - Hard coat film and transparent and electrically conductive film

Info

Publication number: CN104822522B
Application number: CN201380061679.9A
Authority: CN
Inventors: 丰岛裕; 前田清成; 土本达郎
Original assignee: Toray Advanced Film Co Ltd
Current assignee: Toray Advanced Film Co Ltd
Priority date: 2012-11-27
Filing date: 2013-11-06
Publication date: 2017-03-08
Anticipated expiration: 2033-11-06
Also published as: TWI608937B; JP5528645B1; CN104822522A; TW201425035A; WO2014084008A1; KR20150048927A; KR101563564B1; JPWO2014084008A1

Abstract

A kind of hard coat film, it is characterised in that possess the 1st hard conating containing particle at least one side of base material film, the projection formed by the particle is with per 100 μm²It is present in the surface of the 1st hard conating for the density of 300～4000, the center line average roughness (Ra1) of the 1st hard coating surface is less than 30nm, and haze value is less than 1.5%.The present invention provides a kind of high and good hard coat film of sliding and resistance to adhesive of the transparency.

Description

Hard coat film and transparent and electrically conductive film

Technical field

The present invention relates to the high and good hard coat film of sliding and resistance to adhesive of the transparency, more specifically, is related to be suitable for Hard coat film in transparent and electrically conductive film.

Background technology

Hard coat film (which is that laminated hard conating is formed on base material film) be used as display, the surface protection of touch panel, Or the touch panel basilar memebrane of electrode film (for the transparent and electrically conductive film of touch panel).For for the hard of such use For film, it is desirable to which the transparency is high, and sliding and resistance to adhesive good.

For the sliding for improveing hard coat film or polyester film, resistance to adhesive, it is proposed that the scheme for arranging projection on surface is (special Sharp document 1,2).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 7-314628 publication

Patent document 2：Japanese Unexamined Patent Publication 2000-211082 publication

Content of the invention

However, using the technology disclosed in above-mentioned patent document, failing to reach while fully meeting the transparency, sliding And the effect of resistance to adhesive.

Therefore, it is an object of the invention to, in view of the problem that above-mentioned prior art is present, provide a kind of transparency high and The good hard coat film of sliding and resistance to adhesive.Another object of the present invention is to providing the hard painting suitable for transparent and electrically conductive film Film.

The above-mentioned purpose of the present invention can be by following 1)～15) in arbitrary composition reaching.

1) a kind of hard coat film, it is characterised in that possess the 1st hard conating containing particle at least one side of base material film, The projection formed by the particle is with per 100 μm²It is present in the surface of the 1st hard conating for the density of 300～4000, the 1st is hard The center line average roughness (Ra1) of coating surface is less than 30nm, and haze value is less than 1.5%.

2) as 1) as described in hard coat film, wherein, the average grain diameter (r) of the particle is 0.05～0.5 μm.

3) as 1) or 2) as described in hard coat film, wherein, the average grain diameter (r) of the particle is with respect to the thickness of the 1st hard conating The ratio (r/d) of degree (d) is 0.01～0.30.

4) as 1)～3) any one of hard coat film, wherein, the average diameter of the projection is 0.03～0.3 μm, The average height of the projection is 0.03～0.3 μm.

5) as 1)～4) any one of hard coat film, wherein, the equispaced of the projection is 0.10～0.70 μm.

6) as 1)～5) any one of hard coat film, wherein, the thickness (d) of the 1st hard conating is more than 0.5 μm and little In 10 μm.

7) as 1)～6) any one of hard coat film, wherein, with resin bed between base material film and the 1st hard conating, The thickness of the resin bed is 0.005～0.3 μm and contains particle that the average grain diameter of the particle is the 1.3 of resin layer thickness More than times.

8) as 1)～7) any one of hard coat film, wherein, base material film be polyethylene terephthalate film, base Possesses the resin bed that refractive index is 1.55～1.61 between material film and the 1st hard conating.

9) as 1)～8) any one of hard coat film, wherein, between base material film and the 1st hard conating, possess wetting tension Resin bed for below 52mN/m.

10) as 9) as described in hard coat film, wherein, the thickness of the 1st hard conating is less than 2 μm.

11) as 1)～10) any one of hard coat film, wherein, the particle that contains in the 1st hard conating be selected from reality Applied the inorganic particulate of surface treatment for reducing the surface free energy of particle and the surface of particle have passed through silicic acid anhydride Inorganic particulate composition group at least a kind.

12) as 11) as described in hard coat film, wherein, for obtaining the surface free energy that implemented for reducing particle Surface treatment inorganic particulate surface treatment be following (I) or (II).

(I) using the organic silane compound containing fluorine atom represented selected from following formula (1), the organosilan Hydrolysate and the organosilan hydrolysate partial condensate composition group at least a kind of compound carry out surface Process.

C_nF_2n+1-(CH₂)_m-Si(Q)₃Formula (1)

(in formula (1), n represents 1～10 integer, and m represents 1～5 integer.Q represents the alcoxyl that carbon number is 1～5 Base or halogen atom.)

(II) compound represented using following formulas (2) is processed, and then the fluorination represented using following formulas (3) Compound is surface-treated.

B-R⁴-SiR⁵ _n(OR⁶)_3-nFormula (2)

D-R⁷-Rf²Formula (3)

(in formula (2) and (3), B and D represents reactive moieties, R independently of one another⁴And R⁷Represent that carbon is former independently of one another Subnumber is 1～3 alkylidene or the ester structure derived by the alkylidene, R⁵And R⁶Represent hydrogen or carbon atom independently of one another Number is 1～4 alkyl, Rf²Represent fluoroalkyl, n represents 0～2 integer.)

13) as 11) as described in hard coat film, wherein, in silicic acid anhydride spendable hydrophobic compound be selected from tool Have the fluoroalkyl that reactive moieties and carbon number are more than 4 fluorine compounds, with reactive moieties and carbon number be 8 with On alkyl long-chain hydrocarbon compound and with siloxy group and reactive moieties silicone compounds composition group in extremely Few a kind compound, the silicic acid anhydride is the inorganic particulate that have passed through silicic acid anhydride in order to obtain the particle surface And carry out.

14) as 1)～13) any one of hard coat film, wherein, the particle that contains in the 1st hard conating is silica Particle.

15) as 1)～14) any one of hard coat film, wherein, the base material film be provided with the 1st hard conating The contrary face in face on possess the 2nd hard conating, the surface of the 2nd hard conating is created substantially absent the projection formed by particle, and the 2nd The center line average roughness (Ra2) of hard coating surface is below 25nm.

16) a kind of transparent and electrically conductive film, wherein, in above-mentioned 1)～15) any one of hard coat film at least one side On possess nesa coating.

In accordance with the invention it is possible to provide a kind of high and good hard coat film of sliding and resistance to adhesive of the transparency.The present invention Hard coat film be applied to transparent and electrically conductive film basilar memebrane.

Description of the drawings

Fig. 1 is an example of the observation figure of the 1st hard coating surface that is observed with scanning electron microscope.

Fig. 2 be medelling represent the 1st hard coating surface projection flat shape figure.

Fig. 3 is the ideograph of the 1st hard coating surface of medelling earth's surface diagram 1.

Fig. 4 is the ideograph for the part for eliminating Fig. 3.

Specific embodiment

The hard coat film that an embodiment of the invention is related to, has the 1st hard conating at least one side of base material film.Should 1st hard conating contains particle, has per 100 μm on the surface of the 1st hard conating²For the prominent of 300～4000 caused by particle Rise (below, sometimes referred to simply as " projection ").The center line average roughness (Ra1) of the 1st hard coating surface is less than 30nm.As above The haze value of the hard coat film of described present embodiment is less than 1.5%.

On the surface of the 1st hard conating with (100 μm of the per unit area of the 1st hard coating surface²) it is the number of 300～4000 Measurer has projection, and thus sliding and resistance to adhesive become good.

The ranging preferably from per 100 μm of the individual number density of projection²The scope of 400～3500, more preferably 500～ The scope of 3000, the scope of more preferably 600～3000, the scope of particularly preferably 700～2500.

The individual number density of particle is less than per 100 μm²When 300, sliding, resistance to adhesive reduce.On the other hand, particle Individual number density be more than per 100 μm²When 4000, the flatness of the 1st hard coating surface reduces, and haze value becomes big, hard coat film The transparency reduces.

One feature of the hard coat film of present embodiment is：Although having in the 1st hard coating surface as mentioned above more prominent Rise, but the 1st hard coating surface is still more smoothed, and the haze value of hard coat film is little.Specifically, the 1st in present embodiment is hard The center line average roughness (Ra1) of coating surface is less than 30nm, and the haze value of hard coat film is important less than 1.5%.

The center line average roughness (Ra1) of the 1st hard coating surface preferably below 25nm, more preferably below 20nm, Particularly preferably below 18nm.From from the viewpoint of guarantee sliding and resistance to adhesive, under center line average roughness (Ra1) Limit is preferably more than 5nm, more preferably more than 7nm, particularly preferably more than 9nm.

When the center line average roughness (Ra1) of the 1st hard coating surface is more than 30nm, flatness reduces, hard coat film The transparency reduces.That is, the haze value of hard coat film becomes big.

From from the viewpoint of realize high transparent, the haze value of the hard coat film of present embodiment is important less than 1.5%. The haze value of the hard coat film of present embodiment more preferably less than 1.1%, more preferably less than 1.0%.Under haze value Limit is more little more preferred, but is 0.01% or so in practice.

In order to have per 100 μm in the 1st hard coating surface²For the projection of 300～4000, and make the 1st hard coating surface Center line average roughness (Ra1) be less than 30nm, and make the haze value of hard coat film less than 1.5%, it is preferable that make the 1st hard Coating contains the particle that average grain diameter (r) is 0.05～0.5 μm, and makes the particle more be present in the surface of the 1st hard conating Near, thus projection is formed in the 1st hard coating surface.

Further, the average grain diameter (r) (μm) of the particle for containing in the 1st hard conating and the thickness (d) (μm) of the 1st hard conating Ratio (r/d) is preferably 0.01～0.30.Thus, the center line average roughness (Ra1) of the 1st hard coating surface diminishes, hard painting The haze value of film also diminishes.

Hereinafter, each inscape to constituting hard coat film is described in detail.

[base material film]

Base material film is preferably using plastic foil.As the material for constituting base material film, such as poly terephthalic acid second can be enumerated The polyester such as diol ester (PET), PEN (PEN), polyimides, polyphenylene sulfide, aromatic polyamides, poly- third Alkene, polyethylene, PLA, polyvinyl chloride, Merlon, polymethyl methacrylate, ester ring type acrylic resin, cycloolefin tree Fat, cellulose triacetate (triacetylcellulose) and by material obtained by these mixed with resin and/or copolymerization.Can So that above-mentioned resin is made film in an unstretched state or after being stretched uniaxially or biaxially, it is used in combination Make base material film.

In above-mentioned base material film, the transparency of polyester film, dimensional stability, mechanical property, heat resistance, electrical characteristics, chemically-resistant Medicine etc. is excellent, can be particularly preferably using polyethylene terephthalate film (PET film).

With regard to the scope of base material film thickness, 20～300 μm of scope is appropriate, preferably 30～200 μm of scope, More preferably 50～150 μm of scope.

It is preferred that with resin bed as follows on the face of at least laminated 1st hard conating of base material film.That is, base material film with It is preferred with resin bed as follows between 1st hard conating.

[resin bed]

In order to strengthen the adaptation of base material film and the 1st hard conating, arrange in the face of at least laminated 1st hard conating of base material film It is preferred to have resin bed.

Resin bed is the layer containing resin as main component.Specifically, resin bed is containing with respect to resin bed 100 mass % of solid state component total amount is the layer of the resin of more than 50 mass %.As the resin for forming resin bed, polyester can be enumerated Resin, acrylic resin, polyurethane resin, polycarbonate resin, epoxy resin, alkyd resin, urea resin etc..These resins Can be used alone or and planted with plural number.

Resin bed is present between base material film and the 1st hard conating, from the sight of the adaptation for improving base material film and the 1st hard conating Point consideration, containing as resin selected from least a kind in the group of polyester resin, acrylic resin and polyurethane resin composition is Preferably.Particularly preferably resin bed is at least containing polyester resin as resin.

The content of the resin in resin bed is 60 mass % preferably with respect to 100 mass % of solid state component total amount of resin bed Above, it is more preferably more than 70 mass %, is particularly preferably more than 80 mass %.With regard to the upper limit, the containing of the resin in resin bed Amount is preferably below 95 mass %, is more preferably below 90 mass %.

Additionally, resin bed can also be constituted formation with bilayer.During for double-deck composition, from base material film side successively by the 1st resin It is preferred that layer (with polyester resin as main component) and the 2nd resin bed (with acrylic resin as main component) are constituted.With regard to Double-deck composition, will be explained below.

From guarantee the sliding of appropriateness of the hard coat film in manufacturing process, windability from the viewpoint of, resin bed preferably contains There is particle.

As the particle contained in resin bed, be not particularly limited, can enumerate silicon dioxide granule, titanium oxide, aluminum oxide, The inorganic particulates such as zirconium oxide, calcium carbonate, zeolite particles, acrylic particles, organic silicon particle, polyimide particle, Teflon (note Volume trade mark) organic filler such as particle, cross-linked polyester particle, crosslinked polystyrene particle, cross-linking polymer particle, core-shell particles. Wherein, preferred silicon dioxide granule, particularly preferred cataloid.

The average grain diameter of the particle contained in resin bed is preferably greater than the thickness of resin bed.Specifically, average grain diameter is excellent Elect resin layer thickness as more than 1.3 times, more preferably more than 1.5 times, particularly preferably more than 2.0 times.The upper limit is preferably 20 Below times, it is more preferably less than 15 times, particularly preferably less than 10 times.

By directly the laminated 1st on the resin bed containing above-mentioned such average grain diameter more than the particle of the thickness of resin bed Hard conating, sliding and resistance to adhesive are improved further.

The average grain diameter of the particle contained in resin bed can be suitably selected according to the design of the thickness of resin bed, specifically, The scope for ranging preferably from 0.02～1 μm of average grain diameter, more preferably 0.05～0.7 μm of scope, particularly preferably 0.1～ 0.5 μm of scope.When average grain diameter is less than 0.02 μm, there is the situation that sliding, resistance to adhesive reduce.Average grain diameter is more than 1 μ During m, exist particle come off, the transparency reduce or deteriorated appearance situation.

The scope for ranging preferably from 0.005～0.3 μm of the thickness of resin bed.When the thickness of resin bed is less than 0.005 μm, The adaptation of base material film and the 1st hard conating reduces.Additionally, when the thickness of resin bed goes above 0.3 μm, laminated 1st hard conating Resistance to adhesive afterwards reduces sometimes.More preferably more than 0.01 μm of the thickness of resin bed, be more preferably more than 0.015 μm, Particularly preferably more than 0.02 μm.With regard to the upper limit, the thickness of resin bed be preferably less than 0.25 μm, be more preferably less than 0.2 μm, Particularly preferably less than 0.15 μm.When there is plural layer resin bed, by value satisfaction obtained by the thickness total of all resin beds It is preferred to state thickness condition.

The scope of the content of the particle in resin bed preferably with respect to 100 mass % of solid state component total amount of resin bed is The scope of the scope of 0.05～10 mass %, the more preferably scope of 0.1～8 mass %, particularly preferably 0.5～5 mass %. When the content of the particle in resin bed is less than 0.05 mass %, good sliding, resistance to adhesive can not be obtained sometimes, particle When content is more than 10 mass %, there is transparency reduction, the coating of the 1st hard conating deteriorates or base material film and the 1st hard conating The situation that adaptation reduces.

Resin bed preferably also contains crosslinking agent.Resin bed is preferably the heat cure containing resin and crosslinking agent mentioned above Layer.By making resin bed for heat-cured layer as described above, the adaptation of base material film and the 1st hard conating can be improved further. Condition (heating-up temperature, time) during resin bed heat cure is not particularly limited, but heating-up temperature be preferably more than 70 DEG C, more Preferably more than 100 DEG C, particularly preferably more than 150 DEG C, most preferably more than 200 DEG C.With regard to the upper limit, heating-up temperature is preferably Less than 300 DEG C.The scope for ranging preferably from 5～300 seconds of heat time, the scope of more preferably 10～200 seconds.

As above-mentioned crosslinking agent, such as melamine class crosslinking agent, oxazolines crosslinking agent, carbodiimide class can be enumerated and handed over Connection agent, isocyanates crosslinking agent, aziridine class crosslinking agent, epoxies crosslinking agent, refine through methylolation or alkyl Urea class crosslinking agent, acrylic amide crosslinking agent, polyamide-based resin, amide epoxy compound, various silane couplers, various Titante coupling agent etc..Wherein, preferred melamine class crosslinking agent, oxazolines crosslinking agent, carbodiimide class crosslinking agent, different Cyanate crosslinking agent, aziridine class crosslinking agent, particularly preferred melamine class crosslinking agent.

As melamine class crosslinking agent, such as imino-type methylated melamine resins, methylol type three can be enumerated Cymel, methylol type methylated melamine resins, complete alkyl type methylated melamine resins etc..Wherein, may be used Preferably use imino-type melmac, methylolated melamine resin.

The scope of the content of the crosslinking agent in resin bed preferably with respect to 100 mass % of solid state component total amount of resin bed is The scope of the scope of 0.5～40 mass %, the more preferably scope of 1～30 mass %, particularly preferably 2～20 mass %.

Reflected colour across hard coat film obtained from laminated 1st hard conating of resin bed on base material film is preferably neutral (neutral) colourless tone.Consider from above-mentioned viewpoint, polyethylene terephthalate film (PET is used as base material film Film) when, the refractive index of resin bed range preferably from 1.55～1.61 scope, more preferably 1.56～1.60 scope, spy Not You Xuanwei 1.57～1.59 scope.

The refractive index of polyethylene terephthalate film (PET film) is usually 1.62～1.70 or so, by making resin The refractive index of layer is above range (1.55～1.61), and the reflected colour of hard coat film can be made to be close to the colourless of neutrality.That is, PET film Refractive index (np) and resin bed refractive index (nr) difference (np-nr) preferably in the range of 0.02～0.1, more preferably exist In the range of 0.03～0.09, particularly preferably in the range of 0.04～0.08.

In order that the refractive index of resin bed is 1.55～1.61, the polyester resin conduct containing naphthalene nucleus in molecule is preferably used Resin.Polyester resin containing naphthalene nucleus can be by for example being made using polybasic carboxylic acids such as Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, NDAs Synthesize for copolymer composition.

The scope of the content of the polyester resin containing naphthalene nucleus in the molecule in resin bed is total preferably with respect to all resins Measure scope, the scope of more preferably 10～60 mass % that 100 mass % are 5～70 mass %.

With regard to resin bed, it is preferred that be applied on base material film using wet coating (wet coating method), Heat cure is carried out so as to laminated.It may further be preferable that using so-called online rubbing method, (which is the manufacturing process in base material film The method of interior employing wet coating coating resin layer) it is coated, heat cure is carried out so as to laminated.As wet coating, example can be enumerated As reverse roll rubbing method, spraying process, stick coating method (bar coating method), gravure coating process, bar type rubbing method (rod Coating method), die coating method etc..

As described above, resin bed can be constituted using double-deck.The double-deck resin bed for constituting is preferably as follows to be formed：By 1 Kind of coating solution 1 time, occurs from being separated, so as to form the resin bed of double-deck composition in its dry run.That is, preferably adopt Use following methods：Main component (polyester resin) of the coating containing the 1st resin bed and the main component (acrylic acid of the 2nd resin bed Resin) coating fluid, in its dry run, form the 1st resin bed and the 2nd resin bed using each composition from being separated.

When implementing above-mentioned phase disengagement method, main component (polyester resin) and the 2nd resin bed of the 1st resin bed are preferably made The difference of the surface energy of main component (acrylic resin) is larger.That is, preferably use the high polyester resin of surface energy and surface energy is low Acrylic resin.Especially, in order to increase the surface energy of polyester resin, preferably use with sulfonic polyester resin.

In the case that resin bed is for double-deck composition, from the adaptation for strengthening base material film and the 1st hard conating, the anti-of hard coat film is made Penetrate color be close to neutral colourless from the viewpoint of, the thickness of the 1st resin bed is preferred more than the thickness of the 2nd resin bed.1st tree The thickness of lipid layer be preferably more than 1.5 times of the 2nd resin layer thickness, more preferably more than 2.0 times, be particularly preferably 3.0 times with On.

Specifically, the scope for ranging preferably from 0.02～0.2 μm of the thickness of the 1st resin bed, more preferably 0.03～ 0.15 μm of scope, particularly preferably 0.05～0.12 μm of scope.The thickness of the 2nd resin bed range preferably from 0.005～ 0.1 μm of scope, more preferably 0.01～0.07 μm of scope, particularly preferably 0.01～0.05 μm of scope.

With regard to the resin bed being arranged between base material film and the 1st hard conating, the wetting tension on its surface is preferably 52mN/m Below.That is, in the present invention, the wetting tension for being coated with the resin layer surface of the 1st hard conating is preferably below 52mN/m.By at this Direct laminated 1st hard conating on the resin bed of sample, becomes easily to form the projection that caused by particle, knot in the 1st hard coating surface Really, sliding and resistance to adhesive are improved further.Here, wetting tension is physics value specified in JIS-K-6768.

The above-mentioned mode for arranging wetting tension between base material film and the 1st hard conating for the resin bed of below 52mN/m is the The thickness of 1 hard conating is effective compared with hour.The thickness of the 1st hard conating becomes hour, the particle contained in the 1st hard conating absolute Amount also diminishes.But, by laminated 1st hard conating on resin bed of the wetting tension for below 52mN/m, contain in the 1st hard conating Some particles become easily to be partially near surface, as a result, become able to efficiency and form projection well.Which is hard the 1st It is effective and then especially effective when the thickness of the 1st hard conating is less than 1.7 μm when the thickness of coating is less than 2 μm.

Consider from above-mentioned viewpoint, the wetting tension of resin layer surface is more preferably below 50mN/m.On the other hand, from From the viewpoint of guaranteeing the adaptation of base material film and the 1st hard conating, the lower limit of the wetting tension of resin layer surface is preferably 35mN/ More than m, more preferably more than 37mN/m, particularly preferably more than 40mN/m.The wetting tension of resin layer surface is less than 35mN/m When, the adaptation of the 1st hard conating reduces sometimes.

Below 52mN/m is controlled to from by the wetting tension of resin layer surface, and improve base material film and the 1st hard conating From the viewpoint of adaptation, as the resin contained in resin bed, preferably use selected from polyester resin, acrylic resin and gather At least a kind in the group of urethane resin composition.In above-mentioned resin, further preferably using polyester resin and/or acrylic resin, Particularly preferably polyester resin is at least used as resin.

Additionally, the wetting tension of resin layer surface can also be controlled by the species of the above-mentioned crosslinking agent of adjustment, content.Example Such as, when the content of crosslinking agent increases, there is the tendency for diminishing in the wetting tension of resin layer surface, conversely, the content of crosslinking agent subtracts When few, there is the tendency for becoming big in the wetting tension of resin layer surface.

[the 1st hard conating]

1st hard conating contains particle, and the projection caused by the particle is formed in the 1st hard coating surface.With regard to the 1st hard conating The individual number density of the projection on surface, is (100 μm of the per unit area of the 1st hard coating surface²) 300～4000.Further, projection The ranging preferably from per 100 μm of individual number density²The scope of 400～3500, the more preferably scope of 500～3000, enter One step is preferably the scope of 600～3000, is particularly preferably the scope of 700～2500.

The scope for ranging preferably from 0.05～0.5 μm of the average grain diameter (r) of the particle contained in the 1st hard conating, more excellent 0.06～0.4 μm of scope is elected as, particularly preferably 0.07～0.3 μm of scope.

When the average grain diameter (r) of the particle contained in the 1st hard conating is less than 0.05 μm, existing can not be in the 1st hard conating table Face forms sufficiently large projection, can not fully improve the situation of sliding and resistance to adhesive.When average grain diameter (r) is more than 0.5 μm, Following unfavorable conditions are produced sometimes：The flatness of the 1st hard coating surface reduces, and center line average roughness (Ra1) becomes 30nm More than, or the haze value of hard coat film becomes more than 1.5%, and the transparency reduces etc..

The average grain diameter (r) of the particle contained in the 1st hard conating is preferably with respect to foot for the thickness (d) of the 1st hard conating Enough little.That is, the ratio of the thickness (d) of the average grain diameter (r) of particle and the 1st hard conating is preferably in the range of 0.01～0.30. Make such particle more be present in the near surface of the 1st hard conating, formed in the 1st hard coating surface as mentioned above more Projection is preferred.Thereby, it is possible to improve sliding and resistance to adhesive without reducing the flatness of the 1st hard coating surface.

The model of the ratio (r/d) of the average grain diameter (r) of the particle contained in the 1st hard conating and the thickness (d) of the 1st hard conating Enclose more preferably 0.01～0.20 scope, more preferably 0.01～0.15 scope, particularly preferably 0.02～0.10 Scope, be most preferably 0.02～0.08 scope.

The average diameter of the projection formed in the 1st hard coating surface by particle as described above range preferably from 0.03～ 0.3 μm of scope.Further, the scope for ranging preferably from 0.04～0.25 μm of the average diameter of projection, more preferably 0.05～ 0.2 μm of scope.Thereby, it is possible to improve sliding and resistance to adhesive without reducing the transparency.

The scope for ranging preferably from 0.03～0.3 μm of the average height of projection.Further, the scope of the average height of projection Preferably 0.04～0.25 μm of scope, more preferably 0.05～0.2 μm of scope.Thereby, it is possible to improve sliding and resistance to viscous Even property is without reducing the transparency.

The shape for being formed in the projection on the surface of the 1st hard conating is not particularly limited, and preferably has circular or rotund Flat shape.Here, when the flat shape of projection refers to the surface for observing the 1st hard conating with scanning electron microscope (SEM) Flat shape.

Fig. 1 is an example of the surface picture of the 1st hard conating obtained using scanning electron microscope.1st hard painting The surface of layer is formed with the projection 11 caused by particle.

The flat shape of so-called projection is close to circle, refers in the ideograph shown in Fig. 2, with the maximum for representing projection 11 The line segment of diameter (Lmax) is in the ratio of the maximum gauge (Lmax) of the diameter (Lmin) and projection 11 of the orthogonal projection 11 of center Lc Rate (Lmin/Lmax) is more than 0.65.

Above-mentioned ratio (Lmin/Lmax) be preferably more than 0.70, more preferably more than 0.80, particularly preferably 0.85 with On.The upper limit is 1.0.

The flat shape of the projection in the surface picture of Fig. 1 is the shape of circular or defined above " being close to circle ".

In this specification, the diameter of so-called projection, refer to the maximum gauge (Lmax) shown in Fig. 2.The average diameter of projection Can the surface picture of the 1st hard conating that such utilization scanning electron microscope is obtained as shown in Figure 1 obtain.

In this specification, the height of so-called projection, refer to the length from the summit of projection to the 1st hard coating surface.Projection Average height can be measured by the cross-section photograph of the 1st hard conating shot with transmission electron microscope (TEM).

The scope for ranging preferably from 0.10～0.70 μm of the equispaced of the projection of the 1st hard coating surface, more preferably 0.15～0.50 μm of scope, particularly preferably 0.20～0.40 μm of scope.Thereby, it is possible to improve sliding and resistance to adhesive Without reducing the transparency.

The equispaced of projection can be obtained by the surface picture of the 1st hard conating obtained using scanning electron microscope. Fig. 3 be by the figure after the surface picture medelling of the 1st hard conating obtained with scanning electron microscope.Using Fig. 3, to determining The method of the equispaced of projection is illustrated.

First, straight line 20 is transversely drawn, and then draws the longitudinal straight line 30 orthogonal with horizontal straight line 20.Then, pin The all projections (that is, contacted with straight line 20) on horizontal straight line 20 to falling, determine the interval of adjacent protrusions.Straight for longitudinal direction Line 30 is also carried out same operation.Thus obtained institute's bossed interval (distance) is carried out averagely.

Using Fig. 4, it is described in detail to determining the method for equispaced of projection.

Fig. 4 only selects to edit the projection fallen on horizontal straight line 20 or longitudinal straight line 30 in Fig. 3.In Fig. 4, fall in horizontal stroke It is that represented with reference 1～5 5 are raised to raised on straight line 20.The interval of so-called adjacent protrusions, is such as projection 1 And the distance between the projection 2 adjacent with the projection 1 P.Similarly, the interval of metering projection 2 and projection 3, projection 3 and projection 4 Interval, projection 4 and projection 5 interval, for all particles on horizontal straight line 20 that fall, between measuring between adjacent protrusions Every.

Similarly operated, for all projections on longitudinal straight line 30 that fall, measured the interval between adjacent protrusions.

Change the position 3 times of the position of horizontal straight line and longitudinal straight line respectively, implement aforesaid operations, all prominent to obtained Rise interval average, using the mean value as projection equispaced.

As shown in figure 1, it is preferred that each projection of the 1st hard coating surface is formed by 1 particle respectively.Thus, become Easily the center line average roughness (Ra1) of the 1st hard coating surface is adjusted to less than 30nm, and easily by the mist of hard coat film Angle value is adjusted to less than 1.5%.When forming projection with the state of a plurality of particles aggregate, the center line of the 1st hard coating surface is put down All there is the tendency for becoming big in roughness (Ra1), the haze value of hard coat film, not preferably.

The scope of the content of the particle in the 1st hard conating is preferably with respect to 100 matter of solid state component total amount of the 1st hard conating Amount % is the scope of 2.5～17 mass %, is more preferably the scope of 3～15 mass %, is particularly preferably the model of 4～12 mass % Enclose.

As described above, following manner is preferred：Make containing average grain diameter (r) with respect to the 1st hard conating in the 1st hard conating Thickness (d) for sufficiently small particle, make particle more be present in the near surface of the 1st hard conating, so as in the 1st hard painting Layer surface forms more projection.

In order that particle is present in the near surface of the 1st hard conating, need to make particle in the forming process of the 1st hard conating Mobile (floating) is near surface.This can be by for example using surface treatment was implemented, (which is used for reducing the surface of particle certainly By energy) particle or implemented the particle of silicic acid anhydride (which is used for the surface-hydrophobicized of particle) to realize.As above-mentioned Implement the particle for processing, preferably inorganic particulate, particularly preferred silicon dioxide granule.

As the particle contained in the 1st hard conating, preferably using inorganic particulate.As inorganic particulate, preferably enumerate Inorganic particulate comprising the element in Si, Na, K, Ca and Mg.Can further preferably enumerate and include selected from silicon dioxide granule (SiO₂), alkali metal fluoride (NaF, KF etc.) and alkali earth metal fluoride (CaF₂、MgF₂Deng) in compound inorganic grain Son, but from from the aspect of durability etc., particularly preferred silicon dioxide granule.

As the above-mentioned surface treatment for reducing the surface free energy of particle, can enumerate using selected from following formulas (1) hydrolysate of the organic silane compound containing fluorine atom, the hydrolysate of the organosilan and the organosilan that represent The method is surface-treated by least one compound in the group of partial condensate composition.

C_nF_2n+1-(CH₂)_m-Si(Q)₃

Formula (1)

As the compound of formula (1), specifically can the following compounds of example.

C₄F₉CH₂CH₂Si(OCH₃)₃

C₆F₁₃CH₂CH₂Si(OCH₃)₃

C₈F₁₇CH₂CH₂Si(OCH₃)₃

C₆F₁₃CH₂CH₂CH₂Si(OCH₃)₃

C₆F₁₃CH₂CH₂CH₂CH₂Si(OCH₃)₃

C₆F₁₃CH₂CH₂Si(OC₂H₅)₃

C₈F₁₇CH₂CH₂CH₂Si(OC₂H₅)₃

C₆F₁₃CH₂CH₂CH₂CH₂Si(OC₂H₅)₃

C₆F₁₃CH₂CH₂SiCl₃

C₆F₁₃CH₂CH₂SiBr₃

C₆F₁₃CH₂CH₂CH₂SiCl₃

C₆F₁₃CH₂CH₂Si(OCH₃)Cl₂

Additionally, as processing for the other surfaces for reducing the surface free energy of inorganic particulate, can enumerate using following logical The compound that formula (2) represents carries out the side are surface-treated by fluorine compounds for processing and then representing using following formulas (3) Method.

B-R⁴-SiR⁵ _n(OR⁶)_3-n

Formula (2)

D-R⁷-Rf²

Formula (3)

As the reactive moieties that B and D represent, such as vinyl, pi-allyl, acryloyl group, methacryl can be enumerated Base, acryloyl group epoxide, methylacryloyl epoxide, epoxy radicals, carboxyl, hydroxyl etc..

As the specific example of formula (2), acryloyl-oxyethyl trimethoxy silane, acryloxypropyl can be enumerated Trimethoxy silane, acryloxy butyl trimethoxy silane, acryloxy amyltrimethoxysilane, acryloxy Hexyl trimethoxy silane, acryloxy heptyl trimethoxy silane, methacryloxyethyl trimethoxy silane, first Base acryloxypropyl trimethoxy silane, methacryloxy butyl trimethoxy silane, methacryloxy oneself Base trimethoxy silane, methacryloxy heptyl trimethoxy silane, methacryloyloxypropyl methyl dimethoxy Silane, methacryloyloxypropyl methyl dimethoxysilane and it is substituted by including the methoxyl group in above-claimed cpd The compound of other alkoxyls or hydroxyl is in interior material etc..

As the specific example of formula (3), acrylic acid -2 can be enumerated, 2,2- trifluoro ethyl esters, acrylic acid -2,2,3,3,3- five Fluorine propyl ester, acrylic acid -2- perfluoro butyl ethyl ester, acrylic acid -3- perfluoro butyl -2- hydroxy propyl ester, acrylic acid -2- perfluoro hexyl second Ester, acrylic acid -3- perfluoro hexyl -2- hydroxy propyl ester, perfluoroethyl octyl group methyl esters, acrylic acid -2- perfluorooctylethyl, third Olefin(e) acid -3- perfluoro capryl -2- hydroxy propyl ester, acrylic acid -2- perfluoro decyl ethyl ester, acrylic acid -2- perfluor -3- methyl butyl second Ester, acrylic acid -3- perfluor -3- methoxybutyl -2- hydroxy propyl ester, acrylic acid -2- perfluor -5- methylhexyl ethyl ester, acrylic acid - 3- perfluor -5- methylhexyl -2- hydroxy propyl ester, acrylic acid -2- perfluor -7- Methyl Octyl -2- hydroxy propyl ester, acrylic acid tetrafluoro third Ester, acrylic acid octafluoro pentyl ester, dodecafluorhe-ptylacrylate, ten hexafluoro nonyl ester of acrylic acid, hexafluorobutyl acrylate, metering system Acid -2,2,2- trifluoro ethyl esters, methacrylic acid -2,2,3,3,3- five fluorine propyl ester, methacrylic acid -2- perfluoro butyl ethyl ester, first Base acrylic acid -3- perfluoro butyl -2- hydroxy propyl ester, methacrylic acid perfluoro capryl methyl esters, methacrylic acid -2- perfluoro capryl second Ester, methacrylic acid -3- perfluoro capryl -2- hydroxy propyl ester, methacrylic acid -2- perfluoro decyl ethyl ester, methacrylic acid -2- are complete Fluoro- 3- methyl butyl ethyl ester, methacrylic acid -3- perfluor -3- methyl butyl -2- hydroxy propyl ester, methacrylic acid -2- perfluor - 5- methylhexyl ethyl ester, methacrylic acid -3- perfluor -5- methylhexyl -2- hydroxy propyl ester, methacrylic acid -2- perfluor -7- first Base octyl group ethyl ester, methacrylic acid -3- perfluor -7- Methyl Octyl ethyl ester, tetrafluoropropyl propyl ester, methacrylic acid octafluoro Pentyl ester, methacrylic acid octafluoro pentyl ester, dodecafluoroheptyl methacrylate, ten hexafluoro nonyl ester of methacrylic acid, methacrylic acid- 1- trifluoromethyl trifluoro ethyl ester, Hexafluorobutyl mathacrylate etc..

As the above-mentioned hydrophobic compound for implementing silicic acid anhydride to particle surface, can enumerate for example in the molecule Compound with hydrophobic grouping and reactive moieties.Generally, as long as the hydrophobic grouping of hydrophobic compound is with hydrophobic work( Can, it is not particularly limited, as the specific example of hydrophobic grouping, can enumerates and be selected from by carbon number being more than 4 Fluoroalkyl, carbon number are the functional group of at least a kind in the group of more than 8 alkyl and siloxy group composition.

As above-mentioned reactive moieties, changed using free radical (which is to receive the energy such as light or heat and produces) etc. The position of reaction is learned, as specific example, more preferably there is vinyl, pi-allyl, acryloyl group, methylacryloyl, propylene Acyloxy, methylacryloyl epoxide, epoxy radicals, carboxyl, hydroxyl etc. receive the energy such as light or heat carries out the anti-of chemical reaction Answering property position.

That is, have as the hydrophobic compound to particle surface enforcement silicic acid anhydride, preferably using to be selected from Reactive moieties and carbon number be the compound (fluorine compounds) of more than 4 fluoroalkyl, with reactive moieties and carbon atom Number is compound (long-chain hydrocarbon compound) and the compound (silica with siloxy group and reactive moieties of more than 8 alkyl Hydride compounds) at least a kind compound in the group that constitutes.

Long-chain hydrocarbon compound represents that it is more than 8 to have reactive moieties and the carbon number as hydrophobic grouping in the molecule Alkyl compound.Carbon number is that the carbon number of more than 8 alkyl is preferably more than 8 and less than 30.Additionally, carbon atom Several alkyl for more than 8 can select any number of in linear chain structure, branched structure, alicyclic structure.As long-chain hydrocarbon compound, Can be more preferably using the alkylol of the straight-chain that carbon number is more than 10 and less than 22, alkyl epoxide (alkyl Epoxide), alkyl acrylate, alkyl methacrylate, alkyl carboxylates (comprising acid anhydrides and esters) etc..

As the specific example of long-chain hydrocarbon compound, the polyalcohols such as octanol, ethohexadiol, stearyl alcohol, propylene can be enumerated misery Acrylate (the metering systems such as ester, 2-Propenoic acid, 2-methyl-, octyl ester, acrylic acid -2- hydroxyl monooctyl ester, methacrylic acid -2- hydroxyl monooctyl ester Acid esters), alkylalkoxy silane such as octyl group trimethoxy silane etc..

As silicone compounds, can enumerate in the molecule and there is reactive moieties and the siloxy group as hydrophobic grouping Compound.The reactive moieties of silicone compounds are preferably using acryloyl group epoxide, methylacryloyl epoxide.

Additionally, as siloxy group, the polysiloxane group for preferably being represented using following formulas (4).

-(Si(R⁸)(R⁹)-O)_m-

Formula (4)

(in formula (4), R⁸And R⁹Independently of one another represent carbon number be 1～6 alkyl, phenyl, 3- acryloxy- 2- hydroxypropyl epoxide propyl group, 2- acryloxy -3- hydroxypropyl epoxide propyl group, end have acryloyl group epoxide or methyl The polyethylene glycol propyl ether base of acryloyl group epoxide or the polyethylene glycol propyl ether base with terminal hydroxyl, m represent 10～200 whole Number.)

The polysiloxane group represented with formula (4) can be lifted as the specific example of the silicone compounds of hydrophobic grouping Go out the compound of the dimethyl siloxane and reactive moieties represented with following formulas (5).As with formula (5) Dimethyl siloxane and reactive moieties silicone compounds specific example, X-22-164B, X- can be enumerated 22-164C, X-22-5002, X-22-174D, X-22-167B (being trade name above, Shin-Etsu Chemial Co., Ltd's system) etc..

(in formula, R represents the alkyl that carbon number is more than 1 and less than 7, and k represents integer 0 or 1, and m represents 10～200 Integer.)

Additionally, the siliconization of the polysiloxane group represented with reactive moieties and as the formula (4) of hydrophobic grouping Other specific examples of compound, can enumerate that formula (6) represents, with 3- acryloxy -2- hydroxypropyl epoxide propyl group and The compound of methyl；Compound with 2- acryloxy -3- hydroxypropyl epoxide propyl group and methyl that formula (7) represents.

(in formula (6) and (7), R represents the alkyl that carbon number is more than 1 and less than 7, and k represents integer 0 or 1, and m represents Arbitrary integer in 10～200.)

Further, the siliconization of the polysiloxane group for representing with reactive moieties and as the formula (4) of hydrophobic grouping Other specific examples of compound, can enumerate that formula (8) represents, there is acryloyl group epoxide or methyl-prop with methyl and end The compound of the polyethylene glycol propyl ether base of enoyl- epoxide；Poly- second that formula (9) represents, that there is hydroxyl with methyl and end The compound of glycol propyl ether base.

(in formula (8) and (9), R represents the alkyl that carbon number is more than 1 and less than 7, and k represents integer 0 or 1, and x represents 1～10 integer, m represent 10～200 integer.)

Fluorine compounds with the fluoroalkyl that reactive moieties and carbon number are more than 4 are illustrated.Here, fluothane Base can be any number of in linear chain structure or branched structure.Additionally, as fluoroalkyl, preferably carbon number be more than 4 and 8 with Under.As such fluorine compounds, fluoroalkyl alcohol, fluothane based epoxy, fluoroalkyl halide, fluoroalkyl base can be used Ester, perfluoroalkyl methacrylate, carboxylic acid fluothane base ester (comprising acid anhydrides and esters) etc..Wherein, preferably fluoroalkyl base ester, Perfluoroalkyl methacrylate, for example, can using selected from above-mentioned formula (3) example compound in, with carbon number be 4 The compound of above fluoroalkyl.

Fluoroalkyl number in fluorine compounds is not necessary for 1, and fluorine compounds can also be with a plurality of fluoroalkyls.

For the 1st hard conating, in order to suppress to produce damage on hard coat film surface, preferred hardness is higher, preferably JIS Pencil hardness defined in K5600-5-4 (1999) is more than H.It should be noted that the upper limit of pencil hardness is 9H or so.

For the 1st hard conating, thermosetting resin or active energy ray-curable resin is preferably comprised as resin, Particularly preferably include active energy ray-curable resin.Here, so-called active energy ray-curable resin, refers to using purple Outside line, electron ray isoreactivity energy-ray carry out the resin of polymerizing curable.

As for obtaining the polymerizable compound of active energy ray-curable resin, can enumerate with acryloyl group, The chemical combination of the polymerizable functional group such as methylacryloyl, acryloyl group epoxide, methylacryloyl epoxide, vinyl, pi-allyl Thing (monomer, oligomer).

1st hard conating is preferably as follows to be formed：Penetrated using wet coating active-energy of the coating containing above-mentioned polymerizable compound Line solidification compound, after being dried as needed, irradiates active energy beam, is solidified, be consequently formed.

The example below polymerizable compound (monomer, oligomer), but it is not limited to these compounds.Need explanation It is that in the following description, the statement of " (methyl) acrylate " includes " acrylate " and " methyl Acrylate " both compounds.

As monomer, such as (methyl) methyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid second can be enumerated Epoxide diethylene glycol (DEG) ester, (methyl) methoxyethyl triethyleneglycol ester, (methyl) phenoxy ethyl acrylate, (methyl) acrylic acid Tetrahydro furfuryl ester, (methyl) isobornyl acrylate, (methyl) 2-hydroxyethyl acrylate, (methyl) acrylic acid -2- hydroxyl The monofunctional acrylates such as base propyl diester, (methyl) acrylic acid -2- hydroxyl -3- phenoxy group ester, neopentyl glycol two (methyl) propylene Acid esters, 1,6- hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) Acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, four (first of dipentaerythritol Base) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol Three (methyl) acrylate, tripentaerythritol six (methyl) triacrylate, trimethylolpropane (methyl) propylene acid+benzoic acid The polyfunctional acrylic esters such as ester, trimethylolpropane benzoic ether, two (methyl) acrylate hexa-methylene of glycerine, two isocyanide Urethane acrylates such as acid esters, pentaerythrite three (methyl) acrylate hexamethylene diisocyanate etc..

In above-mentioned monomer, preferably using the multifunctional list of the polymerizable functional group in 1 molecule with more than 3 Body.

As oligomer, such as polyester (methyl) acrylate, polyurethane (methyl) acrylate, epoxy (first can be enumerated Base) acrylate, polyethers (methyl) acrylate, alkyd (methyl) acrylate, melamine (methyl) acrylate, poly- silicon Oxygen alkane (methyl) acrylate etc..

In above-mentioned oligomer, preferably using the polyfunctional of the polymerizable functional group in 1 molecule with more than 3 Carbamate (methyl) acrylate oligomer.Polyfunctional carbamate (methyl) acrylate oligomer can Using commercially available product.For example, urethane acrylate AH series, carbamate third that common prosperity society chemistry (strain) makes can be enumerated Olefin(e) acid ester AT series, urethane acrylate UA series, the UN-3320 series that industrial (strain) makes on root, UN-900 are serial, The NK ORIGO U series that Xin Zhong village chemical industry (strain) makes, 1290 series of Ebecryl of DAICEL UCB Co., Ltd. Deng.

The content of the polymerizable compound in Actinic-radiation curable composition is preferably with respect to active energy beam 100 mass % of solid state component total amount of solidification compound is more than 50 mass %, more than more preferably 55 mass %, further More than preferably 60 mass %, more than particularly preferably 70 mass %.The upper limit is preferably below 97 mass %, more preferably 95 matter Amount below %.

When using ultraviolet as active energy beam, Actinic-radiation curable composition preferably comprises photopolymerization and draws Send out agent.As the specific example of the Photoepolymerizationinitiater initiater, can be using such as acetophenone, 2,2- diethoxy acetophenone, to two Methyl acetophenone, to dimethylamino propiophenone, benzophenone, 2- chlorobenzophenone, 4,4 '-dichloro benzophenone, 4,4 '-bis- Diethylamino benzophenone, Michler's keton, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Base ether, methyl benzoylformate, p-isopropyl-Alpha-hydroxy isobutyl group benzophenone, Alpha-hydroxy isobutyl group benzophenone, 2,2- dimethoxy- The carbonyls such as 2- phenyl acetophenone, 1- hydroxycyclohexylphenylketone, tetramethylthiuram monosulfide, tetramethyl autumn Sulphur compounds such as Lan Mu, thioxanthones, CTX, 2- methyl thioxanthones etc..These Photoepolymerizationinitiater initiaters can be used alone, Two or more can also be applied in combination.

Additionally, Photoepolymerizationinitiater initiater is generally commercially available, those commercially available products can be used.For example, Ciba can be enumerated IRGACURE (registration mark) 184, IRGACURE 907 that Specialty Chemicals (strain) makes, IRGACURE 379, IRGACURE 819、IRGACURE 127、IRGACURE 500、IRGACURE 754、IRGACURE 250、IRGACURE 1800th, IRGACURE 1870, IRGACURE OXE01, DAROCUR TPO, DAROCUR 1173 etc., Nihon Speedcure MBB that SiberHegner (strain) makes, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP150, Esacure KTO46 etc., Japanese chemical drug (strain) make KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI etc..

With regard to the scope of the content of above-mentioned Photoepolymerizationinitiater initiater, with respect to the solid-state of Actinic-radiation curable composition It is appropriate, the scope of preferably 0.5～8 mass % that 100 mass % of composition total amount is the scope of 0.1～10 mass %.

Actinic-radiation curable composition can contain various additives further, and for example, antioxidant, ultraviolet are inhaled Receive agent, levelling agent, particle dispersant, organic antistatic additive, lubricant, colouring agent, pigment etc..

Actinic-radiation curable composition contains the particle for forming projection in the 1st hard coating surface.As institute Particle is stated, preferably using the particle for implementing surface treatment or silicic acid anhydride mentioned above.Active energy ray-curable The scope of the content of the particle in composition is preferably with respect to the solid state component total amount 100 of Actinic-radiation curable composition Quality % is the scope of 2.5～17 mass %, is more preferably the scope of 3～15 mass %, is particularly preferably 4～12 mass % Scope.

The refractive index of the 1st hard conating range preferably from 1.48～1.54 scope, more preferably 1.50～1.54 model Enclose.1st hard conating of scope that refractive index be 1.48～1.54 is obtained in the following way can, the mode is：Using wet coating Method is coated with above-mentioned Actinic-radiation curable composition, after being dried as needed, irradiates active energy beam, carries out solid Change, be consequently formed the 1st hard conating.

With regard to the scope of the thickness of the 1st hard conating, 0.5 μm is appropriate less than 10 μm of scope, but is preferably More than 0.8 μm and less than 7 μm of scope, more preferably more than 1 μm and less than 5 μm of scope, particularly preferably more than 1 μm and 3 μ Below m.

When the thickness of the 1st hard conating is less than 0.5 μm, the hardness of the 1st hard conating reduces, and becomes to be readily incorporated damage.Additionally, When the thickness of the 1st hard conating becomes more than 10 μm, following unfavorable conditions are produced sometimes：Sliding, resistance to adhesive reduce, and curling becomes Greatly, or transmitance reduce etc..

[hard coat film]

In hard coat film, there is at least one side of base material film the 1st hard conating.Hard coat film can be only in the one side of base material film With the 1st hard conating, it is also possible to there is the 1st hard conating on the two sides of base material film.

Additionally, as other preferred embodiments of hard coat film, can enumerate have in the one side of base material film the 1st hard conating, There is on the another side of base material film (that is, on the face contrary with the face for being provided with the 1st hard conating of base material film) the 2nd hard conating Hard coat film.

Even if it should be noted that the 2nd hard conating being laminated on the another side of base material film using be laminated at base material The situation of the identical composition of the 1st hard conating in the one side of film (that is, distinguishes laminated 1st hard painting on the two sides of base material film The situation of layer) under, in order to be distinguished with the 1st hard conating in one side, also referred to as the 2nd hard conating sometimes.

[the 2nd hard conating]

Hereinafter, the 2nd hard conating to being arranged on the another side of base material film is illustrated.

For the 2nd hard conating, in order to suppress to produce damage on hard coat film surface, preferred hardness is higher, preferably JIS Pencil hardness defined in K5600-5-4 (1999) is more than H, more preferably more than 2H.It should be noted that pencil hardness The upper limit be 9H or so.

The surface of the 2nd hard conating is preferably smoother and clear (clear).For example, the center line of the 2nd hard coating surface is put down All roughness (Ra2) is preferably below 25nm, more preferably below 20nm, particularly preferably below 15nm.Lower limit is not especially Limit, but be 1nm or so in practice.

For the 2nd hard conating, in order that the center line average roughness (Ra2) of the 2nd hard coating surface be 25nm with Under, the 2nd hard conating is preferably substantially free of particle of the average grain diameter more than 0.5 μm.Here, so-called 2nd hard conating is substantial not Containing particle of the average grain diameter more than 0.5 μm, refer to not purposefully to coating fluid (for example, the activity for forming the 2nd hard conating Energy ray-curable composition) the middle particle for adding average grain diameter more than 0.5 μm.

The surface of the 2nd hard conating is preferably smoother and clear.Therefore, the surface of the 2nd hard conating be created substantially absent by The projection that particle causes is preferred.Here, the surface of so-called 2nd hard conating is created substantially absent the projection caused by particle, Refer to (100 μm of the per unit area of the 2nd hard coating surface²) projection number be less than 100.2nd hard coating surface (100 μm of per unit area²) the number of projection be preferably less than 50, more preferably less than 30, be particularly preferably 0.

2nd hard conating containing the particle that average grain diameter is less than 0.5 μm, but can be considered from above-mentioned viewpoint, preferred pair the 2nd The average grain diameter of the particle contained in hard conating is adjusted.

When in the 2nd hard conating containing particle, the average grain diameter of particle be preferably less than 0.2 μm, be more preferably 0.1 μm with Under.With regard to the scope of the content of particle as described above, it is 0.1 with respect to 100 mass % of solid state component total amount of the 2nd hard conating The scope of～15 mass % is appropriate, the scope of more preferably 0.5～10 mass %, the particularly preferably model of 1～8 mass % Enclose.

For the 2nd hard conating, as resin, thermosetting resin or active energy ray-curable tree is preferably comprised Fat, particularly preferably includes active energy ray-curable resin.Here, so-called active energy ray-curable resin, refers to profit The resin of polymerizing curable is carried out with ultraviolet, electron ray isoreactivity energy-ray.

As the polymerizable compound for obtaining active energy ray-curable resin, can use hard the 1st with above-mentioned The compound identical compound illustrated in coating.

Same with the 1st hard conating, the 2nd hard conating is preferably as follows to be formed：Polymerizable compound is contained using wet coating coating Actinic-radiation curable composition, after being dried as needed, irradiate active energy beam, solidified, thus Formed.

The refractive index of the 2nd hard conating range preferably from 1.48～1.54 scope, more preferably 1.50～1.54 model Enclose.2nd hard conating of scope that refractive index be 1.48～1.54 is obtained in the following way can, the mode is：Using wet coating Method is coated with above-mentioned Actinic-radiation curable composition, after being dried as needed, irradiates active energy beam, carries out solid Change, be consequently formed the 2nd hard conating.

With regard to the scope of the thickness of the 2nd hard conating, 0.5 μm is appropriate less than 10 μm of scope, but is preferably More than 0.8 μm and less than 7 μm of scope, more preferably more than 1 μm and less than 5 μm of scope, particularly preferably more than 1 μm and 3 μ Below m.

When the thickness of the 2nd hard conating is less than 0.5 μm, the hardness of the 2nd hard conating reduces, and becomes to be readily incorporated damage.Additionally, When the thickness of the 2nd hard conating becomes more than 10 μm, following unfavorable conditions are produced sometimes：Sliding, resistance to adhesive reduce, and curling becomes Greatly, or transmitance reduce etc..

In order to strengthen the adaptation of base material film and the 2nd hard conating, above-mentioned resin bed is made to be present in base material film and the 2nd hard painting It is preferred between layer.

[transparent and electrically conductive film]

The hard coat film of present embodiment is suitable as the basilar memebrane of transparent and electrically conductive film.That is, by present embodiment Transparent and electrically conductive film of the hard coat film as basilar memebrane, is laminated electrically conducting transparent at least one side of the hard coat film of present embodiment Film.

Nesa coating only can be laminated in any surface of hard coat film, it is also possible to be laminated on two sides.

Will be as follows for several configuration example examples of transparent and electrically conductive film of the hard coat film of the present invention as basilar memebrane, but the present invention It is not limited to these.

I) 1 hard conating/resin bed/base material film/resin bed/1 hard conating/nesa coating

Ii) nesa coating/1 hard conating/resin bed/base material film/resin bed/1 hard conating/nesa coating

Iii) 1 hard conating/resin bed/base material film/resin bed/2 hard conatings/nesa coating

Iv) nesa coating/1 hard conating/resin bed/base material film/resin bed/the 2nd hard conating

V) nesa coating/1 hard conating/resin bed/base material film/resin bed/2 hard conatings/nesa coating

In above-mentioned configuration example, i) or iii) be preferred.That is, from lamination procedure, the manufacturing procedure for guaranteeing nesa coating In the sliding of hard coat film, from the viewpoint of resistance to adhesive, not laminated nesa coating on the 1st hard conating of side and pre- It is preferred first to expose the 1st hard conating.

Additionally, it may further be preferable that the hard conating in the face of laminated nesa coating is smoother and clear.Therefore, Iii, in configuration example), the center line average roughness (Ra2) of the 2nd hard coating surface is preferably below 25nm, is more preferably Below 20nm, particularly preferably below 15nm.The hard conating (such as in the face of laminated nesa coating is made as described above 2 hard conatings) surface smoother and clear, transparent and electrically conductive film the transparency raising, therefore it is preferred that.

[nesa coating]

As the material for forming transparent conductivity layer, such as tin oxide, indium oxide, antimony oxide, zinc oxide, ITO can be enumerated The metal oxides such as (tin indium oxide), ATO (antimony tin), metal nanometer line (such as nano silver wire), CNT.Wherein, ITO is preferably used.

From guaranteeing sheet resistance value for 10³From the viewpoint of the good electric conductivity of Ω/below, the thickness of nesa coating Degree is preferably more than 10nm, more preferably more than 15nm, particularly preferably more than 20nm.On the other hand, if nesa coating Thickness change is too much, then produce sometimes the unfavorable condition that color sensation (coloring) becomes strong, transparent reduction etc, therefore, electrically conducting transparent The upper limit of the thickness of film is preferably below 60nm, more preferably below 50nm, particularly preferably below 40nm.

As the forming method of nesa coating, it is not particularly limited, existing known method can be used.Specifically, The dry type masking method such as vacuum vapour deposition, sputtering method, ion plating (gas phase masking method) or wet coating can be enumerated.

The nesa coating being filmed as described above can be patterned.With regard to patterning, can be according to transparent The purposes is suitable for by conductive film forms various patterns.It should be noted that forming pattern by the patterning of nesa coating Portion and non-drafting department, as the shape of drafting department, can enumerate such as striated, clathrate etc..

The patterning of nesa coating is generally carried out using etching.For example, using photoetching process, laser explosure method or print process After forming the etchant resist of pattern-like on nesa coating, it is etched processing, thus by electrically conducting transparent film patterning.Transparent After conducting film is patterned, can be peeled off with alkaline aqueous solution and remove etchant resist.

As etching solution, it is possible to use existing known etching solution.For example, can using hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, The inorganic acids such as phosphoric acid, the organic acid such as acetic acid, and their mixture, and their aqueous solution.

Used as the alkaline aqueous solution that can be used for stripping removing etchant resist, the NaOH that can enumerate 1～5 mass % is water-soluble Liquid, potassium hydroxide aqueous solution etc..

[refractive index adjustment layer]

In the configuration example of above-mentioned transparent and electrically conductive film, nesa coating can directly be laminated in the 1st hard conating or the 2nd hard painting On layer, it is preferred that there is refractive index adjustment layer between nesa coating and the 1st hard conating or the 2nd hard conating.Hereinafter, right Refractive index adjustment layer is illustrated.

Refractive index adjustment layer only can be constituted by 1 layer, or more than 2 layers of laminated composition.Refractive index adjustment layer is Layer with following function, the function is：The reflected colour of the laminated nesa coating thereon of adjustment, the function through color, Or suppress that so-called " pattern is visible, and (Japanese is：Bone え) " (which refers to that the drafting department of patterned nesa coating can mesh Depending on identification) function.

As the composition of refractive index adjustment layer, the high refractive index layer that such as refractive index (n1) is 1.60～1.80 can be enumerated Individual layer composition, refractive index (n2) are that the individual layer of 1.30～1.53 low-index layer is constituted or above-mentioned high refractive index layer and low folding Penetrate laminated composition (low-index layer is configured at nesa coating side) of rate layer etc..

The scope of the refractive index (n1) of above-mentioned high refractive index layer is more preferably 1.63～1.78 scope, is more preferably 1.65～1.75 scope.The scope of the refractive index (n2) of above-mentioned low-index layer more preferably 1.30～1.50, more excellent Elect 1.30～1.48 scope, particularly preferably 1.33～1.46 scope as.

Refractive index adjustment layer thickness (for plural layer laminated composition when, refer to gross thickness) be preferably below 200nm, more Preferably below 150nm, particularly preferably below 120nm, most preferably below 100nm.The lower limit of thickness be preferably 30nm with Upper, more preferably more than 40nm, particularly preferably more than 50nm, most preferably more than 60nm.

When nesa coating is patterned, from the viewpoint of suppression " pattern ", refractive index adjustment layer is preferably High refractive index layer and the laminated composition of low-index layer.In this case, the optical thickness of high refractive index layer and low-index layer The summation (nm) of optical thickness preferably meets (1/4) λ (nm).Here, optical thickness (nm) is refractive index and actual thickness degree (nm) product, λ are wave-length coverage, i.e. 380～780 (nm) of visible region.

In this specification, the optical thickness (nm) of so-called high refractive index layer is total with the optical thickness of low-index layer (nm) With satisfaction (1/4) λ (nm), refer to meet with following formula 1.It should be noted that in formula, n1 represents the refractive index of high refractive index layer, D1 represents the thickness (nm) of high refractive index layer, and n2 represents the refractive index of low-index layer, and d2 represents the thickness of low-index layer (nm).

(380nm/4)≤(n1×d1)+(n2×d2)≤(780nm/4)

95nm≤(n1 × d1)+(n2 × d2)≤195nm (formula 1)

That is, the optical thickness (n1 × d1) of high refractive index layer is excellent with the summation of the optical thickness of low-index layer (n2 × d2) Elect more than 95nm and below 195nm as.

Further, the optical thickness of high refractive index layer is more preferably 95 with the scope of the summation of the optical thickness of low-index layer The scope of the scope of～163nm, particularly preferably 95～150nm, especially it is most preferably the scope of 100～140nm.

High refractive index layer for example may be formed：Using wet coating coating containing the metal oxidation that refractive index is more than 1.65 The Actinic-radiation curable composition of thing particulate, after being dried as needed, irradiates active energy beam, carries out solid Change, be consequently formed.Here, Actinic-radiation curable composition was illustrated in above-mentioned 1st hard conating, contained polymerization Property compound and the composition of Photoepolymerizationinitiater initiater.

As metal oxide microparticle, the metal oxide particle of titanium, zirconium, zinc, tin, antimony, cerium, iron, indium etc. can be enumerated.Make For the specific example of metal oxide microparticle, such as titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, oxidation can be enumerated Cerium, iron oxide, zinc antimonates, doped sno_2 indium oxide (ITO), antimony-doped tin oxide (ATO), phosphorus doping tin oxide, aluminium doping Zinc oxide, Ga-doped zinc oxide, fluorine-doped tin oxide etc., these metal oxide microparticles can be used alone, it is also possible to be used in combination Plural number is planted.In above-mentioned metal oxide microparticle, particularly titanium oxide and zirconium oxide can be carried in the case of the transparency is not reduced High index of refraction, therefore it is preferred that.

The content of the metal oxide microparticle in Actinic-radiation curable composition is penetrated preferably with respect to active-energy 100 mass % of solid state component total amount of line solidification compound is more than 30 mass %, more than more preferably 40 mass %, especially More than preferably 50 mass %.The upper limit is preferably below 70 mass %, is more preferably below 60 mass %.

Low-index layer for example may be formed：Low-refraction nothing is contained as low-index material using wet coating coating Machine particle and/or the Actinic-radiation curable composition of fluorochemical, after being dried as needed, irradiate active energy Amount ray, is solidified, is consequently formed.Here, Actinic-radiation curable composition is explanation in above-mentioned 1st hard conating Composition containing polymerizable compound and Photoepolymerizationinitiater initiater that cross.

As low-refraction inorganic particulate, the preferably inorganic particulate such as silica, magnesium fluoride.Further, these inorganic particulates The particle of preferably hollow form or Porous.The content of low-refraction inorganic particulate as described above is preferably with respect to active-energy 100 mass % of solid state component total amount of ray-curable composition is more than 10 mass %, more than more preferably 20 mass %, special You Xuanwei not be more than 30 mass %.The upper limit is preferably below 70 mass %, is more preferably below 60 mass %, is particularly preferably 50 Below quality %.

As fluorochemical, fluorochemical monomer, fluorine-containing oligomer, fluorine-containing polymer compound can be enumerated.Here, fluorine-containing list Body or fluorine-containing oligomer are for having above-mentioned polymerizable functional group (functional group containing carbon-to-carbon double bond group) and fluorine original in the molecule The monomer of son or oligomer.

As fluorochemical monomer, fluorine-containing oligomer, such as (methyl) acrylic acid -2,2,2- trifluoro ethyl esters, (methyl) can be enumerated Acrylic acid -2,2,3,3,3- five fluorine propyl ester, (methyl) acrylic acid -2- (perfluoro butyl) ethyl ester, (methyl) acrylic acid -2- (perfluor Hexyl) ethyl ester, (methyl) acrylic acid -2- (perfluoro capryl) ethyl ester, (methyl) acrylic acid -2- (perfluoro decyl) ethyl ester, (methyl) Fluorine-containing (methyl) esters of acrylic acid such as senecioate-(perfluoro capryl) ethyl ester, two (α-perfluoroalkyl acrylate) -2,2,2- trifluoroethyl second Diol ester, two (α-perfluoroalkyl acrylate) -2,2,3,3,3- five fluoropropyl glycol ester, two (α-perfluoroalkyl acrylate) -2,2,3,3,4,4, Seven fluorine butyl glycol ester of 4-, two (α-perfluoroalkyl acrylate) -2,2,3,3,4,4,5,5,5- nine fluorine amyl group glycol ester, two (α-fluorine Acrylic acid) -2,2,3,3,4,4,5,5,6,6,6- ten one fluorine hexyl glycol ester, two (α-perfluoroalkyl acrylate) -2,2,3,3,4,4, 5,5,6,6,7,7,7- ten trifluoro heptyl glycol esters, two (α-perfluoroalkyl acrylate) -2,2,3,3,4,4,5,5,6,6,7,7,8,8, 15 fluorine octyl group glycol ester of 8-, two (α-perfluoroalkyl acrylate) -3,3,4,4,5,5,6,6,7,7,8,8,8- ten trifluoro octyl group second two Alcohol ester, two (α-perfluoroalkyl acrylate) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9- 17 fluorine nonyl glycol ester etc. two (α-perfluoroalkyl acrylate) fluoroalkyl esters.

As fluorine-containing polymer compound, can enumerate and for example fluorochemical monomer be made with the monomer for giving crosslinkable groups Fluorinated copolymer for Component units.As the specific example of fluorine-containing monomer unit, including such as fluoroolefins class (such as fluorine second Alkene, vinylidene, tetrafluoroethene, hexafluoroethylene, hexafluoropropene, perfluor -2,2- dimethyl -1,3- dioxole etc.), (methyl) acrylic acid partially or completely fluorinated alkyl esters derivative species (such as Viscoat 6FM (Osaka organise length of schooling), M- 2020 (DAIKIN systems) etc.), fluorinated vinyl ethers etc. wholly or in part.As the monomer for giving crosslinkable groups, remove There is in advance as GMA (methyl) acrylate monomer of cross-linking functional group in intramolecular In addition, (methyl) acrylate monomer (such as (methyl) propylene with carboxyl, hydroxyl, amino, sulfonic group etc. can also be enumerated Acid, (methyl) acrylate, (methyl) hydroxyalkyl acrylates, allyl acrylate etc.).

The content of fluorochemical is preferably with respect to 100 matter of solid state component total amount of Actinic-radiation curable composition Amount % is more than 30 mass %, is more preferably more than 40 mass %, is particularly preferably more than 50 mass %.The upper limit is preferably 95 matter Below amount below %, more preferably 90 mass %, below particularly preferably 80 mass %.

In fluorochemical, preferably using fluorochemical monomer, fluorine-containing oligomer.As fluorochemical monomer and fluorine-containing oligomer exist With polymerizable functional group in molecule, the cross-linked structure of the densification for being thus advantageous to form low-index layer, and can realize Low-refraction.

[touch panel]

The hard coat film of present embodiment is preferably used as the composition of touch panel as the transparent and electrically conductive film of basilar memebrane One of part.

Generally, resistive touch panel is following compositions：Upper electrode and lower electrode are configured across space bar Constitute, the hard coat film of present embodiment can be used in upper electrode and lower electrode as the transparent and electrically conductive film of basilar memebrane Either one or both.

Additionally, capacitive touch panel is generally made up of patterned X electrode and Y electrode, by present embodiment Hard coat film can be used for the either one or both in X electrode and Y electrode as the transparent and electrically conductive film of basilar memebrane.

For the transparent and electrically conductive film used in touch panel, it is desirable to the transparency and processability (sliding, resistance to adhesion Property) good, the hard coat film of present embodiment can fully be met above-mentioned characteristic as the transparent and electrically conductive film of basilar memebrane.

Embodiment

Hereinafter, the present invention is illustrated in greater detail by embodiment, but the present invention is not limited by these embodiments.Need Illustrate, the assay method in the present embodiment and evaluation method are as described below.

(1) measure of the refractive index of each layer

Using spin coater by each coating solution on silicon, formed coated film (about 2 μm of dry thickness), for Gained coated film, under 25 DEG C of temperature conditionss, using measuring difference of phases device, (Nikon (strain) is made：NPDM-1000) determine The refractive index of 589nm.

Additionally, for the refractive index of base material film (PET film), being determined using Abbe refractometer according to JIS K7105 (1981) The refractive index of 589nm.

(2) measure of the thickness of resin bed

Ultra-thin section is cut in the section of the laminated base material film for having resin bed, by using RuO₄Dyeing, OsO₄Dyeing or The ultra-thin section decoration method of the double staining of the two, using TEM (transmission electron microscope) cross section structure can be visual with Observed under the conditions of lower, the thickness of resin bed is determined by its cross-section photograph.It should be noted that for there is no grain in measurement site The part of son.It should be noted that being measured to 5 positions, value is averaged as the thickness of resin bed.

Determine device：Transmission electron microscope (Hitachi's (strain) H-7100FA type processed)

Condition determination：Accelerating potential 100kV

Sample is adjusted：Cryoultramicrotome method

Multiplying power：300000 times

(3) the 1st and the 2nd hard conating, high refractive index layer, the measure of the thickness of low-index layer

Ultra-thin section is cut in the section of hard coat film, is entered with accelerating potential 100kV using TEM (transmission electron microscope) Row observation (being observed with 1～300,000 times of multiplying power), determines thickness by its cross-section photograph.It should be noted that hard for the 1st Coating, like that for surface has bossed layer, is the thickness of the part that there is no projection.The measure of thickness is entered at 5 positions OK, value is averaged as thickness.

The measure of the average grain diameter of the particle contained in (4) the 1st hard conatings

The section of (about 10,000～100,000 times) the 1st hard conating is observed using TEM (transmission electron microscope), by its section Photo, measures the respective maximum length of randomly selected 30 particles, they is carried out averagely, using the value of gained as average grain Footpath.

(5) measure of the average grain diameter of the particle contained in resin bed

The resin layer surface on base material film is laminated at using SEM (scanning electron microscope) with 10,000 times of observations of multiplying power, The image (depth of the light brought by particle) of particle is linked to image analyzer (such as CAMBRIDGE INSTRUMENT system QTM900), change look-out station, data are read, following numerical value process are carried out when total population more than 5000 is become, will be by The number average particle diameter d which is obtained is used as average grain diameter (diameter).

D=∑ di/N

Here, di is the equivalent diameter (with the diameter of a circle with the sectional area identical area of particle) of particle, and N is Number.

The measure of the center line average roughness (Ra1, Ra2) of the (6) the 1st and the 2nd hard coating surface

Based on JIS B0601 (1982), using contact pin type surfagauge SE-3400 ((strain) little Ban research institute System) it is measured.

Transfer rate：0.5mm/s

Evaluation length：8mm

Cutoff value (cutoff value) λ c：0.08mm

The metering of the projection number of (7) the 1st hard coating surfaces

Prepare the cutting sample (20cm × 15cm) of hard coat film, (about 10,000 are shot using SEM (scanning electron microscope) ～10 ten thousand times) at the surface 5 of the 1st hard conating of the cutting sample, make 5 images (surface picture).Then, scheme for 5 Picture, respectively metering are present in square (1 μm of the area of 1 μm of the length of side in image²) or 2 μm of the length of side square (4 μm of area²) In the range of projection number, be converted into per 100 μm²The number of area, averages.It should be noted that metering projection The area of number can be suitably changed according to multiplying power is shot.

The measure of the average diameter of the projection of (8) the 1st hard coating surfaces

(about 10,000～10 are shot to the surface of the 1st hard conating of hard coat film using SEM (scanning electron microscope) Ten thousand times), make image (surface picture).Then, determine the diameter of randomly selected 30 projections from the image (most to greatly enhance Degree), average.

The measure of the average height of the projection of (9) the 1st hard coating surfaces

Prepare the cutting sample (20cm × 15cm) of hard coat film, (about 10,000 are shot using SEM (scanning electron microscope) ～10 ten thousand times) at the section 5 of the 1st hard conating of the cutting sample, make 5 cross-section photograph.Then, 5 cross-section photograph are determined Present in the bossed height of institute, average.

(10) equispaced of projection

(about 10,000～10 are shot to the surface of the 1st hard conating of hard coat film using SEM (scanning electron microscope) Ten thousand times), make image (surface picture).Orthogonal each 1 straight line is drawn in the images on horizontal and vertical.Then, pin To (contacting with straight line) all projections on 1 horizontal straight line that fall, the interval of adjacent protrusions is determined.To longitudinal direction 1 Bar straight line is also carried out same operation.Change the position 3 times of the position of horizontal straight line and longitudinal straight line respectively, implement above-mentioned behaviour Make, all projections interval to obtaining carries out average.

(11) measure of hard coat film

Based on JIS K 7136 (2000), the nephelometer " NDH-2000 " that is made using Japan's electricity color industry (strain) is surveyed Fixed.During measure, the side on the surface of the opposing face (that is, the face of the 2nd hard conating is set) of the 1st hard conating of hard coat film is incident to light Formula is configured.

(12) total light transmittance of hard coat film

Based on JIS-K7361 (1997), it is measured using nephelometer NDH2000 (Japan's electricity color industry (strain) system).

(13) visual valuation of the reflected colour of hard coat film

Attach on the 2nd hard conating face of hard coat film black adhesive tape (day east electrician's system " Vinyl Tape No.21 spy width Black "), observe the reflected colour in the 1st hard conating face under three wavelength fluorescent lamp of darkroom by visual observation, evaluated by following benchmark.

Similarly, black adhesive tape (day east electrician's system " Vinyl Tape is attached on the 1st hard conating face of hard coat film Special of No.21 is black "), observe the reflected colour in the 2nd hard conating face under three wavelength fluorescent lamp of darkroom by visual observation, by following benchmark Evaluated.

A：Reflected colour is neutral and almost colourless.

C：Reflected colour presents coloring.

(14) evaluation of sliding

Hard coat film is cut off, makes 2 film piece (20cm × 15cm).The 1st hard conating face and the 2nd with 2 film piece 2 film piece are somewhat staggered by the relative mode in hard conating face, are overlapped and are positioned on smooth objective table, with finger by lower section Film piece is fixed on objective table, using the method for the film piece with the dynamic top of rubber sleeve, judges the quality of sliding.Determination of the environment For 23 DEG C, 55%RH.

A：The sliding of the film piece of top is good.

B：The sliding of the film piece of top is poor, but still more good.

C：The film piece of top is not slided.

(15) evaluation of resistance to adhesive

Hard coat film is cut off, makes 2 film piece (20cm × 15cm).The 1st hard conating face and the 2nd with this 2 sheet materials This 2 film piece are overlapped by the relative mode in hard conating face.Then, sample glass plate obtained by 2 film piece will be overlapped press from both sides Firmly, the counterweight of about 3kg is put, is placed 48 hours under 50 DEG C, the atmosphere of 90% (RH).Then, by visual observation faying surface is observed, After confirming to the generation situation of Newton's ring, both are peeled off, is evaluated by following benchmark.

A：Newton's ring is not produced before peeling off, sound is not peeling when peeling off and gently peels off.

B：Peel off front portion and Newton's ring is produced, little stripping sound is produced when peeling off and peel off.

C：Newton's ring is produced in entire surface before peeling off, big stripping sound is produced when peeling off and peel off.

The pencil hardness of the (16) the 1st and the 2nd hard conating

The surface of the 1st hard conating and the surface of the 2nd hard conating for hard coat film, respectively according to JIS K5600-5-4 (1999) are measured.Load is 750g, and speed is 30mm/min.The superficiality that device is made is determined using new east science (strain) Hardometer (HEIDON；Model 14DR).Environment during measure is 23 DEG C ± 2 DEG C, relative humidity is 55% ± 5%.

(17) the visually recognizable property of electrically conducting transparent film figure

Sample is positioned on the plate of black, the figure of nesa coating can be recognized by following benchmark evaluation by visual observation Case portion.

A：Can not visually recognizable drafting department.

C：Being capable of visually recognizable drafting department.

(18) measure of the wetting tension of resin bed

The laminated base material film for having resin bed is air-dried 6 hours under the atmosphere of normality (23 DEG C, relative humidity 50%), in phase It is measured according to JIS-K-6768 (1999) with atmosphere.

(resin bed formation coating fluid a)

In terms of solid state component mass ratio, by polyester resin a, 54 matter that the Tg (vitrification point) of 26 mass % is 120 DEG C The Tg for measuring % is 80 DEG C of polyester resin b, the melamine class crosslinking agent of 18 mass %, the mix particles of 2 mass %, prepares water Dispersion coating fluid.

Polyester resin a：By the NDA of 43 moles of %, the 5-sodium sulfo isophthalate of 7 moles of %, 50 Polyester resin obtained from the diol component copolymerization comprising ethylene glycol of mole %

Polyester resin b：By the terephthalic acid (TPA) of 38 moles of %, the trimellitic acid of 12 moles of %, the including of 50 moles of % Polyester resin obtained from the diol component copolymerization of ethylene glycol

Melamine class crosslinking agent：Three " the NIKALAC MW 12LF " made with chemical (strain)

Particle：The cataloid that 0.19 μm of average grain diameter

(resin bed formation coating fluid b)

In terms of solid state component mass ratio, the melamine class of following acrylic resins of 80 mass %, 18 mass % is handed over Connection agent, the mix particles of 2 mass %, prepare moisture and dissipate coating fluid.

Acrylic resin (acrylic resin being shaped as by following copolymerization groups)

Particle：The cataloid that 0.19 μm of average grain diameter

<Surface-treated silicon dioxide granule dispersion liquid>

(surface-treated silicon dioxide granule dispersion liquid A)

Cataloid (" the Organo Silica Sol of Nissan Chemical Ind Ltd to 150 mass parts IPA-ST-ZL ") in, mix the methacryloxypropyl trimethoxy silane of 13.7 mass parts and 10 matter of 1.7 mass parts Amount % aqueous formic acid, stirs 1 hour in 70 DEG C.Then, the fluorine compounds (H of 13.8 mass parts is added₂C=CH-COO-CH₂- (CF₂)₈After 2, the 2- azodiisobutyronitrile of F) and 0.57 mass parts, in 90 DEG C of heating stirrings 60 minutes, dispersion liquid is obtained.

(surface-treated silicon dioxide granule dispersion liquid B)

Cataloid (" the Organo Silica Sol of Nissan Chemical Ind Ltd to 150 mass parts IPA-ST-ZL ") in, mix the methacryloxypropyl trimethoxy silane of 13.7 mass parts and 10 matter of 1.7 mass parts Amount % aqueous formic acid, stirs 1 hour in 70 DEG C.Then, the fluorine compounds of 9 mass parts as hydrophobic compound are added (H₂C=CH-COO-CH₂-(CF₂)₈Silicone compounds (the Dainippon Ink. ＆ Chemicals Inc of F) and 4.8 mass parts " PC-4131 " of system) and 2, the 2- azodiisobutyronitrile of 0.57 mass parts after, in 90 DEG C of heating stirrings 60 minutes, divided Dispersion liquid.

(surface-treated silicon dioxide granule dispersion liquid C)

Cataloid (" the Organo Silica Sol of Nissan Chemical Ind Ltd to 330 mass parts IPA-ST-ZL ") in, add acryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system), 2 matter of 8 mass parts Ten trifluoro octyl group trimethoxy silanes (GE Toshiba organosilicon (strain) system) and the acetic aluminium two of 1.5 mass parts for measuring part is different Propyl ester (diisopropoxy aluminum ethyl acetate) is simultaneously mixed, and is subsequently adding the ion exchange of 9 mass parts Water.After its reaction being made 8 hours in 60 DEG C, be cooled to room temperature, add the acetylacetone,2,4-pentanedione of 1.8 mass parts.Then, to the dispersion Add cyclohexanone while solvent displacement is carried out using vacuum distillation under pressure 20kPa in liquid, obtain dispersion liquid.

(surface-treated silicon dioxide granule dispersion liquid D)

Cataloid (" the Organo Silica Sol of Nissan Chemical Ind Ltd to 150 mass parts MEK-ST-2040 ") in, mix the methacryloxypropyl trimethoxy silane of 13.7 mass parts and the 10 of 1.7 mass parts Quality % aqueous formic acid, stirs 1 hour in 70 DEG C.Then, the fluorine compounds (H of 13.8 mass parts is added₂C=CH-COO- CH₂-(CF₂)₈After 2, the 2- azodiisobutyronitrile of F) and 0.57 mass parts, in 90 DEG C of heating stirrings 60 minutes, dispersion liquid is obtained.

(surface-treated silicon dioxide granule dispersion liquid E)

Cataloid (" the Organo Silica Sol of Nissan Chemical Ind Ltd to 150 mass parts MEK-ST-L ") in, mix the methacryloxypropyl trimethoxy silane of 13.7 mass parts and 10 matter of 1.7 mass parts Amount % aqueous formic acid, stirs 1 hour in 70 DEG C.Then, the fluorine compounds (H of 13.8 mass parts is added₂C=CH-COO-CH₂- (CF₂)₈After 2, the 2- azodiisobutyronitrile of F) and 0.57 mass parts, in 90 DEG C of heating stirrings 60 minutes, dispersion liquid is obtained.

[embodiment 1]

Hard coat film is made by following main points.

Refractive index be 1.65, thickness be on 100 μm of the two sides of polyethylene terephthalate film (PET film), point Online coating resin layer not in the manufacturing process of PET film.That is, on the two sides of the PET film that crosses in uniaxial tension along its length, Stick coating method coating resin layer formation coating fluid a is respectively adopted, after being dried in 100 DEG C, is continued twin shaft in the width direction and draws Stretch, implement to heat 20 seconds in 230 DEG C so as to heat cure, be produced on the laminated PET film for having resin bed in two sides.It is laminated at PET The refractive index of the resin bed on the two sides of film is 1.59, and thickness is 0.09 μm.

<1st and the 2nd hard conating laminated>

On the resin bed of the one side of the laminated PET film for having resin bed in two sides, following activity are coated with using gravure coating process Energy ray-curable composition a, after being dried in 90 DEG C, irradiation ultraviolet radiation 400mJ/cm²Its solidification is made, forms the 1st hard Coating.The thickness of the 1st hard conating is 2.6 μm, and refractive index is 1.51.

Then, on the resin bed of the another side (face contrary with the laminated face for having the 1st hard conating) of PET film, also use Actinic-radiation curable composition a, carries out operation as described above and forms the 2nd hard conating, make hard coat film.2nd The thickness of hard conating is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition a>

By the acrylate compounds of the dipentaerythritol acrylate of 50 mass parts, 37 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 8 mass parts and divide Dispersion liquid A, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 2]

2nd hard conating is changed to following Actinic-radiation curable composition b, in addition, similarly to Example 1 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

<Actinic-radiation curable composition b>

By the dipentaerythritol acrylate of 48 mass parts, the urethane acrylate oligomer of 47 mass parts (" UN-901T " of industrial (strain) on root；In molecule include 9 polymerizable functional group), the Photoepolymerizationinitiater initiater of 5 mass parts (Ciba Specialty Chemicals (strain) makes " IRGACURE 184 ") dispersing and dissolving is in organic solvent (Methylethyl Ketone) in, it is prepared.

[embodiment 3]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition c, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition c>

By the dipentaerythritol acrylate of 87 mass parts, to be converted into solid state component be the surface-treated of 8 mass parts Silicon dioxide granule dispersion liquid B, 5 mass parts Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) make " IRGACURE 184 ") it is blended in organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 4]

2nd hard conating is changed to above-mentioned Actinic-radiation curable composition b, in addition, similarly to Example 3 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

[embodiment 5]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition d, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition d>

By the dipentaerythritol acrylate of 87 mass parts, to be converted into solid state component be the surface-treated of 8 mass parts Silicon dioxide granule dispersion liquid C, 5 mass parts Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) make " IRGACURE 184 ") (mass ratio of methyl ethyl ketone and cyclohexanone is molten for 8: 2 mixing in organic solvent for dispersing and dissolving Agent) in, it is prepared.

[embodiment 6]

2nd hard conating is changed to above-mentioned Actinic-radiation curable composition b, in addition, similarly to Example 5 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

[embodiment 7]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition e, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition e>

By the acrylate compounds of the dipentaerythritol acrylate of 50 mass parts, 37 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 8 mass parts and divide Dispersion liquid D, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 8]

2nd hard conating is changed to above-mentioned Actinic-radiation curable composition b, in addition, similarly to Example 7 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

[embodiment 9]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition f, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition f>

By the acrylate compounds of the dipentaerythritol acrylate of 50 mass parts, 37 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 8 mass parts and divide Dispersion liquid E, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 10]

2nd hard conating is changed to above-mentioned Actinic-radiation curable composition b, in addition, similarly to Example 9 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

[comparative example 1]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition g, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition g>

By the dipentaerythritol acrylate of 87 mass parts, it is converted into the titanium dioxide silicon grain that solid state component is 8 mass parts The photopolymerization of sub (" the Organo Silica Sol IPA-ST-ZL " of Nissan Chemical Ind Ltd), 5 mass parts causes Agent (Ciba Specialty Chemicals (strain) makes " IRGACURE 184 ") dispersing and dissolving is in organic solvent (Methylethyl The mass ratio of ketone and cyclohexanone is 8: 2 mixed solvent) in, it is prepared.

[comparative example 2]

2nd hard conating is changed to above-mentioned Actinic-radiation curable composition b, in addition, same with comparative example 1 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

[comparative example 3]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition h, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.52.

<Actinic-radiation curable composition h>

By the dipentaerythritol acrylate of 87 mass parts, it is converted into the polymethyl that solid state component is 8 mass parts Sour methyl esters particle (comprehensive grind " MX-150H " that chemical (strain) makes), Photoepolymerizationinitiater initiater (the Ciba Specialty of 5 mass parts Chemicals (strain) makes " IRGACURE 184 ") dispersing and dissolving is in the organic solvent (mass ratio of methyl ethyl ketone and cyclohexanone Mixed solvent for 8: 2) in, it is prepared.

[comparative example 4]

2nd hard conating is changed to above-mentioned Actinic-radiation curable composition b, in addition, same with comparative example 3 Ground operation, makes hard coat film.The thickness of the 2nd hard conating is 2.6 μm, and refractive index is 1.52.

[embodiment 11]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition i, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition i>

By the acrylate compounds of the dipentaerythritol acrylate of 54 mass parts, 37 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 4 mass parts and divide Dispersion liquid A, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 12]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition j, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition j>

By the acrylate compounds of the dipentaerythritol acrylate of 52 mass parts, 37 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 6 mass parts and divide Dispersion liquid A, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 13]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition k, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition k>

By the acrylate compounds of the dipentaerythritol acrylate of 50 mass parts, 35 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 10 mass parts and divide Dispersion liquid A, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[embodiment 14]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition l, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition l>

By the acrylate compounds of the dipentaerythritol acrylate of 50 mass parts, 33 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 12 mass parts and divide Dispersion liquid A, the Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " IRGACURE 184 ") of 5 mass parts are mixed Close in organic solvent (methyl ethyl ketone), be prepared.

[comparative example 5]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition m, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition m>

By the acrylate compounds of the dipentaerythritol acrylate of 56 mass parts, 37 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 2 mass parts and divide Dispersion liquid A, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[comparative example 6]

Following active-energies will be changed to for the Actinic-radiation curable composition for forming the 1st and the 2nd hard conating Ray-curable composition n, in addition, is operated similarly to Example 1, makes hard coat film.The thickness of the 1st and the 2nd hard conating Degree is 2.6 μm, and refractive index is 1.51.

<Actinic-radiation curable composition n>

By the acrylate compounds of the dipentaerythritol acrylate of 45 mass parts, 30 mass parts, (East Asia synthesizes strain " the ARONIX M111 " of formula commercial firm), be converted into the surface-treated silicon dioxide granule that solid state component is 20 mass parts and divide Dispersion liquid A, Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) makes " the IRGACURE 184 ") mixing of 5 mass parts In organic solvent (methyl ethyl ketone), it is prepared.

[comparative example 7]

In the making of the laminated PET film for having resin bed of embodiment 1, resin bed formation coating fluid is changed to resin Layer formation coating fluid b, in addition, operates similarly to Example 1, is produced on the laminated PET film for having resin bed in two sides.Layer The respective refractive index of resin bed together in the two sides of PET film is 1.52, and thickness is 0.09 μm.

<1st and the 2nd hard conating laminated>

In the above-mentioned laminated PET film for having resin bed, operate in the same manner as comparative example 5, laminated 1st and the 2nd hard conating, system Make hard coat film.The thickness of the 1st and the 2nd hard conating is 2.6 μm, and refractive index is 1.51.

[evaluation of hard coat film]

With regard to the embodiment that obtained by aforesaid operations and the hard coat film of comparative example, the composition of the 1st and the 2nd hard conating is shown In table 1, the evaluation result of these hard coat films is shown in table 2.

Additionally, for the representational sample in above-described embodiment and comparative example, determining the projection of the 1st hard coating surface Average diameter, average height and equispaced.As a result table 3 is shown in.

[table 3]

According to the above results, following conclusions can be drawn：In embodiment 1～14, per unit is formed with the 1st hard coating surface (100 μm of area²) it is that the projection of 300～10000, therefore sliding and resistance to adhesive are good.Additionally, following knots can be drawn By：The center line average roughness (Ra1, Ra2) of the 1st and the 2nd hard conating is less than 30nm, and the haze value of hard coat film diminishes and (is less than 1.5%), the transparency is good, and therefore total light transmittance is high.

[embodiment 15～24]

On the 2nd hard conating face of the hard coat film of embodiment 1～10, laminated as nesa coating using sputtering method Ito film, makes the thickness of ito film become 25nm, makes transparent and electrically conductive film.For these transparent and electrically conductive films, sliding is evaluated With resistance to adhesive.As a result table 4 is shown in.

[table 4]

	Hard coat film	Sliding	Resistance to adhesive
				Embodiment 15	Embodiment 1	A	A
Embodiment 16	Embodiment 2	A	A
				Embodiment 17	Embodiment 3	A	A
Embodiment 18	Embodiment 4	A	A
				Embodiment 19	Embodiment 5	A	A
Embodiment 20	Embodiment 6	A	A
				Embodiment 21	Embodiment 7	A	A
Embodiment 22	Embodiment 8	A	A
				Embodiment 23	Embodiment 9	B	B
Embodiment 24	Embodiment 10	B	B

It should be noted that the evaluation of sliding with regard to transparent and electrically conductive film and resistance to adhesive, " (14) slide above-mentioned In the evaluation of property " and " evaluation of (15) resistance to adhesive ", it is changed in the way of the 1st hard conating face is relative with electrically conducting transparent face Overlap, in addition, similarly evaluated.

The sliding of any one of the transparent and electrically conductive film of embodiment 15～24 and resistance to adhesive all good.

[embodiment 25～29]

On the 2nd hard conating face of the hard coat film of embodiment 2,4,6,8 and 10, laminated following high refractive index layers and low successively Index layer, then forms following nesa coatings on low-index layer, makes for the saturating of capacitive touch panel Bright conductive film.

Gravure coating process is utilized to be coated with following Actinic-radiation curable composition for forming high refractive index layer, in After 90 DEG C are dried, irradiation ultraviolet radiation 400mJ/cm²Its solidification is made, forms high refractive index layer of the thickness for 50nm.The height folding The refractive index for penetrating rate layer is 1.68.

(for forming the Actinic-radiation curable composition of high refractive index layer)

By the dipentaerythritol acrylate of 21 mass parts, the urethane acrylate oligomer of 21 mass parts (" UN-901T " of industrial (strain) on root；Include 9 polymerizable functional group in molecule), the zirconium oxide of 55 mass parts and 3 mass parts Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals (strain) make " IRGACURE 184 ") be dispersed or dissolved in organic In solvent (propylene glycol monomethyl ether), it is prepared.

<Low-index layer laminated>

Gravure coating process is utilized to be coated with following Actinic-radiation curable composition for forming low-index layer, in After 90 DEG C are dried, irradiation ultraviolet radiation 400mJ/cm²Its solidification is made, forms low-index layer of the thickness for 40nm.The low folding The refractive index for penetrating rate layer is 1.40.

(for forming the Actinic-radiation curable composition of low-index layer)

By two (α-perfluoroalkyl acrylate) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9- of 87 mass parts 17 fluorine nonyl Ethyl glycol ester, the dipentaerythritol acrylate of 10 mass parts, the Photoepolymerizationinitiater initiater (Ciba of 3 mass parts Specialty Chemicals (strain) makes " IRGACURE184 ") it is dispersed or dissolved in organic solvent (methyl ethyl ketone), enter Prepared by row.

Using the laminated ito film of sputtering method, the thickness of ito film is made to become 25nm, pattern processing (etch processes) becomes clathrate Pattern, forms nesa coating.

[evaluation]

For the transparent and electrically conductive film of embodiment 25～29, sliding, resistance to adhesive and electrically conducting transparent film figure is evaluated Visually recognizable property.As a result table 5 is shown in.

[table 5]

It should be noted that the evaluation of sliding with regard to transparent and electrically conductive film and resistance to adhesive, " (14) are sliding above-mentioned In the evaluation of dynamic property " and " evaluation of (15) resistance to adhesive ", the side relative with electrically conducting transparent face with the 1st hard conating face is changed to Formula is overlapped, and in addition, is similarly evaluated.

The transparent and electrically conductive film of embodiment 25～29 all shows good sliding, resistance to adhesive and nesa coating The visually recognizable property of pattern.

[embodiment 31～40]

As follows, prepare 5 kinds of different resin bed formation coating fluids of wetting tension.

(resin bed formation coating fluid c；Wetting tension 42mN/m)

In terms of solid state component mass ratio, by following polyester resin c of 27 mass %, the polyester resin d of 54 mass %, 18 matter The melamine class crosslinking agent of amount %, the mix particles of 1 mass %, prepare moisture and dissipate coating fluid.

Polyester resin c：By 43 moles of NDA, 7 moles of %/5-sodium sulfo isophthalate %/ethylene glycol The polyester resin that 45 moles of %/diethylene glycol (DEG)s, 5 moles of % are constituted.

Polyester resin d：By 38 moles of terephthalic acid (TPA), 12 moles of %/trimellitic acid, 45 moles of %/bis- of %/ethylene glycol are sweet The polyester resin that 5 moles of % of alcohol are constituted.

Melamine class crosslinking agent：Three " the NIKALAC MW12LF " made with chemical (strain)

Particle：The cataloid that 0.19 μm of average grain diameter.

(resin bed formation coating fluid d；Wetting tension 44mN/m)

In terms of solid state component mass ratio, by following polyester resin e of 42 mass %, the acrylic resin a of 42 mass %, 6 The epoxies crosslinking agent of quality %, the surfactant of 9 mass %, the mix particles of 1 mass %, prepare moisture and dissipate coating fluid.

Polyester resin e：By 35 moles of terephthalic acid (TPA), 11 moles of %/M-phthalic acid %/M-phthalic acid -5- sulfonic acid 4 moles of sodium, 45 moles of %/ethylene glycol, 4 moles of %/diethylene glycol (DEG), 1 mole of %/polyethylene glycol (number of repeat unit n=23) % is constituted Polyester resin.

Acrylic resin a：By 75 moles of methyl methacrylate, 18 moles of %/ethyl acrylate %/N- methylol third The acrylic acid that 4 moles of acrylamide, 3 moles of %/methoxy poly (ethylene glycol) (number of repeat unit n=10) methacrylate % is constituted Resin.

Epoxies crosslinking agent：1,3- double (N, N- diglycidyl amine) hexamethylenes

Surfactant：Polyoxyethylene lauryl ether (polyoxyethylene lauryl ether)

Particle：The cataloid that 0.19 μm of average grain diameter.

(resin bed formation coating fluid e；Wetting tension 48mN/m)

In terms of solid state component mass ratio, by following polyester resin f of 40 mass %, the acrylic resin b of 40 mass %, 10 The melamine class crosslinking agent of quality %, the surfactant of 9 mass %, the mix particles of 1 mass %, prepare moisture and dissipate coating Liquid.

Polyester resin f：By 30 moles of terephthalic acid (TPA), 15 moles of %/M-phthalic acid %/M-phthalic acid -5- sulfonic acid The polyester resin that 5 moles of sodium, 30 moles of %/ethylene glycol, 20 moles of %/BDO % is constituted.

Acrylic resin b：Rubbed by 75 moles of methyl methacrylate, 22 moles of %/ethyl acrylate %/acrylic acid 1 The acrylic resin that your 2 moles of % of %/N- NMA are constituted

Surfactant：Polyoxyethylene lauryl ether

Particle：The cataloid that 0.19 μm of average grain diameter.

(resin bed formation coating fluid f；Wetting tension 51mN/m)

In terms of solid state component mass ratio, by following polyester resin g of 45 mass %, the acrylic resin c of 45 mass %, 5 The melamine class crosslinking agent of quality %, the surfactant of 4 mass %, the mix particles of 1 mass %, prepare moisture and dissipate coating Liquid.

Polyester copolymer g：By 32 moles of terephthalic acid (TPA), 12 moles of %/M-phthalic acid %/M-phthalic acid -5- sulphur The polyester copolymer that 6 moles of sour sodium, 46 moles of %/ethylene glycol, 4 moles of %/diethylene glycol (DEG) % is constituted.

Acrylic resin c：By 70 moles of methyl methacrylate, 22 moles of %/ethyl acrylate %/N- methylol third The acrylic copolymer that 4 moles of acrylamide, 4 moles of %/N, N- DMAA % is constituted.

Surfactant：Polyoxyethylene lauryl ether

Particle：The cataloid that 0.19 μm of average grain diameter.

(resin bed formation coating fluid g；Wetting tension 53mN/m)

In terms of solid state component mass ratio, by the polyurethane resin of 85 mass %, the epoxies crosslinking agent of 5 mass %, 9 matter The surfactant of amount %, the mix particles of 1 mass %, prepare coating fluid.

Polyurethane resin：" HYDRAN AP-20 " that big Japanese ink chemical industry (strain) is made

Epoxies crosslinking agent：Triethylene glycol diglycidyl ether

Surfactant：Polyoxyethylene lauryl ether

Particle：The cataloid that 0.19 μm of average grain diameter.

[embodiment 31]

Hard coat film is made by following main points.

Refractive index be 1.65, thickness be on 100 μm of the two sides of polyethylene terephthalate film (PET film), point Online coating resin layer not in the manufacturing process of PET film.That is, on the two sides of the PET film that crosses in uniaxial tension along its length, Stick coating method coating resin layer formation coating fluid c is respectively adopted, after being dried in 100 DEG C, is continued twin shaft in the width direction and draws Stretch, implement to heat 20 seconds in 230 DEG C so as to heat cure, be produced on the laminated PET film for having resin bed in two sides.It is laminated at PET The thickness of the resin bed on the two sides of film is 0.08 μm.

<1st and the 2nd hard conating laminated>

On the resin bed of the one side of the laminated PET film for having resin bed in two sides, using in gravure coating process coating Examples 1 Actinic-radiation curable composition a for using, after being dried in 90 DEG C, irradiation ultraviolet radiation 400mJ/cm²Solidify which, Form the 1st hard conating.The thickness of the 1st hard conating is 1.6 μm.

Then, on the resin bed of the another side (face contrary with the laminated face for having the 1st hard conating) of PET film, using reality Apply Actinic-radiation curable composition b used in example 2 to be operated as described above, the 2nd hard conating is formed, make Hard coat film.The thickness of the 2nd hard conating is 1.6 μm.

[embodiment 32～35]

Resin bed formation is changed as shown in table 6 with coating fluid, in addition, is operated in the same manner as embodiment 31, Make hard coat film.

[embodiment 36～40]

The thickness of the 1st hard conating is changed to 2.6 μm, and the thickness of the 2nd hard conating is changed to 2.6 μm, except this with Outward, operate in the same manner as embodiment 31～35, make hard coat film.

[evaluation of hard coat film]

The hard coat film of the embodiment 31～40 with regard to being obtained by aforesaid operations, the composition of the 1st and the 2nd hard conating is shown in Table 6, the evaluation result of these hard coat films is shown in table 7.

According to the above results, by directly laminated 1st hard painting on resin bed of the wetting tension for below 52mN/m Layer, easily forms the projection (understanding that the projection number of per unit area becomes many) caused by particle in the 1st hard coating surface.And And, it is known that in the case that the thickness of the 1st hard conating is less than 2 μm, the impact of the wetting tension of resin layer surface becomes notable. That is, on resin bed of the wetting tension for below 52mN/m directly for the mode of laminated 1st hard conating, in the 1st hard painting In the case that the thickness of layer is less than 2 μm, the particle contained in the 1st hard conating is easily near surface partially, as a result, being capable of efficiency The projection that by particle caused is formed well.Additionally, by making the thickness of the 1st hard conating less than 2 μm, haze value becomes less, The transparency is improved.

Description of reference numerals

1～5 projection

11 projections

20 horizontal straight lines

30 longitudinal straight lines

Claims

1. a kind of hard coat film, it is characterised in that possess the 1st hard conating containing particle at least one side of base material film, by institute The projection of particle formation is stated with per 100 μm²It is present in the surface of the 1st hard conating for the density of 300～4000, the projection Average diameter is 0.03～0.3 μm, and the average height of the projection is 0.03～0.3 μm, and the center line of the 1st hard coating surface is put down All roughness Ra 1 is less than 30nm, and haze value is less than 1.5%, and the thickness (d) of the 1st hard conating is 0.5 μm less than 10 μm.

2. hard coat film as claimed in claim 1, wherein, the average grain diameter (r) of the particle is 0.05～0.5 μm.

3. hard coat film as claimed in claim 1 or 2, wherein, the average grain diameter (r) of the particle is with respect to the 1st hard conating The ratio (r/d) of thickness (d) is 0.01～0.30.

4. hard coat film as claimed in claim 1 or 2, wherein, the equispaced of the projection is 0.10～0.70 μm.

5. hard coat film as claimed in claim 1 or 2, wherein, the 1st hard conating is solid comprising thermosetting resin or active energy beam The property changed resin is used as resin, and the refractive index of the 1st hard conating is in the range of 1.48～1.54.

6. hard coat film as claimed in claim 1 or 2, wherein, possessing thickness between the base material film and the 1st hard conating is 0.005～0.3 μm of resin bed, the resin bed contain more than 1.3 times that average grain diameter is the resin layer thickness of particle.

7. hard coat film as claimed in claim 1 or 2, wherein, the base material film is formed by polyethylene terephthalate, institute State the resin bed for possessing between base material film and the 1st hard conating that refractive index is 1.55～1.61.

8. hard coat film as claimed in claim 1 or 2, wherein, possessing wetting tension between the base material film and the 1st hard conating is The resin bed of below 52mN/m.

9. hard coat film as claimed in claim 8, wherein, the thickness of the 1st hard conating is less than 2 μm.

10. hard coat film as claimed in claim 1 or 2, wherein, the particle contained in the 1st hard conating is comprising inorganic matter, right The surface of the particle implements process or the silicic acid anhydride for reducing surface free energy.

11. hard coat films as claimed in claim 10, wherein, for the surface of the particle contained in the 1st hard conating, use Formula 1 is C_nF_2n+1-(CH₂)_m-Si(Q)₃The organic silane compound of expression, the hydrolysate of the organic silane compound or institute The partial condensate of hydrolysate is stated, the process for reducing surface free energy is implemented,

Wherein, in formula 1, n represents 1～10 integer, and m represents 1～5 integer, and Q represents the alcoxyl that carbon number is 1～5 Base or halogen atom.

12. hard coat films as claimed in claim 10, wherein, for the surface of the particle contained in the 1st hard conating, make It is B-R with formula 2⁴-SiR⁵ _n(OR⁶)_3-nAfter the compound of expression is processed, the use of formula 3 is D-R⁷-Rf²The fluorine of expression Compound is processed, and has thus carried out hydrophobization,

Wherein, in formula 2 and 3, B and D represents reactive moieties, R independently of one another⁴And R⁷Represent carbon atom independently of one another Number is 1～3 alkylidene or the ester structure derived by the alkylidene, R⁵And R⁶Represent hydrogen or carbon number independently of one another For 1～4 alkyl, Rf²Represent fluoroalkyl, n represents 0～2 integer.

13. hard coat films as claimed in claim 10, wherein, for the surface of the particle contained in the 1st hard conating, use Fluorine compounds with the fluoroalkyl that reactive moieties and carbon number are more than 4, it is 8 with reactive moieties and carbon number The long-chain hydrocarbon compound of above alkyl or the silicone compounds with siloxy group and reactive moieties are processed, by This has carried out hydrophobization.

14. hard coat films as claimed in claim 1 or 2, wherein, the particle contained in the 1st hard conating is titanium dioxide silicon grain Son.

15. hard coat films as claimed in claim 1 or 2, wherein, in the base material film and the face phase for being provided with the 1st hard conating Possesses the 2nd hard conating on anti-face, the surface of the 2nd hard conating is created substantially absent the projection formed by particle, and the 2nd hard conating The center line average roughness Ra2 on surface is below 25nm.

A kind of 16. transparent and electrically conductive films, wherein, at least one side of the hard coat film any one of claim 1～15 Possesses nesa coating.