CN101204697A - Production method of hard coating thin film, hard coating thin film, polarizing disc and image display apparatus - Google Patents
Production method of hard coating thin film, hard coating thin film, polarizing disc and image display apparatus Download PDFInfo
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- CN101204697A CN101204697A CNA2007101991745A CN200710199174A CN101204697A CN 101204697 A CN101204697 A CN 101204697A CN A2007101991745 A CNA2007101991745 A CN A2007101991745A CN 200710199174 A CN200710199174 A CN 200710199174A CN 101204697 A CN101204697 A CN 101204697A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
Abstract
The present invention provides a excellent manufacturing method for hard coating thin film having continuous productivity, capable of using simple manufacturing mean, preventing hard coating thin film from coil and break by the simple method, and manufacturing smooth and high hardness hard coating thin film without increasing any working procedure. The manufacturing method is the manufacturing method of the hard coating thin film having hard coat layer on at least one surface on the transparent plastic film substrate, wherein including hard coating layer forming material containing hard coat resin and solvent, the coating film is formed by coating the said hard coat layer forming material to at least one surface of the transparent plastic film substrate, the said hard coat layer is formed by solidifying the coat film. The ratio of the thickness of the hard coat layer and the thickness of the transparent plastic film is adjusted to the above range of 1/2.6 in at least one procedure of the preparation and the coating film forming.
Description
Technical field
The present invention relates to manufacture method, hard-coated film, polarizer and the image display device of hard-coated film.
Background technology
Follow technological progress in recent years, as image display device, except CRT (Cathode Ray Tube) in the past, liquid crystal indicator (LCD), plasm display device (PDP) and el display device (ELD) etc. are developed always, and realize practicability.Wherein, follow that relevant high visual angleization, height become more meticulous, the technological innovation of high-speed response, color reprodubility etc., utilize the application of LCD also to change to TV from notebook type microcomputer and controller.The basic comprising of LCD is a following structures: possess the glass substrate on the flat board of transparency electrode respectively across the relative configuration of dividing plate in the mode with the gap that reaches certain intervals, inject liquid crystal material and sealing and make liquid crystal cells between above-mentioned glass substrate, the lateral surface at a pair of glass substrate is provided with polarizer respectively again.In the past, the cover plate that is formed by glass or plastics was installed, the polarizer that the liquid crystal cells surface attaches was caused damage so that prevent on the liquid crystal cells surface.But, just unfavorable aspect cost and weight if cover plate is installed, become gradually on the polarizer surface and be coated with processing firmly.
Being coated with firmly in the processing above-mentioned, generally is to use the hard-coated film that has formed hard conating on the single face of transparent plastic film base material or two sides.Above-mentioned hard conating uses thermohardening type resin or ultraviolet curing resin to wait usually and forms.
Domestic TV is transferred in application by LCD, even general domestic TV user easily the imagination used the TV of LCD, also and utilization in the past the TV of glass system CRT carry out same operation.Therefore, require hardness to improve to the hard-coated film that on LCD, uses.
The bed thickness increase that the hardness of hard-coated film improves by making hard conating becomes possibility.But,, just might produce curling (or crimping) by the cure shrinkage when forming hard conating if increase bed thickness.In addition, when forming hard conating on roller shape transparent plastic film base material, the boundary vicinity that forms the dispensing area of material and other parts (being that hard conating forms the coated portion of material and the uncoated part of transparent plastic film base material end) at the hard conating of the width of above-mentioned transparent plastic film base material might produce fracture (or folding) on hard-coated film.If above-mentioned hard-coated film produces and fractures, bring obstacle to the stacked operation of attachings such as polarizer then can for the continuous production process and the hard-coated film of hard-coated film.
At this problem, proposed bed thickness, thereby the cure shrinkage power when reducing to form hard conating prevents that hard-coated film from the method for curling and fractureing taking place by the attenuate hard conating.But, in the method, if the bed thickness of attenuate hard conating, with regard to the problem that has hard-coated film hardness to descend.
In addition, proposed on the surface of the side opposite of transparent plastic film base material, to be formed for to prevent the manufacture method (with reference to patent documentation 1) of the hard-coated film of the back coating that curls with forming hard conating.But the method that forms above-mentioned back coating has the manufacturing installation complicated problems that becomes.In addition, this method also has the problem that process number increases, produces rate variance.This method can't solve the problem that above-mentioned hard-coated film fractures.
Patent documentation 1: TOHKEMY 2004-109771 communique
Summary of the invention
Therefore, the object of the present invention is to provide the manufacture method of the hard-coated film of continuous productivity ratio excellence, it can use easy manufacturing installation, prevent hard-coated film generation curling (or crimping) and fracture (or folding) with easy method, can make the hard-coated film of smooth and high rigidity under the situation that does not increase process number.
In order to achieve the above object, the manufacture method of hard-coated film of the present invention is the manufacture method that has the hard-coated film of hard conating at least one surface of transparent plastic film base material, it is characterized in that comprising following operation: prepare to contain and resinize firmly and the hard conating of solvent forms the preparatory process of material; The above-mentioned hard conating of coating forms material and forms the formation operation of filming of filming at least one surface of above-mentioned transparent plastic film base material; With by making above-mentioned curing of coating, thereby the hard conating that forms above-mentioned hard conating forms operation; Wherein adjust at least one in above-mentioned hard conating thickness (A) and the above-mentioned transparent plastic film base material thickness (B) so that the ratio (A/B) of above-mentioned hard conating thickness (A) and above-mentioned transparent plastic film base material thickness (B) is more than 1/2.6.
Hard-coated film of the present invention is the hard-coated film of being made by the manufacture method of the hard-coated film of the invention described above.
Polarizer of the present invention is the polarizer with polarizer and hard-coated film, it is characterized in that, above-mentioned hard-coated film is the hard-coated film of the invention described above.
Image display device of the present invention is at least one the image display device that comprises in hard-coated film and the polarizer, it is characterized in that above-mentioned hard-coated film is the hard-coated film of the invention described above, and above-mentioned polarizer is the polarizer of the invention described above.
As mentioned above, in the manufacture method of hard-coated film of the present invention, adjust at least one in above-mentioned hard conating thickness (A) and the above-mentioned transparent plastic film base material thickness (B) so that the ratio (A/B) of hard conating thickness (A) and transparent plastic film base material thickness (B) is more than 1/2.6.By adjusting in this wise, when above-mentioned curing of coating shrank, above-mentioned transparent plastic film base material also shrank with the above-mentioned broad ways of filming, the result, and whole hard-coated film broad ways is shunk.Therefore, manufacture method of the present invention has prevented that hard-coated film from taking place to curl and fracture.Therefore, manufacturing method according to the invention can be made smooth hard-coated film under the situation that does not increase process number.In addition, in manufacture method of the present invention, realize preventing that by the extremely easy like this method of the adjustment of above-mentioned ratio (A/B) hard-coated film from taking place to curl and fracture, so can use easy manufacturing installation (for example known in the past manufacturing installation).Then, in manufacture method of the present invention, even, can prevent that also hard-coated film from taking place to curl and fracture, so productivity ratio excellence continuously because when on roller shape transparent plastic film base material for example, forming hard-coated film.Manufacturing method according to the invention as long as adjust above-mentioned ratio (A/B), even thicken the bed thickness of above-mentioned hard conating, can prevent that also hard-coated film from taking place to curl and fracture.Therefore, manufacturing method according to the invention can obtain having the hard-coated film of the high rigidity of abundant thickness on hard conating.
Description of drawings
Fig. 1 is the generalized section of structure of an example of expression hard-coated film of the present invention.
Fig. 2 is the generalized section of structure of another example of expression hard-coated film of the present invention.
Fig. 3 is the generalized section of structure of another example of expression hard-coated film of the present invention.
Fig. 4 is the figure of assay method of the cure shrinkage power of explanation width of filming of the present invention.Fig. 4 (A) is that figure, Fig. 4 (B) of the preparation method of explanation test film is the figure of the assay method of explanation cure shrinkage power.
Fig. 5 is the curve map of relation of the cure shrinkage power of the thickness of hard conating of explanation embodiments of the invention and the width of filming.
Fig. 6 is the curve map of relation of shrinkage factor of representing the width of the cure shrinkage power of the width of filming in an embodiment of the present invention and hard-coated film.
Symbol description
1 transparent plastic film base material
2 hard conatings
3,5,7 hard-coated films
4 particulates
6 anti-reflection layers
8 film
9 test films
10 tension draftomters (digital force gauge)
The specific embodiment
In the manufacture method of hard-coated film of the present invention, in preferred adjustment above-mentioned hard conating thickness (A) and the above-mentioned transparent plastic film base material thickness (B) at least one more preferably adjusted at least one in above-mentioned hard conating thickness (A) and the above-mentioned transparent plastic film base material thickness (B) so that the ratio (A/B) of above-mentioned hard conating thickness (A) and above-mentioned transparent plastic film base material thickness (B) is more than 1/2.0 so that the ratio (A/B) of above-mentioned hard conating thickness (A) and above-mentioned transparent plastic film base material thickness (B) is more than 1/2.5.
In the manufacture method of hard-coated film of the present invention, above-mentioned hard conating thickness (A) preferably is adjusted into the scope of 15～35 μ m, and above-mentioned transparent plastic film base material thickness (B) preferably is adjusted into the scope of 15～50 μ m.Above-mentioned hard conating thickness (A) more preferably is adjusted into the scope of 16～30 μ m, further preferably is adjusted into the scope of 16～25 μ m.In addition, above-mentioned transparent plastic film base material thickness (B) more preferably is adjusted into the scope of 20～50 μ m, further preferably is adjusted into the scope of 35～45 μ m.
In the manufacture method of hard-coated film of the present invention, form in the operation at above-mentioned hard conating, the cure shrinkage power of above-mentioned width of filming is 9N/cm preferably
2More than.Above-mentioned cure shrinkage power is more preferably 10N/cm
2More than, further 13N/cm preferably
2More than.The upper limit of above-mentioned cure shrinkage power has no particular limits, and for example is 34N/cm
2Above-mentioned cure shrinkage power is 9～19N/cm preferably
2Scope, be more preferably 10～16N/cm
2Scope.Above-mentioned cure shrinkage power for example can be measured with the method for putting down in writing in embodiment described later.
In the manufacture method of hard-coated film of the present invention, above-mentioned resinizing firmly preferably contained following (A) composition, (B) composition and (C) composition.
(A) composition: at least one in urethane acrylate and the urethane methacrylate:
(B) composition: at least one in polyalcohol acrylate and the polyalcohol methacrylate;
(C) composition: by following (C1) with the mixed polymer of at least one polymer that forms (C2) or copolymer or above-mentioned polymer and copolymer;
(C1): alkyl acrylate with the alkyl that comprises at least one group among hydroxyl and the acryloyl group; With
(C2): alkyl methacrylate with the alkyl that comprises at least one group among hydroxyl and the acryloyl group.
The manufacture method of hard-coated film of the present invention also preferably comprises the operation that forms anti-reflection layer.At this moment, above-mentioned anti-reflection layer preferably contains hollow and spherical silicon oxide particle.
In hard-coated film of the present invention, the outer surface structure optimization of above-mentioned hard conating is a concaveconvex structure.
Then, describe the present invention in detail.But the present invention is not limited by following record.
Hard-coated film of the present invention is to form material by preparing to contain the hard conating of resinizing firmly with solvent, the above-mentioned hard conating of coating forms material and forms and film at least one surface of transparent plastic film base material, and makes above-mentioned curing of coating and form hard conating manufacturing.
Above-mentioned transparent plastic film base material has no particular limits.Above-mentioned transparent plastic film base material is preferably the light penetration excellence (preferred light penetration is more than 90%) of visible light, the base material of the transparency excellent (preferred haze value is below 1%).The formation material of above-mentioned transparent plastic film base material for example comprises polyester based polymer, cellulose-based polymer, Merlon based polymer, acrylic acid series polymeric compounds etc.Above-mentioned polyester based polymer for example comprises PETG, poly-naphthoic acid glycol ester etc.Above-mentioned cellulose-based polymer for example comprises diacetyl cellulose, tri acetyl cellulose (TAC) etc.Aforesaid propylene acid based polymer for example comprises polymethyl methacrylate etc.The formation material of above-mentioned transparent plastic film base material for example also comprises styrenic, olefin polymer, vinyl chloride-based polymer, acid amides based polymer etc.Above-mentioned styrenic for example comprises polystyrene, acrylonitritrile-styrene resin etc.Above-mentioned olefin polymer for example comprises polyethylene, polypropylene, contain the polyolefin of circulus, contain polyolefin, ethylene-propylene copolymer of ENB structure etc.Above-mentioned acid amides based polymer for example comprises nylon, aromatic polyamide etc.The formation material of above-mentioned transparent plastic film base material for example also comprises the blend of imide series polymer, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol based polymer, vinylidene chloride based polymer, polyvinyl butyral resin based polymer, arylide based polymer, polyformaldehyde based polymer, epoxy based polymer and above-mentioned polymer etc.In these materials, the material that birefringence is few on the optics can be fit to use.Hard-coated film of the present invention for example also can be used as diaphragm and uses in polarizer.At this moment, as above-mentioned transparent plastic film base material, the film that forms by TAC, Merlon, acrylic acid series polymeric compounds, the polyolefin that comprises circulus, the polyolefin that comprises the ENB structure etc. preferably.In the present invention, above-mentioned transparent plastic film base material also can be a polarizer itself.If such structure, the protective layer that need do not formed by TAC etc. just can simplifying the structure polarizer.Thus, the worker ordinal number of polarizer or image display device is reduced, realized the raising of production efficiency.In addition, if such structure can also make the further thin layerization of polarizer.When above-mentioned transparent plastic film base material was polarizer, hard conating is the effect of performance protective layer in the past just.If such structure, hard-coated film just has the function of the cover plate that is installed in the liquid crystal cells surface concurrently.
In the present invention, above-mentioned transparent plastic film base material thickness as mentioned above.In addition, the thickness of adjusting above-mentioned transparent plastic film base material comprises: select the transparent plastic film base material of suitable thickness according to the present invention and by in the adjustment transparent plastic film base material thickness such as stretchings, contraction at least one.The refractive index of above-mentioned transparent plastic film base material is not particularly limited, and for example is 1.30～1.80 scope, preferably 1.40～1.70 scope.
As previously mentioned, above-mentioned hard conating forms material and comprises and resinize firmly and solvent.
Resinize firmly as above-mentioned, for example can list thermohardening type resin, thermoplastic resin, ultraviolet curing resin, ionizing radiation gel-type resin, bi-component hybrid resin etc.In these resins, especially preferably use by the ultraviolet ray irradiation and solidify the ultraviolet curing resin that the simple process operation of handling just can form hard conating expeditiously.In addition, in above-mentioned ultraviolet curing resin, can cooperate ultraviolet polymerization initiator (Photoepolymerizationinitiater initiater).
As above-mentioned ultraviolet curing resin, for example can list various resins such as polyester system, acrylic acid series, polyurethane series, siloxane-based, epoxy system.This ultraviolet curing resin comprises ultraviolet hardening monomer, oligomer, polymer etc.As the preferred especially ultraviolet curing resin that uses, can list the resin of functional group with polymerizable ultraviolet, especially comprise and have more than 2, particularly have the acrylic monomer of 3～6 above-mentioned functional groups and a resin of oligomer.
The object lesson of such ultraviolet curing resin for example can list methacrylate resins such as the acrylates such as acrylate of polyalcohol, the methacrylate of polyalcohol, by the synthetic multi-functional polyurethane acrylate resin of vulcabond, polyalcohol and acrylic acid hydroxy alkyl ester, by synthetic multi-functional urethane methacrylate resin such as the methacrylic acid hydroxyl ester of polyalcohol and methacrylic acid etc.In addition, can also be as required, suitably use polyether resin with acrylic ester functional group, mylar, epoxy resin, alkyd resins, spiral shell acetal resin, polybutadiene, polymercaptan polyene resin etc.In addition, also can preferably use melamine is that resin, polyurethane series resin, alkyd are resin, siloxane-based resin etc.
As above-mentioned Photoepolymerizationinitiater initiater, for example can list 2,2-dimethoxy-2-phenyl acetophenone, acetophenone, benzophenone, xanthene ketone, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, benzoin propyl ether, benzyl dimethyl ketal, N, N, N ', N '-tetramethyl-4,4 '-diaminobenzophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone etc. can use thioxanthones based compound etc. in addition.
Above-mentioned resinizing firmly can be used alone, and also two or more kinds may be used.In addition, also can use commercially available ultraviolet curing resin etc. to resinize firmly as above-mentioned.
As previously mentioned, above-mentioned resinizing firmly preferably contained following (A) composition, (B) composition and (C) composition.
(A) composition: at least one in urethane acrylate and the urethane methacrylate;
(B) composition: at least one in polyalcohol acrylate and the polyalcohol methacrylate;
(C) composition: by following (C1) with the mixed polymer of at least one polymer that forms (C2) or copolymer or above-mentioned polymer and copolymer;
(C1): alkyl acrylate with the alkyl that comprises at least one group among hydroxyl and the acryloyl group; With
(C2): alkyl methacrylate with the alkyl that comprises at least one group among hydroxyl and the acryloyl group.
As above-mentioned (A) composition is above-mentioned urethane acrylate and urethane methacrylate, can use to contain acrylic acid, methacrylic acid, acrylate, methacrylate, polyalcohol, the vulcabond compound as constituent.For example, at least a monomer and polyalcohol among use acrylic acid, methacrylic acid, acrylate and the methacrylate, making has the crylic acid hydroxy ester of 1 above hydroxyl and has in the methacrylic acid hydroxyl ester of 1 above hydroxyl at least 1, by making itself and di-isocyanate reaction, just can make at least one in urethane acrylate and the urethane methacrylate.In above-mentioned (A) composition, urethane acrylate and urethane methacrylate can be used alone or two or more kinds may be used.
The aforesaid propylene acid esters for example comprises alkyl acrylate, acrylic acid cycloalkyl ester etc.The aforesaid propylene acid alkyl ester for example comprises methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate etc.Aforesaid propylene acid cycloalkyl ester for example comprises cyclohexyl acrylate etc.Above-mentioned methacrylate for example comprises alkyl methacrylate, methacrylic acid cycloalkyl ester etc.Above-mentioned alkyl methacrylate for example comprises methyl methacrylate, EMA, isopropyl methacrylate, butyl methacrylate etc.Above-mentioned methacrylic acid cycloalkyl ester for example comprises cyclohexyl methacrylate etc.
Above-mentioned polyalcohol is the compound with at least 2 hydroxyls.Above-mentioned polyalcohol for example comprises ethylene glycol, 1, ammediol, 1, the 2-propane diols, diethylene glycol, DPG, neopentyl glycol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, 1, the 10-decanediol, 2,2,4-trimethyl-1, the 3-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, the hydroxy new pentane acid DOPCP, cyclohexanedimethanol, 1, the 4-cyclohexanediol, the spiroglycol, tricyclodecane methanol, the hydrogenation bisphenol-A, oxirane addition bisphenol-A, expoxy propane addition bisphenol-A, trimethylolethane, trimethylolpropane, glycerine, 3-methylpentane-1,3, the 5-triol, pentaerythrite, dipentaerythritol, tripentaerythritol, grape carbohydrate etc.
As above-mentioned vulcabond, for example can use aromatic series, aliphatic or alicyclic various diisocyanates.Above-mentioned vulcabond for example comprises tetramethylene diisocyanate, hexamethylene diisocyanate, IPDI, 2,4-toluene di-isocyanate(TDI), 4,4-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, XDI, trimethyl hexamethylene diisocyanate, 4,4-methyl diphenylene diisocyanate etc. also comprise their hydride etc.
The cooperation ratio of above-mentioned (A) composition has no particular limits.Above-mentioned by using (A) composition can make the flexibility of formed above-mentioned hard conating and the adhesive force of above-mentioned transparent plastic film base material is improved.From the viewpoint of the hardness of these aspects and above-mentioned hard conating etc., form whole resinous principle in the material with respect to above-mentioned hard conating, the cooperation ratio of above-mentioned (A) composition for example is the scope of 15～55 weight %, preferably the scope of 25～45 weight %.So-called above-mentioned whole resinous principle, be meant (A) composition, (B) composition and (C) the total amount of composition, perhaps when using other resinous principle, being meant the total amount of above-mentioned three kinds of compositions and the total amount amount altogether of above-mentioned resinous principle, below also is same.
Above-mentioned (B) composition for example comprises pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, 1,6-hexylene glycol acrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, dipentaerythritol hexamethyl acrylate, 1,6-hexylene glycol methacrylate etc.They can use separately, and also two or more kinds may be used.For example, as above-mentioned polyalcohol acrylate, be preferably and comprise the monomer component that the polymer by pentaerythritol triacrylate and tetramethylol methane tetraacrylate forms and the blending constituent of pentaerythritol triacrylate and tetramethylol methane tetraacrylate.
The cooperation ratio of above-mentioned (B) composition has no particular limits.For example, with respect to above-mentioned (A) composition, the cooperation ratio of above-mentioned (B) composition is the scope of 70～180 weight % preferably, is more preferably the scope of 100～150 weight %.If the cooperation ratio of above-mentioned (B) composition is more than the 70 weight % of above-mentioned (A) composition, the hardness of formed hard conating is further improved, marresistance is improved.
In above-mentioned (C) composition, above-mentioned (C1) and abovementioned alkyl (C2) for example are that carbon number is 1～10 alkyl.Abovementioned alkyl can be the straight chain shape, also can be a chain.As the composition of above-mentioned (C), for example can list the mixture of polymer, copolymer or the above-mentioned polymer and the above-mentioned copolymer of the repetitive that contains following general formula (1).
In above-mentioned formula (1), R
1Be-H or-CH
3, R
2Be-CH
2CH
2OX or by the group of following general formula (2) expression, above-mentioned X be-H or by the acryloyl group of following general formula (3) expression.
In above-mentioned general formula (2), above-mentioned X is-H or by the acryloyl group of following general formula (3) expression, and above-mentioned X can identical, also can be different.
As above-mentioned (C) composition, for example can list by from acrylic acid 2,3-two hydroxypropyl acrylates, acrylic acid 2,3-two propylene acyloxy propyl ester, acrylic acid 2-hydroxyl-3-acryloxy propyl ester, acrylic acid 2-acryloxy-3-hydroxypropyl acrylate, methacrylic acid 2,3-two hydroxypropyl acrylates, methacrylic acid 2,3-two propylene acyloxy propyl ester, methacrylic acid 2-hydroxyl-3-acryloxy propyl ester, methacrylic acid 2-acryloxy-3-hydroxypropyl acrylate, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-acryloxy ethyl ester, the polymer that at least one monomer of selecting in the group that methacrylic acid 2-hydroxyl ethyl ester and methacrylic acid 2-acryloxy ester are formed forms, copolymer, the mixture of perhaps above-mentioned polymer and above-mentioned copolymer.
The cooperation ratio of above-mentioned (C) composition has no particular limits.For example, with respect to the cooperation ratio of above-mentioned (A) composition, above-mentioned (C) composition scope of 25～110 weight % preferably, be more preferably the scope of 45～85 weight %.If the cooperation ratio of above-mentioned (C) composition is below the 110 weight % with respect to above-mentioned (A) composition, then hard conating forms the coating excellence of material.
There is no particular limitation for above-mentioned solvent.Above-mentioned solvent for example comprises butyl oxide, dimethoxymethane, dimethoxy-ethane, diethoxyethane, expoxy propane, 1, the 4-diox, 1,3-two oxa-s penta ring, 1,3, the 5-trioxane, oxolane, acetone, MEK, diethyl ketone, butyrone, isobutyrone, cyclopentanone, cyclohexanone, methyl cyclohexanone, Ethyl formate, propyl formate, the formic acid n-pentyl ester, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-amyl acetate, acetylacetone,2,4-pentanedione, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethanol, the 1-propyl alcohol, the 2-propyl alcohol, the 1-butanols, the 2-butanols, the 1-amylalcohol, 2-methyl-2-butanols, cyclohexanol, isobutyl acetate, methylisobutylketone (MIBK), methyln-hexyl ketone, 2 pentanone, methyl-n-butyl ketone, the 2-heptanone, the 3-heptanone, ethylene glycol monoethylether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether etc.These solvents can use separately, also two or more kinds may be used.The viewpoint that improves from the adhesive force that makes above-mentioned transparent plastic film base material and above-mentioned hard conating, above-mentioned solvent preferably contains ethyl acetate with the ratio that accounts for more than the 20 whole weight %, the ratio that is more preferably to account for more than the 25 whole weight % contains ethyl acetate, and best is to contain ethyl acetate with the ratio that accounts for 30～70 whole weight %.The ratio of the ethyl acetate in the above-mentioned solvent just can make the evaporation rate of solvent suitable if below the 70 weight %, can prevent crawling or uneven drying effectively.Have no particular limits with the solvent species of above-mentioned ethyl acetate and usefulness.Above-mentioned solvent for example comprises butyl acetate, MEK, ethylene glycol monobutyl ether, propylene glycol monomethyl ether etc.
Form in the material at above-mentioned hard conating, can add various levelling agents.As above-mentioned levelling agent, for example can list fluorine system or siloxane-based levelling agent, siloxane-based levelling agent preferably.Above-mentioned siloxane-based levelling agent for example comprises reactive siloxane, dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, poly-methyl alkyl siloxane etc.In these siloxane-based levelling agents, preferred especially above-mentioned reactive siloxane.By adding above-mentioned reactive siloxane, thereby give lubricity to the surface, make during long-time in lasting marresistance.In addition, if use and have the reactive siloxane of hydroxyl as above-mentioned reactive siloxane, then form the anti-reflection layer during as anti-reflection layer (low-index layer) contain silicone component on above-mentioned hard conating, the adhesive force of above-mentioned anti-reflection layer and above-mentioned hard conating improves.
With respect to above-mentioned whole resinous principle 100 weight portions, the use level of above-mentioned levelling agent for example is below 5 weight portions, preferably the scope of 0.01～5 weight portion.
Form in the material at above-mentioned hard conating, can add various reactive diluents.There is no particular limitation for above-mentioned reactive diluent.Above-mentioned reactive diluent for example comprises: ratio of viscosities lower 1, the 6-hexanediyl ester, 1, the 6-hexanediol dimethacrylate, tripropylene glycol diacrylate, the tripropylene glycol dimethylacrylate, diethylene glycol diacrylate, the diethylene glycol dimethylacrylate, the hexylene glycol acrylate, the hexylene glycol methacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, neopentylglycol diacrylate, monomer that 2 officials such as neopentylglycol dimethacrylate energy is above and oligomer etc.Above-mentioned reactive diluent for example also comprises: as the N-vinyl pyrrolidone of monofunctional monomer, ethyl acrylate, esters of acrylic acids such as propyl acrylate, EMA, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, EHMA, methacrylic acid 2-hydroxyl ethyl ester, cyclohexyl methacrylate, methyl acrylic esters such as methacrylic acid nonyl phenyl ester, derivatives such as methacrylic acid tetrahydrofuran ester and caprolactone modification thing thereof, styrene, AMS, acrylic acid etc. and their mixture etc.
As required, in the scope of not damaging performance, in the formation material of above-mentioned hard conating, also can add pigment, filler, dispersant, plasticizer, ultra-violet absorber, surfactant, antioxidant, thixotropic agent etc.Above-mentioned additive can be used alone or two or more kinds may be used.
The above-mentioned hard conating of coating forms the method for material on above-mentioned transparent plastic film base material, for example can use rubbing methods such as spraying rubbing method, slit die rubbing method, method of spin coating, spraying rubbing method, intaglio plate rubbing method, roller rubbing method, the excellent rubbing method of coiling.
Be coated with above-mentioned hard conating and form material, on above-mentioned transparent plastic film base material, form and film.
Then, make above-mentioned curing of coating.Before above-mentioned curing, preferably make above-mentioned dried coating film.For example, above-mentioned filming can air dry, also can be air-dry by drying, also can heat drying, and also can be these method of combination.
Above-mentioned curing means of filming have no particular limits.Above-mentioned curing means are ultraviolet curing or ionizing radiation curing preferably.Above-mentioned curing means can be used various active-energies.Above-mentioned active-energy is ultraviolet ray preferably.As the energy line source, line sources such as preference such as high-pressure sodium lamp, halogen lamp, xenon lamp, Metal halogen lamp, nitrogen laser, electronics line accelerator, radioactive element.The exposure of above-mentioned energy line source is cumulative exposure amount 50～5000mJ/cm preferably of 365nm in ultraviolet wavelength
2If above-mentioned exposure is 50mJ/cm
2More than, then curing becomes more abundant, and formed above-mentioned hard conating hardness also becomes more abundant.If above-mentioned exposure is 5000mJ/cm
2Below, can prevent that then formed above-mentioned hard conating is painted, the transparency is improved.
In above-mentioned curing, the cure shrinkage power of above-mentioned width of filming as mentioned above.In addition, the cure shrinkage of above-mentioned width of filming for example is the scope more than 0.2%, and preferably the scope more than 0.3% is more preferably the scope more than 0.4%.The cure shrinkage power of above-mentioned width of filming and cure shrinkage form the composition (above-mentionedly resinize firmly, the kind of solvent, additive and match ratio etc.) of material according to above-mentioned hard conating and different, above-mentioned coating thickness is thick more, and then cure shrinkage power and cure shrinkage are big more.In addition, the cure shrinkage power of for example above-mentioned width of filming and cure shrinkage can be by adjusting the composition that above-mentioned hard conating forms material, adjust above-mentioned coating thickness (thickness of hard conating) etc. and regulate, for persons skilled in the art, need not carry out excessive trial (it is poor to try), can easily obtain having filming of above-mentioned rerum natura (cure shrinkage power, cure shrinkage etc.).Here, in the manufacture method of hard-coated film of the present invention, as mentioned above, adjust at least one in above-mentioned hard conating thickness (A) and the above-mentioned transparent plastic film base material thickness (B) so that the ratio (A/B) of above-mentioned hard conating thickness (A) and above-mentioned transparent plastic film base material thickness (B) is more than 1/2.6.In the present invention, the adjustment of above-mentioned hard conating thickness can be undertaken by adjusting above-mentioned thickness of filming.That is,, can adjust above-mentioned hard conating thickness as its solidfied material by adjusting above-mentioned coating thickness.That is,, just can hold the relation of above-mentioned coating thickness and above-mentioned hard conating thickness easily, need not carry out excessive trial (it is poor to try), just can realize hard conating thickness of the present invention for persons skilled in the art.In addition, because hard conating as thin as a wafer, so above-mentioned coating thickness and above-mentioned hard conating thickness can be regarded as identical (coating thickness ≈ hard conating thickness).By adjusting above-mentioned ratio (A/B), above-mentioned transparent plastic film base material becomes the thickness that has with above-mentioned contraction broad ways contraction of filming.Its result is because shrink on the whole broad ways of hard-coated film, so can prevent that hard-coated film from taking place to curl and fracture.
According to above operation,, can make hard-coated film of the present invention by forming above-mentioned hard conating at least one face in above-mentioned transparent plastic film base material.The hardness of hard-coated film of the present invention has no particular limits, and for example is more than the 4H in pencil hardness for example.
Fig. 1 is the generalized section of an example of expression hard-coated film of the present invention.As shown in fig. 1, the hard-coated film 3 of this example comprises transparent plastic film base material 1, forms hard conating 2 on the single surface of this transparent plastic film base material 1.The present invention is not limited to the structure of Fig. 1.Hard-coated film also can comprise transparent plastic film base material 1, and forms hard conating 2 on its two sides.The hard conating 2 of this example is an individual layer.But the present invention is not limited to this.Above-mentioned hard conating 2 also can be stacked sandwich construction more than 2 layers.
Above-mentioned hard conating is a concaveconvex structure in order to make its surface texture, also can contain particulate.This is because if the surface texture of above-mentioned hard conating is made concaveconvex structure, just can give anti-dazzle property.Above-mentioned particulate for example has inorganic particles and organic fine particles.There is no particular limitation for above-mentioned inorganic particles.Above-mentioned inorganic particles for example comprises silicon oxide particle, titanium oxide microparticle, alumina particulate, zinc oxide fine particles, tin oxide particulate, calcium carbonate microparticle, barium sulfate particulate, talcum powder particulate, kaoline par-tides, calcium sulfate particulate etc.There is no particular limitation for above-mentioned organic fine particles.Above-mentioned organic fine particles for example comprises plexiglass powder (PMMA particulate), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic acid styrene resin powder, benzoguanamine resin powder, melmac powder, vistanex powder, polyester resin powder, polyamide powder, polyimide resin powder, polyfluoroethylene resin powder etc.These inorganic particles and organic fine particles can be used alone or two or more kinds may be used.
The shape of above-mentioned particulate has no particular limits.The shape of above-mentioned particulate for example can be the roughly spherical of bead.For example, the shape of above-mentioned particulate also can be unbodied shapes such as powder.The weight average particle diameter of above-mentioned particulate for example is the scope of 1～30 μ m, the scope of 2～20 μ m preferably, and the particulate that above-mentioned particulate is preferably roughly spherical is more preferably aspect ratio and is the roughly particulate of sphere 1.5 below.
The match ratio of above-mentioned particulate has no particular limits.The cooperation ratio of above-mentioned particulate can suitably be set.Form material with respect to the above-mentioned hard conating of 100 weight portions, the cooperation ratio of above-mentioned particulate for example is the scope of 2～60 weight portions, preferably the scope of 1～50 weight portion.
From preventing to produce viewpoints such as light scattering and interference fringe, preferably reduce the refringence of above-mentioned particulate and above-mentioned hard conating at the interface of above-mentioned particulate and above-mentioned hard conating.The above-mentioned interference striped is to inject the phenomenon that outer reflection of light light in the hard-coated film presents the form and aspect of the color of appearing in the sky.Recently, in office etc., use the three-wavelength fluorescent lamp of bright property excellence mostly.Under above-mentioned three-wavelength fluorescent lamp, the above-mentioned interference striped significantly manifests.Because the refractive index of above-mentioned hard conating is normally in 1.4～1.6 scope, so preferably have particulate near the refractive index of this ranges of indices of refraction.The difference of the refractive index of above-mentioned particulate and above-mentioned hard conating is preferably less than 0.05.
Fig. 2 is the generalized section of an example that expression has the hard-coated film of the present invention of the hard conating that has been endowed anti-dazzle property.In Fig. 2, to the part mark identical symbol identical with Fig. 1.As shown in Figure 2, the hard conating 2 of this routine hard-coated film 5 comprises particulate 4, and the surface of above-mentioned hard conating 2 is a concaveconvex structure.If the surface of above-mentioned hard conating 2 is concaveconvex structures, can bring into play anti-dazzle property (the anti-photosensitiveness of dazzling).The hard-coated film of this example is except the surface of above-mentioned hard conating is concaveconvex structure, and the hard-coated film of other and Fig. 1 is identical.
In hard-coated film of the present invention, on above-mentioned hard conating, also can form anti-reflection layer (low-index layer).Fig. 3 is the generalized section of an example that expression has the hard-coated film of the present invention of above-mentioned anti-reflection layer.In Fig. 3, to the part mark identical symbol identical with Fig. 2.As shown in Figure 3, the hard-coated film 7 of this example is the structure that forms anti-reflection layer (low-index layer) 6 on the surface is the hard conating 2 of concaveconvex structure, and other structure is identical with the hard-coated film shown in Fig. 2.When illumination was mapped on the object, the reflection that takes place on its interface, the absorption that takes place in inside, the phenomenon of scattering were carried out repeatedly, saw through from the object back side and went.For example, when in image display device, hard-coated film being installed,, can list light reflection at air and hard conating interface as making one of visuognosis main reasons for decrease of image.Anti-reflection layer is the layer that its surface reflection is descended.In addition, in the hard-coated film 7 as shown in FIG. 3, anti-reflection layer 6 is individual layers.But the present invention is not limited to these.Above-mentioned anti-reflection layer 6 also can be stacked sandwich construction more than 2 layers.
In the present invention, above-mentioned anti-reflection layer be with strict control the optical thin film of thickness and refractive index or above-mentioned optical thin film stacked more than 2 layers and the anti-reflection layer that obtains.Above-mentioned anti-reflection layer utilizes the interference of light effect that incident light is cancelled each other mutually with the position of reverberation counter-rotating and manifests anti-reflective function.For example, making the wavelength region may of the luminous ray that above-mentioned anti-reflective function manifests is 380～780nm, and particularly the wavelength region may that visibility is high is the scope of 450～650nm.Above-mentioned anti-reflection layer preferably is that the reflectivity of 550nm is designed to minimum with its centre wavelength.
In design,, the method for the refringence that increases above-mentioned anti-reflection layer and above-mentioned hard conating is for example arranged as the means that its interference effect is improved based on the above-mentioned anti-reflection layer of interference of light effect.In general, in the multilayer anti-reflection layer of the structure that stacked 2 to 5 layers optics thin layer (strict control the film of thickness and refractive index) forms, only form multilayer with the specific thickness composition that refractive index is different.Therefore, the optical design free degree of above-mentioned anti-reflection layer improves, and anti-reflection effect is further improved, and divides reflective character also can become in the visible region evenly (smooth).Demanding thickness and precision in above-mentioned optical thin film.Therefore, the formation of each layer generally is the enforcement such as vacuum evaporation, sputter, CVD with dry type.
As above-mentioned multilayer anti-reflection layer, the preferred anti-reflection layer of 2 layers of structure that the folded low silicon oxide layer (refractive index is about 1.45) of refractive index forms on the high titanium oxide layer of refractive index (refractive index is about 1.8) upper strata.More preferably stacked silicon oxide layer, stacked other titanium oxide layer, the four-layer structure anti-reflection layer that forms of stacked other silicon oxide layer thereon thereon on titanium oxide layer.By forming these two layers of anti-reflection layers or four layers of anti-reflection layer, can reduce the reflection of the wavelength region may (for example scope of 380～780nm) of luminous ray equably.
By on above-mentioned hard conating, forming the optical thin film (anti-reflection layer) of individual layer, also can show anti-reflection effect.In general, when the formation of individual layer anti-reflection layer, adopt rubbing methods such as for example injection coating (fountain coating), the slit die of wet type are coated with, rotation is coated with, spraying coating, intaglio plate coating, roller coat cloth, the excellent coating of coiling.
The formation material of above-mentioned individual layer anti-reflection layer for example comprises resinous materials such as ultraviolet hardening acrylic resin, inorganic particles such as cataloid is dispersed in the resin and the sol-gel class material of metal alkoxides salt such as the mixed stocker material that obtains, tetraethoxysilane, use purity titanium tetraethoxide etc.In above-mentioned formation material,, preferably contain fluorine-based formation material in order to give the surface soiling metachromia.In above-mentioned formation material, for reasons such as marresistances, the many formation materials of preferred inorganic constituents content are more preferably above-mentioned sol-gel class material.Above-mentioned sol-gel based material can use after the part condensation.
Above-mentioned anti-reflection layer (low-index layer) is preferably by containing siloxane oligomer that the number-average molecular weight that converts in ethylene glycol is 500～10000 scopes and be 5000 or more, have an anti-reflection layer that the material (opening the material of putting down in writing in the 2004-167827 communique the spy) of the fluorine compounds of fluoroalkyl structure and polysiloxane structure forms in the number-average molecular weight of polystyrene conversion, reflects etc. because it can be taken into account marresistance and hang down.
In above-mentioned anti-reflection layer (low-index layer), in order to improve film-strength, also can contain inorganic sol, there is no particular limitation for above-mentioned inorganic sol.Above-mentioned inorganic sol for example comprises silica, aluminium oxide, magnesium fluoride etc.In these, preferred silica dioxide gel.With respect to all solids composition of the above-mentioned anti-reflection layer formation of 100 weight portions material, the cooperation ratio of above-mentioned inorganic gel for example is the scope of 10～80 weight portions.Inorganic particles particle diameter in the above-mentioned inorganic gel is preferably the scope of 2～50nm, more preferably the scope of 5～30nm.
In the formation material of above-mentioned anti-reflection layer, preferably contain hollow and spherical silica ultramicron.The average grain diameter of above-mentioned silica ultramicron preferably about 5～300nm, is more preferably the scope of 10～200nm.Above-mentioned silica ultramicron is the hollow spheres that is formed with the cavity in the inside of the shell with pore.Solvent when above-mentioned cavity comprises above-mentioned silica ultramicron and prepares and at least one in the gas.In addition, the precursor substance that is used to form the above-mentioned cavity of above-mentioned silica ultramicron preferably remains in the above-mentioned cavity.The thickness of above-mentioned shell is the scope about 1～50nm, and about 1/50～1/5 scope of the average grain diameter of preferably above-mentioned silica ultramicron.Above-mentioned shell is preferably formed by a plurality of cover layers.In above-mentioned silica ultramicron, preferred above-mentioned pore by inaccessible, above-mentioned cavity by above-mentioned body seal.This is because in above-mentioned anti-reflection layer, and the porous matter of above-mentioned silica ultramicron or cavity are kept, and the refractive index of above-mentioned anti-reflection layer is further reduced.The suitable manufacture method of for example opening disclosed silica-based particulate in the 2000-233611 communique that adopts of the manufacture method of such hollow and spherical silica ultramicron the spy.
The drying when forming above-mentioned anti-reflection layer (low-index layer) and the temperature of curing have no particular limits.For example, the temperature of above-mentioned drying and curing is 60～150 ℃ scope, 70～130 ℃ scope preferably, and the time of above-mentioned drying and curing for example is 1～30 minute scope, under the situation of considering productivity ratio, and 1～10 minute scope preferably.In addition, above-mentioned drying and solidify after, by further carrying out heat treated, can obtain having the hard-coated film of the high rigidity of anti-reflection layer.The temperature of above-mentioned heat treated has no particular limits.The temperature of above-mentioned heat treated for example is 40～130 ℃ a scope, preferably 50～100 ℃ scope.The time of above-mentioned heat treated has no particular limits.The time of above-mentioned heat treated for example is 1 minute～100 hours, from improving the viewpoint of marresistance, more preferably carries out heat treated more than 10 hours.Above-mentioned heat treated can be implemented by the method for having used electric hot plate, baking oven, band oven etc.
Install when having the hard-coated film of above-mentioned anti-reflection layer in image display device, above-mentioned anti-reflection layer becomes outermost frequency height.Therefore, above-mentioned anti-reflection layer is subjected to the pollution from external environment condition easily.Than simple transparent panel etc., the pollution of above-mentioned anti-reflection layer is obvious easily.Surface reflectivity takes place and changes owing to for example adhering to pollutants such as fingerprint, original handwriting, sweat and hair finishing agent in above-mentioned anti-reflection layer, and attachment appears in one's mind out and displaying contents becomes not obvious with turning white sometimes.Prevent that in order to improve above-mentioned pollutant from adhering to and removing the easiness of the above-mentioned pollutant of attachment removal, preferably the stacked anti-contamination layer that forms by the silane based compound that contains fluoro substituents or organic compound of containing fluoro substituents etc. on above-mentioned anti-reflection layer.
In hard-coated film of the present invention, preferably in above-mentioned transparent plastic film base material and the above-mentioned hard conating at least one carried out surface treatment.If above-mentioned transparent plastic film base material is carried out surface treatment, just can further improve adhesive force with above-mentioned hard conating, polarizer or polarizer.In addition, if above-mentioned hard coating surface is carried out surface treatment, just can further improve adhesive force with above-mentioned anti-reflection layer, polarizer or polarizer.As above-mentioned surface treatment, for example can list low pressure plasma processing, ultraviolet treatment with irradiation, sided corona treatment, flame treatment, acid or alkali treatment.As above-mentioned transparent plastic film base material, the surface treatment when using the TAC film is preferably alkali treatment.This alkali treatment for example can be after making TAC film surface contact aqueous slkali, washes and drying is implemented.Above-mentioned aqueous slkali for example can use potassium hydroxide solution, sodium hydroxide solution.The normal concentration of the hydroxide ion of above-mentioned aqueous slkali (molar concentration) preferably 0.1～3.0N (mol/L) scope, be more preferably the scope of 0.5～2.0N (mol/L).
Hard-coated film of the present invention can be fitted in above-mentioned transparent plastic film base material one side on the optical component that uses among LCD and the ELD by adhesive and bonding agent usually.When this is fitted, also can carry out above-mentioned various surface treatments to above-mentioned transparent plastic film substrate surface.
As above-mentioned optical component, for example can list polarizer or polarizer.Polarizer comprises polarizer, generally uses the polarizer that forms transparent protective film on the one or both sides of above-mentioned polarizer.When on the two sides of above-mentioned polarizer transparent protective film being set, the diaphragm of front and back can be identical materials, also can be different materials.Polarizer is configured in the both sides of liquid crystal cells usually.Polarizer is configured to following mode: the mutual approximate vertical of the absorption axes of 2 polarizers.
Then, to the stacked optical component of hard-coated film of the present invention, be that example describes with the polarizer.Use adhesive and bonding agent etc., hard-coated film of the present invention and polarizer or polarizer is stacked, the polarizer that can obtain having function of the present invention.
There is no particular limitation for above-mentioned polarizer.As above-mentioned polarizer, can list: for example, make polyvinyl alcohol mesentery, part dimethoxym ethane polyvinyl alcohol mesentery, vinyl-vinyl acetate copolymer pastern divide bitintability material such as hydrophilic macromolecule film such as saponification film absorption iodine and bitintability dyestuff and uniaxial tension and the film that obtains; The polyene of the desalination acid treatment thing of the processed thing of polyvinyl alcohol and polyvinyl chloride etc. is an alignment films etc.Wherein, the polarization of the polarizer of being made up of bitintability materials such as polyvinyl alcohol mesentery and iodine is double-colored than high, so be preferred.Above-mentioned polarizer thickness has no particular limits.Above-mentioned polarizer thickness for example is about 5～80 μ m.
The polyvinyl alcohol mesentery of iodine staining and carry out uniaxial tension and the polarizer that obtains for example can be by dyeing the polyethenol series film immersion in the aqueous solution of iodine, is made for 3～7 times that are stretched to original length.As required, the aqueous solution of above-mentioned iodine also can contain boric acid and zinc sulfate, zinc chloride etc.In addition, in the aqueous solution that contains boric acid and zinc sulfate, zinc chloride etc., also can flood the polyvinyl alcohol mesentery.As required, before dyeing, also can with the polyethenol series film immersion in water, wash.By washing polyvinyl alcohol mesentery, can wash the dirt and the anti-blocking agent on polyvinyl alcohol mesentery surface, also have in addition by making polyvinyl alcohol mesentery swelling, thereby prevent to dye unequal uneven effect.Stretching can be carried out after with iodine staining, also can stretch on the Edge Coloring limit, still can use iodine staining after stretching.Also can in the aqueous solution of boric acid and KI etc. He in the water-bath, stretch.
As the transparent protective film that single face or two sides at above-mentioned polarizer are provided with, the transparent protective film that the stability of preferably clear, mechanical strength, heat endurance, covering property of moisture, phase difference value etc. are excellent.The material that forms above-mentioned transparent protective film for example can list and the same material of above-mentioned transparent plastic film base material.
As above-mentioned transparent protective film, can list the polymeric membrane of opening record in the 2001-343529 communique (WO01/37007) the spy.For example, the polymeric membrane of putting down in writing in above-mentioned communique for example can list by containing (A) to have the thermoplastic resin of at least one imino group in substituted imido and the non-substituted imido and (B) have the polymeric membrane that the resin combination of the thermoplastic resin of at least one phenyl in substituted-phenyl and the non-substituted-phenyl and nitro forms on side chain on side chain.As the polymeric membrane that forms by above-mentioned resin combination, for example can list the polymeric membrane that the resin combination of the alternate copolymer that formed by isobutene and N-methyl maleimide and acrylonitritrile-styrene resin forms.Above-mentioned polymeric membrane can be by being membranaceous the manufacturing with above-mentioned resin combination extrusion molding.Above-mentioned polymeric membrane is because phase difference is little, photoelastic coefficient is little, so during as the diaphragm of polarizer etc., can eliminate the rough sledding such as even that is caused by distortion.Above-mentioned polymeric membrane is because moisture permeability is little, so the humidification excellent in te pins of durability.
From viewpoints such as polarization characteristic and durability, above-mentioned transparent protective film is the film of cellulose-based resin manufacture such as TAC and the film that norbornene resin is made preferably.For example, the commercially available product of above-mentioned transparent protective film can list trade name " Fujitac " (Fuji Photo Film Co., Ltd.'s production), trade name " Zeonor " (Japanese Zeon company produce), trade name " Arton " (production of JSR society) etc.
Above-mentioned transparency protected film thickness has no particular limits.From aspects such as operations such as intensity, operability, thin layers, above-mentioned transparency protected film thickness for example is the scope of 1～500 μ m.If above-mentioned scope is then mechanically protected polarizer, even be exposed to hot and humid time, polarizer does not also shrink, and can keep stable optical characteristics.The thickness of above-mentioned transparent protective film is the scope of 5～200 μ m preferably, is more preferably the scope of 10～150 μ m.
The structure of the polarizer of stacked hard-coated film has no particular limits.Above-mentioned polarizer for example can be the structure that stacks gradually transparent protective film, polarizer and transparent protective film on hard-coated film.Above-mentioned polarizer for example also can be to stack gradually the structure that polarizer, transparent protective film form on hard-coated film.
Hard-coated film of the present invention can preferably use in CRT, liquid crystal indicator (LCD), plasm display device (PDP) and el display device various image display devices such as (ELD) with the various optical elements such as polarizer that used this hard-coated film.Liquid crystal indicator of the present invention has and the same structure of liquid crystal indicator in the past except using hard-coated film of the present invention.For example, can make: suitably assemble optical components such as liquid crystal cells, polarizer and illuminator as required (back light etc.) and wait each structural elements, and be assembled into drive circuit by following method.Above-mentioned liquid crystal cells has no particular limits, and for example, can use all kinds such as TN type, STN type, π type.
In the present invention, the structure of liquid crystal indicator has no particular limits.Liquid crystal indicator of the present invention for example comprises: the liquid crystal indicator that has disposed above-mentioned optical element on the one or both sides of liquid crystal cells; With liquid crystal indicator that in illuminator, has used back light source or reflecting plate etc.In these liquid crystal indicators, optical element of the present invention can be configured on the one or both sides of liquid crystal cells.When the both sides of above-mentioned liquid crystal cells disposed above-mentioned optical element, they can be identical, also can be different.In above-mentioned liquid crystal indicator, for example also can dispose diffuser plate, anti-various optical components and the optical elements such as photosphere, anti-reflection layer, baffle, prism array, lens array sheet, light diffusing sheet, back light source of dazzling.
Embodiment
Below, embodiments of the invention and comparative example are described together.But the present invention is not subjected to following embodiment and any qualification of comparative example or restriction.In addition, the mensuration of various characteristics in each embodiment and each comparative example and rerum natura and evaluation are implemented by following method.
(thickness of hard conating)
The amesdial thickness instrumentation that uses Mitutoyo company to produce is decided the whole thickness of hard-coated film, deducts the transparent plastic film base material thickness from above-mentioned whole thickness.Calculate the thickness of hard conating thus.
(cure shrinkage power)
Shown in Fig. 4 (A), after the coating hard conating forms material on the single face of transparent plastic film base material 1, heat drying and form and film 8.Then, from above-mentioned film 8 cut out the section of filming of 40mm * 115mm, with it as test film 9.Then, shown in Fig. 4 (B), an end (left end among this figure) of fixing above-mentioned test film 9 is 40cm with ultraviolet irradiated area
2Mode the other end (right-hand end among this figure) of above-mentioned test film 9 is fixed on the tension draftomter (digital force gauge) 10.After this, shine by ultraviolet ray and to solidify above-mentioned test film 9, the stress when measuring cure shrinkage with above-mentioned tension draftomter 10, thus obtain cure shrinkage power.
(shrinkage factor)
Measure the length (L1) that the coating hard conating forms the width of the transparent plastic film base material before the material with ruler.Then, the coating hard conating forms material on the single face of above-mentioned transparent plastic film base material, shines by ultraviolet ray and solidifies, thereby form hard conating.Measure the length (L2) of the transparent plastic film base material behind the above-mentioned formation hard conating with ruler, obtain shrinkage factor (%) by following formula (I).
Shrinkage factor (%)={ 1-(L2/L1) } * 100 (I)
L1: the length (mm) of the transparent plastic film before hard conating forms
L2: the length of the transparent plastic film after hard conating forms (mm)
(crimp values)
Go out the wide hard-coated film section of 100mm between 610～710mm from an end-grain cutting that forms the transparent plastic film base material (width is 1330mm) behind the hard conating, use the width (W) of the above-mentioned hard-coated film section after digital slide measure mensuration is curled, obtain crimp values (mm) by following formula (II).
Crimp values (mm)=100-W (II)
W: the width (mm) of the hard-coated film section after curling
(pencil hardness)
With transparent plastic film base material one side down, mounting hard-coated film on glass plate.After this, according to the pencil hardness test (wherein loading is 500g) of JIS K5400 record, above-mentioned hard coating surface is measured pencil hardness.
(embodiment 1)
The TAC film of preparing thickness and be 40 μ m, width and be 1330mm is as the transparent plastic film base material.In addition, form material as hard conating, prepare according to following mode: be acrylate by isocyanuric acid, pentaerythritol triacrylate, (big Japanese ink chemical industry society produces the ultraviolet curing resin that IPDI polyurethane is formed, trade name " GRANDICPC-1070 ") in, (big Japanese ink chemical industry society produces to add 0.5 weight portion levelling agent with respect to per 100 parts by weight resin solid constituents, trade name " GRANDIC PC-4100 "), the material of gained thus is diluted to the material that solid component concentration is 50 weight % with ethyl acetate.
On the single face of above-mentioned transparent plastic film base material, the part of removing 10mm from the both side ends of the width of above-mentioned transparent plastic film base material is coated with above-mentioned hard conating with the slit die coating machine and forms material and form and film.At this moment, adjust above-mentioned coating thickness so that hard conating thickness (A) is 20 μ m.Then, by heating 1 minute down, make above-mentioned dried coating film at 100 ℃.After this, be 300mJ/cm with high voltage mercury lamp radiation accumulation light quantity
2Ultraviolet ray be cured processing, be the hard conating of 20 μ m thereby form thickness.By such operation, make the hard-coated film of present embodiment.The above-mentioned hard conating thickness (A) in the present embodiment and the ratio (A/B) of above-mentioned transparent plastic film base material thickness (B) are 1/2.
(embodiment 2)
Except changing above-mentioned coating thickness, forming the hard conating that thickness is 16 μ m and embodiment 1 similarly operate the hard-coated film of making present embodiment.The above-mentioned hard conating thickness (A) in the present embodiment and the ratio (A/B) of above-mentioned transparent plastic film base material thickness (B) are 1/2.5.
(comparative example 1)
Except changing above-mentioned coating thickness, forming the hard conating that thickness is 14 μ m and embodiment 1 similarly operates, make the hard-coated film of this comparative example.The above-mentioned hard conating thickness (A) in this comparative example and the ratio (A/B) of above-mentioned transparent plastic film base material thickness (B) are 1/2.86.
(comparative example 2)
Except changing above-mentioned coating thickness, forming the hard conating that thickness is 11 μ m and embodiment 1 similarly operates, make the hard-coated film of this comparative example.The above-mentioned hard conating thickness (A) in this comparative example and the ratio (A/B) of above-mentioned transparent plastic film base material thickness (B) are 1/3.64.
(comparative example 3)
Except used thickness be 80 μ m, width be 1330mm the TAC film as the transparent plastic film base material and embodiment 1 similarly operate, make the hard-coated film of this comparative example.The above-mentioned hard conating thickness (A) in this comparative example and the ratio (A/B) of above-mentioned transparent plastic film base material thickness (B) are 1/4.
The embodiment that obtained by aforesaid way and each hard-coated film of comparative example are carried out the mensuration and the evaluation of various characteristics and rerum natura.Its result is presented in the following table 1.In addition, in the curve map of Fig. 5, expressed the hard conating thickness in embodiment 1,2 and comparative example 1,2 and the relation of the cure shrinkage power of the width of filming.In addition, in the curve map of Fig. 6, expressed the relation of shrinkage factor of the width of the cure shrinkage power of the width of filming in embodiment 1,2 and comparative example 1,2 and hard-coated film.
Table 1
| Hard conating thickness (A) (μ m) | Base material thickness (B) (μ m) | A/B | Cure shrinkage power (N/cm 2) | Shrinkage factor (%) | Crimp values (mm) | | |
| Embodiment | |||||||
| 1 | 20 | 40 | 1/2 | 13.45 | 0.60 | 5.6 | |
| Embodiment | |||||||
| 2 | 16 | 40 | 1/2.5 | 10.3 | 0.30 | 17.2 | 4H |
| Comparative example 1 | 14 | 40 | 1/2.86 | 8.38 | 0.15 | 55.6 | 3H |
| Comparative example 2 | 11 | 40 | 1/3.64 | 5.07 | 0.075 | 62.6 | 2H |
| Comparative example 3 | 20 | 80 | 1/4 | 14.3 | 0.00 | 54.8 | 4H |
The cure shrinkage power of the width of filming as shown in Figure 5, becomes thick more with hard conating thickness and becomes big more.In addition, as shown in Figure 6, the shrinkage factor of the width of hard-coated film becomes big more with the cure shrinkage power of the width of filming and becomes big more.From shown in the above-mentioned table 1 as can be known, in the ratio (A/B) of above-mentioned hard conating thickness (A) and above-mentioned transparent plastic film base material thickness (B) is embodiment 1 (A/B=1/2) and embodiment 2 (A/B=1/2.5) more than 1/2.6, when above-mentioned curing of coating shrinks, above-mentioned film shrink in, above-mentioned transparent plastic film base material also broad ways shrinks, thereby obtains the little smooth hard-coated film of crimp values.Relative therewith, above-mentioned than (A/B) less than 1/3.6 comparative example 1 (A/B=1/2.86) and comparative example 2 (A/B=1/3.64) in because have only the above-mentioned broad ways cure shrinkage of filming, above-mentioned transparent plastic film base material does not shrink, so that crimp values becomes is big.In addition, thick at above-mentioned transparent plastic film base material, above-mentioned ratio (A/B) also has only the above-mentioned broad ways cure shrinkage of filming less than in 1/2.6 the comparative example 3 (A/B=1/4), and above-mentioned transparent plastic film base material does not shrink, so crimp values becomes greatly.
According to the manufacture method of hard-coated film of the present invention, just can make the hard-coated film of smooth and high rigidity.Therefore, hard-coated film of the present invention can compatibly use in various image display devices such as optical elements such as for example polarizer, CRT, LCD, PDP and ELD, and its purposes is unrestricted, can be applied to extensive fields.
Claims (12)
1. the manufacture method of a hard-coated film, this hard-coated film is to have hard conating at least one surface of transparent plastic film base material, and the manufacture method of this hard-coated film comprises following operation: prepare to comprise and resinize firmly and the hard conating of solvent forms the preparatory process of material; The described hard conating of coating forms material and forms the formation operation of filming of filming at least one surface of described transparent plastic film base material; With by making described curing of coating, thereby the hard conating that forms described hard conating forms operation; Wherein adjust at least one among described hard conating thickness A and the described transparent plastic film base material thickness B so that the ratio A/B of described hard conating thickness A and described transparent plastic film base material thickness B is the scope more than 1/2.6.
2. the manufacture method of hard-coated film as claimed in claim 1 is wherein adjusted at least one among described hard conating thickness A and the described transparent plastic film base material thickness B so that the ratio A/B of described hard conating thickness A and described transparent plastic film base material thickness B is the scope more than 1/2.5.
3. the manufacture method of hard-coated film as claimed in claim 1, wherein said hard conating thickness A is adjusted into the scope of 15～35 μ m, and described transparent plastic film base material thickness B is adjusted into the scope of 15～50 μ m.
4. the manufacture method of hard-coated film as claimed in claim 1 wherein forms in the operation at described hard conating, and the cure shrinkage power of described width of filming is 9N/cm
2More than.
5. the manufacture method of hard-coated film as claimed in claim 1, wherein said resinizing firmly comprises following A composition, B composition and C composition,
A composition: at least one in urethane acrylate and the urethane methacrylate;
B composition: at least one in polyalcohol acrylate and the polyalcohol methacrylate;
The C composition: by the mixed polymer of at least one polymer that forms among following C1 and the C2 or copolymer or described polymer and copolymer,
C1: alkyl acrylate with the alkyl that comprises at least one group among hydroxyl and the acryloyl group; With
C2: alkyl methacrylate with the alkyl that comprises at least one group among hydroxyl and the acryloyl group.
6. the manufacture method of hard-coated film as claimed in claim 1, it also comprises the operation that forms anti-reflection layer.
7. the manufacture method of hard-coated film as claimed in claim 6, wherein said anti-reflection layer contain hollow and spherical silicon oxide particle.
8. hard-coated film of making by the described manufacture method of claim 1.
9. hard-coated film as claimed in claim 8, the outer surface structure of wherein said hard conating is a concaveconvex structure.
10. polarizer, it has polarizer and hard-coated film, and wherein said hard-coated film is the described hard-coated film of claim 8.
11. an image display device, it comprises hard-coated film, and wherein said hard-coated film is the described hard-coated film of claim 8.
12. an image display device, it comprises polarizer, and wherein said polarizer is the described polarizer of claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006339637A JP2008151998A (en) | 2006-12-18 | 2006-12-18 | Manufacturing method of hard coat film, hard coat film, polarizing plate and image display apparatus |
| JP339637/2006 | 2006-12-18 |
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| Publication Number | Publication Date |
|---|---|
| CN101204697A true CN101204697A (en) | 2008-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007101991745A Pending CN101204697A (en) | 2006-12-18 | 2007-12-18 | Production method of hard coating thin film, hard coating thin film, polarizing disc and image display apparatus |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2008151998A (en) |
| KR (1) | KR20080056642A (en) |
| CN (1) | CN101204697A (en) |
| TW (1) | TW200838700A (en) |
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| CN101712844B (en) * | 2008-09-30 | 2014-02-12 | 共荣社化学株式会社 | Composition for hard coat and molded product provided with hard coat layer |
| CN103732391A (en) * | 2011-08-09 | 2014-04-16 | 三菱树脂株式会社 | Transparent laminated film |
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| JP5116166B2 (en) * | 2008-11-28 | 2013-01-09 | 日東電工株式会社 | Hard coat film, optical element and image display device |
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| CN1790060A (en) * | 2004-12-17 | 2006-06-21 | 日东电工株式会社 | Hard-coated film and method of manufacturing the same |
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| CN103347968B (en) * | 2011-02-15 | 2015-07-08 | 藤仓化成株式会社 | Hard-coat composition for metal substrate, and molded article |
| CN103347968A (en) * | 2011-02-15 | 2013-10-09 | 藤仓化成株式会社 | Hard-coat composition for metal substrate, and molded article |
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| CN107849390B (en) * | 2015-08-03 | 2020-06-16 | 株式会社Lg化学 | Flexible plastic film |
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| CN111164473A (en) * | 2017-10-03 | 2020-05-15 | 日东电工株式会社 | Polarizing plate, image display device, and method for manufacturing polarizing plate |
| CN111164473B (en) * | 2017-10-03 | 2022-09-27 | 日东电工株式会社 | Polarizing plate, image display device, and method for manufacturing polarizing plate |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200838700A (en) | 2008-10-01 |
| KR20080056642A (en) | 2008-06-23 |
| JP2008151998A (en) | 2008-07-03 |
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