CN100560353C - The manufacture method of hard-coated film, hard-coated film, optical element and image display device - Google Patents
The manufacture method of hard-coated film, hard-coated film, optical element and image display device Download PDFInfo
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- CN100560353C CN100560353C CNB2007100884727A CN200710088472A CN100560353C CN 100560353 C CN100560353 C CN 100560353C CN B2007100884727 A CNB2007100884727 A CN B2007100884727A CN 200710088472 A CN200710088472 A CN 200710088472A CN 100560353 C CN100560353 C CN 100560353C
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Abstract
The invention provides a kind of hard-coated film, it uses hard conating to form material and form hard conating at least one face of transparent plastic film base material, described hard conating forms material and comprises: (A) composition, urethane acrylate and carbamate methacrylate at least a; (B) composition, polyalcohol acrylate and polyalcohol methacrylate at least a; Reach (C) composition, comprise the polymer of the repetitive of following general formula (1).
Description
Technical field
The present invention relates to manufacture method, optical element and the image display device of a kind of hard-coated film, hard-coated film.
Background technology
In recent years, along with technological progress, on the basis of existing C RT (Cathode Ray Tube), also exploitation has LCD (LCD), plasma display (PDP) and electroluminescent display (ELD) etc., and with its practicability.Wherein, with regard to LCD, be accompanied by with high visual field angling, height become more meticulous, relevant technological innovation such as high-speed responsive, color reproduction, utilize the application of LCD also to transform to TV from subnotebook PC or monitor.The basic comprising of LCD is, the flat glass substrate of transparency electrode will be possessed respectively, dispose by the dividing plate subtend in the mode that becomes slit with certain intervals, between described glass substrate, inject liquid crystal material, sealing, as liquid crystal cells, and then polarizer is set respectively at the lateral surface of described a pair of glass substrate.Be that the cover plate that is made of glass or plastics is installed on described liquid crystal cells surface in the past, prevented to damage the described polarizer that on described liquid crystal cells surface, attaches.But, when described cover plate is installed, be disadvantageous aspect cost and the weight.Thereby, then described polarizer surface is coated with processing firmly.
Described be coated with firmly to handle to use usually on the one or both sides of transparent plastic film base material, be formed with the hard-coated film of thin hard conating that thickness is 2～3 μ m.Described hard conating uses hard conatings such as heat-curing resin or uv curing resin to form usually and forms with resin.When the above-mentioned hard conating of coating on glass plate forms when with resin above-mentioned hard conating being set, demonstrate hardness more than the 4H in pencil hardness.But in substrate is under the situation of above-mentioned transparent plastic film base material, if the thickness low LCL of above-mentioned hard conating is abundant, is subjected to the influence of above-mentioned transparent plastic film base material usually, and above-mentioned pencil hardness is reduced to below the 3H.
Travel to home-use TV machine by application,, also carry out and the same operation of television set that utilizes glass system CRT in the past even the user of general home-use TV machine can easily imagine the television set that has used LCD with LCD.The pencil hardness of above-mentioned glass system CRT is about 9H.For this reason, for the hard-coated antiglare film that uses among the LCD, require to improve hardness.
In order to increase the hardness of hard-coated film, can realize by the bed thickness that increases hard conating.But the increase of above-mentioned bed thickness causes splitting of hard conating, and the crimping that the cure shrinkage by hard conating causes also can take place.At these problems, for example propose to have the spy to open flat 9-113728 communique, spy and open that flat 11-300873 communique, spy are opened the 2000-52472 communique, the spy opens the described technology of flat 7-287102 communique.
Open in the flat 9-113728 communique the spy, disclose and at least one face of transparent resin film, formed the polarizer protective film that constitutes the cured coating film layer by the composition that comprises ultra-violet solidified polyalcohol (methyl) acrylic ester resin.And then it also discloses above-mentioned ultra-violet solidified polyalcohol (methyl) acrylic ester resin is the acrylic acid dipentaerythritol ester.Opening flat 9-113728 communique according to the spy, under situation about using by the cured coating film layer that constitutes as the resin of principal component with above-mentioned acrylic acid dipentaerythritol ester, is more than the 10 μ m by making its thickness, and can make pencil hardness is more than the 4H.In addition, also record by and be that resin can reduce the crimping that caused by cure shrinkage with epoxy.But open in the described invention of flat 9-113728 communique the spy, be difficult to fully suppress crimping.
Open in the flat 11-300873 communique the spy, disclose at least one face of plastic basis material film that to be provided with by thickness be the hard-coated film that the cushion that constitutes of 1 layer of 3～50 μ m or multilayer and then the hard conating that forms thick 3～15 μ m on this cushion form.The pencil hardness that Te Kaiping 11-300873 communique also discloses as above-mentioned hard-coated film integral body is 4H～8H.But, make the two-layer structure of above-mentioned cushion and above-mentioned hard conating, there is the problem that operation quantity increases, production efficiency reduces.
Open in the 2000-52472 communique the spy, disclose and possess cured resin by the hard-coated film of rete, wherein, described cured resin is that setting contains the ultramicronized curing resin layer of internal crosslinking of inanimate matter or organic matter as the 1st hard conating on base material by rete, then, and then the film do not contain inanimate matter or the organic ultramicronized transparent cured resin of internal crosslinking is set forms as the 2nd hard conating.But, be the two-layer structure of above-mentioned the 1st hard conating and above-mentioned the 2nd hard conating because make above-mentioned cured resin by rete, to open the described invention of flat 11-300873 communique identical with the spy, has the problem that operation quantity increases, production efficiency reduces.
Open in the flat 7-287102 communique the spy, disclose the antireflective film that at least one face at the table back side of transparent base film, has hard conating, low-index layer at least, and then as the material that can be used for above-mentioned hard conating, it also enumerates solvent seasoning type resin.When containing polymer with reactive group, have cure shrinkage that suppresses generations when solidifying such as ionizing radiation curable resin and the effect that suppresses the appearance of crimping, but when adding such polymer, has the problem that can't obtain enough case hardnesses.
Summary of the invention
The objective of the invention is to, provide a kind of and have enough hardness, can prevent that hard conating from crackle occurring, preventing crimping and the hard-coated film that can make with comparalive ease, its manufacture method, the optical element that uses this hard-coated film and image display device that the cure shrinkage by hard conating causes.
In order to reach above-mentioned purpose, the invention provides a kind of hard-coated film, it comprises the transparent plastic film base material, also be included in the hard conating that forms at least one face of above-mentioned plastic film substrate, it is characterized in that, described hard conating be to use comprise following (A) composition, (B) composition and (C) hard conating of composition form material and form.Wherein, form in the material at described hard conating, with respect to described (B) components in proportions of described (A) composition scope at 70～180 weight %, and with respect to described (C) components in proportions of described (A) composition scope at 25～110 weight %.
(A) composition: urethane acrylate (urethane methacrylate) and the carbamate methacrylate is at least a
(B) composition: polyalcohol acrylate and polyalcohol methacrylate at least a
(C) composition: by at least a polymer that forms of following (C1) and following (C2) or the mixed polymer of copolymer or above-mentioned polymer and copolymer
(C1): the alkyl acrylate of alkyl with at least a group of hydroxyl and acryloyl group
(C2): the alkyl methacrylate of alkyl with at least a group of hydroxyl and acryloyl group
Manufacture method of the present invention is included in the manufacture method of the hard-coated film of the hard conating that forms at least one face of transparent plastic film base material, and it comprises: prepare in solvent dissolving or be dispersed with following (A) composition, (B) composition and operation that (C) hard conating that forms of composition forms material; The described hard conating of coating forms material and forms the operation of filming at least one face of described transparent plastic film base material; With the operation that makes described curing of coating and then formation hard conating.Wherein, form in the material at described hard conating, with respect to described (B) components in proportions of described (A) composition scope at 70～180 weight %, and with respect to described (C) components in proportions of described (A) composition scope at 25～110 weight %.
(A) composition: urethane acrylate and carbamate methacrylate at least a
(B) composition: polyalcohol acrylate and polyalcohol methacrylate at least a
(C) composition: by at least a polymer that forms of following (C1) and following (C2) or the mixed polymer of copolymer or above-mentioned polymer and copolymer
(C1): the alkyl acrylate of alkyl with at least a group of hydroxyl and acryloyl group
(C2): the alkyl methacrylate of alkyl with at least a group of hydroxyl and acryloyl group
Optical element of the present invention comprises optical component, and it forms the hard-coated film of the invention described above at least one face of described optical component.
Image display device of the present invention possesses aforementioned hard-coated film of the present invention.
Other image display device of the present invention possesses aforementioned optical element of the present invention.
With regard to hard-coated film of the present invention, the function of above-mentioned three kinds of compositions combines, and has enough hardness, can prevent that crackle from appearring in hard conating, prevents the generation of the crimping that caused by described hard conating cure shrinkage, and can make with comparalive ease.With regard to described hard conating formed material, above-mentioned by containing (A) composition for example, can be given elasticity and flexible to the hard conating that forms; With regard to described hard conating formed material, above-mentioned by containing (B) composition for example, can fully improve the hardness of the above-mentioned hard conating of formation, and marresistance was also good; With regard to described hard conating formed material, above-mentioned by containing (C) composition for example, can relax the cure shrinkage that produces when forming above-mentioned hard conating, prevent crimping.So, in hard-coated film of the present invention,, can prevent that crackle from appearring in above-mentioned hard conating, prevent the crimping that causes by described hard conating cure shrinkage even the hard conating of individual layer also has enough hardness.Therefore, hard-coated film of the present invention can lower the worker ordinal number, and it is easy that its manufacturing becomes.Need to prove that the function of these each compositions, the record of effect are illustration, the present invention is not limited thereto.As described later, in the present invention, above-mentioned hard conating also can be the sandwich construction that is laminated more than two layers.
Description of drawings
Fig. 1 is the profile schema diagram of formation of an example of expression hard-coated film of the present invention.
Fig. 2 is the profile schema diagram of formation of other examples of expression hard-coated film of the present invention.
The specific embodiment
In hard-coated film of the present invention and manufacture method thereof, above-mentioned (B) composition preferably contains at least a of pentaerythritol triacrylate and pentaerythritol tetracrylate.Its reason is, thus can keep high rigidity and good flexible in, more effectively prevent the generation of crimping.
In hard-coated film of the present invention and manufacture method thereof, above-mentioned (C) composition preferably comprises the mixture of polymer, copolymer or the above-mentioned polymer and the above-mentioned copolymer of the repetitive that contains following general formula (1).Its reason is, can more effectively prevent the generation of crimping thus.
In above-mentioned formula (1), R
1For-H or-CH
3, R
2For-CH
2CH
2OX or with the group of following general formula (2) expression, above-mentioned X be-H or the acryloyl group represented with following general formula (3).
In above-mentioned general formula (2), above-mentioned X is-H or with the acryloyl group of following general formula (3) expression, above-mentioned X can be identical, also can be different.
In hard-coated film of the present invention, in order to give anti-dazzle property, the outer surface structure that can be above-mentioned hard conating is the embodiment of concaveconvex structure.Above-mentioned concaveconvex structure can the interpolation particulate forms in the material by for example forming at above-mentioned hard conating.
In hard-coated film of the present invention,, can be the embodiment that is formed with anti-reflection layer at the outer surface of above-mentioned hard conating for the reflection of the light on the interface that is reduced in hard conating and air.Be applied to for example image display device as long as will be provided with the hard-coated film of anti-reflection layer, just can improve the identification of the image of display frame.
Above-mentioned anti-reflection layer preferably contains siloxane oligomer and fluoride.The number-average molecular weight of passing through the ethylene glycol conversion of described siloxane oligomer is 500～10000.The number-average molecular weight of passing through polystyrene conversion of described fluoride is more than 5000, and has fluoro-alkyl structure and polysiloxane structure.Its reason is, as long as anti-reflection layer contains above-mentioned siloxane oligomer and has the fluoride of fluoro-alkyl structure and polysiloxane structure, because of reacting, above-mentioned siloxane oligomer and above-mentioned polysiloxane structure solidify, so the marresistance of the above-mentioned anti-reflection layer that forms improves.By the above-mentioned number-average molecular weight that makes above-mentioned siloxane oligomer is more than 500, can prevent that anti-reflection layer from forming material generation gelation, and the coating and the storage stability of above-mentioned formation material are good.By the above-mentioned number-average molecular weight that makes above-mentioned siloxane oligomer is below 10000, and above-mentioned anti-reflection layer can become the good layer of marresistance.
Above-mentioned anti-reflection layer preferably contains hollow and spherical silica ultra micron.
In hard-coated film of the present invention and manufacture method thereof, the formation material of preferred above-mentioned hard conating contains levelling agent.
In the manufacture method of hard-coated film of the present invention, above-mentioned solvent preferably contains ethyl acetate.Its reason is, the above-mentioned hard conating of the formation adhesiveness of stating the transparent plastic film base material of closing is outstanding, can prevent peeling off of above-mentioned hard conating.The above-mentioned relatively solvent total amount of above-mentioned ethyl acetate contain proportional being preferably more than the 20 weight %.
Below, the present invention is described in detail.But the present invention is not limited to following record.
Hard-coated film of the present invention comprises the transparent plastic film base material, at the one or both sides formation hard conating of above-mentioned transparent plastic film base material.
Above-mentioned transparent plastic film base material is not particularly limited.The material (preferred turbidity value is below 1%) that the light transmittance of the preferred visible light of above-mentioned transparent plastic film base material outstanding (preferred light transmittance is more than 90%) and the transparency are outstanding.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.Described polyester based polymer for example comprises PETG, PEN etc.Described cellulose-based polymer for example comprises diacetyl cellulose, triacetyl cellulose (TAC) etc.Described acrylic acid series polymeric compounds 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.Described styrenic for example comprises polystyrene, acrylonitritrile-styrene resin etc.Described olefin polymer for example comprises polyethylene, polypropylene, have the polyolefin of circulus, have polyolefin, ethylene-propylene copolymer of ENB structure etc.Described acid amides based polymer for example comprises nylon, aromatic amides etc.The formation material of above-mentioned transparent plastic film base material for example also comprises imide series polymer, sulfone based polymer, polyether sulfone based polymer, polyethers-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 mixture of polymers etc.Wherein, be particularly suitable for the film that uses optic birefringence few.Hard-coated film of the present invention for example also can be used as protective film and is used for polarizer.At this moment, as above-mentioned transparent plastic film base material, the preferred film that forms by triacetyl cellulose, Merlon, acrylic acid series polymeric compounds, polyolefin, polyolefin etc. with ENB structure with circulus.In the present invention, above-mentioned transparent plastic film base material can be a polariscope self.If such formation, the protective layer that need be made of TAC etc. and can make the structure simplification of polarizer can not reduce the worker ordinal number of polarizer or image display device thus, improves production efficiency.And, if such formation can make the further thin layerization of polarizer.At above-mentioned transparent plastic film base material is under the polariscopic situation, the effect of above-mentioned hard conating performance protective layer in the past.If such formation, hard-coated film can have the function that is installed in the lip-deep cover plate of liquid crystal cells concurrently.
In the present invention, the thickness to above-mentioned transparent plastic film base material is not particularly limited.If consider for example aspect such as operation such as intensity or operability and thin layer usually, above-mentioned thickness is preferably the scope of 10～500 μ m, and the scope of 20～300 μ m more preferably most preferably is the scope of 30～200 μ m.Refractive index to above-mentioned transparent plastic film base material is not particularly limited.Above-mentioned refractive index for example is 1.30～1.80 scope, is preferably 1.40～1.70 scope.
Above-mentioned hard conating be to use comprise following (A) composition, (B) composition and (C) hard conating of composition form material and form.
(A) composition: urethane acrylate and carbamate methacrylate at least a
(B) composition: polyalcohol acrylate and polyalcohol methacrylate at least a
(C) composition: by at least a polymer that forms of following (C1) and following (C2) or the mixed polymer of copolymer or above-mentioned polymer and copolymer
(C1): the alkyl acrylate of alkyl with at least a group of hydroxyl and acryloyl group
(C2): the alkyl methacrylate of alkyl with at least a group of hydroxyl and acryloyl group
As the urethane acrylate and the carbamate methacrylate of above-mentioned (A) composition, use and to contain acrylic acid, methacrylic acid, acrylate, methacrylate, polyalcohol, vulcabond material as constituent.Described urethane acrylate and carbamate methacrylate at least a, for example can adopt method as follows to make, promptly, use at least a monomer and the polyalcohol of acrylic acid, methacrylic acid, acrylate and methacrylate, make hydroxy acrylate and have hydroxyl-metacrylate at least a of 1 above hydroxyl, make by itself and vulcabond are reacted with 1 above hydroxyl.In above-mentioned (A) composition, above-mentioned urethane acrylate and carbamate methacrylate can be used alone, and also two or more kinds may be used.
The aforesaid propylene acid esters for example has: alkyl acrylate, acrylic acid cycloalkyl ester etc.The aforesaid propylene acid alkyl ester for example has: methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate etc.Aforesaid propylene acid cycloalkyl ester for example has: cyclohexyl acrylate etc.Above-mentioned methacrylate for example has: alkyl methacrylate, methacrylic acid cycloalkyl ester etc.Above-mentioned alkyl methacrylate for example has: methyl methacrylate, EMA, isopropyl methacrylate, butyl methacrylate etc.Above-mentioned methacrylic acid cycloalkyl ester for example has: cyclohexyl methacrylate etc.
Above-mentioned polyalcohol is the compound with at least 2 hydroxyls.Above-mentioned polyalcohol for example has: ethylene glycol, 1, ammediol, 1, the 2-propane diols, diethylene glycol (DEG), 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 3-hydroxypivalic acid DOPCP, the tristane dihydroxymethyl, 1, the 4-cyclohexane diol, the spiroglycol, the tristane dihydroxymethyl, hydrogenated 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 has: tetramethylene diisocyanate, hexamethylene diisocyanate, IPDI, 2, the 4-toluenediisocyanate, 4, the 4-diphenyl diisocyanate, 1,5-naphthyl vulcabond, 3,3-dimethyl-4, the 4-diphenyl diisocyanate, XDI, trimethyl hexamethylene diisocyanate, 4,4-methyl diphenylene diisocyanate etc., and then also have their hydride etc.
Cooperation ratio to above-mentioned (A) composition is not particularly limited.Above-mentioned by using (A) composition, can improve formation hard conating flexibility and with respect to the adhesiveness of above-mentioned transparent plastic film base material.From the considerations such as viewpoint of the hardness of these aspects and above-mentioned hard conating, form total resinous principle in the material with respect to above-mentioned hard conating, the cooperation ratio of above-mentioned (A) composition is the scope of 15～55 weight % for example, is preferably the scope of 25～45 weight %.So-called above-mentioned total resinous principle is meant (A) composition, (B) composition and (C) total amount of composition, perhaps when other resinous principle of use, is meant that total amount with above-mentioned ternary total amount and above-mentioned resinous principle adds amount together, and is as follows.
Above-mentioned (B) composition for example has: diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, six acrylic acid dipentaerythritol ester, acrylic acid 1,6-hexylene glycol ester, dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, hexamethyl acrylic acid dipentaerythritol ester, methacrylic acid 1,6-hexylene glycol ester etc.These materials can use separately.They can also be also with two or more.For example, as above-mentioned polyalcohol acrylate, the preferred monomer component that constitutes by the polymer of pentaerythritol triacrylate and pentaerythritol tetracrylate and contain pentaerythritol triacrylate and the blending constituent of pentaerythritol tetracrylate.
Cooperation ratio to above-mentioned (B) is not particularly limited.For example, with respect to above-mentioned (A) composition, the cooperation ratio of above-mentioned (B) composition is preferably the scope of 70～180 weight %, the more preferably scope of 100～150 weight %.When the cooperation ratio of above-mentioned (B) composition is 180 weight % when following with respect to above-mentioned (A) composition, can effectively prevent the cure shrinkage of the above-mentioned hard conating that forms.Its result can prevent the crimping of hard-coated antiglare film, can prevent that its flexibility from reducing.As long as the cooperation ratio of above-mentioned (B) composition is more than the 70 weight % of above-mentioned (A) composition, just can further improve the hardness of formed above-mentioned hard conating, can improve its marresistance.In hard-coated film of the present invention, above-mentioned marresistance is preferably in 0～0.7 scope, more preferably in 0～0.5 scope.The mensuration of above-mentioned marresistance for example can be implemented with the assay method of embodiment described later.
In above-mentioned (C) composition, the abovementioned alkyl of above-mentioned (C1) and above-mentioned (C2) for example is that carbon number is 1～10 alkyl.Abovementioned alkyl can be the straight chain shape, also can be a chain.As above-mentioned (C) composition, for example, can enumerate the mixture of polymer, copolymer or the above-mentioned polymer and the above-mentioned copolymer of the repetitive that comprises above-mentioned general formula (1).As above-mentioned (C) composition, for example can enumerate the polymer that forms by at least a monomer that is selected from the group that following material constitutes, the mixture of copolymer or above-mentioned polymer and above-mentioned copolymer, described material for example has: 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, methacrylic acid 2-hydroxyl ethyl ester and 2-acryloxy methacrylate.
Cooperation ratio to above-mentioned (C) composition is not particularly limited.For example, with respect to above-mentioned (A) composition, the cooperation ratio of above-mentioned (C) composition is preferably the scope of 25～110 weight %, the more preferably scope of 45～85 weight %.As long as cooperation ratio above-mentioned relatively (A) composition of above-mentioned (C) composition is below the 110 weight %, just can make the screening characteristics of above-mentioned hard conating formation material good.As long as the cooperation ratio of above-mentioned (C) composition is more than the 25 weight % with respect to above-mentioned (A) composition, just can prevent the above-mentioned hard conating generation cure shrinkage that forms.Its result in hard-coated film, for example, can prevent crimping at 30mm with interior.The occurrence degree of above-mentioned crimping is preferably in the 20mm, more preferably in the 10mm.The evaluation that described crimping takes place, can use-case as described later the described method of embodiment implement.
As mentioned above, for the surface texture with above-mentioned hard conating makes concaveconvex structure, above-mentioned hard conating can contain particulate.Its reason is, as long as the surface texture of above-mentioned hard conating is made concaveconvex structure, just can give anti-dazzle property.As above-mentioned particulate, inorganic particles and organic fine particles are for example arranged.Above-mentioned inorganic particles is not particularly limited, silicon oxide particle, titanium oxide microparticle, alumina particulate, zinc oxide fine particles, tin oxide particulate, calcium carbonate microparticle, barium sulfate particulate, talcum particulate, kaoline par-tides, calcium sulfate particulate etc. are for example arranged.Above-mentioned organic fine particles is not particularly limited, polymethyl methacrylate acrylate powder (PMMA particulate), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic acid phenylethylene resin series powder, benzoguanamine toner, melmac powder, vistanex powder, polyester resin powder, polyamide powder, polyimide resin powder, polyfluoroethylene resin powder etc. are for example arranged.These inorganic particles and organic fine particles can be used alone, and also two or more kinds may be used.
Shape to above-mentioned particulate is not particularly limited, and for example, can be the roughly spherical of pearl, can also be the particulate of indefinite form such as powder.The weight average particle diameter of above-mentioned particulate is the scope of 1～30 μ m for example, is preferably the scope of 2～20 μ m.As above-mentioned particulate, preferred roughly spherical particulate, more preferably its asperratio is the roughly spherical particulate below 1.5.
Cooperation ratio to above-mentioned particulate is not particularly limited, and can suitably set.Form material 100 weight portions with respect to above-mentioned hard conating, the cooperation ratio of above-mentioned particulate is the scope of 2～60 weight portions for example, is preferably the scope of 1～50 weight portion.
Consider from aspects such as the light scattering that prevents to produce or interference fringes, 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 the phenomenon that the outer reflection of light light that incides hard-coated film presents the form and aspect of iridescent colors.Recently, in office etc., use the good three-wavelength fluorescent lamp of definition more.Under above-mentioned three-wavelength fluorescent lamp, can manifest interference fringe more significantly.Because the refractive index of above-mentioned hard conating is generally 1.4～1.6 scope, therefore, preferred index is near the particulate of this ranges of indices of refraction.The refringence of above-mentioned particulate and above-mentioned hard conating is preferably below 0.05.
When with the difference of the refractive index of the refractive index of above-mentioned transparent plastic film base material and above-mentioned hard conating during as d, above-mentioned d is preferably below 0.04.As long as above-mentioned d is below 0.04, just can suppress the generation of above-mentioned interference striped.Above-mentioned d is more preferably below 0.02.
The thickness of above-mentioned hard conating for example is 15～25 μ m, is preferably the scope of 18～23 μ m.As long as above-mentioned thickness is in the afore mentioned rules scope, above-mentioned hard conating just can become the also sufficient hard conating (for example, counting more than the 4H with pencil hardness) of hardness.As long as above-mentioned thickness in the afore mentioned rules scope, just can more effectively prevent the generation of crimping.When the surface texture that makes above-mentioned hard conating was concaveconvex structure, the thickness of above-mentioned hard conating for example was the scope of 15～35 μ m, the more preferably scope of 20～30 μ m.
Hard-coated film of the present invention can utilize following method to make, for example, prepare that above-mentioned three compositions are dissolved or dispersed in the hard conating that forms in the solvent and form material, at least one face at described transparent plastic film base material applies described hard conating formation material, formation is filmed, and makes described curing of coating and forms described hard conating.
Above-mentioned solvent is not particularly limited, butyl oxide is for example arranged, dimethoxymethane, dimethoxy-ethane, diethoxyethane, expoxy propane, 1, the 4-diox, 1, the 3-dioxolane, 1,3, the 5-trioxane, oxolane, acetone, methyl ethyl ketone, diethyl ketone, two acetone, diisobutyl ketone, 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, DAA, 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, hexone (MIBK), methyl n-heptyl ketone, 2 pentanone, methyl-n-butyl ketone, the 2-heptanone, the 3-heptanone, ethoxyethyl acetate(EA), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (EGMBE), glycol monomethyl ether, propane diols monomethyl ether acetic acid esters, propane diols monomethyl ether etc.These materials can be used alone, and also two or more kinds may be used.Consider from the adhesiveness aspect that improves described transparent plastic film base material and described hard conating, preferred above-mentioned solvent contains ethyl acetate with the ratio that accounts for more than the whole 20 weight %, more preferably contain ethyl acetate, most preferably contain ethyl acetate with the ratio that accounts for whole 30～70 weight % with the ratio that accounts for more than the whole 25 weight %.As long as the ratio of the ethyl acetate in the above-mentioned solvent is below the 70 weight %, just can suitably control the evaporation rate of solvent, can effectively prevent to apply inequality or uneven drying.Solvent types with above-mentioned ethyl acetate and usefulness is not particularly limited.Above-mentioned solvent for example has butyl acetate, methyl ethyl ketone, ethylene glycol monobutyl ether (EGMBE), propane diols monomethyl ether etc.
Form in the material at above-mentioned hard conating, can add various levelling agents.Described levelling agent for example has the levelling agent of fluorine system or silicone-based, preferred silicone-based levelling agent.Described silicone-based levelling agent is responding property silicone, dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, poly-methyl alkyl siloxane etc. for example.In these silicone-based levelling agents, preferred especially above-mentioned reactive silicone.By adding above-mentioned reactive silicone, give sliding and long term maintenance marresistance to the surface.If use the material with hydroxyl as above-mentioned reactive silicone, when form the layer during as anti-reflection layer (low-index layer) that contains silicone component on above-mentioned hard conating, the adhesiveness of then above-mentioned anti-reflection layer and above-mentioned hard conating improves.
With respect to above-mentioned total resinous principle 100 weight portions, the use level of above-mentioned levelling agent for example is below 5 weight portions, to be preferably the scope of 0.01～5 weight portion.
In the formation material of above-mentioned hard conating, in the scope that does not influence performance, can add pigment, filler, dispersant, plasticizer, ultra-violet absorber, surfactant, antioxidant, thixotropic agent etc. as required.Above-mentioned additive can be used alone, and can also use simultaneously more than 2 kinds.
Form in the material at above-mentioned hard conating, can use known in the past Photoepolymerizationinitiater initiater.Above-mentioned Photoepolymerizationinitiater initiater for example has: 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 also use thioxanthones based compound etc. in addition.
As the method for the above-mentioned hard conating formation of coating on transparent plastic film base material material, for example can use: spray coating process such as coating (fountain coating) method, punch die formula coating (die coating) method, spin-coating method, spraying process, intaglio printing rubbing method, rolling method, excellent Tu Fa.
Apply above-mentioned hard conating and form material, on above-mentioned transparent plastic film base material, form and film, make above-mentioned curing of coating.Before above-mentioned curing, preferably make above-mentioned dried coating film.With regard to above-mentioned drying, for example, can be air dry, also can be the air-dry of blowing, can also be heat drying, can also be the method that these drying means are combined.
The curing means of filming that above-mentioned hard conating formed material are not particularly limited.The preferred ionizing radiation of above-mentioned curing means solidifies.In above-mentioned curing means, can use various active-energies.Above-mentioned active-energy is ultraviolet ray preferably.As the energy line source, line sources such as for example preferred high-pressure mercury-vapor lamp, Halogen lamp LED, xenon lamp, metal halide lamp, nitrogen laser, electron ray accelerator, radioactive element.With regard to the exposure of above-mentioned energy line source, as the accumulated exposure amount at ultraviolet wavelength 365nm place, preferred 50～5000mJ/cm
2As long as above-mentioned exposure is 50mJ/cm
2More than, just can make curing more abundant, it is more abundant that the hardness of the above-mentioned hard conating of formation also becomes.As long as above-mentioned exposure is 5000mJ/cm
2Below, just can prevent that the above-mentioned hard conating that forms is painted, can improve the transparency.
As mentioned above, form above-mentioned hard conating, can make hard-coated film of the present invention by at least one face at above-mentioned transparent plastic film base material.Hard-coated film of the present invention also can utilize the manufacture method beyond the said method to make.The hardness of hard-coated film of the present invention in pencil hardness, for example has the above hardness of 4H.
The profile schema diagram of Fig. 1 is represented an example of hard-coated film of the present invention.As shown in the figure, the hard-coated film 3 of this embodiment is to be formed with hard conating 2 on the one side of transparent plastic film base material 1.In the present invention, being not limited to the formation of Fig. 1, also can be the hard-coated antiglare film that is formed with hard conating 2 on the two sides of transparent plastic film base material 1.This routine hard conating 2 is individual layers.But the present invention is not limited thereto.Above-mentioned hard conating 2 can also be the sandwich construction that is laminated more than 2 layers.
In hard-coated film of the present invention, can on above-mentioned hard conating, dispose anti-reflection layer (low-index layer).The profile schema diagram of Fig. 2 represents to comprise an example of the hard-coated film of the present invention of above-mentioned anti-reflection layer.As shown in the figure, the hard-coated film 5 of this embodiment has following formation, promptly forms hard conating 2 on the one side of transparent plastic film base material 1, forms anti-reflection layer 4 on this hard conating 2.When illumination is mapped to object, repeats in the reflection at its interface, in the absorption of inside, the phenomenon of scattering, and see through to the back side of object.For example, when on image display device, hard-coated film being installed,, can enumerate reflection of light at air and hard conating interface as the one of the main reasons that the identification that makes image reduces.Above-mentioned anti-reflection layer is the layer that reduces its surface reflection.In hard-coated film shown in Figure 25, above-mentioned hard conating 2 and above-mentioned anti-reflection layer 4 can be formed on the one side of transparent plastic film base material 1.But the present invention is not limited thereto.In hard-coated film of the present invention, also above-mentioned hard conating 2 and above-mentioned anti-reflection layer 4 can be formed on the two sides of above-mentioned transparent plastic film base material 1.In hard-coated film shown in Figure 25, above-mentioned hard conating 2 and above-mentioned anti-reflection layer 4 are respectively individual layer, but the present invention is not limited thereto.Above-mentioned hard conating 2 and above-mentioned anti-reflection layer 4 can be respectively the sandwich construction that is laminated more than 2 layers.
In the present invention, above-mentioned anti-reflection layer is the layer that the strict optical thin film of having controlled thickness and refractive index or stacked above-mentioned optical thin film more than 2 layers form.Above-mentioned anti-reflection layer shows anti-reflective function by the phase place of utilizing the interference of light effect to eliminate incident light and catoptrical reverse mutually.Demonstrating the wavelength region may of the luminous ray of anti-reflective function, for example is 380～780nm, special decision design anti-reflection layer, and making the high wavelength region may of visibility is the scope of 450～650nm, and makes its reflectivity as the 550nm of its centre wavelength become minimum.
In design,, for example, the method for the refringence that increases above-mentioned anti-reflection layer and above-mentioned hard conating is arranged as the means of improving its interference effect based on the above-mentioned anti-reflection layer of interference of light effect.Usually, with regard to being laminated with 2～5 layers the multilayer anti-reflection layer of structure of optics thin layer (film of thickness and refractive index has been controlled in strictness), by only forming the different composition of multilayer refractive index with the thickness of stipulating, the free degree increases aspect the optical design of anti-reflection layer, can further improve anti-reflection effect, dividing reflective character to become in the visible region evenly (to flatten) also becomes possibility.Because require the thickness and precision height of above-mentioned optical thin film, so, usually adopt vacuum evaporation as the dry type mode, sputter, CVD etc. to carry out the formation of each layer.
As above-mentioned multilayer anti-reflection layer, preferably the high titanium oxide layer of refractive index (refractive index: about 1.8) silicon oxide layer that the folded refractive index in upper strata is low (refractive index: the anti-reflection layer of 2 layers of structure that about 1.45) obtain, more preferably stacked silicon oxide layer on the titanium oxide layer and stacked titanium oxide layer on this silicon oxide layer and on this titanium oxide layer stacked silicon oxide layer and the anti-reflection layer of 4 layers of structure forming.By forming these 2 layers of anti-reflection layers or 4 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, can demonstrate anti-reflection effect.Usually when forming the individual layer anti-reflection layer, coating process such as can adopt that injection coating, the coating of punch die formula, spin coating, spraying, intaglio printing coating, roller coat, rod as the wet type mode is coated with.
Form the formation material of anti-reflection layer as above-mentioned individual layer, for example can enumerate resin system material such as ultraviolet curing based acrylic resin, in resin, disperseed inorganic particles such as colloidal silica mixed stocker material, tetraethoxysilane, used the sol-gel based material of metal alkoxides such as purity titanium tetraethoxide etc.In above-mentioned formation material,, preferably contain fluorine-based material in order to give anti fouling performance to the surface.In above-mentioned formation material, from reasons such as marresistances, the many formation materials of preferred inorganic constituents content, more preferably above-mentioned sol-gel based material.Above-mentioned sol-gel based material can use in the part condensation.
As above-mentioned anti-reflection layer (low-index layer), by to contain siloxane oligomer that the number-average molecular weight that converts by ethylene glycol is 500～10000 scope and the number-average molecular weight by polystyrene conversion be more than 5000 and have the material that the material (spy opens the described material of 2004-167827 communique) of the fluorine compounds of fluoro-alkyl structure and polysiloxane structure forms, because of its marresistance and low reflection can and be deposited etc., so preferred.
In above-mentioned anti-reflection layer (low-index layer), can contain inorganic sol in order to improve film-strength.Above-mentioned inorganic sol is not particularly limited, for example can enumerates silica, aluminium oxide, magnesium fluoride etc.Wherein, preferred silica sol.With regard to the cooperation ratio of above-mentioned inorganic sol, for example form total solid composition 100 weight portions of material with respect to above-mentioned anti-reflection layer, be the scope of 10～80 weight portions.The particle diameter of the inorganic particles in the above-mentioned inorganic sol is preferably in the scope of 2～50nm, more preferably in the scope of 5～30nm.
In the formation material of above-mentioned anti-reflection layer, preferably contain hollow and spherical silica ultra micron.The ultramicronized average grain diameter of above-mentioned silica is preferably about 5～300nm, more preferably the scope of 10～200nm.Above-mentioned silica ultra micron is to form the hollow spheres that the cavity forms in the enclosure with pore, and solvent and at least a of gas when including the above-mentioned silica ultra micron of modulation in this cavity form.In addition, the precursor substance that is preferred for forming the ultramicronized above-mentioned cavity of above-mentioned silica remains in this cavity.The thickness of above-mentioned shell is preferably in the scope about 1～50nm, and in about 1/50～1/5 scope of the ultramicronized average grain diameter of above-mentioned silica.Above-mentioned shell preferably is made of the cover layer of multilayer.In above-mentioned silica ultra micron, preferred above-mentioned pore is sealed, and above-mentioned cavity is by above-mentioned body seal.Its reason is, in above-mentioned anti-reflection layer, keeps ultramicronized porous matter of above-mentioned silica or cavity, can further reduce the refractive index of above-mentioned anti-reflection layer.As such hollow and the spherical ultramicronized manufacture method of silica, for example, can suitably adopt the spy to open that disclosed silica is the manufacture method of particulate in the 2000-233611 communique.
The drying when forming above-mentioned anti-reflection layer (low-index layer) and the temperature of curing are not particularly limited, and for example are 60 ℃～150 ℃ scope, preferred 70 ℃～130 ℃ scope.The time of above-mentioned drying and curing for example is 1～30 minute scope, under the situation of considering productivity ratio, is preferably 1～10 minute scope.In addition,, further carry out heat treated, obtain having the hard-coated film of the high rigidity of anti-reflection layer thus in above-mentioned drying with after solidifying.Temperature to above-mentioned heat treated is not particularly limited, and the temperature of above-mentioned heat treated for example is 40 ℃～130 ℃ a scope, preferred 50 ℃～100 ℃ scope.The above-mentioned heat treated time is not particularly limited.The above-mentioned heat treated time for example is 1 minute～100 hours, considers from improving the marresistance aspect, more preferably carries out more than 10 hours.Above-mentioned heat treated can adopt by the method for heating plate, baker, band oven etc. and implement.
When the hard-coated film that will comprise above-mentioned anti-reflection layer was installed on the image display device, it is higher that above-mentioned anti-reflection layer becomes the most surperficial frequency.Therefore, above-mentioned anti-reflection layer is subjected to the pollution from external environment condition easily.Above-mentioned anti-reflection layer is compared with simple transparent panel etc., pollutes more obvious.For example, above-mentioned anti-reflection layer is easily because of adhering to pollutants such as fingerprint, hand dirt, sweat or haircut material, surface reflectivity changed or attachment turns white and floats, and seems that displaying contents do not know or the like.In order to prevent easily the removing property of adhering to and improve the above-mentioned pollutant that has adhered to of above-mentioned pollutant, the preferred stacked anti-contamination layer that forms by fluorine-containing silane based compound or fluorine-containing organic compound etc. on above-mentioned anti-reflection layer.
In hard-coated film of the present invention, preferably at least one of above-mentioned transparent plastic film base material and above-mentioned hard conating carried out surface treatment.As long as above-mentioned transparent plastic film substrate surface is carried out surface treatment, just can further improve adhesiveness with above-mentioned hard conating or polariscope or polarizer.As long as above-mentioned hard coating surface is carried out surface treatment, just can further improve adhesiveness with above-mentioned anti-reflection layer or polariscope or polarizer.As above-mentioned surface treatment, for example can use low pressure plasma processing, ultraviolet treatment with irradiation, sided corona treatment, flame treatment, acid or alkali treatment.As the surface treatment during as above-mentioned transparent plastic film base material with triacetylcellulose film, preferred bases is handled.For example, after making triacetylcellulose film surface contact aqueous slkali, wash and drying, can carry out this alkali treatment thus.As 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) is preferably the scope of 0.1N～3.0N (mol/L), more preferably the scope of 0.5N～2.0N (mol/L).
On the one side of above-mentioned transparent plastic film base material, be formed with in the hard-coated film of above-mentioned hard conating,, can carry out solvent to its another side and handle in order to prevent crimping.Above-mentioned solvent is handled and can be made the solvent of its dissolving that the solvent of its swelling is carried out by making above-mentioned transparent plastic film base material contact.Handle by above-mentioned solvent, give power, thus, offset the power of the generation crimping that the formation because of above-mentioned hard conating causes, can prevent the generation of crimping to above-mentioned its another side side crimping.Equally, on the one side of above-mentioned transparent plastic film base material, be formed with in the hard-coated film of above-mentioned hard conating,, also can form transparent resin layer at its another side in order to prevent the generation of crimping.As above-mentioned transparent resin layer, for example can enumerate with thermoplastic resin, radiation-curable resin, heat-curing resin, other reactive resins is the layer of principal component.Wherein, especially preferably with the layer of thermoplastic resin as principal component.
Hard-coated film of the present invention can pass through adhesive or adhesive usually, and above-mentioned transparent plastic film base material side is fitted in the optical component that is used for LCD or ELD.When fitting, can implement and aforesaid various surface treatments above-mentioned transparent plastic film substrate surface.
As above-mentioned optical component, for example can enumerate polariscope or polarizer.Above-mentioned polarizer uses the polarizer that comprises polariscope and formed transparent protective film in above-mentioned polariscopic one or both sides usually.When on above-mentioned polariscopic two sides transparent protective film being set, inside and outside above-mentioned transparent protective film can be an identical materials, can also be different materials.Above-mentioned polarizer is configured in the both sides of liquid crystal cells usually.Above-mentioned polarizer is so that the roughly mutually orthogonal mode of the absorption axes of two polarizers disposes.
Then, in being laminated with the optical component of hard-coated film of the present invention, be that example describes with the polarizer.By using adhesive or adhesive etc. that hard-coated film of the present invention and polariscope or polarizer is stacked, the polarizer that can obtain having function of the present invention.
Above-mentioned polariscope is not particularly limited, as above-mentioned polariscope, for example can enumerate, divide on the hydrophilic macromolecule film such as saponification film the material of simple tension after the dichroic substance such as absorption iodine or dichroic dye at polyvinyl alcohol film, part dimethoxym ethane polyvinyl alcohol film, ethylene-vinyl acetate copolymer pastern; Polyenes such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol or polyvinyl chloride are oriented film etc.Wherein, by the polariscope that dichroic substance such as polyvinyl alcohol film and iodine are formed, its polarization dichroic ratio height, preferred.Above-mentioned polariscopic thickness is not particularly limited, and above-mentioned polariscopic thickness for example is about 5～80 μ m.
With polyvinyl alcohol film with iodine staining after the polariscope that simple tension forms for example, can make for 3～7 times that be stretched to raw footage by after dyeing in the aqueous solution that polyvinyl alcohol film be impregnated in iodine.As required, the aqueous solution of above-mentioned iodine also can contain boric acid or zinc sulfate, zinc chloride etc.In addition, also polyvinyl alcohol film can be impregnated in the aqueous solution that comprises boric acid or zinc sulfate, zinc chloride etc.As required, also can be before dyeing polyvinyl alcohol film be impregnated in the water and wash.By the washing polyvinyl alcohol film, except can the lip-deep dirt of flush away polyvinyl alcohol film or anti-blocking agent, also can prevent non-uniform phenomenons such as stain by making the polyvinyl alcohol film swelling.Stretch and both can after with iodine staining, carry out,, perhaps also can after stretching, dye with iodine on one side also can stretch by an Edge Coloring.Also can or stretch in the water-bath in the aqueous solution of boric acid or KI etc.
As the transparent protective film that is arranged on described polariscopic one or both sides, preferably stability of its transparency, mechanical strength, heat endurance, moisture shielding, phase difference value etc. is good.As the material that forms above-mentioned transparent protective film, for example can enumerate and the same material of above-mentioned transparent plastic film base material.
As above-mentioned transparent protective film, can enumerate the macromolecule membrane of opening record in the 2001-343529 communique (WO01/37007) the spy.The macromolecule membrane of putting down in writing in the above-mentioned communique for example can be enumerated by containing (A) and has substituted imido and the thermoplastic resin of at least a imino group and (B) have the macromolecule membrane that the resin combination of the thermoplastic resin of at least a phenyl and itrile group in substituted-phenyl and the unsubstituted phenyl forms at side chain in the substituted imido not at side chain.As the macromolecule membrane that forms by above-mentioned resin combination, can be exemplified as the macromolecule membrane that forms by the resin combination that contains the alternate copolymer formed by isobutene and N-methyl maleimide and acrylonitritrile-styrene resin.Above-mentioned macromolecule membrane can be by making above-mentioned resin combination extrusion molding for the film shape.Because the phase difference of above-mentioned macromolecule membrane is little, the photoelasticity modulus is little, so when being applied to the protective film of polarizer etc., can eliminate the bad situation such as inhomogeneous that is caused by deformation.Because the moisture permeability of above-mentioned macromolecule membrane is less, so the humidification durability is outstanding.
As described transparent protective film, from viewpoints such as polarization characteristic or durability, the film of cellulose-based resinous film such as preferred triacetyl cellulose and norbornene resin system.As the commercially available product of above-mentioned transparent protective film, for example can enumerate trade name " FUJITAC " (Fuji Photo Film Co., Ltd.'s system), trade name " ZEONOA " (Japanese Zeon corporate system), trade name " ARTON " (JSR corporate system) etc.
Thickness to described transparent protective film is not particularly limited.From viewpoints such as operability, thin layer such as intensity, the property handled, the thickness of described transparent protective film for example is the scope of 1～500 μ m.If in above-mentioned scope, just can mechanically protect polariscope, also do not shrink even be exposed to hot and humid polariscope down, guarantee stable optical characteristics.The thickness of described transparent protective film is preferably the scope of 5～200 μ m, more preferably the scope of 10～150 μ m.
Formation to the polarizer that is laminated with hard-coated film is not particularly limited.Described polarizer for example can be the formation that stacked above one another has transparent protective film, polariscope and transparent protective film on hard-coated film.Described polarizer for example can also be the formation that stacked above one another has polariscope, transparent protective film on hard-coated film.
Hard-coated film of the present invention and the various optical components such as polarizer that used this hard-coated film can be preferred for various image display devices such as liquid crystal indicator.Liquid crystal indicator of the present invention except using hard-coated film of the present invention and liquid crystal indicator in the past be same formation.Liquid crystal indicator of the present invention for example can wait by optical components such as appropriate combination liquid crystal cells, polarizer and the illuminator various component parts such as (backlights etc.) that add as required and the drive circuit of packing into and make.Above-mentioned liquid crystal cells is not particularly limited, can uses for example various types of liquid crystal cells such as TN type, STN type, π type.
In the present invention, the formation to liquid crystal indicator is not particularly limited.The one or both sides that liquid crystal indicator of the present invention for example is included in liquid crystal cells have disposed the liquid crystal indicator of above-mentioned optical component, used the liquid crystal indicator of backlight or reflecting plate etc. in illuminators.In these liquid crystal indicators, optical component of the present invention can be arranged on the one or both sides of liquid crystal cells.When optical component was arranged on the both sides of above-mentioned liquid crystal cells, they both can be identical, also can be different.On above-mentioned liquid crystal indicator, can dispose for example various optical components and opticses such as diffuser plate, antiglare layer, anti-reflection layer, baffle, prism array, lens arra thin slice, light diffusing sheet, backlight.
Embodiment
Below, embodiments of the invention and comparative example are described.But the present invention is not limited to the following examples and comparative example.
(embodiment 1)
Be ready to resin raw material (big Japanese ink corporate system, trade name: GRANDIC PC1071), this resin raw material is in the mixed solvent of ethyl acetate and butyl acetate, is that 66 weight % contain (A) composition as follows, (B) composition and (C) raw material that forms of the resinous principle of composition and Photoepolymerizationinitiater initiater with solid component concentration.In this resin raw material, add levelling agent 0.5 weight %.Then, the resin raw material that has added above-mentioned levelling agent is diluted with ethyl acetate, so that butyl acetate: ethyl acetate (weight ratio)=46: 54 (the ethyl acetate ratio of total solvent is 54 weight % relatively), solid component concentration is 50 weight %.Modulate hard conating thus and form material.Above-mentioned levelling agent is with dimethyl siloxane: the hydroxypropyl siloxanes: the own ester cyamelide of 6-isocyanates: aliphatic polyester=6.3: 1.0: 2.2: the copolymer of 1.0 mol ratio generation copolymerization.
(A) composition: by pentaerythrite is the urethane acrylate (100 weight portion) that acrylate and hydrogenated xylene diisocyanate constitute
(B) composition: 41 parts of six acrylic acid dipentaerythritol ester (below, B1 composition (monomer)), 49 weight portions, pentaerythritol tetracrylate (below, B4 composition (monomer)) and pentaerythritol triacrylate (below, B5 composition (monomer)) 24 weight portions
(C) composition: mixture (59 weight portion) with polymer, copolymer or above-mentioned polymer and copolymer of the repetitive of representing with above-mentioned general formula (1)
Photoepolymerizationinitiater initiater: trade name Irgacure 184 (Ciba Specialty Chemicals corporate system) 3 weight portions
Mixed solvent: butyl acetate: ethyl acetate (weight ratio)=89: 11
(on the triacetylcellulose film of thick 80 μ m (refractive index: 1.48)), use rod to be coated with machine and apply above-mentioned hard conating formation material, formation is filmed at the transparent plastic film base material.After above-mentioned coating,, make above-mentioned dried coating film by heating 1 minute down at 100 ℃.To above-mentioned dried coating, with metal halide light irradiation accumulative total light quantity 300mJ/cm
2Ultraviolet ray, be cured the hard conating that handle to form thick 20 μ m, make the hard-coated film of present embodiment thus.
(embodiment 2)
In the present embodiment, except the thickness with hard conating changes to 15 μ m, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 3)
In the present embodiment, except the thickness with hard conating changes to 25 μ m, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 4)
In the present embodiment, except the use level with above-mentioned (C) composition is altered to 96 weight portions, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 5)
In the present embodiment, except the use level with above-mentioned (C) composition is altered to 36 weight portions, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 6)
In the present embodiment, add in the material outside the crosslink propylene granulates that average grain diameter is 10 μ m (trade name: MX1000 combines chemistry (strain) system of grinding) 30 weight portions, adopt the method identical, the making hard-coated film with embodiment 1 except forming at hard conating.
(embodiment 7)
In the present embodiment, on the hard conating that anti-reflection layer is arranged at the hard-coated film that in embodiment 1, obtains, adopt the method identical, the making hard-coated film with embodiment 1.
Anti-reflection layer forms material and adopts method modulation as follows.That is, at first, as the formation material of anti-reflection layer, the number-average molecular weight that preparation converts by ethylene glycol is 500～10000 siloxane oligomer (COLCOAT N103 (COLCOAT corporate system, solid constituent 2 weight %)).Then, measure the number-average molecular weight of above-mentioned siloxane oligomer.Its result, above-mentioned number-average molecular weight are 950.Secondly, prepare Opstar JTA105 (JSR (strain) system, solid constituent 5 weight %), be more than 5000 and have the fluorine compounds of fluoro-alkyl structure and polysiloxane structure as number-average molecular weight by polystyrene conversion.Then, measure the number-average molecular weight of above-mentioned fluorine compounds.Its result, the number-average molecular weight by polystyrene conversion is 8000.Prepare JTA105A (JSR corporate system, solid constituent 5 weight %) as curing agent.
Then, mix above-mentioned Opstar JTA105, the above-mentioned JTA105A of 1 weight portion, the above-mentioned COLCOAT N103 of 590 weight portions and the butyl acetate of 151.5 weight portions of 100 weight portions, modulate above-mentioned anti-reflection layer and form material.Use punch die formula coating machine on hard conating, to apply this anti-reflection layer and form material, and its width is painted identical with above-mentioned hard conating.After above-mentioned coating, by heating 3 minutes down at 120 ℃, dry, curing forms anti-reflection layer (low-index layer, thickness 0.1 μ m, refractive index 1.43).
(embodiment 8)
In the present embodiment, forms the anti-reflection layer (thickness 95nm) that material forms the method that employing and embodiment 7 are identical, making hard-coated film except being provided with by anti-reflection layer as described below.
Promptly; in the mixed solvent of isopropyl alcohol/butyl acetate/hexone (54/14/32 (weight ratio)); disperse tetraalkoxysilane 54 weight portions, have fluoro-alkyl structure and polysiloxane structure silane coupling agent 23 weight portions, carry out surface treatment and the diameter of hydrophobization is the hollow of 60nm and spherical silica ultra micron 23 weight portions with silane coupling agent with acryloyl group; solid component concentration is adjusted to 2.0%, obtains anti-reflection layer and form material.
Use this anti-reflection layer to form material, adopt method and the condition identical, on hard conating, form anti-reflection layer with embodiment 7, thus, the hard-coated film of making present embodiment.
(embodiment 9)
In the present embodiment, except the thickness with hard conating is altered to 30 μ m, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 10)
In the present embodiment, except the thickness with hard conating is altered to 10 μ m, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 11)
In the present embodiment, using the mixed proportion of butyl acetate and ethyl acetate is that the solvent of 79: 21 (the ethyl acetate ratio with respect to total solvent is 21%) is as mixed solvent.In the present embodiment, solid component concentration is diluted into 63 weight %, the preparation hard conating forms material, uses this to be coated with firmly and forms material and form hard conating, in addition, adopts the method identical with embodiment 1, the making hard-coated film.
(embodiment 12)
At first, with the embodiment 1 the same hard-coated film of making present embodiment.Then, be coated with firmly on the face (with the face of the opposite side of formation face of hard conating) triacetylcellulose film non-, using wire bar that coating liquid described later is applied and make wet thickness is 20 μ m, and formation is filmed.After above-mentioned coating, the above-mentioned drying of carrying out 1 minute under 80 ℃ of filming is handled.In addition, as above-mentioned coating liquid, use that to cooperate diacetyl cellulose and make solid component concentration in the mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol)=37: 58: 5 be 0.5% liquid.
(embodiment 13)
In the present embodiment,, use acetone: ethyl acetate: IPA=37 as the non-coating liquid that applies on the face that is coated with firmly at triacetylcellulose film: 58: 5 mixed solvent, in addition, adopt method similarly to Example 12, make hard-coated film.
(embodiment 14)
In the present embodiment, except not adding reactive silicone, adopt the method making hard-coated film identical with embodiment 1 as levelling agent.
(embodiment 15)
In the present embodiment, use contains resin raw material (the big Japanese ink chemical industrial company system of following composition, trade name: PC4-Y243), described resin raw material use as (A) composition by pentaerythrite be the urethane acrylate that constitutes of acrylate and IPDI (below, the A1 composition) 100 weight portions, B1 composition 59 weight portions as (B) composition, B4 composition 37 weight portions and B5 composition 15 weight portions, above-mentioned (C) composition 26 weight portions, with respect to total resinous principle is the above-mentioned Photoepolymerizationinitiater initiater (trade name Irgacure 184) of 2 weight portions, in addition, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 16)
In the present embodiment, use contains resin raw material (the big Japanese ink chemical industrial company system of following composition, trade name: PC4-6097), described resin raw material uses A1 composition 100 weight portions as (A) composition, B1 composition 38 weight portions as (B) composition, B4 composition 40 weight portions and B5 composition 16 weight portions, above-mentioned (C) composition 30 weight portions, with respect to total resinous principle is that the Photoepolymerizationinitiater initiater of 3.5 weight portions (has cooperated 2 of the trade name Irgacure 184 of 1 weight portion and 2.5 weight portions, 4, the material that 6-trimethylbenzene acyloin phenyl phosphine oxide forms), in addition, adopt the method identical, the making hard-coated film with embodiment 1.
(embodiment 17)
In the present embodiment, except the thickness with hard conating changes to 29 μ m, adopt the method identical, the making hard-coated film with embodiment 6.
(comparative example 1)
In this comparative example, mismatch above-mentioned (A) composition and above-mentioned (C) composition, and cooperate six acrylic acid dipentaerythritol ester, 100 weight portions as (B) composition, and then cooperation acrylic acid butanediol ester (below, the B3 composition) 9 weight portions, in addition, adopt the method identical, the making hard-coated film with embodiment 1.
(comparative example 2)
In this comparative example, use B4 composition 22 weight portions and B5 composition 5 weight portions as (B) composition.In addition, use polymethyl methacrylate acrylate polymer 133 weight portions to replace above-mentioned (C) composition, in addition, adopt the method identical, the making hard-coated film with embodiment 1.
(comparative example 3)
In this comparative example, the mixture that uses B4 composition 22 weight portions and B5 composition 5 weight portions is as (B) composition.In addition, use polymethyl methacrylate acrylate polymer 55 weight portions to replace above-mentioned (C) composition, in addition, adopt the method identical, the making hard-coated film with embodiment 1.
Estimate
(thickness of hard conating)
Used thickness meter (the micrometer formula of (strain) Mitutoyo system), the gross thickness of measurement hard-coated film.Deduct the thickness of transparent plastic film base material from above-mentioned gross thickness.Calculate the thickness of hard conating thus.The results are shown in following table 1.
(thickness of anti-reflection layer)
The moment MCPD2000 of many sidelights system (trade name) of Shi Yong Da mound electronics (strain) system calculates the thickness of anti-reflection layer by the waveform of interference spectrum.
(crimping)
It is square that hard-coated film is cut into 10cm, makes test film.Be placed on described test film on the glass plate and make hard conating (or anti-reflection layer) up, be determined at described test film in 4 angles, with the mean value of this measured value evaluation index as crimping from the lifting length (mm) of above-mentioned glass plate.Need to prove, the film that becomes circle is made as " can't measure ".It the results are shown in following table 1.
(turbidity)
Turbidity (mist degree) with JIS K 7136 (version in 1981) is a benchmark, uses nephelometer HR300 (trade name, color technical research institute system in the village) to measure turbidity.It the results are shown in following table 1.
(flexibility)
To allow the transparent plastic film base material become the mode of the different metallic roll of inboard and direct contact diameter, the coiling hard-coated film has or not in the visual judgement hard conating (or anti-reflection layer) and crackle occurs.The diameter that crackle do not occur is measured as the value of flexibility.It the results are shown in following table 1.
(pencil hardness)
Make not form facing down of hard conating mounting hard-coated film on glass plate.Then, to above-mentioned hard coating surface,, measure pencil hardness according to the described pencil hardness test of JIS K-5400 (wherein, load 500g).It the results are shown in following table 1.
(reflectivity)
By the adhesive phase that on the face that does not form hard conating of hard-coated film, the forms thick about 20 μ m black acrylic panel (thick 2.0mm, the Rayon of Mitsubishi corporate system) of fitting, make the areflexia at the described hard-coated film back side thus.For this hard-coated film, obtain the reflectivity of hard coating surface.Described reflectivity uses trade name UV2400PC (the having 8 ° of inclination integrating spheres) spectrophotometer of Shimadzu Seisakusho Ltd.'s system, measures spectral reflectance (specular reflectivity+diffuse reflectance), obtains the total reflectivity (Y value) in ° visual field, illuminant-C/2 by calculating.It the results are shown in following table 1.
(refractive index of hard conating)
Use multi-wavelength Abbe refractometer (Atago of Co., Ltd. corporate system, trade name: the DR-M2/1550) refractive index of mensuration hard conating.It the results are shown in following table 1.
(marresistance)
At the value of the power of the marresistance of hard-coated film, obtain with following content of the test.It the results are shown in following table 1.
(1) sample is cut into wide at least 25mm, the size more than the long 100mm, it is positioned on the glass plate.Obtain initial turbidity value subsequently.
(2) on the level and smooth section of the cylinder of diameter 25mm, evenly be installed on the steel wool #0000, with load 1.5kg simultaneously with the speed of the about 100mm of per second reciprocal 100 times at specimen surface.Obtain the turbidity value after the test then.
(3) will from the turbidity value after the above-mentioned test, deduct the value that initial turbidity value obtains, as the index of marresistance.It the results are shown in following table 1.In steel wool test, produce damage on the surface of hard conating or anti-reflection layer, the turbidity value after the above-mentioned test rises, and also rises with the difference of above-mentioned initial turbidity value.Thereby, in this is estimated, can followingly judge: turbidity value after the above-mentioned test and above-mentioned initial turbidity value poor, promptly refer to that as above-mentioned marresistance target value is big more, marresistance is low more, and is more little as the value of These parameters, marresistance is high more.
(adhesiveness)
Hard conating is estimated by carrying out JIS K 5400 described gridiron pattern disbonded tests with respect to the adhesiveness of transparent plastic film base material.That is, carry out 100 times disbonded test, the quantity that the counting hard conating is peeled off from film substrate is represented with peeling off quantity/100.It the results are shown in following table 1.
Table 1
| The refractive index of film substrate | The refractive index of hard conating | The thickness of hard conating (μ m) | Reflectivity (%) | Pencil hardness | Crimping (mm) | Flexibility (mm Φ) | Turbidity | Adhesiveness | Marresistance | |
| Embodiment 1 | 1.48 | 1.51 | 20 | 4 | 4H | 22 | 9.5 | - | 0/100 | 0.2 |
| Embodiment 2 | 1.48 | 1.51 | 15 | 4 | 4H | 15 | 9.5 | - | 0/100 | 0.2 |
| Embodiment 3 | 1.48 | 1.51 | 25 | 4 | 4H | 30 | 11 | - | 0/100 | 0.2 |
| Embodiment 4 | 1.48 | 1.51 | 20 | 4 | 4H | 10 | 8 | - | 0/100 | 0.4 |
| Embodiment 5 | 1.48 | 1.51 | 20 | 4 | 5H | 29 | 14 | - | 0/100 | 0.2 |
| Embodiment 6 | 1.48 | 1.51 | 20 | 4 | 4H | 20 | 9.5 | 60 | 0/100 | 0.2 |
| Embodiment 7 | 1.48 | 1.51 | 20 | 2.5 | 4H | 10 | 9.5 | - | 0/100 | 0.3 |
| Embodiment 8 | 1.48 | 1.51 | 20 | 1.6 | 4H | 10 | 9.5 | - | 0/100 | 0.3 |
| Embodiment 9 | 1.48 | 1.51 | 30 | 4 | 5H | 36 | 12.5 | - | 0/100 | 0.2 |
| Embodiment 10 | 1.48 | 1.51 | 10 | 4 | 3H | 10 | 8 | - | 0/100 | 0.4 |
| Embodiment 11 | 1.48 | 1.51 | 20 | 4 | 4H | 24 | 9.5 | - | 10/100 | 0.2 |
| Embodiment 12 | 1.48 | 1.51 | 20 | 4 | 4H | 0 | 9.5 | - | 0/100 | 0.2 |
| Embodiment 13 | 1.48 | 1.51 | 20 | 4 | 4H | 0 | 9.5 | - | 0/100 | 0.2 |
| Embodiment 14 | 1.48 | 1.51 | 20 | 4 | 4H | 22 | 9.5 | - | 0/100 | 0.5 |
| Embodiment 15 | 1.48 | 1.53 | 20 | 4 | 4H | 29 | 14 | - | 0/100 | 0 |
| Embodiment 16 | 1.48 | 1.53 | 20 | 4 | 4H | 27 | 14 | - | 0/100 | 0 |
| Embodiment 17 | 1.48 | 1.51 | 29 | 4 | 5H | 28 | 12.5 | 63 | 0/100 | 0.2 |
| Comparative example 1 | 1.48 | 1.51 | 20 | 4 | 5H | More than the critical value | 15.5 | - | 10/100 | 1.8 |
| Comparative example 2 | 1.48 | 1.51 | 20 | 4 | 3H | 0 | 11 | - | 0/100 | 1.4 |
| Comparative example 3 | 1.48 | 1.51 | 20 | 4 | 3H | 20 | 12.5 | - | 0/100 | 0.8 |
Shown in above-mentioned table 1, all characteristic goods such as the hardness of the hard-coated film of present embodiment, marresistance, adhesiveness and flexibility, and can effectively prevent the generation of crimping.With respect to this, the crimping characteristic and the marresistance of the hard-coated film of comparative example 1 are poor, and the hardness and the marresistance of comparative example 2 and 3 hard-coated film are poor.
In above-mentioned comparative example 1～3,54) or the mixed solvent of butyl acetate and butanols (butyl acetate: use the mixed solvent (butyl acetate: MIBK=46: of butyl acetate and MIBK butanols=46: 54) as mixed solvent, form hard-coated film, estimate its adhesiveness.Its result, its adhesiveness are 75/100～100/100, and poor adhesion has taken place to peel off.
Claims (16)
1. hard-coated film, it comprises the transparent plastic film base material,
At least one face at described transparent plastic film base material is formed with hard conating,
Described hard conating be to use comprise following (A) composition, (B) composition and (C) hard conating of composition form material and form, wherein
Form in the material at described hard conating, with respect to described (B) components in proportions of described (A) composition scope at 70～180 weight %, and with respect to described (C) components in proportions of described (A) composition scope at 25～110 weight %,
(A) composition: urethane acrylate and carbamate methacrylate at least a
(B) composition: polyalcohol acrylate and polyalcohol methacrylate at least a
(C) composition: by at least a polymer that forms of following (C1) and following (C2) or the mixed polymer of copolymer or described polymer and copolymer
(C1): the alkyl acrylate of alkyl with at least a group of hydroxyl and acryloyl group
(C2): the alkyl methacrylate of alkyl with at least a group of hydroxyl and acryloyl group.
2. hard-coated film according to claim 1, wherein,
Described (B) composition contains at least a of pentaerythritol triacrylate and pentaerythritol tetracrylate.
3. hard-coated film according to claim 1, wherein,
Described (C) composition comprises the mixture of polymer, copolymer or the described polymer and the described copolymer of the repetitive that contains following general formula (1),
In described formula (1), R
1For-H or-CH
3, R
2For-CH
2CH
2OX or with the group of following general formula (2) expression, described X be-H or the acryloyl group represented with following general formula (3),
In described general formula (2), described X is-H or with the acryloyl group of following general formula (3) expression, described X can be identical, also can be different
4. hard-coated film according to claim 1, wherein,
The outer surface structure of described hard conating is a concaveconvex structure.
5. hard-coated film according to claim 1, wherein,
On the outer surface of described hard conating, be formed with anti-reflection layer.
6. hard-coated film according to claim 5, wherein,
Described anti-reflection layer contains siloxane oligomer and fluoride,
The number-average molecular weight of passing through the ethylene glycol conversion of described siloxane oligomer is 500～10000,
The number-average molecular weight of passing through polystyrene conversion of described fluoride is more than 5000, and has fluoro-alkyl structure and polysiloxane structure.
7. hard-coated film according to claim 5, wherein,
In described anti-reflection layer, contain hollow and spherical silica ultra micron.
8. hard-coated film according to claim 1, wherein,
The formation material of described hard conating contains levelling agent.
9. the manufacture method of a hard-coated film is to comprise the transparent plastic film base material reaches the hard-coated film of the hard conating that forms at least one face of described plastic film substrate manufacture method, and wherein, it comprises:
Preparation in solvent, dissolve or be dispersed with following (A) composition, (B) composition and (C) hard conating of composition form the operation of material,
On at least one face of described transparent plastic film base material the described hard conating of coating form material and form the operation of filming and
Make the operation of described curing of coating and then formation hard conating; Wherein
Form in the material at described hard conating, with respect to described (B) components in proportions of described (A) composition scope at 70～180 weight %, and with respect to described (C) components in proportions of described (A) composition scope at 25～110 weight %,
(A) composition: urethane acrylate and carbamate methacrylate at least a
(B) composition: polyalcohol acrylate and polyalcohol methacrylate at least a
(C) composition: by at least a polymer that forms of following (C1) and following (C2) or the mixed polymer of copolymer or described polymer and copolymer
(C1): the alkyl acrylate of alkyl with at least a group of hydroxyl and acryloyl group
(C2): the alkyl methacrylate of alkyl with at least a group of hydroxyl and acryloyl group.
10. the manufacture method of hard-coated film according to claim 9, wherein,
Described (B) composition contains at least a of pentaerythritol triacrylate and pentaerythritol tetracrylate.
11. the manufacture method of hard-coated film according to claim 9, wherein,
Described (C) composition comprises the mixture of polymer, copolymer or the described polymer and the described copolymer of the repetitive that contains following general formula (1),
In described formula (1), R
1For-H or-CH
3, R
2For-CH
2CH
2OX or with the group of following general formula (2) expression, described X be-H or the acryloyl group represented with following general formula (3),
In described general formula (2), described X is-H or with the acryloyl group of following general formula (3) expression, described X can be identical, also can be different
12. the manufacture method of hard-coated film according to claim 9, wherein,
Described solvent comprises ethyl acetate.
13. the manufacture method of hard-coated film according to claim 12, wherein,
Described relatively solvent total amount, described ethyl acetate to contain proportional be more than the 20 weight %.
14. an optical element, wherein,
It comprises optical component,
On at least one face of described optical component, be formed with the described hard-coated film of claim 1.
15. an image display device, wherein,
It possesses the described hard-coated film of claim 1.
16. an image display device, wherein,
It possesses the described optical element of claim 14.
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| KR101379491B1 (en) * | 2012-05-31 | 2014-04-01 | 주식회사 엘지화학 | Hard coating film and method of preparing of hard coating film |
| WO2014013922A1 (en) * | 2012-07-19 | 2014-01-23 | 日産化学工業株式会社 | Structure having stainproof microrelief surface and process for producing same |
| KR101415841B1 (en) * | 2012-08-23 | 2014-07-09 | 주식회사 엘지화학 | Hard coating film |
| KR101470463B1 (en) * | 2012-08-23 | 2014-12-08 | 주식회사 엘지화학 | Hard coating film |
| KR101436616B1 (en) * | 2012-08-23 | 2014-09-03 | 주식회사 엘지화학 | Hard coating film |
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| JP7261738B2 (en) * | 2017-03-31 | 2023-04-20 | 東洋紡株式会社 | Liquid crystal displays, polarizers and protective films for polarizers |
| EP3717583B1 (en) * | 2017-12-01 | 2021-11-17 | CommScope Connectivity Belgium BVBA | Methods of preparing low tack soft gel compositions and such gel compositions prepared therefrom |
| KR102198801B1 (en) * | 2017-12-07 | 2021-01-05 | 삼성에스디아이 주식회사 | Color conversion panel and manufacturing method thereof |
| KR102487552B1 (en) | 2018-02-05 | 2023-01-11 | 삼성전자주식회사 | Composition for protective film against sawing process and method of manufacturing semiconductor package using the composition |
| US20200073019A1 (en) * | 2018-09-04 | 2020-03-05 | GM Global Technology Operations LLC | Protective film for a lens of a sensor |
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| CN102652062B (en) * | 2010-02-10 | 2015-04-15 | 乐金华奥斯有限公司 | Sheet for forming hard coating |
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