CN101374654A - Easy-adhesion film for optical sheet and method for manufacturing the same - Google Patents
Easy-adhesion film for optical sheet and method for manufacturing the same Download PDFInfo
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- CN101374654A CN101374654A CNA2007800038026A CN200780003802A CN101374654A CN 101374654 A CN101374654 A CN 101374654A CN A2007800038026 A CNA2007800038026 A CN A2007800038026A CN 200780003802 A CN200780003802 A CN 200780003802A CN 101374654 A CN101374654 A CN 101374654A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
This invention provides a method for manufacturing an easy-adhesion film for an optical sheet, which can prevent blocking after coating of an easy-adhesion layer in a process (coating, transfer, and carrying) for forming an optical functional layer in the manufacture of an optical functional film, or a process for manufacturing an easy-adhesion support, which does not cause layer separation in handling (for example, transport, cutting, or lamination) and has excellent adhesion even in a high-temperature and high-humidity atmosphere, and a method for manufacturing the easy-adhesion film. In this method, an easy-adhesion layer coated onto the surface of a web (W) as a support contains an aqueous urethane resin and a crosslinking agent or contains a styrene-butadiene copolymer and a crosslinking agent, and the upper most layer in a back layer formed on the backside of the web (W) is a polyolefin layer.
Description
Technical field
The present invention relates to easy-adhesion film for optical sheet and manufacture method thereof, particularly can prevent to be coated with the easy-adhesion film for optical sheet and the manufacture method thereof of the adhesion (blocking) behind the easy adhesive linkage.
Background technology
The mylar mesentery, particularly the biaxial stretching film of PET (PET) is owing to have excellent in mechanical properties, anti-flammability and resistance to chemical reagents etc., therefore as tape, photographic film, film for packaging, ohp film and in recent years the base material of the antireflection film used of general OCR machine etc., the expansion of its demand is very remarkable in recent years.
In these purposes, require to have cementability for this mylar mesentery.For example, in film for packaging, wish with printing good with the cementability of black liquid or laminated material, in photographic film, wish with to be formed at the cementability of the photosensitive layer on the base material film good, equally in tape, wish with the cementability of magnetic recording layer good, in addition, in the antiultraviolet film that the OCR machine is used, wish with the cementability of ultraviolet radiation absorption coating good.But polyester film is because crystal orientation, surperficial coherency height, thus have in relatively poor problem aspect the cementability of various materials.
Be directed to this, as the prima facie approach that improves polyester film, known have sided corona treatment, plasma treatment and a flame treatment etc., uses in a part.But these approach are that the shape with the film surface physically changes and realizes the approach of the raising of cementability, have performance pass in time and reduce, shortcoming that the transparency also reduces.
As other the method that overcomes above-mentioned shortcoming, can enumerate the method that on film, is coated with paint, easy adhesive linkage is set.As this easy adhesive linkage, the material that can with an organic solvent be and the material of water system.Wherein, problem, the health on the safety such as the ecological deterioration that causes by volatilization and save problem aspect such as resource and consider the material of preferred water system.Thus, propose use water system paint, and for example used the mylar of water-soluble or water dispersible to form the scheme of this easy adhesive linkage.
But, though above-mentioned easy adhesive linkage is because of the former of rerum natura thereby good with the cementability of polyester film, but just like inferior problem, promptly, with the compatibility of stacked smears, binding agent, black liquid etc. low, or on the contrary, when the cementability that will improve with these layers, then the cementability with polyester film reduces, thereby very difficult material of selecting to have as enough cementabilities in intermediate layer.In addition, also have following variety of issue, that is, the variation because of temperature in the keeping or humidity sticks together between the film, in addition, is difficult to carry out the even coating of top layer agent such as diazonium coating or UV China ink liquid.
In order to address this problem, for example in patent documentation 1, the polyester film that has acrylic resin and the crosslinked easy adhesive linkage that forms of acrylic acid modified polyester resin is disclosed.In addition, in patent documentation 2, the polyester film with the layer that contains styrene-butadiene resin or acrylonitrile-butadiene resin and specific mylar is disclosed.
In addition, in patent documentation 3 and patent documentation 4, proposed to make the cementability of acrylic resin and the scheme that fissility becomes good.Wherein, in the patent documentation 3, disclose following content, that is, formed transparent primer on the two sides of base material, its acrylic acid series polymeric compounds scope with 0.1～40 weight % in molecule has the functional group who has the optical polymerism unsaturated group.
In the patent documentation 4, disclose following formation, that is, in the 2P method, resin bed has been made as 2 layers of formation, made the fissility of reaction solidfied material of first resin bed of die side be higher than the reaction solidfied material of second resin of base material side.
Patent documentation 1: 1-No. 108037 communiques of Japanese kokai publication hei
Patent documentation 2: special fair 3-No. 22899 communiques of Japan
Patent documentation 3: 2002-No. 365405 communiques of TOHKEMY
Patent documentation 4: 2004-No. 249655 communiques of TOHKEMY
But, under the situation of easy to be bonding film that will utilize above-mentioned method in the past to make, abundant inadequately with the bonding force of optical functional layer as supporting mass.For example, under the situation of optical functional layer for the layers of prisms that constitutes by the UV cured resin, the bonding force that has layers of prisms and a supporting mass inadequate problem that becomes easily.
And the bonding force of said here supporting mass and layers of prisms is meant: when during fabrication layers of prisms being peeled off from mould, supporting mass and layers of prisms are peeled off and the UV cured resin can not residue in the bonding force of die side; Perhaps when the processing of the stamping-out of prismatic lens, be used to make the UV cured resin can be from the bonding force of dry linting on the supporting mass; Even and the bonding force that under the service condition of liquid crystal panel material, also can continue etc.
In order to address the above problem, find that following way is effective, that is, on the layers of prisms formation face of the mylar system film that becomes supporting mass, form butadiene-styrene copolymerized latex layer or the aqueous polyurethane resin bed that contains crosslinking agent at least in one side as easy adhesive linkage.
But the bonding good easy adhesive linkage of these and layers of prisms has the shortcoming that is easy to generate adhesion in manufacturing process.Following problem is just arranged, is located on the film being coated with as priming coat, passed through the coiling operation after, produce adhesion, become the state that can't use as optical sheet.
Summary of the invention
Given this present invention plants situation and finishes, its purpose is, a kind of easy-adhesion film for optical sheet is provided, in the manufacturing process of its formation optical functional layer in the manufacturing of optically functional film (coating, transfer printing, conveyance) or when disposing (conveying, cutting, applying etc. time) do not have peeling off of layer, even under hot and humid atmosphere, also have the adhesion that also can prevent from the manufacturing process of easy bonding supporting mass of good cementability to be coated with behind the easy adhesive linkage, and its manufacture method be provided.
In order to solve described problem, the invention provides a kind of easy-adhesion film for optical sheet, it is characterized in that the easy adhesive linkage that is coated with the surface of being located at supporting mass contains the aqueous polyurethane resin and carbodiimide is a crosslinking agent, the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
In addition, the invention provides a kind of easy-adhesion film for optical sheet, it is characterized in that, the easy adhesive linkage that is coated with the surface of being located at supporting mass contains aqueous polyurethane resin and epoxy crosslinking agent, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
In addition, the invention provides a kind of easy-adhesion film for optical sheet, it is characterized in that, it is crosslinking agent that the easy adhesive linkage that is coated with the surface of being located at supporting mass contains styrene-butadiene copolymer and dichloro-s-pyrrolotriazine derivatives or carbodiimide, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
According to the present invention, optical functional layer at supporting mass forms on the face (surface), be coated with styrene-butadiene copolymer latex layer or the aqueous polyurethane resin bed that contains crosslinking agent as easy adhesive linkage, the superiors at the back side of supporting mass (being coated with the opposing face of the face of easy adhesive linkage) form polyolefin layer.
Like this, surface at the easy adhesive linkage of the easy-adhesion film of gained, formation gets as optical functional layer in the manufacturing process of acrylic acid series uv curing resin layer for example, when the conveyance, can have adhesion ground not carry out conveyance well in that easy bonding film is sent.
So, utilize the prismatic lens that the present invention obtains owing to have good cementability, there is not adhesion, therefore the transparency is good, can stably make.
More than, according to the present invention, can provide the easy-adhesion film for optical sheet that prevents to be coated with the adhesion behind the easy adhesive linkage.
And, the prescription of the priming coat of patent documentation 3 different with the present invention (light-cured types), in addition, object also is a biconvex lens, in addition, does not mention back sheet, and is different with the present invention.
In addition, though patent documentation 4 to give between transfer printing layer and the supporting mass adhesive linkage aspect identical with the present invention, yet when transfer printing process, give adhesive linkage in the patent documentation 4, different with the present invention who before transfer printing process, gives adhesive linkage.In addition, patent documentation 4 is also not mentioned for the back sheet as feature of the present invention.
Among the present invention, best described supporting mass is a polyester film, and described back sheet possesses: contain acrylic latex and tin oxide ground floor, be formed at the second layer on this ground floor as polyolefin layer.In addition, among the present invention, best described supporting mass is a polyester film, and described back sheet possesses: contain electric conductive polymer ground floor, be formed at the second layer on this ground floor as polyolefin layer.If this kind back sheet then can further obtain effect of the present invention.
In addition, among the present invention, best described supporting mass is a PET.Though also can use PET polyester film in addition as supporting mass, if PET then can obtain effect of the present invention ideally.
In addition, among the present invention, be preferably on the described easy adhesive linkage and form optical functional layer, best described optical functional layer is the layers of prisms that is made of ultraviolet curable resin.
In addition, the invention provides a kind of manufacture method of easy-adhesion film for optical sheet, it is characterized in that possessing: be coated with on the surface of supporting mass easy adhesive linkage operation, be coated with operation that the superiors are the back sheet of polyolefin layer at the back side of described supporting mass, will be coated with the operation that forms optical functional layer on the described easy adhesive linkage of operation, the operation that dried described supporting mass is reeled of the described supporting mass drying of described easy adhesive linkage and back sheet, the described supporting mass of having reeled.
According to the present invention, can provide the easy-adhesion film for optical sheet that prevents to be coated with the adhesion behind the easy adhesive linkage.
Description of drawings
Fig. 1 is the table of the weight ratio of the expression compound that constitutes resin liquid used among the embodiment.
Fig. 2 is the schematic diagram of formation of the manufacturing installation of expression embossed flakes.
Fig. 3 is the roughly figure of expression along the axial section of rotation of knurling rolls.
The result's of mist value, belt stripping test and the adhesion test of Fig. 4 embossed flakes that to be expression make based on embodiment 1～5 and comparative example 1～6 table.
Wherein, 10 ... the manufacturing installation of embossed flakes, 11 ... the sheet supply unit, 12 ... coating part, 13 ... knurling rolls, 14 ... niproll, 15 ... resin solidification portion, 16 ... stripper roll, 17 ... the diaphragm feed mechanism, 18 ... the sheet winding mechanism, H ... diaphragm, W ... sheet
The specific embodiment
Below will preferred embodiment describing to easy-adhesion film for optical sheet of the present invention and manufacture method thereof.
Among the present invention, as the polyester based resin (the following polyester that suitably is called) that constitutes supporting mass (film)), can enumerate by aromatic acid or its ester formation property derivative and glycol or the synthetic wire saturated polyester of its ester formation property derivative.
Concrete example as the polyester that can be used for the present invention, can enumerate PET, polyethylene isophthalate, PEN, polybutylene terephthalate (PBT), poly terephthalic acid 1,4-hexamethylene dimethyl ester, poly-2,6-benzene dicarboxylic acid glycol ester (polyethylene-2,6-phthalenedicarboxylate) etc.Wherein, consider preferred PET, PEN etc. from the viewpoint of the easiness, economy and the effect that obtain.
In addition, as the raw material of film, only otherwise damage effect of the present invention, then also can use their copolymer or the mixture of other resins of they and small scale etc.
In addition, good in order to make sliding in this polyester film, can contain a spot of inorganic or organic particulate, for example inorganic fillers such as titanium oxide, calcium carbonate, silica, barium sulfate, silicone; ア Network リ Le), the organic filler of benzoguanamine, teflon (registration mark), epoxy-ester (エ Port キ シ) etc. and so on acrylate (Japanese:; Improved in adhesion agent or antistatic agent interferings such as polyethylene glycol (PEG), neopelex.
Polyester film of the present invention can be made membranaceously by foregoing mylar utilization is melt extruded, and utilizes vertically and the oriented crystallineization that horizontal biaxial tension realizes and the crystallization that utilizes heat treatment to realize form.The manufacture method of these films, condition can suitably select to use known method, condition.
The thickness of used here polyester film is not particularly limited, and can suitably select according to the application target of film, yet in general preferably be made as 5～500 μ m and use.
The feature of used easy adhesive linkage is among the present invention, contains styrene-butadiene copolymer (following suitably abbreviate as " SBR ") or aqueous polyurethane resin and crosslinking agent.SBR is meant the copolymer based on styrene and butadiene, and as required also copolymerization other the copolymer of composition.Known by adjusting this copolymer styrene and butadiene contain ratio, can obtain the material of various rerum naturas.
Under the situation that forms easy adhesive linkage as in the present invention, styrene-butadiene copolymer is preferably latex.Specifically, can adopt Nipor (trade name) from Japanese Zeon company, from the Naugatex (trade name) of Sumitomo Naugatuck, from the Croslene (trade name) of military field pharmaceutical industries, from the Dowlatex (trade name) of rising sun Dow, in addition, can also use the commercially available product of selling by big Japanese ink chemical industrial company or overseas producer.
For the situation of latex, the particle diameter of dispersion particle is preferably below 5 μ m, more preferably below 1 μ m, further preferably below 0.2 μ m.Under the big situation of particle diameter, the problem that transparency, gloss that has the cohesion that is easy to generate particle in painting process or film etc. becomes bad.In addition, make at needs under the situation of thinner thickness of coating layer, then need to reduce correspondingly particle diameter.
Easily the ratio that contains of the phenylethylene/butadiene in the styrene-butadiene copolymer of adhesive linkage is preferably about 50/50～80/20.The ratio of contained SBR is preferably 30～50 weight % in the latex as solid constituent weight.
In addition, in this easy adhesive linkage, adding crosslinking agent for the rerum natura that improves SBR, is crosslinking agent as the preferred triazine of used here crosslinking agent.
When making easy-adhesion film of the present invention, be preferably in and be coated with on the polyester based resin film matrix behind the coating fluid that contains styrene-butadiene copolymer, crosslinking agent its high temperature drying, form easy adhesive linkage.
For the aqueous polyurethane resin, preferably given some hydrophilic groups or hydrophily fragment and become the resin of water-soluble or self-dispersion type polyurethane resin, also can use the self-emulsifying type that in side chain, contains silanol group.Specifically, can use the Superflex (trade name) of the first industrial drugmaker system or the Takelac (trade name) of the military field of Mitsui chemical company.
For urethane resin layer, in order to improve the rerum natura of polyurethane resin, also be added with crosslinking agent, the preferred average epoxy functionalized radix of used here crosslinking agent is preferably at epoxy crosslinking agent more than 3.5 or carbodiimide crosslinking agent.
Below, the back sheet that the back side was coated with that has been coated with the supporting mass of easy adhesive linkage on the surface is described.As being coated with the back sheet of being located at the back side, polyolefin layer is very good.If polyolefin, then can obtain the bonding force with the appropriateness of supporting masses such as polyester film, can prevent and be coated with the adhesion of the easy adhesive linkage of being located at opposing face (surface).
In addition, on back sheet, preferably be coated with the conductive layer or the electric conductive polymer layer that constitute by acrylic latex and tin oxide.So just can prevent to adhere to by the dust that static causes.Among the present invention, the conductive layer that can be coated with polyolefinic individual layer or constitute, perhaps coating polyolefin layer and be dried the operation that is applied to reel on the electric conductive polymer layer at easily adhesive linkage and its back side by acrylic latex and tin oxide.
For polyolefin, can use the polyolefin aqueous liquid dispersion of Mitsui Chemicals system or the ethene of Dong Bang chemical company system is copolymer emulsion.
Used device when using easy adhesive linkage with coating fluid and polyolefin-coated liquid on polyester film can use with reverse coating machine (reverse coater), intaglio plate coating machine (gravure coater), the rod shown in former rugged brave work, " コ-テ イ Application グ mode (coating method) ", in October, 1979 distribution of careful bookstore and be coated with any one of known apparatus for coating headed by machine (rod coater), the air doctor blade coating machine (air doctor coater) etc.
The easy adhesive linkage of coating is with before period of coating fluid and polyolefin-coated liquid being biaxial tension, after the biaxial tension or when facing before the coating skin-material etc. on polyester film.In addition, also can use following method, promptly, be coated with the smears on the uniaxial tension polyester film that illustrated roller pulling method obtains in utilizing 41-No. 8470 grades of Japanese Patent Publication, implement suitable drying, perhaps do not implement drying and, heat-treat (being designated hereinafter simply as the coating pulling method) immediately along stretching with the rectangular direction of previous draw direction.
If utilize the coating pulling method, can carry out the drying of coating layer simultaneously with stretching, by coating layer is stretched, just coating thickness can be reduced, and the stack membrane of the wide cut that the method except that being coated with pulling method is difficult to obtain can be obtained to utilize.
Easy adhesive linkage on the polyester film and the thickness of polyolefin layer that is formed at the back side of easy adhesive linkage are preferably the scope of 0.005～0.5 μ m.If the thickness of coating layer is less than 0.005 μ m, then, therefore in product, produce crawling easily owing to be difficult to coating equably, or with the cementability of stacked layers of prisms abundant inadequately.On the other hand, if the thickness of coating layer surpasses 0.5 μ m, then possible film is bonding easily each other, and perhaps the light transmission of film integral body reduces.
In described each coating fluid, also can contain as required stationarity modifying agent, coating modifying agent, defoamer, ultra-violet absorber, antioxidant, antistatic agent interfering, lubricant, inorganic be particulate, dye well pigment etc.For the polyolefin layer that is formed at the back side, be preferably in its lower floor and be coated with conductive layer or the electric conductive polymer layers such as polythiophene or polyaniline that constitute by acrylic latex and tin oxide as the antistatic interfere with layer.
In order to estimate the cementability of the easy-adhesion film that so obtains, the surface that is preferably in easy adhesive linkage forms the uv curing resin layer, when carrying out belt stripping test, all has the intensity of not being stripped from the interface arbitrarily between each adjacent layer.
As above shown in the explanation, the following formation of easy-adhesion film of the present invention promptly, forms described easy adhesive linkage in the one side of polyester film base material, and the superiors at its back side form polyolefin layer.
Embodiment
The present invention is described in detail will to enumerate concrete example below, yet the present invention is not limited to them.
[embodiment 1]
The making of-supporting material-
(1) making of supporting mass
After PET (PET) film longitudinally being reached the biaxial tension of laterally having carried out being stretched as 3.3 times respectively, the PET film is carried out 20 seconds heat fixations under 240 ℃, laterally make it lax about 4% afterwards in identical with it temperature lower edge.Chuck portion to stenter carried out joint-cutting (slit) processing after, two ends carried out annular knurl processing, and reel thereafter.So just obtained having the supporting mass of drum of matrix 36 of the thickness of 180 μ m.
(2) easy adhesive linkage
Before coating, carried out following surface treatment.Use the solid-state corona treatment of Pillar corporate system (6KVA model), the two sides of supporting mass is at room temperature handled with 20m/ minute transporting velocity.According to the electric current of this moment, the read value of voltage, supporting mass has been carried out 0.375kVA minute/m
2Processing.
The processing frequency of this moment is 9.6kHz, and the gap clearance of electrode and dielectric roller is 1.6mm.Thereon with the coating fluid of following composition with 6ml/m
2Coat the one side of film base material, drying is 5 minutes under 185 ℃, has formed the easy adhesive linkage of thick 0.15 μ m.
(composition of coating fluid)
Butadiene-styrene copolymerized latex (solid constituent 43%, Butadiene weight ratio=32/68): 13ml
2,4-dichloro-6-hydroxyl-S-triazine sodium salt 8% aqueous solution: 7ml
Polystyrene particle (average grain diameter: 2% aqueous solution: 0.5ml 1.8 μ m)
Distilled water: 79.5ml
(3) coating of backing ground floor (conductive layer)
At the back side of supporting mass (surface of a side of easy adhesive linkage is not set), utilize rod to be coated with the machine coating by the following antistatic interfere with layer coating fluid that constitutes of forming, drying is 5 minutes under 185 ℃, has formed the antistatic interfere with layer of thick 0.15 μ m.
(composition of coating fluid)
Acrylic resin aqueous dispersions 1.9 weight portions
(Jurimer ET410, solid constituent 30 weight %, Japanese pure medicine (strain) system)
Tin ash-antimony composite metal oxide water dispersion 9.1 weight portions
(TDL-S Mitsubishi Materials corporate system 17 weight %)
Dodecyl diphenyl ether sodium disulfonate 0.1 weight portion
(the サ Application デ Star ト BL Sanyo system of changing into 44.6%)
Polyoxyethylene phenyl ether 0.1 weight portion
Epoxy crosslinking agent
(Denacol EX-614B Nagase changes into corporate system)
Interpolation distilled water is mixed with and reaches 100 weight portions in above-mentioned mixture.
(4) coating of the backing second layer (polyolefin layer)
On above-mentioned backing ground floor, be coated with the polyolefin latex aqueous dispersions of following composition, make dry film thickness reach 0.08 μ m.It is following dry 3 minutes at 140 ℃.
(composition of coating fluid)
Polyolefin 1.6 weight portions
(Chemipearl S-120,27 weight %, Mitsui petrochemistry (strain) system)
Polyethylene particulate 0.04 weight portion
(Chemipearl W950,40 weight %, Mitsui petrochemistry (strain) system)
Silica gel 1.1 weight portions
(Snowtex C, 20 weight % daily output chemistry (strain) system)
Epoxy crosslinking agent 0.2 weight portion
(Denacol EX-614B, Nagase change into (strain) system)
In above-mentioned mixture, add distilled water and be formulated as total amount and reach 100 weight portions.
The making of-optical functional layer (layers of prisms)-
(1) preparation of resin liquid
Compound shown in the table of Fig. 1 is mixed with the weight ratio put down in writing, be heated to be 50 ℃ and stirring and dissolving has obtained resin liquid.And, the title of each compound and the contents are as follows shown in.
EB3700:Ebecryl 3700, Daicel UC (strain) system,
Bisphenol type epoxy base acrylate,
(viscosity: 2200mPas/65 ℃)
BPE200:NK ester BPE-200, Xin Zhong village chemistry (strain) system,
Oxirane addition bisphenol-A methacrylate,
(viscosity: 590mPas/25 ℃)
BR-31:New Frontier BR-31, the first industrial pharmaceuticals industry (strain) system,
Tribromophenoxy ethyl propylene acid esters,
(normal temperature is down that solid, fusing point are more than 50 ℃)
M110:Aronix m-110, East Asia synthetic (strain) system,
To cumyl phenol oxirane modification acrylate
(viscosity: 130mPas/25 ℃)
The optical free radical initator of LR8893X:Lucirin LR8893X, BASF (strain) system
Ethyl-2,4,6-trimethylbenzene formyl ethoxyl phenenyl phosphine oxide
MEK: MEK
(2) layers of prisms is synthetic
Use the manufacturing installation 10 of the embossed flakes of formation shown in Figure 2, on supporting mass, formed layers of prisms.
As supporting mass (sheet) W, used the supporting material of wide 500mm.As knurling rolls 13, used length (width of sheet W) as 700mm, diameter as the S45C system of 300mm and the material on surface is made as the roller of nickel.In the wide full week of roughly 500mm on the surface of roller, utilize the machining of having used diamond segment (single-point), formed roll shaft to spacing be the groove of 50 μ m.
The section shape of groove is the triangle of drift angle 90 degree, and the bottom of groove also is the triangle that does not have 90 degree of flat.That is, well width is 50 μ m, and groove depth is about 25 μ m.Therefore this groove utilizes these knurling rolls 13 can form the prism lens on sheet W owing to be the ring-type that does not have seam on the circumferencial direction of roller.On the surface of roller, after groove processing, implemented nickel plating.The summary section of knurling rolls 13 is shown among Fig. 3.
As coating mechanism 12, used mould to be coated with machine, it has used the dispense tip 12C of extrusion type.As coating fluid F (resin liquid), used the liquid shown in the table of having stated.
For the thickness of the moisture state of coating fluid F (resin), utilize feedway 12B to control quantity delivered to each coating fluid F of dispense tip 12C, make the dried thickness of organic solvent reach 20 μ m.
Used the drying device of heated air circulation type as drier 19.The temperature of hot blast is made as 100 ℃.As niproll 14, used diameter to form the roller that rubber hardness is the layer of 90 silicon rubber as 200mm, on the surface.Utilize the clamp pressure (effectively clamp pressure) of knurling rolls 13 and niproll 14 extrusion edge eyeglass W to be made as 0.5Pa.
As resin solidification mechanism 15, use metal halide lamp, utilize 1000mJ/cm
2Energy shine.
Utilize above operation, obtained the embodiment 1 prismatic lens W corresponding, that formed relief pattern shown in the table with Fig. 4.
[embodiment 2]
Except the coating fluid of easy adhesive linkage is following composition, obtained optical film (prismatic lens) in the same manner with embodiment 1.
(composition of coating fluid)
Takelac W6061 (the military field of Mitsui chemical company system aqueous polyurethane resin) 30% aqueous dispersions: 7.9ml
Denacol EX-521 (Nagase Chemtex corporate system) 100%:0.5ml
Polystyrene particle (average grain diameter: 2% aqueous solution: 0.5ml 1.8 μ m)
Emalex 710 (Japanese Emulsion corporate system polyoxyethylene alkyl ether) 1%:0.7ml
Distilled water: 90.4ml
[embodiment 3]
Except with the coating fluid of following composition with 6ml/m
2Coat the one side of supporting mass, drying is 5 minutes under 100 ℃, has formed beyond the easy adhesive linkage of thick 0.15 μ m, and operation has obtained optical film (prismatic lens) similarly to Example 1.
(composition of coating fluid)
Superflex 460 (the first industrial drugmaker system aqueous polyurethane resin) 38%:6.2ml
Polystyrene particle (average grain diameter: 2% aqueous solution: 0.3ml 1.8 μ m)
CARBODILITE V-02-L2 (day is spun corporate system clearly) solid constituent 40%:1.6ml
Distilled water: 90.4ml
[embodiment 4]
Except with the coating fluid of following composition with 6ml/m
2Coat the one side of supporting mass, drying is 5 minutes under 130 ℃, has formed beyond the easy adhesive linkage of thick 0.15 μ m, and operation has obtained optical film (prismatic lens) similarly to Example 1.
(composition of coating fluid)
Butadiene-styrene copolymerized latex (solid constituent 43%, Butadiene weight ratio=32/68): 13ml
CARBODILITE V-02-L2 (day is spun corporate system clearly) solid constituent 40%:1.6ml
Polystyrene particle (average grain diameter: 2% aqueous solution: 0.5ml 1.8 μ m)
Distilled water: 79.5ml
[embodiment 5]
Except the coating fluid of the conductive layer of backing ground floor was following composition, operation had obtained optical film (prismatic lens) similarly to Example 1.
(composition of coating fluid)
Acrylic resin aqueous dispersions 1.9 weight portions
(Jurimer ET410, solid constituent 30 weight %, Japanese pure medicine (strain) system)
Polyaniline 2.7 weight portions
(conductive polyaniline aqueous dispersions, ORMECON corporate system, 1.9 weight %)
Dodecyl diphenyl ether sodium disulfonate 0.1 weight portion
(the サ Application デ Star ト BL Sanyo system of changing into 44.6%)
Polyoxyethylene phenyl ether 0.1 weight portion
Carbodiimide crosslinking agent 0.45 weight portion
(CARBODILITE V-02-L2 day is spun corporate system solid constituent 40% clearly)
Be formulated as to wherein adding distilled water and reach 100 weight portions.
[comparative example 1]
Except in embodiment 1 back sheet at the back side only being coated with 1 layer, and be not coated with beyond 2 layers, operation has similarly to Example 1 obtained easy the to be bonding tunic before optical functional layer is coated with.
[comparative example 2]
Except in embodiment 2 back sheet at the back side only being coated with 1 layer, and be not coated with beyond 2 layers, operation has similarly to Example 2 obtained easy the to be bonding tunic before optical functional layer is coated with.
[comparative example 3]
Except in embodiment 3 back sheet at the back side only being coated with 1 layer, and be not coated with beyond 2 layers, operation has similarly to Example 3 obtained easy the to be bonding tunic before optical functional layer is coated with.
[comparative example 4]
Except in embodiment 4 back sheet at the back side only being coated with 1 layer, and be not coated with beyond 2 layers, operation has similarly to Example 4 obtained easy the to be bonding tunic before optical functional layer is coated with.
[comparative example 5]
Except in embodiment 5 back sheet at the back side only being coated with 1 layer, and be not coated with beyond 2 layers, operation has similarly to Example 5 obtained easy the to be bonding tunic before optical functional layer is coated with.
[comparative example 6]
Except be not coated with the back sheet at any back side in embodiment 1, operation has similarly to Example 1 obtained easy the to be bonding tunic before optical functional layer is coated with.
[evaluation of easy-adhesion film: mist value]
The method of being put down in writing in the mist value based on JIS-K-6714-1977 has been measured the mist value of the film (supporting material) before forming layers of prisms on the prismatic lens, as the index of transparency of expression prismatic lens.The mensuration of this mist value is to use mist value instrument (NDH-1001P, Japanese electric look industry (strain) system) to carry out.And the numerical value of mist value is big more, and then the transparency is more for good.
[the cementability evaluation of product: belt stripping test]
Utilize the NT cutting machine to form 11 otch on the surface of the prismatic lens of gained.This otch is respectively to the otch that runs through polyester film (net W) with the crosscut of 1mm width.
After this, be subjected to comprehensive attaching cellophane adhesive tape (Cellotape (registration mark): the Nichiban corporate system), carried out disbonded test on the surface of sample with this cellophane tape stripping at this.This disbonded test is repeated respectively 3 times along prism crest line direction and prism parallel direction.After this, counting is attached on the cellophane adhesive tape and the number of the cutting blade of the layers of prisms of peeling off.
In the table of Fig. 4,, represent to have produced partly that with △ whole ground that the sample of peeling off of layers of prisms, usefulness * expression spread all over the cellophane adhesive tape has produced the sample of peeling off of layers of prisms with zero sample of peeling off of representing not produce fully layers of prisms.
[adhesion test of easy bonding film]
To be coated with easy to be bonding film before the optical functional layer after having placed 3 hours under 23 ± 3 ℃, the atmosphere of 50 ± 5%RH, easy bonding film is cut out the size of cutting to 35mm * 35mm, two two ground overlap 5 groups, under identical atmosphere, the time that has applied under the state of load of 84kg is tested with 24 hours and 72 hours two kinds of levels.
, this film taken out, film is peeled off, measured the adhesion area thereafter.3.5mm * 3.5mm is made as 1 frame (Japanese: コ マ), according to having several frames that adhesion has taken place, set the grade of A～D in whole 100 frames.Adhesion is classified as grade A less than the situation of 0.5 frame, with 0.5～less than 10 be classified as grade B, with 10～less than 50% be classified as grade C, will less than 50% be classified as grade D.
Wherein, if grade A can use, yet grade B then can produce the restriction that is subjected to coiling condition, preservation condition and not good situation.In addition, grade C and grade C are difficult to use.
More than, according to the table of Fig. 4, the evaluation result of the adhesion test of the evaluation (mist value) of comparison easy-adhesion film, the cementability evaluation (belt stripping test) of product and easy bonding film.
For the mist value,, then in pairing each embodiment and comparative example, there is not very big difference if it is low beyond 1.5% sample to remove comparative example 6.
For belt stripping test, each embodiment and comparative example all be do not produce fully layers of prisms peel off zero, in each embodiment and comparative example, do not have difference.
For adhesion test, embodiment is A under any condition.Different with it, comparative example all is B, C or D under any condition, obviously relatively poor.
According to above overall merit, can confirm the excellent results of present embodiment.
Claims (according to the modification of the 19th of treaty)
The 19th of PCT revises statement
The typing error " two chloro-s-triarine derivatives " of claim 3 corrected be " two chloro-s-pyrrolotriazine derivatives ", the clear and definite structure of easy-adhesion film for optical sheet of the present invention.
Submit to amended claims to replace totally 2 pages of pages or leaves.
Zhongke Patent ﹠ Trademark Agency Co., Ltd
On July 28th, 2008
1. an easy-adhesion film for optical sheet is characterized in that, the easy adhesive linkage that is coated with the surface of being located at supporting mass contains the aqueous polyurethane resin and carbodiimide is a crosslinking agent, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
2. an easy-adhesion film for optical sheet is characterized in that, the easy adhesive linkage that is coated with the surface of being located at supporting mass contains aqueous polyurethane resin and epoxy crosslinking agent, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
3. easy-adhesion film for optical sheet, it is characterized in that, it is crosslinking agent that the easy adhesive linkage that is coated with the surface of being located at supporting mass contains styrene-butadiene copolymer and dichloro-s-pyrrolotriazine derivatives or carbodiimide, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
4. according to each described easy-adhesion film for optical sheet in the claim 1～3, it is characterized in that,
Described supporting mass is a polyester film,
Described back sheet possesses: contain the ground floor of acrylic latex and tin oxide and be formed at the second layer as polyolefin layer on the described ground floor.
5. according to each described easy-adhesion film for optical sheet in the claim 1～3, it is characterized in that,
Described supporting mass is a polyester film,
Described back sheet possesses: contain the ground floor of electric conductive polymer and be formed at the second layer as polyolefin layer on the described ground floor.
6. according to each described easy-adhesion film for optical sheet in the claim 1～5, it is characterized in that described supporting mass is a PET.
7. according to each described easy-adhesion film for optical sheet in the claim 1～6, it is characterized in that, on described easy adhesive linkage, be formed with optical functional layer.
8. easy-adhesion film for optical sheet according to claim 7 is characterized in that, described optical functional layer is the layers of prisms that is made of ultraviolet curable resin.
9. the manufacture method of an easy-adhesion film for optical sheet is characterized in that, comprising:
Be coated with on the surface of supporting mass easy adhesive linkage operation,
Be coated with at the back side of described supporting mass operation that the superiors are the back sheet of polyolefin layer,
Be coated with the described supporting mass drying of described easy adhesive linkage and back sheet operation,
The operation that dried described supporting mass is reeled,
On the described easy adhesive linkage of the described supporting mass of having been reeled, form the operation of optical functional layer.
10. the manufacture method of easy-adhesion film for optical sheet according to claim 9 is characterized in that, described optical functional layer is the layers of prisms that is made of ultraviolet curable resin.
Claims (10)
1. an easy-adhesion film for optical sheet is characterized in that, the easy adhesive linkage that is coated with the surface of being located at supporting mass contains the aqueous polyurethane resin and carbodiimide is a crosslinking agent, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
2. an easy-adhesion film for optical sheet is characterized in that, the easy adhesive linkage that is coated with the surface of being located at supporting mass contains aqueous polyurethane resin and epoxy crosslinking agent, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
3. easy-adhesion film for optical sheet, it is characterized in that, it is crosslinking agent that the easy adhesive linkage that is coated with the surface of being located at supporting mass contains styrene-butadiene copolymer and dichloro-s-triarine derivative or carbodiimide, and the superiors of back sheet that are formed at the back side of described supporting mass are polyolefin layers.
4. according to each described easy-adhesion film for optical sheet in the claim 1～3, it is characterized in that,
Described supporting mass is a polyester film,
Described back sheet possesses: contain the ground floor of acrylic latex and tin oxide and be formed at the second layer as polyolefin layer on the described ground floor.
5. according to each described easy-adhesion film for optical sheet in the claim 1～3, it is characterized in that,
Described supporting mass is a polyester film,
Described back sheet possesses: contain the ground floor of electric conductive polymer and be formed at the second layer as polyolefin layer on the described ground floor.
6. according to each described easy-adhesion film for optical sheet in the claim 1～5, it is characterized in that described supporting mass is a PET.
7. according to each described easy-adhesion film for optical sheet in the claim 1～6, it is characterized in that, on described easy adhesive linkage, be formed with optical functional layer.
8. easy-adhesion film for optical sheet according to claim 7 is characterized in that, described optical functional layer is the layers of prisms that is made of ultraviolet curable resin.
9. the manufacture method of an easy-adhesion film for optical sheet is characterized in that, comprising:
Be coated with on the surface of supporting mass easy adhesive linkage operation,
Be coated with at the back side of described supporting mass operation that the superiors are the back sheet of polyolefin layer,
Be coated with the described supporting mass drying of described easy adhesive linkage and back sheet operation,
The operation that dried described supporting mass is reeled,
On the described easy adhesive linkage of the described supporting mass of having been reeled, form the operation of optical functional layer.
10. the manufacture method of easy-adhesion film for optical sheet according to claim 9 is characterized in that, described optical functional layer is the layers of prisms that is made of ultraviolet curable resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006024850A JP2007203593A (en) | 2006-02-01 | 2006-02-01 | Easy adhesion film for optical sheet, and its manufacturing method |
| JP024850/2006 | 2006-02-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101374654A true CN101374654A (en) | 2009-02-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800038026A Pending CN101374654A (en) | 2006-02-01 | 2007-01-16 | Easy-adhesion film for optical sheet and method for manufacturing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2007203593A (en) |
| KR (1) | KR20080090437A (en) |
| CN (1) | CN101374654A (en) |
| WO (1) | WO2007088721A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020194A1 (en) * | 2007-08-09 | 2009-02-12 | Teijin Dupont Films Japan Limited | Polyester film for brightness enhancement sheet |
| JP5063421B2 (en) * | 2008-03-13 | 2012-10-31 | ユニチカ株式会社 | Film for semiconductor manufacturing process |
| KR101124581B1 (en) * | 2009-01-19 | 2012-03-15 | 에스케이씨 주식회사 | Optical polyester film having good adhesion property |
| JP5585359B2 (en) * | 2010-09-30 | 2014-09-10 | 日本ゼオン株式会社 | Optical laminate and surface light source device |
| JP5832128B2 (en) * | 2011-04-18 | 2015-12-16 | 株式会社トクヤマ | Photochromic lens |
| JP2015134841A (en) * | 2012-03-27 | 2015-07-27 | 日本ペイントホールディングス株式会社 | Curable resin composition for forming adhesive layer and method for integrating substrate and substrate to be adhered |
| JP5783657B2 (en) * | 2012-12-22 | 2015-09-24 | 三菱樹脂株式会社 | Laminated polyester film |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5858661B2 (en) * | 1975-11-27 | 1983-12-26 | 富士写真フイルム株式会社 | Shashin Zairiyou |
| JPH11123869A (en) * | 1997-10-23 | 1999-05-11 | Gunze Ltd | Sheet for printing with water-based ink |
| JPH11221892A (en) * | 1998-02-06 | 1999-08-17 | Fuji Photo Film Co Ltd | Low heat shrinkage polyester film and low heat shrinkage thermal developing photosensitive material |
| JPH11286092A (en) * | 1998-04-02 | 1999-10-19 | Toray Ind Inc | Laminated polyester film and manufacture thereof |
| JP2000029165A (en) * | 1998-07-10 | 2000-01-28 | Fuji Photo Film Co Ltd | Low heat shrinking film and heat developable photographic sensitive material using that film as supporting body |
| JP2001341241A (en) * | 2000-06-06 | 2001-12-11 | Toray Ind Inc | Laiminated film and method for preparing the same |
| JP4934894B2 (en) * | 2000-09-05 | 2012-05-23 | 東レ株式会社 | Laminated polyester film and method for producing the same |
| JP4547104B2 (en) * | 2001-04-19 | 2010-09-22 | 富士フイルム株式会社 | Cellulose acylate film and method for producing the same |
| JP2003131344A (en) * | 2002-07-15 | 2003-05-09 | Fuji Photo Film Co Ltd | Method for manufacturing photosensitive material supporting body made of low heat-shrinkage film and method for manufacturing heat developable photographic sensitive material |
| JP2004195775A (en) * | 2002-12-18 | 2004-07-15 | Toray Ind Inc | Polyester film |
| JP4259166B2 (en) * | 2003-04-11 | 2009-04-30 | 三菱樹脂株式会社 | Biaxially oriented polyester film |
-
2006
- 2006-02-01 JP JP2006024850A patent/JP2007203593A/en not_active Abandoned
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2007
- 2007-01-16 CN CNA2007800038026A patent/CN101374654A/en active Pending
- 2007-01-16 WO PCT/JP2007/050475 patent/WO2007088721A1/en active Application Filing
- 2007-01-16 KR KR1020087017815A patent/KR20080090437A/en not_active Application Discontinuation
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| JP2007203593A (en) | 2007-08-16 |
| KR20080090437A (en) | 2008-10-08 |
| WO2007088721A1 (en) | 2007-08-09 |
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Application publication date: 20090225 |