CN102218856B - Hard coating film and manufacturing method thereof - Google Patents
Hard coating film and manufacturing method thereof Download PDFInfo
- Publication number
- CN102218856B CN102218856B CN201110072453.1A CN201110072453A CN102218856B CN 102218856 B CN102218856 B CN 102218856B CN 201110072453 A CN201110072453 A CN 201110072453A CN 102218856 B CN102218856 B CN 102218856B
- Authority
- CN
- China
- Prior art keywords
- dope
- film
- casting films
- coating film
- cellulose acylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Moulding By Coating Moulds (AREA)
Abstract
The invention provides a hard coating film and a manufacturing method thereof, which is provided with a first concentrated solution (41) and a second concentrated solution (42) in a casting way so as to form a cast film (46) where the first concentrated solution (41) overlaps the second concentrated solution (42). The first concentrated solution (41) comprises a first cellulose acylate, a curing compound and a curing agent. The concentration of the curing compound in the first concentrated solution (41) ranges from 7 weight percent to 28 weight percent. The second concentrated solution (42) comprises a second cellulose acylate. The cast film (46) which is stripped is adopted as a wet film (47) which is dried and used as a dry film (51). A curing device (55) is adopted to irradiate ultraviolet rays on the dry film (51) and make the dry film cured. The obtained hard coating film (10) comprises a hard-coating layer, a film basic layer and a mixed layer, wherein, the thickness sum of the hard-coating layer and the mixed layer is more than ten percent of the total thickness.
Description
Technical field
The present invention relates to a kind of hard coating film and the manufacture method thereof that possess hard conating.
Background technology
In the sheet material for optical devices such as liquid crystal displays, majority is the parts manufactured from polymer film.Because most polymers film produces flaw because of the contact or friction with other materials, therefore most parts for arranging hard conating on polymer film in sheet material, in order to avoid produce scratch etc. in the manufacture process or use of optical device.
This hard conating with so-called Marresistance passes through the coating fluid be coated with forming hard conating on polymer film, and implements predetermined curing process to be formed to coated film.Can enumerate as curing process and irradiate light to solidify the operation of cure component contained in coated film to coated film.Such as, the method disclosing irradiation ultraviolet radiation to solidify in Japanese Patent Publication 2001-205179 publication.
So far, also proposed the various composition solidified by irradiation light.Such as, in Japanese Patent Publication 9-137089 publication, propose have the putty composition solidified by the irradiation of near infrared light.This putty composition comprises containing polymerism unsaturated group resin, polymerizable unsaturated compound and near infrared light polymerization initiator.
Further, also propose by irradiating the composition that the composition that solidifies of light uses as the composition of the dope of solution film-forming to have.Such as, the dope composition containing ethylene unsaturated monomer is recorded in Japanese Patent Publication 2002-20410 publication.
But, by the coating solution of formation hard conating being formed coated film in polymer film and making this coated film solidify in the hard coating film of such previous methods manufacture, its hard conating is less with the adhesion of the supporter (film basal layer) be made up of polymer film, and hard conating is peeled off sometimes from supporter.
Further, the time needed for two operations in the past forming the operation of the polymer film being used as supporter and the operation that forms hard conating on supporter is longer, expects the manufacture efficiency improving hard coating film.
Further, in formation in the past by when being coated with and solidifying the hard conating produced, there is the problem that hardness is lower and so on.
Summary of the invention
The present invention completes to solve above-mentioned problem, its object is to provide a kind of and more effectively can manufacture than ever and improve hard coating film and the manufacture method thereof of the adhesion of hard conating and supporter.Its another object is the manufacture method of the hard coating film providing a kind of high rigidity.
To achieve these goals, hard coating film of the present invention possesses hard conating, film basal layer and is mixed in layer.Hard conating comprises the condensate that the 1st cellulose acylate and curability compound solidify.Described curability compound is solidified by ultraviolet irradiation.Film basal layer comprises the 2nd cellulose acylate and does not contain described condensate.Being mixed in layer is the layer that described condensate and described 2nd cellulose acylate mix.The described layer that is mixed in is disposed between described hard conating and described film basal layer.Wherein, described hard conating and the described thickness sum being mixed in layer are at least 10% relative to the thickness of hard coating film.
The amount of described 2nd cellulose acylate be mixed in layer preferably increases progressively towards described film basal layer continuously along with from described hard conating, described in the described polymeric amount be mixed in layer successively decrease continuously towards described film basal layer along with from described hard conating.
The manufacture method of hard coating film of the present invention possesses casting step (step A), strip step (step B), peels off rear drying steps (step C) and curing schedule (D step).Wherein, in the mode of the 1st dope and the 2nd dope overlap, described 1st dope and the common curtain coating of described 2nd dope are formed casting films on supporter in step A.Described 1st dope comprises the 1st cellulose acylate, curability compound and curing agent.Described curability compound is solidified by ultraviolet irradiation.Described curing agent promotes the solidification of described curability compound.The concentration of the described curability compound in described 1st dope is in the scope of below more than 7 quality % 28 quality %.Described 2nd dope comprises the 2nd cellulose acylate and does not contain described curing agent.Described casting films is peeled from described supporter in step B.Dry from the described casting films after described supporter is peeled off in step C.In D step to the described casting films on described supporter, to peel any one irradiation ultraviolet radiation the described casting films come and casting films after described step C from described supporter to solidify described curability compound.
Preferred described curability compound is at least any one party in dipentaerythritol acrylate and urethane acrylate.
Preferably the ultraviolet irradiation in described D step is carried out to the film by described step C drying.
The manufacture method of preferred hard coating film possesses cooling step (E step).E step cools casting films and makes it gelation on described supporter.Send into gas in this cooling period to described casting films and solidify the exposed surface of described casting films.
The manufacture method of preferred hard coating film possesses peels off front drying steps (F step) and semi-solid preparation step (G step).Casting films in F step on dry described supporter, and drying was completed before casting films bone dry.To the described casting films irradiation ultraviolet radiation on the described supporter through described F step and curability compound described in semi-solid preparation in G step.
Preferably in the step A, the 1st dope and described 2nd dope described in curtain coating altogether continuously on supporter, described F step can carry out, from the degree of the transmission after described supporter is peeled off continuously, terminating the drying of described casting films.
Preferably can carry out, from the degree of the transmission after described supporter is peeled off continuously, terminating the semi-solid preparation of described curability compound in described G step.
Invention effect
Can improve the adhesion of hard conating and supporter (film basal layer) while hard coating film of the present invention can more effectively manufacture than ever, therefore hard conating not easily peels.Further, manufacturing method according to the invention, more effectively can manufacture the hard coating film of the adhesion improving hard conating and supporter than ever.Except this effect, manufacturing method according to the invention, can produce the hard coating film that hardness is high.
Accompanying drawing explanation
Those skilled in the art, can easy understand above-mentioned purpose and advantage by referring to accompanying drawing and the detailed description of preferred embodiments when read.
Fig. 1 is the sectional view of hard coating film of the present invention.
Fig. 2 is the chart of the time of flight secondary ion massspectrometry result of hard coating film.Solid line represents C
6h
5o
2, dotted line represents C
2h
3.
Fig. 3 is the concise and to the point figure of the film manufacturing device manufacturing hard coating film of the present invention.
Fig. 4 is the concise and to the point figure of the film manufacturing device manufacturing hard coating film of the present invention.
Detailed description of the invention
As shown in Figure 1, hard coating film 10 of the present invention possesses hard conating 11, film basal layer 12 and is mixed in layer 13.Be mixed in layer 13 to be formed between hard conating 11 and film basal layer 12.Like this, hard coating film 10 possesses hard conating 11 on the face of a side.In addition, conveniently, illustrate hard conating 11 in FIG and be mixed in the boundary of layer 13 and film basal layer 12 and the boundary being mixed in layer 13.But this boundary is the abstract boundary of the combination according to formed material, cannot use visual identity.
Hard conating 11 comprises the condensate that the 1st cellulose acylate and curability compound are polymerized.Owing to using curing agent when forming hard conating 11, therefore also remain curing agent in hard conating 11.Curing agent is the material promoting curability compound cures.
Film basal layer 12 comprises the 2nd cellulose acylate.Film basal layer 12 does not comprise the condensate that described curability compound is polymerized.
Be mixed in layer 13 for comprising the 2nd cellulose acylate and described condensate both sides and both layers of mixing.To be mixed in layer 13 except the 2nd cellulose acylate and described condensate, the 1st cellulose acylate can also be comprised.
The thickness of hard coating film 10 is set to TA, and the thickness of hard conating 11 is set to T11, and the thickness of film basal layer 12 is set to T12, and the thickness being mixed in layer 13 is set to T13.The thickness T11 making hard conating 11 and the thickness T13 sum being mixed in layer 13 are greater than based on the ratio in the hard coating film be in the past coated with relative to the ratio of the thickness TA of hard coating film 10.The thickness T11 of hard conating 11 is at least set to 10% with the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10.Thus, the adhesion of hard conating 11 become higher than in the past based on coating adhesion.In addition, the thickness T11 of hard conating 11 refers to the use { percentage (unit: %) that (T11+T13)/TA} × 100 are obtained with the thickness T13 sum being mixed in layer 13 relative to the ratio of the thickness TA of hard coating film 10.More preferably hard conating 11 thickness T11 and the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10 more than 10% less than 30% scope.
In the hard coating film in the past manufactured by coating, that sometimes can also see the membranaceous cellulose acylate that is coated with coating fluid and form that the condensate of hard conating mixes is mixed in layer.But, in order to strengthen the thickness of hard conating as described above and be mixed in the ratio of thickness sum relative to the thickness of hard coating film of layer, need the coating successively repeatedly carrying out coating fluid.The process number increased for the manufacture of hard coating film along with so increasing application frequency, and the thickness of hard coating film also becomes large.In contrast, hard coating film of the present invention by manufacture method described later, keep with based on other thickness of the ad eundem of hard coating film be in the past coated with.Further, the process number needed for the manufacture of hard coating film of the present invention with in the past based on the hard coating film be coated with manufacture method compared with, can with less process number manufacture.Among other benefits, the adhesion of hard conating 11 is greater than the adhesion in hard coating film in the past.
The longitudinal axis of Fig. 2 is secondary ion intensity (counts/s), and transverse axis represents the thickness direction of hard coating film 10.The A11 of transverse axis is the region of hard conating 11, and A12 is the region of film basal layer 12, and A13 is the region being mixed in layer 13.
As everyone knows, time of flight secondary ion massspectrometry instrument (Time-of-flight secondary ion massspectrometer, following abbreviation is TOF-SIMS) is irradiate primary ions bundle to the test portion as material for testing and carry out detecting one of device of the SIMS (SIMS) of the ion (secondary ion) of now releasing from the surface of test portion.In order to analyze, using from the sample embedding of sampling as the hard coating film 10 of material for testing in the epoxy.Use slicer to cut the sample of embedding state with the angular slope of about relative to the face of hard coating film 10 15 degree, and make sample be exposed on the surface and appear analysis face.Primary ions is radiated in the membrane portions of exposing surface.Mass spectrograph uses time of-flight mass spectrometer (TOF-MS).In the present embodiment, when carrying out TOF-SIMS, use TOF-SIMS5 and the Bi3+ primary ions rifle that ION-TOF commercial firm manufactures, but the present invention is not limited thereto.
The C of the solid line (A) in Fig. 2
6h
5o
2cellulose acylate is used as by the chart of (fragment from the glucopyranose skeleton of TAC).This solid line (A) illustrates with two side's sums of the 1st cellulose acylate and the 2nd cellulose acylate.Cellulose acylate in hard conating 11 is the 1st cellulose acylate.The cellulose acylate be mixed in layer 13 is the 1st cellulose acylate and the 2nd cellulose acylate.Cellulose acylate in film basal layer 12 is the 2nd cellulose acylate.
The C of the dotted line (B) in Fig. 2
2h
3chart be used as condensate.
As shown in solid line (A), the amount being mixed in the cellulose acylate in layer 13 increases progressively towards film basal layer 12 along with from hard conating 11, and this to increase progressively be continuous print.The polymeric amount be mixed in layer 13 is successively decreased towards film basal layer 12 along with from hard conating 11, and this successively decreases is continuous print.According to the distribution on this cellulose acylate and polymeric thickness direction, the adhesion of hard conating 11 uprises really.Further, even if from hard conating 11 in the scope being mixed in layer 13, increasing progressively and being polymerized successively decreasing of the scale of construction of cellulose acylate amount is also continuous print.Thereby, it is possible to more positively prevent hard conating 11 from being peeled off at hard conating 11 and the boundary being mixed in layer 13.
Further, as shown in dotted line (B), the polymeric amount be mixed in layer 13 is successively decreased towards film basal layer 12 along with from hard conating 11.Further, even if from hard conating 11 in the scope being mixed in layer 13, increasing progressively of the scale of construction of polymerization is also continuous print.This continuity on polymeric thickness direction is distributed with the adhesion helping hard conating 11.
In the hard coating film in the past manufactured by coating; even if the amount implemented repeatedly to be coated with and be mixed in the cellulose acylate in layer is along with increasing progressively from hard conating towards film basal layer; this increases progressively also is interim, is also interim from hard conating increasing progressively in the scope being mixed in layer.
Be described with reference to the 1st embodiment of Fig. 3 to the manufacture method of hard coating film.As shown in Figure 3, membrane producing device 40 is the solution film-forming equipment being made hard coating film 10 by solution film-forming by the 1st dope 41 and the 2nd dope 42.1st dope 41 forms hard conating 11.2nd dope 42 forms the film basal layer 12 as supporter.
1st dope 41 comprises: the 1st cellulose acylate; Curability compound, if serve as irradiation ultraviolet radiation, the composition solidified by this irradiation; And curing agent, promote the solidification of curability compound.Wherein, the 1st cellulose acylate is dissolved in solvent composition.
The concentration of the 1st cellulose acylate in the 1st dope 41 is set to the value of the following scope of more than 2 quality % 20 quality %.The concentration of the curability compound in the 1st dope 41 is set to the value of the following scope of more than 7 quality % 28 quality %.So, in the present invention, formed hard conating 11 the 1st dope 41 in curability compound concentration with in the past by be coated with form hard conating coating fluid compared with high.Like this, owing to comprising curability compound with very high concentration, therefore with in the past by be coated with form hard conating coating fluid compared with, the viscosity of the 1st dope 41 is very high.Detailed content for curability compound and curing agent is carried out aftermentioned.
Even if make the 1st cellulose acylate be contained in the 1st dope 41 with above-mentioned concentration range, the hardness of the hard conating 11 of the hard coating film 10 obtained also is not less than the hard conating of the hard coating film in the past based on coating, manifests the hardness of more than equal rank.Further, if the concentration of curability compound is less than 7 quality %, then the hardness can saying very sufficient level as hard conating cannot be reached.As more than, the amount reducing cellulose acylate to make to comprise a large amount of curability compounds in the 1st dope 41, but the hard conating 11 forming pencil hardness 2H above hardness.
The above-mentioned concentration of the 1st cellulose acylate in the 1st dope 41 be the quality of the 1st dope 41 is set to X11, the quality of the 1st cellulose acylate when being set to Y11 by the { value that Y11/X11} × 100 are obtained.Further, the above-mentioned concentration of the curability compound in the 1st dope 41 be the quality of the 1st dope 41 is set to X11, the quality of curability compound when being set to Z11 by the { value that Z11/X11} × 100 are obtained.
2nd dope 42 is the dopes be dissolved in by the 2nd cellulose acylate in solvent.Not containing curing agent in 2nd dope 42.The concentration of the 2nd cellulose acylate in the 2nd dope 42 is set to below more than 16 quality % 25 quality %.Further, the concentration of the 2nd cellulose acylate in the 2nd dope 42 is set to the concentration higher than the 1st cellulose acylate in the 1st dope 41.Thereby, it is possible to positively acquisition is mixed in the amount of the 2nd cellulose acylate in layer 13 along with the hard coating film increased progressively continuously towards film basal layer 12 from hard conating 11.
The above-mentioned concentration of the 2nd cellulose acylate in the 2nd dope 42 be the quality of the 2nd dope 42 is set to X12, the quality of the 2nd cellulose acylate when being set to Y12 by the { value that Y12/X12} × 100 are obtained.
1st cellulose acylate and the 2nd cellulose acylate can be mutually the same, and the kind of acyl group and the substitution value of acyl group etc. also can be different.
Membrane producing device 40 possesses curtain coating portion 50, drying section 52, solidification equipment 55 and devices for taking-up 56.Curtain coating portion 50 forms the casting films 46 that is made up of the 1st dope 41 and the 2nd dope 42 and moistening film 47 as the solvent-laden state of bag peels.The dry moistening film 47 of drying section 52 is as desciccator diaphragm 51.Solidification equipment 55 irradiation ultraviolet radiation solidifies curability compound.Devices for taking-up 56 batches obtained hard coating film 10 and makes roll.
Curtain coating mould 61, cylinder 62 and roller 63 is had in curtain coating portion 50.Curtain coating mould 61 flows out the 1st dope 41 and the 2nd dope 42 that are supplied to.Cylinder 62 is for being disposed in the below of curtain coating mould 61 and the supporter of curtain coating for no reason rotated in the circumferential.When peeling off casting films 46 from cylinder 62, support moistening film 47 by roller 63.
1st dope 41 and the 2nd dope 42 are all from a curtain coating mould 61 to cylinder 62 curtain coating.That is, this curtain coating mode is well-known curtain coating mode altogether.This common curtain coating, in cylinder 62, flows out the 1st dope 41 in the mode forming on the 2nd dope 42 casting films 46 of overlapping 1st dope 41 from curtain coating mould 61 and the 2nd dope 42 carries out.If form casting films in the mode that the 1st dope 41 is in direct contact with on cylinder 62, be then difficult to from drum peel casting films, therefore preferably do not implement the common curtain coating as the 1st dope 41 is contacted with cylinder 62.In addition, in the viewpoint peeling off easness, the thickness of the 2nd dope 42 on cylinder 62 can be thinner.
In curtain coating mould 61, be formed with the 1st runner (not shown) that the 1st dope 41 that is supplied to flows in inside, the 2nd runner (not shown) that the 2nd dope 42 that is supplied to flows and the 1st runner and the 2nd runner be at interflow, position, interflow and the common runner (not shown) that flows of the 1st dope 41 and the 2nd dope 42 simultaneously.To this curtain coating mould 61 independent supply the 1st dope 41 and the 2nd dope 42, each dope 41,42 is collaborated in the inside of curtain coating mould 61 and makes it to flow out from curtain coating mould 61.
3rd dope (not shown) and the 1st dope 41 and the 2nd dope 42 together can be total to curtain coating.Such as, the mode that can be contacted with cylinder 62 lower than the 3rd dope of the 2nd dope 42 with the concentration of cellulose acylate flows out the 1st dope 41, the 2nd dope 42 and the 3rd dope from curtain coating mould.That is, to overlap on the 3rd dope and the 1st dope 41 overlaps the mode of the casting films of the form on the 2nd dope 42 to form the 2nd dope 42 on cylinder 62, these 3 dopes are flowed out at interflow, the inside of curtain coating mould.Thus, even if accelerate the rotating speed of cylinder 62 further and improve curtain coating speed further, also more positively can prevent air from entering between casting films and cylinder 62, or more easily produce the hard coating film with level and smooth face.
The temperature control part (not shown) all surface temperatures being controlled to predetermined temperature is possessed in cylinder 62.Can the side face of heated roller 62, to make the temperature of raising casting films 46, also can the side face of chilling roll 62, to make the temperature of reduction casting films 46.In the present embodiment, the side face of chilling roll 62, makes it gelation to make casting films 46 be cooled to predetermined temperature.
The upstream side of the curtain coating mould 61 preferably in the direction of rotation of cylinder 62 arranges pressure-reducing chamber 64.The space should reduced pressure in pressure-reducing chamber 64 and space outerpace separate, and are attracted the gas in the space reduced pressure by attracting mechanism.Thus, attract the air in the district of the liquid pearl upstream side formed than transferring to cylinder 62 from curtain coating mould 61 and reduce pressure.
Can certain distance be kept with the side face of cylinder 62 and arrange the air-supply arrangement 65 of eluting gas.Air-supply arrangement 65 possesses conduit 77, the pressure fan 78 be connected with conduit 77 that the side face along cylinder 62 extends and is connected with pressure fan 78 and the controller 79 of the flow controlled from the gas of pressure fan 78 and temperature.Conduit 77 has the opening (not shown) opposed with the side face of cylinder 62, and releases dry gas from this opening.By controlling the flow velocity of gas that pressure fan 78 controls to spray from conduit 77 or flow and temperature according to controller 79.
Air-supply arrangement 65 is blown to casting films 46.The flow direction of the gas in this air-supply is preferably opposed wind rightabout relative to the direct of travel of casting films 46, namely against the wind.The exposed surface of casting films 46 is solidified more particularly by the air-supply from this air-supply arrangement 65.The exposed surface of casting films 36 refers to the face with the face opposite side of a side of the cylinder 62 being contacted with casting films 46, is namely exposed to outside face.
Roller 63 possesses near the stripping position should peeling off casting films 46 from cylinder 62.Roller 63 is opposed with cylinder 62 and arrange, to make long side direction consistent with the long side direction of cylinder 62.When peeling off casting films 46 from cylinder 62, roller 63 supports moistening film 47, thus, peels off position and is retained as constant.
If casting films 46 has self-supporting, then can peel off from cylinder 62.To wrap the casting films that solvent-laden state is peeled off from cylinder 62, namely moistening film 47 is directed to the stenter 66 of drying section 52.
In stenter 66, be equipped with the clip 67 of the maintaining body of multiple side end as the moistening film 47 of maintenance respectively in the both sides of the transmission path of moistening film 47.When moistening film 47 cannot stand the holding based on clip 67, such as, when the containing ratio of solvent too high and because of hold break time etc., pin can be used to replace clip 67, and with pin puncture at the side end of moistening film 47, keep moistening film 47 thus.
Multiple clip 67 possesses on the chain be for no reason continuously traveling (not shown).The track of advancing of clip 67 can be changed by advancing of this chain of displacement.The distance of the clip 67 and clip 67 that also suitably can adjust the both sides being disposed in moistening film 47 is respectively to control the width of moistening film 47.
Have in stenter 66 and the dry air adjusted by temperature is jetted to the air-supply conduit 68 of moistening film 47.By carrying out being kept by clip 67 from the air-supply of this air-supply conduit 68 and the drying of moistening film 47 during transmitting.
In addition, when supporting with the side face of roller and can being transmitted by the rotation of roller, also stenter 66 can be arranged.
The moistening film 47 removing the holding of clip 67 is directed to the device for excising 70 possessed in the downstream of stenter 66.The vestige of holding is remained in the holding position held by clip 67 of moistening film 47.Device for excising 70 with this holding vestige with become hard coating film 10 product middle body from the side end of the moistening film 47 of mode continuous shear stress.
There is in the downstream of device for excising 70 hothouse 73 of supply dry air.Hothouse 73 possesses multiple rollers 72 of the moistening film 47 supporting cut both side ends with side face.Comprise in roller 72 and transmit the driven roller of moistening film 47 by rotary actuation in the circumferential.The dry air be supplied to is adjusted to predetermined temperature and humidity, and moistening film 47 carries out drying and bone dry further by this dry air.The degree of being somebody's turn to do " completely " is the degree of the drying as product degree out of question, and solvent residues amount can not be necessarily 0 (zero).In the following description the film of such bone dry is called desciccator diaphragm 51.
Solidification equipment 55 is the ultraviolet light source of injection, to directed desciccator diaphragm 51 irradiation ultraviolet radiation of coming.Curability compound cures is made by this irradiation.When curability compound is the compound by irradiating polymerization, the carrying out of this polymerization is equivalent to the carrying out of solidifying.
In addition, solidification equipment 55 also can be arranged at the downstream that curtain coating portion 50, stenter 66 and hothouse 73 replace the drying section 52 be arranged at as present embodiment.That is, can to any one irradiation ultraviolet radiation in casting films 46, moistening film 47 and desciccator diaphragm 51.Further, solidification equipment 55, except being arranged at the downstream as the drying section 52 of present embodiment, also can be arranged at curtain coating portion 50, stenter 66 and hothouse 73.So, ultraviolet irradiation is carried out to any one in casting films 46, moistening film 47 and desciccator diaphragm 51.When manufacturing hard coating film 10 by implementing 1 curing process based on the irradiation of 1 solidification equipment 55, more preferably the moistening film irradiation ultraviolet radiation after becoming below 120 quality % to solvent residues rate, further preferably as the present embodiment that the membrane producing device 40 by Fig. 3 manufactures to desciccator diaphragm 51 irradiation ultraviolet radiation that solvent has evaporated.
By the ultraviolet irradiation of solidification equipment 55, form hard conating 11 at the face of a side of desciccator diaphragm 51.
The hard coating film 10 obtained batches with roll and is being sheathed on the core 76 of reeling end 56.
Face as a side of the hard coating film 10 of above-mentioned manufacture is hard conating.Its hard conating demonstrates very high adhesion.Such as, according to the evaluation of the cross cut test (grid belt stripping test) in accordance with JIS DO202-1988, the result of less than more than 90/,100 100/100 scope is drawn.100/100 refers to that in lattice by shearing cancellate 100 lattice formed, 100 lattice are all unstripped and residual.The lattice number that the numerical value recorded in denominator is formed is the unstripped and residual lattice number of molecule.That is, less than more than 90/,100 100/100 refer to that lattice in 100 lattice formed by cancellate shearing more than 90 lattice below 100 lattice is unstripped and residual.
In the past, at least operation in 2 stages that the film making process of enforcement making film basal layer is such with the painting process forming hard conating, therefore the manufacture efficiency of hard coating film was lower.In contrast, if according to method of the present invention, owing to also forming hard conating in film-forming process, therefore manufacture efficiency obviously higher than previous methods.
Further, form hard conating according in film-forming process, hard conating demonstrates adhesion higher by the adhesion in the hard coating film of coating manufacture than ever.In the present invention, from the viewpoint according to the manufacture of curtain coating altogether, preferably make the viscosity of dope very higher than the viscosity by the coating fluid be coated with when forming hard conating.In order to so make full-bodied dope, monomer that molecular weight is larger or oligomer can be used as the composition of dope.As the molecular weight of monomer or oligomer, preferably more than 1000.By using the larger monomer of this molecular weight or oligomer as the composition of dope, full-bodied dope can be produced.In contrast, the composition of monomer as coating fluid of molecular weight is used in the coating fluid when being formed hard conating by coating in the past.If molecular weight, then sometimes formed and lack the hard conating of uniformity, but formed by the monomer that uses molecular weight higher in common curtain coating or oligomer evenly hard conating.
Below, each composition of the 1st dope 41 and the 2nd dope 42 and formula are described.
[the 1st cellulose acylate and the 2nd cellulose acylate]
1st cellulose acylate and the 2nd cellulose acylate especially carry out the ratio of the hydroxyl of esterified cellulose preferably by carboxylic acid; namely the substitution value (hereinafter referred to as acyl substitution) of acyl group meets all conditions of following formula (1) ~ (3).In addition, in (1) ~ (3), A and B is acyl substitution, and the acyl group in A is acetyl group, the acyl group in B to be carbon number be 3 ~ 22 acyl group.
2.5≤A+B≤3.0......(1)
0≤A≤3.0......(2)
0≤B≤2.9......(3)
Form cellulose and the glucose unit of β-Isosorbide-5-Nitrae bonding has hydroxyl freely 2,3 and 6.Cellulose acylate is that the esterified and hydrogen of hydroxyl of part or all of this cellulosic hydroxyl is by the polymer of the acyl substituted of carbon element more than 2.In addition, if the esterification of one of them hydroxyl in glucose unit is 100%, then substitution value is 1, and therefore when for cellulose acylate, if the hydroxyl of 2,3 and 6 is respectively by 100% esterification, then substitution value becomes 3.
Wherein, the acyl substitution of glucose unit 2 is set to DS2, the acyl substitution of 3 is set to DS3, the acyl substitution of 6 is set to DS6 and is preferably 2.00 ~ 3.00 with total acyl substitution that " DS2+DS3+DS6 " obtains; be more preferably 2.22 ~ 2.90, more preferably 2.40 ~ 2.88.In addition, " DS6/ (DS2+DS3+DS6) " is preferably more than 0.32, is more preferably more than 0.322, and more preferably 0.324 ~ 0.340.
Acyl group can be only a kind, also can be two or more.When acyl group is two or more, preferably one of them is acetyl group.The hydrogen of the hydroxyl of 2,3 and 6 is set to DSA based on the summation of the substitution value of acetyl group, when being set to DSB based on the summation of the substitution value of the acyl group beyond acetyl group in 2,3 and 6; the value of " DSA+DSB " is preferably 2.2 ~ 2.86, is especially preferably 2.40 ~ 2.80.DSB is preferably more than 1.50, is especially preferably more than 1.7.Further, preferably it more than 28% is the replacement of 6 hydroxyls to DSB, but more than 31%, especially preferably more than 32% is preferably the replacement of 6 hydroxyls more preferably more than 30%, further.In addition, the value of " DSA+DSB " of 6 of cellulose acylate is preferably more than 0.75, is more preferably more than 0.80, is especially preferably more than 0.85.By using cellulose acylate described above, can obtain to be produced on the polymer solution that uses in solution film-forming and preferably dissolubility, and, the better and polymer solution that viscosity is lower of filterability can be produced.When especially using chlorine-free organic solvent, preferably cellulose acylate described above.
Acyl group as carbon element more than 2 both can be fatty group, also can be aryl, without particular limitation of.Such as have cellulosic alkyl carbonyl ester, alkene carbonyl ester or aromatic carbonyl ester and aromatic series alkyl carbonyl ester etc., these can have the group be substituted respectively further.Propiono, bytyry, valeryl, caproyl, caprylyl, capryl, dodecane acyl group, tridecane acyl group, tetradecane acyl group, hexadecane acyl group, octadecanoyl, isobutyryl, tertiary bytyry, cyclohexane carbo, oleoyl, benzoyl, naphthalene carbonyl and cinnamoyl etc. can be enumerated.Wherein more preferably propiono, bytyry, dodecane acyl group, octadecanoyl, tertiary bytyry, oleoyl, benzoyl, naphthalene carbonyl and cinnamoyl etc., especially preferably propiono, bytyry.
[curability compound]
Curability compound can be any one in monomer and oligomer.Preferred consolidation compound comprises polyfunctional acrylic ester.More preferably the dipentaerythritol acrylate (DPHA) shown in following formula (I) is enumerated as monomer.More preferably urethane acrylate is enumerated as oligomer.Also can be used together DPHA and urethane acrylate.
[changing 1]
[curing agent]
As curing agent, well-known Photoepolymerizationinitiater initiater can be used.Such as preferred 2-methyl isophthalic acid [4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone.The relative concentration of preferred consolidation agent in the quality of curability compound in the scope of below more than 1 quality % 8 quality %.The concentration of this curing agent be the quality of curability compound is set to Z11, the quality of curing agent when being set to V11 by the { value that V11/Z11} × 100 are obtained.
One example of the formula of the 1st dope 41 and the 2nd dope 42 is as follows.In addition, as 2-methyl isophthalic acid [4-(methyl mercapto) the phenyl]-2-morpholinyl-1-acetone of following curing agent component, IRGACURE (login trade mark) 907 is had.
[Formulation Example of the 1st dope]
Cellulose acylate: Triafol T (TAC) ... 100 mass parts
Solvent: carrene is set to solvent composition 1, methyl alcohol is set to solvent composition 2.
Carrene ... 840 mass parts
Methyl alcohol ... 210 mass parts
Curability compound: DPHA......278 mass parts
Curing agent: 2-methyl isophthalic acid [4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone ... 14 mass parts
[Formulation Example of the 2nd dope]
Cellulose acylate: Triafol T (TAC) ... 100 mass parts
Solvent: carrene is set to solvent composition 1, methyl alcohol is set to solvent composition 2.
Carrene ... 261 mass parts
Methyl alcohol ... 65 mass parts
In addition, in order to control the thickness T11 of hard conating 11 and be mixed in the ratio of thickness T13 sum relative to the thickness TA of hard coating film 10 of layer 13, the 1st dope 41 and the flow-rate ratio of the 2nd dope 42 in curtain coating mould 61 is changed.Flow-rate ratio in curtain coating mould 61 refers to the ratio of the flow of the 1st dope 41 in described 1st runner and the flow of the 2nd dope 42 in the 2nd runner.In order to control the flow-rate ratio in curtain coating mould 61, control be supplied to the flow of the 1st dope 41 of the 1st runner and be supplied to the flow of the 2nd dope 42 of the 2nd runner.The 1st dope 41 supplied to the 1st runner and the 2nd runner and the flow of the 2nd dope 42, undertaken by the adjustment etc. of the rotating speed of liquid-feeding pump.
The 1st dope 41 enumerated about being used as the example of above-mentioned formula and the situation of the 2nd dope 42, the example of the flow-rate ratio of the 1st dope 41 and the 2nd dope 42 is as follows.When the thickness T11 manufacturing hard conating 11 is the hard coating film 10 of 10% with the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10, by (flow of the 1st dope 41): (flow of the 2nd dope 42) is set to general 1: 10.4.And, when the thickness T11 manufacturing hard conating 11 is the hard coating film 10 of 30% with the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10, by (flow of the 1st dope 41): (flow of the 2nd dope 42) is set to general 1: 2.7.So, more raising the 1st dope 41 is relative to the flow-rate ratio of the 2nd dope 42, more can improve the ratio of T11 and T13 sum relative to TA.Further, more the flow of increase the 1st dope 41, more can increase the thickness T11 of hard conating 11, forms the higher hard conating 11 of hardness thus.But, if hard conating 11 is blocked up, then also fragility step-down sometimes, therefore from the viewpoint of fragility, more preferably the thickness T11 of hard conating 11 is set on the basis of the scope of less than 30% with the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10, thickeies the thickness of hard conating.
Be described with reference to the 2nd embodiment of Fig. 4 to the manufacture method of hard coating film.The membrane producing device 140 of Fig. 4 is identical with the membrane producing device 40 of the Fig. 3 as the 1st embodiment, is a kind of solution film-forming equipment being made hard coating film 10 by solution film-forming from the 1st dope 41 and the 2nd dope 42.
Membrane producing device 140 possesses curtain coating portion 150 to replace the curtain coating portion 50 of the membrane producing device 40 of Fig. 3.Other structure is identical with the membrane producing device 40 of Fig. 3.The membrane producing device 140 of present embodiment is except the downstream of drying section 52, also possesses solidification equipment in curtain coating portion 150, therefore the solidification equipment in curtain coating portion 150 is called the 1st solidification equipment, and the solidification equipment in the downstream of drying section 52 is called the 2nd solidification equipment.
The upstream of the stripping position that the downstream of the air-supply arrangement 65 of curtain coating portion 150 in the direction of rotation of cylinder 62 and casting films 46 are stripped from cylinder possesses the 1st solidification equipment 166.That is, from the upstream side of the direction of rotation of cylinder 62 is provided with the 1st dope 41 and the 2nd dope 42 flowed out from curtain coating mould 61 successively, is contacted with curtain coating starting position, air-supply arrangement 65, the 1st solidification equipment 166 on cylinder 62 and peels off position.
Air-supply arrangement 65 is blown to casting films 46.In the present embodiment, the flow direction from the gas in the air-supply of air-supply arrangement 65 is not limited.Air-supply from this air-supply arrangement 65 is the wind for dry casting films 46, but terminates this drying before casting films 46 bone dry.That is, under the state that casting films 46 is half-dried, drying is terminated.More preferably can terminate before casting films 46 bone dry, stop this dry drying under carrying out the degree transmitted in the operation of moistening film 47 after peeling off from cylinder 60, and suppress dry in the mode preventing drying from proceeding to more than transmissible degree.
Because casting films 46 is peeled off from cylinder 60 to wrap solvent-laden state, the moistening film 47 therefore peeled off be attached to roller 62 sometimes or than roller 62 closer on the connecting gear in downstream.As connecting gear just like present embodiment stenter 76 till transmission path on the clip 77 etc. of the roller 75 that arranges or stenter described later 76.Therefore be dried to the transmissible degree of the adhesive degree losing moistening film 47, prevent from attaching to these connecting gears.
By making the drying based on air-supply arrangement 65 terminate before casting films 46 bone dry, in casting films 46, being cured property compound is from the diffusion of the 1st dope 41 side direction the 2nd dope 42 side.Thereby, it is possible to obtain adhesion to be greater than the hard coating film and the hard coating film of high rigidity that are coated with manufacture as passed through in the past.In addition, according to the present embodiment, adhesion can be obtained and be more greater than the 1st embodiment, and, the hard coating film that hardness is higher.Manufacture the hard coating film that hardness is the pencil hardness of more than 3H.Further, curability compound increases progressively from the concentration of the 2nd dope 42 side direction the 1st dope 41 side according to carrying out this diffusion.Thereby, it is possible to obtain the hard coating film being mixed in the polymeric concentration that formed by curability compound in layer and increasing progressively towards hard conating from film basal layer side.
In addition, by by the drying based on air-supply arrangement 65 in the degree not proceeding to more than the degree that can transmit moistening film 47, namely stop under transmissible degree, the positively more deeply diffusion of being cured property compound in casting films 46 in the 2nd dope side.In other words, in order to the mode spread with curability compound retains solvent, can carry out terminating drying under namely next process transmits the degree of operation.So, in the scope not hindering next process, determine the degree of the drying undertaken by air-supply arrangement 65.Thereby, it is possible to more positively obtain the comparatively large and hard coating film of high rigidity of adhesion, in addition, be mixed in the polymeric concentration formed by curability compound in layer and more positively increase progressively towards hard conating from film basal layer side.
Cooling curtain coating mode is that the cylinder 60 be cooled by side face is cooled and solidifies the mode of casting films 46.Dry curtain coating mode is the mode by be heated and solidify based on the air-supply of air-supply arrangement 65 casting films 46 by the casting films 46 of the cylinder 60 heated based on side face.The degree of transmissible drying is different in cooling curtain coating mode and dry curtain coating mode.In cooling curtain coating mode, if carry out drying and amount of residual solvent becomes 150 quality % and just can transmit, and in dry curtain coating mode, if carry out drying and amount of residual solvent becomes 30 quality % and just can transmit.
If casting films 46 reaches the drying regime of expection described above by air-supply arrangement 65, then casting films 46 is directed to the 1st solidification equipment 166.1st solidification equipment 166 is the ultraviolet light sources of injection.The distance of the stripping position of being peeled off to casting films 46 from cylinder 60 the curtain coating starting position being contacted with cylinder 60 from the 1st dope 41 and the 2nd dope 42 is set to D.This distance D is linking curtain coating starting position and the distance peeled off on the straight line of position, but from curtain coating starting position to peeling off the cylinder 60 of position along the distance the side face of side face.More preferably the 1st solidification equipment 166 is arranged to the distance from casting position is that the position of 0.9 × D is opposed to peeling off the cylinder 60 of position.
1st solidification equipment 166 penetrates ultraviolet to the casting films 46 on opposed cylinder 60.During when being guided by cylinder 60 towards stripping position, according to the 1st solidification equipment 166 to casting films 46 irradiation ultraviolet radiation by the 1st solidification equipment 166.Thus, the curability compound semi-solid preparation in casting films 46 is made.Semi-solid preparation refer to curability compound solidify completely before state.Before curability compound solidifies completely, stop solidification, namely terminate solidification process, even if curability compound uncured thus or the still less condensate of the solidification degree of polymerization also continue afterwards to the 2nd dope 42 side diffusion, thus more positively manifest and be mixed in polymeric concentration gradient in layer.
Solidification is terminated under the degree of the moistening film 47 of this semi-solid preparation operation preferably after can transmitting stripping.Thus, positively manifest further and be mixed in polymeric concentration gradient in layer.
In addition, in the present embodiment, with what cover that casting films 46 passes through, room (not shown) is set by the mode of path and the 1st solidification equipment 166, prevents the solvent of the gas evaporated from casting films 46 thus, i.e. solvent gas blow-through.
If casting films 46 to carry out based on the stripping of roller 62 or drying, semi-solid preparation to the degree can carrying out later transmission, then peeling off from cylinder 60.To wrap the casting films that solvent-laden state is peeled off from cylinder 60, namely moistening film 47 is directed to the stenter 76 of drying section 52.
2nd solidification equipment 55 in the downstream of hothouse 83 is by the light source of the casting films 46 on cylinder 60 extremely opposed for ultraviolet injection.When directed desciccator diaphragm 51 of coming is towards devices for taking-up 56, by the 2nd solidification equipment 55 to casting films 46 irradiation ultraviolet radiation by the 2nd solidification equipment 55.Not completely crued curability compound is cured by this irradiation.When curability compound is the compound by irradiating polymerization, the carrying out of this polymerization is equivalent to the carrying out of solidifying, if maximum remains constant in the polymeric degree of polymerization, then can be considered as solidifying completely.
By the Ultraviolet radiation of the 2nd solidification equipment 55, form hard conating at the face of a side of desciccator diaphragm 51.
Further, by forming hard conating in film-forming process, hard conating demonstrates the higher adhesion of adhesion in hard coating film than ever.Further, by the diffusion of being cured property compound in casting films 46 from the 1st dope 41 side direction the 2nd dope 42 side, the hard coating film with more high rigidity can be obtained.
[embodiment]
In embodiment 1 ~ 6, produce hard coating film 10 by the membrane producing device 140 shown in Fig. 4.That is, in embodiment 1 ~ 6, drying process and the curing process based on the 2nd solidification equipment 55 after drying process before the stripping based on air-supply arrangement 65, the semi-solid preparation operation based on the 1st solidification equipment 166, the stripping based on stenter 66 and hothouse 73 is implemented.In the hard coating film 10 produced, the thickness T11 of hard conating 11 is 10% with the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10.
Curtain coating mode is set to cooling curtain coating mode or dry curtain coating mode.In addition, even if when being cooling curtain coating mode, also implementing the air-supply based on air-supply arrangement 65, also carry out the drying of casting films 46 thus.Curtain coating mode for each embodiment is recorded in " curtain coating mode " hurdle of table 1.
In Table 1, " amount of residual solvent of the casting films of semi-solid preparation operation start time " (unit: quality %) value that is dry basis.This value the quality of determinand casting films 46 is set to MB, casting films 46 quality almost after bone dry when being set to MA, with { the percentage that (MB-MA)/MA} × 100 are obtained.The amount of residual solvent of the casting films of this semi-solid preparation operation start time is the amount of residual solvent of the position of the upstream extremity of the 1st solidification equipment 166.In addition, the 1st solidification equipment 166 is arranged to the distance from casting position is that cylinder 60 side face of the position of 0.9 × D is opposed.Further, in table 1, the amount of residual solvent of the casting films in the moment of the stripping from cylinder 62 is recorded in " amount of residual solvent (unit: quality %) peeling off the casting films in moment " hurdle.
To the adhesion of obtained hard coating film 10 evaluation hardness and hard conating 11.
The evaluation of hardness is implemented according to the pencil hardness test in accordance with JIS K5600-5-4.In this experiment, first, at the pencil of the sheathed predetermined hardness of pencil maintaining part of experimental rig.With the hard conating 11 of the core point pressing determinand hard coating film 10 of pencil.Under the state of pressing, staff makes pencil maintaining part at least displacement 7mm with the speed of 0.5mm/s ~ 1mm/s.Detect by an unaided eye the hard conating 11 after displacement checking with or without scar.Replace to hardness higher, namely harder pencil, check with or without scar equally.Continuation like this improves hardness level, confirms with or without scar.Continue to improve hardness level until produce the scar of more than 3mm at the test position that the core point by displacement contacts.The hardness not producing the hardest pencil of scar is pencil hardness test result.
By following benchmark evaluation hardness.A ~ C is equivalent to qualified, and D is equivalent to defective.
More than A:4H
B：3H
C：2H
D: less than 2H
The evaluation of adhesion is implemented by described cross cut test (in accordance with JIS D0202-1988).
The metewand of adhesion is as follows.In addition, A ~ C is equivalent to qualified, and D is equivalent to defective.
A：100/100
B:(95/100) (99/100) more than below
C:(90/100) (94/100) more than below
D: less than (90/100)
In embodiment 7 ~ 10, manufacture hard coating film 10 by the membrane producing device 40 shown in Fig. 3.Namely, in embodiment 7 ~ 10, do not implement the semi-solid preparation operation based on the 1st solidification equipment 166 implemented in embodiment 1 ~ 6, but implement based on drying process before the stripping of air-supply arrangement 65, based on drying process after the stripping of stenter 76 and hothouse 83, curing process based on solidification equipment 55 (being equivalent to the 2nd solidification equipment in Fig. 4).Owing to not implementing semi-solid preparation operation, be therefore recited as "-" in the hurdle of " amount of residual solvent of the casting films of semi-solid preparation operation start time " of table 1.Other condition is set to identical with embodiment, and have studied the manufacture of hard coating film.Result is shown in table 1.In addition, about the hard coating film 10 manufactured, the thickness T11 of hard conating 11 is 10% with the thickness T13 sum being mixed in layer 13 relative to the thickness TA of hard coating film 10.
[table 1]
Claims (9)
1. a hard coating film, is characterized in that, possesses:
Hard conating, comprises the condensate of the 1st cellulose acylate and curability compound cures, and described curability compound is solidified by ultraviolet irradiation;
Film basal layer, comprises the 2nd cellulose acylate and does not contain described condensate; And
Be mixed in layer, described condensate and described 2nd cellulose acylate mix, and are disposed between described hard conating and described film basal layer, and,
Wherein, described hard conating and the described thickness sum being mixed in layer are at least 10% relative to the thickness of hard coating film;
Described hard conating is formed by the 1st dope, and described film basal layer is formed by the 2nd dope, and,
The concentration of described 1st cellulose acylate in described 1st dope is the scope of below more than 2 quality % 20 quality %; the concentration of the described curability compound in described 1st dope is the scope of below more than 7 quality % 28 quality %; the concentration of described 2nd cellulose acylate in described 2nd dope is the scope of below more than 16 quality % 25 quality %, and the concentration of described 2nd cellulose acylate in described 2nd dope is higher than the concentration of described 1st cellulose acylate in described 1st dope.
2. hard coating film as claimed in claim 1; it is characterized in that; the amount of described described 2nd cellulose acylate be mixed in layer increases progressively towards described film basal layer continuously along with from described hard conating, described in the described polymeric amount be mixed in layer successively decrease continuously towards described film basal layer along with from described hard conating.
3. a manufacture method for hard coating film, is characterized in that, possesses following steps:
(A) in the mode of the 1st dope and the 2nd dope overlap, described 1st dope and the common curtain coating of described 2nd dope are formed casting films on supporter, described 1st dope comprises the 1st cellulose acylate, curability compound and curing agent, described curability compound is solidified by ultraviolet irradiation, described curing agent promotes the solidification of described curability compound, the concentration of the described curability compound in described 1st dope is in the scope of below more than 7 quality % 28 quality %, and described 2nd dope comprises the 2nd cellulose acylate and containing described curing agent;
(B) described casting films is peeled from described supporter;
(C) dry peel off from described supporter after described casting films; And
(D) to the described casting films on described supporter, to peel any one irradiation ultraviolet radiation the described casting films come and casting films after described step C from described supporter to solidify described curability compound.
4. the manufacture method of hard coating film as claimed in claim 3, is characterized in that, described curability compound is at least any one party in dipentaerythritol acrylate and urethane acrylate.
5. the manufacture method of hard coating film as claimed in claim 3, is characterized in that, carry out the ultraviolet irradiation in described D step to the film by described step C drying.
6. the manufacture method of hard coating film as claimed in claim 3, it is characterized in that, possesses step (E), described step (E) cools casting films and makes it gelation on described supporter, sends into gas and solidify the exposed surface of described casting films in this cooling period to described casting films.
7. the manufacture method of hard coating film as claimed in claim 5, is characterized in that possessing following steps:
(F) casting films on dry described supporter, and terminated dry before casting films bone dry; And
(G) to the described casting films irradiation ultraviolet radiation on the described supporter through described F step and curability compound described in semi-solid preparation.
8. the manufacture method of hard coating film as claimed in claim 7, is characterized in that, in the step A, supporter is total to the 1st dope and described 2nd dope described in curtain coating continuously,
Described F step can carry out, from the degree of the transmission after described supporter is peeled off continuously, terminating the drying of described casting films.
9. the manufacture method of hard coating film as claimed in claim 8, is characterized in that, described G step can carry out, from the degree of the transmission after described supporter is peeled off continuously, terminating the semi-solid preparation of described curability compound.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010068965 | 2010-03-24 | ||
| JP068965/2010 | 2010-03-24 | ||
| JP213259/2010 | 2010-09-24 | ||
| JP2010213259 | 2010-09-24 | ||
| JP226728/2010 | 2010-10-06 | ||
| JP2010226728 | 2010-10-06 | ||
| JP045956/2011 | 2011-03-03 | ||
| JP2011045956A JP5518768B2 (en) | 2010-03-24 | 2011-03-03 | Hard coat film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102218856A CN102218856A (en) | 2011-10-19 |
| CN102218856B true CN102218856B (en) | 2015-04-22 |
Family
ID=44775680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110072453.1A Expired - Fee Related CN102218856B (en) | 2010-03-24 | 2011-03-24 | Hard coating film and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102218856B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201534469A (en) * | 2014-03-05 | 2015-09-16 | Fujifilm Corp | Hard coat film, polarizing plate and image display device containing the same, and method of manufacturing hard coat film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100062187A1 (en) * | 2008-09-10 | 2010-03-11 | Hiroshi Takahashi | Anti-glare film and process for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4075147B2 (en) * | 1998-08-04 | 2008-04-16 | 凸版印刷株式会社 | Hard coat film or sheet, and hard coat film or sheet with functional inorganic thin film |
| JP2008012675A (en) * | 2006-06-30 | 2008-01-24 | Dainippon Printing Co Ltd | Optical laminate and its manufacturing method |
| JP2009234059A (en) * | 2008-03-27 | 2009-10-15 | Konica Minolta Opto Inc | Hard coat film |
-
2011
- 2011-03-24 CN CN201110072453.1A patent/CN102218856B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100062187A1 (en) * | 2008-09-10 | 2010-03-11 | Hiroshi Takahashi | Anti-glare film and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102218856A (en) | 2011-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10207287B2 (en) | Machine and treatment process via chromatogenous grafting of a hydroxylated substrate | |
| CN101870164B (en) | Stretch method of polymer film and manufacturing method of polymer film | |
| US20170051438A1 (en) | Flexible composite prepreg materials | |
| JPS63162204A (en) | Process and device for hot melt prepreg tow | |
| US20220143913A1 (en) | Methods to produce low-defect composite filaments for additive manufacturing processes | |
| JP5537857B2 (en) | Method for producing porous film | |
| CN102218856B (en) | Hard coating film and manufacturing method thereof | |
| CN101327651A (en) | Casting device, solution casting apparatus, and solution casting method | |
| KR20210061305A (en) | Composite sheet molding method and molding device | |
| JP5518768B2 (en) | Hard coat film and method for producing the same | |
| CN102765271A (en) | Ink hot pressing transfer carrier membrane and manufacture method of ink hot pressing transfer carrier membrane | |
| JP5279861B2 (en) | Knurling forming method and apparatus, and solution casting method | |
| TWI673302B (en) | Manufacturing method and device of carbon fiber sheet molding compound | |
| CN104070759A (en) | Method of manufacturing multilayer film | |
| CN101380794A (en) | Solution casting method and apparatus | |
| JP6765052B2 (en) | Method for manufacturing scaffolds for culture and fiber aggregates, and equipment for manufacturing scaffolds for culture | |
| JP2010076105A (en) | Method and equipment of manufacturing porous film | |
| CN101713841A (en) | Method for manufacturing phase difference film | |
| CN104245158A (en) | Production method for film with coating | |
| TWI782154B (en) | Manufacturing apparatus and manufacturing method of polymer film | |
| DE102018222371B4 (en) | Method for producing an adhesive filament, apparatus, adhesive filament and use | |
| EP1644172B1 (en) | Direct coating method and apparatus | |
| CN105835376B (en) | Solution film-forming method and device | |
| JP2016144935A (en) | Solution film forming method and apparatus | |
| CN103358446A (en) | Casting method and apparatus, casting film, method and facility for manufacturing film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150422 Termination date: 20210324 |