WO2007032170A1 - 帯電防止防眩フィルム - Google Patents
帯電防止防眩フィルム Download PDFInfo
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- WO2007032170A1 WO2007032170A1 PCT/JP2006/315934 JP2006315934W WO2007032170A1 WO 2007032170 A1 WO2007032170 A1 WO 2007032170A1 JP 2006315934 W JP2006315934 W JP 2006315934W WO 2007032170 A1 WO2007032170 A1 WO 2007032170A1
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- B32B2307/408—Matt, dull surface
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/702—Amorphous
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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
- B32B2457/00—Electrical equipment
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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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/204—Plasma displays
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the present invention prevents reflection of external light and makes it easy to see an image by pasting or arranging it on the front of a display such as a liquid crystal display, a cathode ray tube display (CRT), or a plasma display panel.
- a display such as a liquid crystal display, a cathode ray tube display (CRT), or a plasma display panel.
- the present invention relates to an antistatic antiglare film in which antistatic properties are imparted to an antiglare film having a function of
- This antiglare film is generally formed by coating a resin containing a filler such as silicon dioxide (silica) on the surface of a transparent substrate film.
- a filler such as silicon dioxide (silica)
- an organic filler having a particle size larger than the film thickness of the coating film is added to the resin, in which the surface of the antiglare layer is formed by agglomeration of particles such as agglomerated silica.
- the surface of the antiglare layer is formed by agglomeration of particles such as agglomerated silica.
- the above-described display or the like requires antistatic properties in order to remove a failure caused by static electricity generated on the surface.
- metal oxides are mainly used. However, in order to achieve antistatic properties by incorporating a metal oxide in the antiglare layer, it is necessary to contain a large amount of the metal oxide, which causes a problem that the film is tinted. Metal oxides are not preferred.
- Antistatic agents include organic antistatic agents.
- Conventional methods using an organic antistatic agent A commonly used method is to use a low molecular weight surfactant as an organic antistatic agent, and add it to the coating composition for forming the antistatic layer to form a coating film. And forming an antistatic layer or applying the surfactant to the surface.
- low molecular weight surfactants are: (1) antistatic agent drops off by washing with water, wiping cloth, etc., lasting antistatic effect; (2) poor heat resistance, many Easily decomposes during molding and has no persistence in antistatic effect; (3) Easy to bleed out on the surface, resulting in deterioration of surface characteristics such as blocking; (4) Concentration and coating at the coating film interface Since the adhesion of the film is impaired, peeling from the upper layer is likely to occur; (5) Since the film tends to bleed out to the surface, it becomes whitish and the transparency is impaired.
- Patent Document 4 As organic antistatic agents used for antistatic processing, ionic polymer compounds are also disclosed (Patent Document 4).
- Patent Document 1 Japanese Patent Application Laid-Open No. 2002-254573
- Patent Document 2 Japanese Patent Laid-Open No. 2002-277602
- Patent Document 3 Japanese Patent Laid-Open No. 2003-39607
- Patent Document 4 Japanese Patent Laid-Open No. 2000-352620
- the present invention has been achieved in view of the above-described circumstances, and its purpose is to provide antistatic properties and transparency even when used for a long time, particularly for a long time under high temperature or high humidity.
- An object of the present invention is to provide an antistatic antiglare film that maintains the above.
- the antistatic antiglare film according to the present invention comprises an antiglare layer containing a polymer-type antistatic agent, translucent fine particles and a binder, which is at least laminated on a transparent substrate film.
- the binder component contained in the antiglare layer and the polymer antistatic agent are entangled to form a coating film. While the molecular antistatic agent gathers near the surface of the paint film and exhibits an antistatic effect, even when washed with water or wiped with cloth, the white anti-glare layer that does not easily fall off from the surface of the antiglare layer deteriorates the transparency. That's true. Furthermore, the polymer antistatic agent has higher heat resistance than the antistatic agent such as a low molecular weight surfactant.
- the antiglare layer in the present invention is used for a long time, particularly at a high temperature or in a high humidity, while the antistatic agent gathers near the surface of the coating film and effectively exhibits antistatic properties.
- the antistatic property and transparency are maintained, and the surface characteristics are hardly deteriorated.
- the antiglare layer according to the present invention has the function of an antistatic layer as a single layer. As a result, it is not necessary to separately laminate the antiglare layer and the antistatic layer, thereby reducing the number of coating steps. This has the advantage that the cost can be reduced.
- the antistatic agent is a polymer type quaternary ammonium salt, adhesion and long-term use under high temperature and high humidity. This is preferable from the viewpoint of maintaining good properties.
- the polymer type quaternary ammonium salt is a polymer containing 1 to 70 mol% of a repeating unit containing a quaternary ammonium salt. And is preferable from the viewpoint of balance in which transparency is increased.
- the antiglare layer has a surface resistivity of 10 13.
- a low refractive index layer having a refractive index lower than that of the antiglare layer is laminated on the antiglare layer. From More preferred.
- the antistatic antiglare film according to the present invention maintains its antistatic property and transparency even when used for a long time, particularly for a long time under high temperature or high humidity.
- the antistatic antiglare film according to the present invention includes an antiglare layer having antistatic properties, improves production efficiency, and can be obtained at low cost.
- FIG. 1 schematically shows a cross section of an example of an antistatic antiglare film according to the present invention.
- FIG. 2 schematically shows a cross section of another example of the antistatic antiglare film according to the present invention.
- (meth) atallylol represents attalyloyl and methacryloyl
- (meth) attalylate represents acrylate and methacrylate.
- the antistatic antiglare film according to the present invention includes a polymer type antistatic agent, a translucent fine particle, and an antiglare layer containing a binder at least laminated on the transparent substrate film. Since such an antistatic antiglare film contains a polymer antistatic agent in the antiglare layer, the antistatic agent gathers in the vicinity of the surface of the antiglare layer and effectively exhibits antistatic properties for a long time. The antistatic property and transparency are maintained even when used for a long time, particularly under high temperature and high humidity, and the surface properties are hardly deteriorated.
- the antiglare layer in the antistatic antiglare film according to the present invention has the function of an antistatic layer as a single layer, which eliminates the need for laminating the antiglare layer and the antistatic layer separately. It has the merit that it can reduce and cost can be reduced.
- the antistatic antiglare film according to the present invention is obtained by laminating at least an antiglare layer containing a polymer type antistatic agent on a transparent base film, and in addition, a hard coat layer, One or a plurality of functional layers such as a low refractive index layer may be further laminated.
- FIG. 1 and FIG. 2 are diagrams showing examples of the cross-sectional structure of the antistatic antiglare film of the present invention.
- the antistatic antiglare film 1 of the present invention is obtained by laminating an antiglare layer 3 having antistatic properties on a transparent substrate film 2, and the antiglare layer 3 is a layer 3 The fine particles for light diffusion are dispersed therein, and the upper surface of the antiglare layer 3 has irregularities 10 due to the dispersion of fine particles.
- the antistatic antiglare film 1 of the present invention has a low refractive index layer 4 having a lower refractive index than the antiglare layer 3 laminated on the antiglare layer 3 as shown in FIG. It may be a thing.
- the light transmission layer is composed of only the low refractive index layer, but another light transmission layer having a different refractive index may be further provided.
- the layer structure of the antistatic antiglare film according to the present invention is not particularly limited, but specific examples include a transparent substrate film / antiglare layer, and a transparent substrate film / hard coat layer / antiglare layer. And transparent substrate film / antiglare layer / low refractive index layer, transparent substrate film / hard coat layer / antiglare layer / low refractive index layer, and the like.
- the “antiglare layer” may be a single layer or a plurality of layers.
- the material of the transparent substrate film is not particularly limited, and a general material used for an antiglare film can be used. Among them, those having smoothness and heat resistance and excellent in mechanical strength are preferable.
- triacetate cellulose TAC
- PET polyethylene terephthalate
- PET polyethylene naphthalate
- diacetyl cellulose acetate butyl cellulose
- polyether sulfone acrylic resin (polymethyl acrylate) , Polymethyl methacrylate, polyacrylate, polymethacrylate, etc.), polyurethane resin, polycarbonate, polysulfone, polyether, polyamide, polyimide, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylacetal
- films formed of various resins such as polyether ketone and (meth) acrylonitrile.
- the antiglare film of the present invention it is preferable to use triacetyl senolenose quinolem or polyester (polyethylene terephthalate, polyethylene naphthalate) as the transparent substrate film.
- the antistatic antiglare film according to the present invention is also suitable for use as a protective film for protecting the polarizing layer of the polarizing plate.
- an amorphous olefin polymer (Cyclo-Olefm-Polymer: CP) film having an alicyclic structure can also be used.
- This is a base material on which norbornene polymer, monocyclic cyclic olefin polymer, cyclic conjugation polymer, vinyl alicyclic hydrocarbon polymer resin, etc. are used.
- norbornene polymer monocyclic cyclic olefin polymer, cyclic conjugation polymer, vinyl alicyclic hydrocarbon polymer resin, etc.
- ZEONEX ZEONOR norbornene resin manufactured by Sumitomo Bakelite Co., Ltd. Sumilite FS_1700, JSR Co., Ltd. Arton (modified norbornene resin), Mitsui Chemicals Co., Ltd.
- Abel cyclic olefin copolymer
- Examples include Topas (cyclic olefin copolymer) manufactured by Ticona, and Optretz OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd.
- FV series low birefringence, low photoelastic modulus film
- Asahi Kasei Chemicals Corporation is also preferred as an alternative base material for triacetyl cellulose.
- thermoplastic resins it is preferable to use these thermoplastic resins as a film-like body rich in thin film flexibility.
- these thermoplastic resin plates or It is also possible to use a glass plate.
- the substrate thickness is usually 25! ⁇ 1000 zm or so.
- the thickness of the substrate is preferably 20 ⁇ m or more and 300 ⁇ m or less, more preferably the upper limit is 200 ⁇ m or less, and the lower limit is 30 ⁇ m or more.
- the thickness may exceed these thicknesses.
- the thickness is usually about 25 to 111 to 111.
- Preferred thickness is 30 111-90 111, especially preferred A thickness of 35 ⁇ m ⁇ 80 ⁇ m. If it is less than 25 ⁇ m, handling during film formation becomes difficult.
- an anchor agent or primer When forming an antiglare layer on the base material, in order to improve adhesion, in addition to physical treatment such as corona discharge treatment and oxidation treatment, application of a coating called an anchor agent or primer is applied. Go ahead.
- the antiglare layer in the present invention is a layer having a fine uneven shape on the surface and providing an antiglare function.
- the antiglare layer in the present invention contains, as essential components, a polymer-type antistatic agent, translucent fine particles for imparting antiglare properties, and a noinder for imparting adhesion to adjacent layers. Further, if necessary, the antiglare layer is formed by containing an additive such as a leveling agent, refractive index adjustment, crosslinking shrinkage prevention, inorganic filler for imparting high indentation strength, etc. It may be a concavo-convex layer single layer, or may be composed of multiple layers. When the antiglare layer is a multilayer, it is preferable that the surface unevenness layer and the surface shape adjusting layer force provided on the surface unevenness layer are provided.
- the surface shape adjusting layer is a layer having a function of adjusting the surface shape of the underlying uneven layer to a more appropriate uneven shape.
- the polymer antistatic agent is more preferably contained in a layer on the viewer side of the display, and the surface shape adjustment provided on the base uneven layer.
- it has a layer, it is preferable that it be contained in the surface shape adjusting layer installed on the viewer side of the display.
- the underlying concavo-convex layer when the antiglare layer is a multi-layer has a concavo-convex shape on the surface, and can be obtained by substantially the same method as the antiglare layer when it is a single concavo-convex layer.
- a polymer type antistatic agent is used to impart antistatic properties to the antiglare layer.
- the polymer antistatic agent can form a coating film intertwined with the binder component contained in the antiglare layer, so it gathers near the surface of the coating film and has an antistatic effect. Even when washed with water, wiped with cloth, etc., the whitening that does not easily fall off the surface of the antiglare layer does not deteriorate and the transparency is not deteriorated.
- the polymer antistatic agent has higher heat resistance than the antistatic agent such as a low molecular weight surfactant.
- the antiglare layer in the present invention is used for a long time, particularly at a high temperature or in a high humidity, for a long time, while the antistatic agent gathers near the surface of the coating film and effectively exhibits antistatic properties.
- the antistatic property and transparency are maintained, and the surface properties are hardly deteriorated.
- Examples of the polymer antistatic agent used in the antiglare layer of the present invention include Japanese Patent Publication No. 49-2828, Japanese Patent Publication No. 491-123827, Japanese Patent Publication No. 47-28937;
- Ionene type polymers having a dissociation group in the main chain as seen in JP 18175, JP 57-18176, JP 57-56059, etc .; JP-B 57-15376, JP-B 53-45231, JP-B 55-1457 83), JP-B 55-65950, JP-B 55-67746, JP-B 57-11342, JP-B JP Kokoku 57-19735, JP Kokoku 58-56858, JP Kokoku 61-27853, JP Kokoku 62-9346, JP 10-279833, JP 2000-80169 And cationic polymer compounds that can be seen.
- a particularly preferable polymer type antistatic agent is a polymer type quaternary ammonium salt (polymer type cationic antistatic agent) containing a quaternary ammonium cation.
- an antistatic agent consisting of a high molecular weight quaternary ammonium salt
- good adhesion is maintained even after high temperature resistance and high humidity tests, and transparent after high temperature resistance and high humidity tests. From the point which the fall of property is most suppressed.
- the structure S of the quaternary ammonium salt contained in the polymer type antistatic agent is as follows. The present invention is not limited to this.
- RRRR is substituted or unsubstituted alkyl having 14 carbon atoms.
- a nitrogen-containing heterocycle such as piperazine by combining R and R and / or R and R
- X is an anion.
- a B and J are each a substituted or unsubstituted alkylene group having 2 10 carbon atoms, an arylene group, an alkenylene group, an arylene alkylene group, RCOR -R COOR OCOR R OCR COOR
- R R R and R are alkylene groups, R R R R and R are respectively
- a linking group selected from a substituted or unsubstituted alkylene group, alkenylene group, arylene group, aryleneanolylene group, and alkylenearylene group.
- n is a positive integer of 1 4 Represents.
- the substituted or unsubstituted alkyl group having 14 carbon atoms is not particularly limited, and a linear or branched alkyl group can be used. Specifically, for example, a methyl group, an ethyl group, and the like can be used. Group, n_propyl group, isopropyl group, n_butyl group, isobutyl group, t-butynol group, pentyl group and the like.
- halogen ions are preferred, especially C1
- the polymer type quaternary ammonium salt is a polymer containing a repeating unit containing a quaternary ammonium salt, and a co-polymer containing a repeating unit containing a quaternary ammonium salt or a repeating unit containing a quaternary ammonium salt.
- Examples of coalescence include the following. However, the present invention is not limited to these.
- the polymer type quaternary ammonium salt is a repeating unit containing a quaternary ammonium salt (in the above chemical formula, m and X ) In an amount of 1 to 70 mol% is preferable from the viewpoint of imparting antistatic performance and increasing transparency. Antistatic performance is not exhibited if the repeating unit containing quaternary ammonium salt is less than mol%. If it is more than 70 mol%, the compatibility with the binder component may be deteriorated. Furthermore, the repeating units comprising quaternary Anmoniumu salt in a polymeric quaternary Anmoniumu salt, preferably included from 3 to 50 mole 0/0.
- the polymer type quaternary ammonium salt contains a hydrophobic group such as a polyoxyethylene group because the solubility in a solvent or a binder described later is improved.
- the polymeric antistatic agent has a polymerizable functional group
- the binder is an ionizing radiation curable binder
- a chemical bond is caused by ultraviolet irradiation or electron beam irradiation.
- the antistatic agent is more firmly fixed in the binder component, and furthermore, the antistatic agent can be prevented from falling off due to bleeding out, washing with water, wiping cloth, etc., which is preferable.
- the polymerizable functional group include, but are not limited to, an ethylenically unsaturated bond such as an acryl group, a bur group, and a allyl group, and an epoxy group.
- the content of the polymer antistatic agent in the antiglare layer is preferably 3 to 20% by mass of the total solid content of the antiglare layer.
- the antiglare layer according to the present invention contains a binder from the viewpoints of film formability and film strength.
- a binder a transparent material that transmits light when formed into a coating film is used.
- the mechanical strength of the coating film is excellent in scratch resistance, etc. Furthermore, the polymer type antistatic agent gathered near the coating film surface does not easily move or modify even under high temperature and high humidity.
- an ionizing radiation curable resin composition and / or a thermosetting resin composition can be preferably used. Above all, it improves the performance of the paint film such as scratch resistance and strength, and also provides the function of a hard coat layer that exhibits a hardness of “H” or higher in the pencil hardness test specified in JIS5600-5-4: 1999.
- An ionizing radiation curable resin composition and / or a thermosetting resin composition is preferably used. The ionizing radiation curable resin composition is more preferably used because it can be cured in a short time.
- the ionizing radiation curable resin composition undergoes a reaction that causes a large molecule such as polymerization or dimerization directly when irradiated with ionizing radiation or indirectly by the action of an initiator.
- a large molecule such as polymerization or dimerization directly when irradiated with ionizing radiation or indirectly by the action of an initiator.
- a radically polymerizable monomer or oligomer having an ethylenically unsaturated bond such as a (meth) atallyloyl group, biell group, or allyl group, or a cross-linking bond is generated between molecules of the binder component preferred by the oligomer.
- a polyfunctional binder component having two or more, preferably three or more curing reactive functional groups in one molecule.
- photoradical polymerization reaction can be caused directly or indirectly by the action of an initiator by irradiation with ionizing radiation such as ultraviolet rays or electron beams. Handling including the curing process is relatively easy.
- ionizing radiation such as ultraviolet rays or electron beams.
- a (meth) atallyloyl group is preferable because of its excellent productivity.
- other ionizing radiation curable binder components can also be used.
- photopower thione polymerizable monomers and oligomers such as epoxy group-containing compounds may be used.
- the ionizing radiation curable resin composition preferably has a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin having an ethylenically unsaturated bond such as an acrylate functional group.
- oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiolpolyene resin, polyhydric alcohols, and reactive diluents It consists of ionizing radiation curable resin.
- Examples of the reactive diluent include monofunctional monomers such as ethyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, styrene, vinylol toluene, N-vinyl pyrrolidone, and polyfunctional monomers such as trimethylol.
- monofunctional monomers such as ethyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, styrene, vinylol toluene, N-vinyl pyrrolidone, and polyfunctional monomers such as trimethylol.
- the ionizing radiation curable resin described above is used as an ultraviolet curable resin, as a photopolymerization initiator in the binder for a resin having a radical polymerizable functional group, a acetophenone or a benzophenone is used.
- a acetophenone or a benzophenone is used as a photopolymerization initiator in the binder for a resin having a radical polymerizable functional group.
- Michler's benzoyl benzoate, bismuth oxime ester, thixanthone, and n-butylamine, triethylamine, A mixture of n-butylphosphine and the like can be used.
- photopolymerization initiators For resins having a cationically polymerizable functional group, aromatic diazonium salts, aromatic sulfone salts, aromatic iodine salts, meta-octene compounds, benzoin sulfonic acid esters, etc., alone or as a mixture, are used as photopolymerization initiators. Can be used as Various examples of photopolymerization initiators are also described in the latest UV curing technology (P. 159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, Inc., published in 1991). Photopolymerization initiators can also be used in the present invention.
- photocleavable photoradical polymerization initiators include Irgacure 651 and Irgacure 184 (1-hydroxy-cyclohexylroyl 2-ketone) and Irgacure 907 manufactured by Ciba Specialty Chemicals Co., Ltd. (Each brand name) etc. are mentioned as a preferable example.
- the photopolymerization initiator is preferably used in the range of 0.:! To 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. is there.
- the ionizing radiation curable resin composition may contain a solvent-drying resin.
- a thermoplastic resin is mainly used as the solvent-drying resin.
- the thermoplastic resin is not particularly limited, and examples thereof include styrene resins, (meth) acrylic resins, vinyl acetate resins, butyl ether resins, halogen-containing resins, alicyclic olefin resins, and polycarbonate resins. Examples thereof include resins, polyester resins, polyamide resins, cellulose derivatives, silicone resin, rubber, and elastomers.
- the thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds).
- thermoplastic resin examples include cellulose resin strength S such as nitrocellulose, acetyl cellulose, cellulose acetate propionate, ethyl hydroxyethyl cellulose, and adhesion when a triacetyl cellulose film is used as a transparent substrate film. And advantageous in terms of transparency.
- thermosetting resin composition is a hardened resin that can be cured by heating to cause a large molecular weight reaction such as polymerization or crosslinking between the same functional group or another functional group.
- Monomers, oligomers, and polymers having functionalized reactive functional groups can be used.
- examples of the thermosetting resin include monomers and oligomers having an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a hydrogen bond forming group, and the like.
- thermosetting resins include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine resin. Urea co-condensation resin, key resin, polysiloxane resin, etc. are used. These thermosetting resin compositions are used by adding a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator, a solvent, and a viscosity modifier as necessary.
- a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator, a solvent, and a viscosity modifier as necessary.
- the binder content in the antiglare layer is preferably 15 to 85 mass% of the total solid content of the antiglare layer.
- the antiglare layer in the present invention contains translucent fine particles in order to form surface irregularities and impart antiglare properties.
- the translucent fine particles can be used in a mixture of two or more of those having different components, different shapes, and different particle size distributions. Preferably, use:! ⁇ 3 types. However, a variety of particles can be used for purposes other than forming irregularities.
- the one kind or two or more kinds of light-transmitting fine particles used in the present invention are more preferably spherical, for example, spherical, elliptical, or the like.
- the average particle diameter ( ⁇ m) of one kind or two or more kinds of light-transmitting fine particles is preferably 0.5 ⁇ im / 20 to 20 ⁇ m, 0.5 ⁇ to 10 ⁇ ⁇ ⁇ ⁇ or less is more preferable. More preferred.
- the thickness is less than 0.5 ⁇ m, sufficient antiglare property and light diffusion effect can be obtained unless the addition amount of the translucent fine particles to be added to the antiglare layer is very large.
- the average particle size of the light-transmitting fine particles represents the average particle size when each contained particle is a monodisperse type particle (particle having a single shape), and has a broad particle size distribution. In the case of irregular shaped particles, the average particle size is represented by the particle size of the most abundant particles by particle size distribution measurement.
- the particle size of the fine particles is mainly It can be measured by one counter method. In addition to this method, measurement can also be performed by laser diffraction and SEM photography.
- the translucent fine particles may be agglomerated particles. In the case of agglomerated particles, the secondary particle diameter is preferably within the above range.
- each of the translucent fine particles 80% or more (preferably 90% or more) of the entire translucent fine particles may be within the range of each average particle diameter ⁇ 1.0 (preferably 0.3) xm. preferable. This makes it possible to improve the uniformity of the uneven shape of the antiglare layer.
- fine particles with an average particle size of less than 3.5 xm use fine particles that are outside the above particle size distribution range, for example, amorphous particles of 2.5 xm and 1.5 xm. Also good.
- the translucent fine particles are not particularly limited, and inorganic and organic particles can be used.
- a plastic bead can be cited.
- Plastic beads include styrene beads (refractive index 1.6
- melamine beads reffractive index 1 ⁇ 57
- acrylic beads reffractive index 1 ⁇ 50 ⁇ :! ⁇ 53
- attalinole styrene beads reffractive index 1 ⁇ 54 ⁇ : 1.58
- benzoguanamine beads benzoguanamine '
- examples include formaldehyde condensation beads, polycarbonate beads, and polyethylene beads.
- the plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads.
- inorganic fine particles include amorphous silica force and inorganic silica beads.
- amorphous silica it is preferable to use silica beads having a particle diameter of 0.5 to 5 ⁇ m having good dispersibility.
- the amorphous surface is treated with an organic substance to make it hydrophobic. It is preferred to use silica.
- the organic treatment there is a method of chemically bonding a compound to the surface of the bead, or a physical method of penetrating a void existing in a composition that forms a bead that does not chemically bond to the bead surface.
- a chemical treatment method using an active group on a silica surface such as a hydroxyl group or a silanol group is preferably used from the viewpoint of treatment efficiency.
- a silane-based, siloxane-based, or silazane-based material having high reactivity with the active group described above is used.
- a linear chain such as methyltrichlorosilane
- examples include a rualkyl monosubstituted silicone material, a branched alkyl monosubstituted silicone material, a linear alkyl polysubstituted silicone compound such as di-n-butyldichlorosilane and ethyldimethylchlorosilane, and a branched alkyl multisubstituted silicone compound.
- mono-substituted, poly-substituted siloxane materials, and silazane materials having a linear alkyl group or a branched alkyl group can also be used effectively.
- those having a hetero atom, an unsaturated bond group, a cyclic bond group, an aromatic functional group, etc. may be used at the terminal or intermediate part of the alkyl chain.
- the average particle size of the first fine particles is R (zm)
- the average particle size of the second fine particles is R (z xm)
- R force S0.25R or more facilitates dispersion of the coating liquid and causes particles to aggregate.
- the two or more kinds of fine particles preferably have different average particle diameters as described above, but those having the same average particle diameter are also suitable. Used for
- the total mass ratio per unit area of the binder, the first microparticles, and the second microparticles is the total mass per unit area of the first microparticles.
- the total mass per unit area of fine particles is M, and the total mass of binder per unit area is M
- the content of the second fine particles is preferably 3 to 100% by mass with respect to the content of the first fine particles.
- the content of the third fine particles is preferably 3 to 100% by mass of the second fine particles. It is preferable to follow this relationship for the content of particles after the fourth particle.
- the antiglare layer in the present invention has internal scattering properties (a large difference in refractive index) caused by the difference in the refractive index between the matrix and the light-transmitting fine particles, which are formed only by forming irregularities on the surface and imparting antiglare properties. It is preferable that the internal scattering property is increased.
- This internal scattering is a glare that is a problem with anti-glare films (surface irregularities act as lenses, especially in the case of high-definition displays with a small pixel size, causing variations in brightness and reducing visibility. Phenomenon to cause) It can be improved.
- the light-transmitting fine particles imparting such a glare-improving property it is preferable to use those having a difference from the refractive index of the binder of 0.03-0.20.
- the difference in refractive index between the binder contained in the antiglare layer and the light-transmitting fine particles is preferably 0.03 or more and 0.20 or less because the difference in refractive index is less than 0.03.
- the difference in refractive index is too small to obtain a light diffusion effect, and if the difference in refractive index is greater than 0.20, the light diffusivity is too high and the entire film is whitened. Because.
- the difference in refractive index between the translucent fine particles and the binder is particularly preferably 0.04 or more and 0.16 or less.
- the refractive indexes of the translucent fine particles are respectively It can be regarded as an average value according to the refractive index and the usage ratio of the translucent fine particles, and the fine refractive index can be set by adjusting the mixing ratio of the translucent fine particles, making control easier than with one type.
- the fine refractive index can be set by adjusting the mixing ratio of the translucent fine particles, making control easier than with one type.
- Various designs are possible.
- the difference in refractive index between the first translucent fine particles and the second translucent fine particles is 0.03 or more and 0.10 or less.
- the difference in refractive index between the first light transmitting fine particles and the second light transmitting fine particles is determined. 0.03 or more and 0.10 or less are preferred because if the difference in refractive index is less than 0.03, the difference in refractive index between the two is too small, and even if both are mixed, the refractive index is controlled.
- the refractive index difference is more preferably 0.04 or more and 0.09 or less, and particularly preferably 0.05 or more and 0.08 or less.
- the first light-transmitting fine particles contained in the antiglare layer are preferably those in which the difference in refractive index from the binder having high transparency is the above-mentioned numerical value.
- Specific examples of organic fine particles used for the first light-transmitting fine particles include acrylic beads (refractive index 1.49 to: 1.53 3), acrylic-styrene copolymer beads (refractive index 1.55). , Melamine beads (refractive index 1.57), polycarbonate beads (refractive index 1.57), and the like.
- Inorganic fine particles include amorphous silica beads (refractive index: 1.45-1.50).
- organic fine particles are suitable, and it is preferable to use a combination of those having a refractive index difference with the light-transmitting resin having high transparency in particular as described above.
- organic fine particles used for the second light-transmitting fine particles include styrene beads (refractive index 1.60), polychlorinated bule beads (refractive index 1.60), benzoguanamine'formaldehyde condensed beads (1 ⁇ 66).
- the particle diameter of the first translucent fine particles> second It is also preferable to set the particle size of the light-transmitting fine particles, but it is possible to freely select the ratio of the first light-transmitting fine particles and the second light-transmitting fine particles by aligning the particle sizes of the two types of fine particles. It can also be used, and in this way, light diffusibility can be easily designed.
- organic fine particles from which monodispersed particles can be easily obtained are preferable.
- the total content of the light-transmitting fine particles is based on the total solid mass of the antiglare layer consisting of the single layer or the underlying uneven layer. 5 quality It is preferable that the amount is not less than 40% by mass. More preferably, it is 10 mass% or more and 30 mass% or less. If it is less than 5% by mass, sufficient antiglare property and internal scattering property cannot be imparted. If it exceeds 40% by mass, the film strength is lowered, and hard coat properties cannot be imparted to the antiglare layer. Les.
- an inorganic filler such as silica may be added to prevent sedimentation.
- Inorganic fillers are effective in preventing sedimentation of translucent fine particles as the amount added increases, but depending on the particle size and amount used, the transparency of the coating film is adversely affected. Therefore, it is preferable that an inorganic filler having a particle size of 0.5 zm or less is contained so as not to impair the transparency of the coating film with respect to the binder.
- the antiglare layer may contain an inorganic filler for the purpose of adjusting the refractive index.
- the refractive index of the matrix of the antiglare layer in the portion excluding the translucent fine particles in which the translucent fine particles are diffused is set.
- an inorganic filler may be appropriately placed in the solder.
- the inorganic filler used in this case does not scatter because the particle size is sufficiently smaller than the wavelength of light, and the dispersion in which the inorganic filler is dispersed in the binder behaves as an optically uniform substance. Is preferable.
- the refractive index of the bulk of the mixture of the binder, translucent fine particles and inorganic filler of the antiglare layer of the present invention is preferably 1.48 to 2.00. It is more preferably ⁇ 1.55 to 1.80, more preferably ⁇ 1.54 to 1.70. In addition, it is preferable that the refractive index of the matrix of the antiglare layer in the portion excluding the transparent tense particles is 1.50-2.00.
- the type and amount ratio of the binder, the light-transmitting fine particles, the soot or the inorganic filler may be appropriately selected. How to select can be easily known in advance by experiments.
- silicone-based or fluorine-based antifouling agents and slipping agents are used.
- Etc. can be added as appropriate.
- these additives it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the antiglare layer, more preferably in the range of 0.05 to 10% by mass. It is a case where it is added, particularly preferably in the range of 0.:! To 5% by mass.
- the antiglare layer further contains an ultraviolet blocking agent, an ultraviolet absorber, a surface conditioner (leveling agent) or other components.
- the layer included in the anti-glare layer, or the surface shape adjusting layer is a layer having a function of adjusting the surface shape of the underlying uneven layer to a more appropriate uneven shape.
- the surface shape adjustment layer is a scale that is 1/10 or less of the unevenness scale (the height of the unevenness and the interval between the unevennesses) in the surface roughness of the underlying unevenness layer, and carries the fine unevenness that exists along the uneven shape, Smooth the uneven surface by applying smoothing, or adjust the uneven crest pitch, crest height, and crest frequency (number).
- the surface shape adjusting layer installed on the viewer side is further provided with functions such as refractive index adjustment, high hardness, and antifouling property. Also good.
- the surface shape adjusting layer By making the surface shape adjusting layer a more appropriate uneven shape, for example, the original black color can be reproduced.
- the reflection angle of light incident on the anti-glare film from a wide range is reflected, the light is reflected in all directions (diffuse reflection) according to the uneven angle of the anti-glare film surface.
- the original black color is not reproduced and appears gray (that is, only part of the diffused light reaches the observer's eyes).
- the incident light is concentrated and reflected in the vicinity of the regular reflection angle as a more appropriate uneven shape by the surface shape adjustment layer, the light from the light source is hardly diffusely reflected and becomes regular reflected light. Since the light other than the specularly reflected light does not reach the observer's eyes, the original wet black color is reproduced (hereinafter, this original black color is sometimes referred to as darkness in this specification).
- the image The darkness of the display device is the black reproducibility when the image display device displays black in a bright room environment and can be evaluated by visual observation.
- a mode in which incident light is concentrated and reflected in the vicinity of the regular reflection angle includes a gradual concavo-convex shape in which the average interval of the concavo-convex surface is relatively large. More specifically, for example, when the average interval between the concave and convex portions of the outermost layer of the antiglare layer is Sm, the average inclination angle of the concave and convex portions is ⁇ a, and the ten-point average roughness of the concave and convex portions is Rz (Definition of Sm, ⁇ a, Rz conforms to JIS B0601 1994)
- Sm is 50 ⁇ m or more and 200 ⁇ m or less
- 0 & is 0.3 degree or more and 1. 0 degree or less
- Rz is 0.3 111 or more and 1. O z m or less is preferable.
- the surface shape adjusting layer formed for such a purpose is composed of (1) a binder resin and (2) a composition containing organic fine particles and Z or inorganic fine particles and a binder resin.
- the coating force for forming the surface shape adjusting layer comprising (1) or (2) can be applied on the underlying concavo-convex layer, and a curing reaction can be caused as required, thereby forming force S.
- the shape of the inorganic fine particles that can be contained in the surface shape adjusting layer is not particularly limited, and may be, for example, spherical, plate-like, fibrous, amorphous, hollow, or the like.
- the kind of the inorganic fine particles is not particularly limited, for example, Examples thereof include silica, alkali metal oxides, alkaline earth oxides, titanium oxides, zinc oxides, aluminum oxides, boron oxides, phosphorus oxides, and dinoleconium oxides.
- the organic fine particles that can be contained in the surface shape adjusting layer have hard crosslinked fine particles that have an appropriate cross-linked structure inside the particles and are less likely to swell by active energy ray-curable resins, monomers, solvents, and the like.
- styrene resin, styrene-acrylic copolymer resin, styrene-acrylic copolymer resin, styrene-acrylic copolymer resin, styrene-acrylic copolymer resin, silicone resin, urethane resin, melamine resin, styrene monoisoprene resin, benzoguanamine resin, etc. Can be used.
- the organic fine particles or inorganic fine particles may have a core / shell structure.
- the shell portion may have a polymerizable functional group introduced on the surface.
- the shell part has a structure in which a monomer, oligomer, or polymer having a polymerizable functional group directly or having a polymerizable functional group is grafted and bonded to the core by a chemical reaction; polymerizable on the surface of the particle part (core) Examples thereof include a structure in which a monomer, oligomer, or polymer having a functional group is combined in a film form by a chemical reaction.
- the particle portion (core) of the fine particles having the core / shell structure may be organic or inorganic component, or the shell portion may be either organic or inorganic component.
- Examples of fine particles having a core / shell structure include those composed entirely of organic components (such as polymer latex), those composed entirely of inorganic components, and those composed entirely of organic / inorganic composite components.
- one of the particle part (core) and the part having a polymerizable functional group attached to the surface (graft part or shell part) is an organic material, and the other is an inorganic material. Also included are fine particles and core / shell fine particles.
- a coating liquid using a resin binder having a polymerizable functional group is prepared, and the coating liquid is used as the base. It is preferable to apply and cure on the surface of the uneven layer.
- the polymerizable functional group on the fine particle surface and the polymerizable functional group of the binder component react with one component of the binder when the coating is cured to form a covalent bond between the binder component and the core Z shell fine particles.
- the surface irregularity of the underlying irregularity layer is highly effective in improving the strength and adhesion of the coating film. This is preferable because the following effect on the shape is large.
- a polyfunctional binder component having two or more polymerizable functional groups in one molecule is preferable to use as the resin binder because a cross-linking bond can be formed.
- the binding force can be greatly improved at the contact point between the fine particles, and the surface of the underlying uneven layer can be improved. This is very preferable because it can further improve the followability to the uneven shape.
- the fine particles used for forming the surface shape adjusting layer it is generally preferable to use particles whose primary particle diameter is in the range of 1 nm to 500 nm. If the primary particle diameter is less than lnm, it is difficult to impart sufficient hardness and strength to the coating film. On the other hand, if the primary particle diameter exceeds 500 nm, the transparency of the coating film is impaired and may not be applied depending on the application. It may be possible.
- the particle diameters of the fine particles may be uniform or have a good distribution. In addition, two or more kinds of fine particles having different particle diameters can be mixed and used as long as the strength of the coating film is not lowered.
- the primary particle diameter of the fine particles may be mechanically measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. It is also possible to visually measure secondary electron emission image photographs obtained with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the average particle diameter of the conductive metal oxide fine particles can be measured by a dynamic light scattering method or the like.
- colloidal silica means a colloidal solution in which colloidal silica particles are dispersed in water or an organic solvent.
- the colloidal silica preferably has a particle size (diameter) of, for example, ultrafine particles of 1 to 70 nm.
- the particle diameter of colloidal silica in the present invention is determined by measuring the specific surface area based on the average particle diameter according to the BET method (BET (Brunauer, Emmett, Teller) Method) and converting the average particle diameter to be true spheres. To calculate).
- the colloidal silica is a known one, and commercially available ones include, for example, “methanol silica sol”, “MA—ST—M”, “IPA—ST”, “EG—ST”, “EG” — ST—ZL ”,“ NPC—ST ”,“ DMAC—ST ”,“ MEK: ”,“ XBA—ST ”,“ MIBK—ST ”(all products from Nissan Chemical Industries, Ltd.) ), "OSCAL1132", “ ⁇ SCAL1232”, “ ⁇ SCAL1332 ”,“ ⁇ SCAL1432, ”“ OSCAL1532, ”“ ⁇ SCAL1632, ”“ ⁇ SCAL1132, ”(and above, products of Catalytic Chemical Industry Co., Ltd., all trade names) it can.
- the amount added is a force that varies depending on the fine particles to be added S. In the case of colloidal silica, the amount of added calories is preferably 5Z100-80 / 100 force. If it exceeds 80/100, the anti-glare property will not change even if it is added more than that, so there is no point in adding it, and if it exceeds this, poor adhesion to the lower layer will occur. It is good to be.
- the binder resin used for the surface shape adjusting layer is not particularly limited as long as it is a light-transmitting resin that transmits light when formed into a coating film.
- the ionizing radiation curable resin composition and / or the thermosetting resin composition as described above can be used. More preferably, it is an ionizing radiation curable resin composition.
- the binder resin used in the surface shape adjusting layer the same resin as described in the above “binder” can be used.
- a solvent-drying resin in combination coating defects on the coated surface can be effectively prevented, and a superior darkness can be obtained.
- a compound having a high refractive index and containing one or more curing reactive functional groups which contains a fluorine atom, a sulfur atom or a fluorene skeleton, may be used together with a compound having three or more curing reactive functional groups, or alone.
- the surface shape adjusting layer may optionally contain other components as described in the antiglare layer.
- the antiglare layer (including the above-described surface shape adjusting layer) composed of the above components is usually used for forming the antiglare layer by dissolving each of the above components in a solvent and performing a dispersion treatment according to a general adjustment method.
- a coating solution is prepared, and the coating solution is applied onto the transparent base film or one or more functional layers on the transparent base film, dried, and cured as necessary. It can be formed more. Moreover, you may form an uneven
- the method for forming the antiglare layer is not particularly limited thereto.
- antiglare layer-forming coating liquid which preferably uses a solvent for dissolving and dispersing solid components.
- a solvent for dissolving and dispersing solid components.
- alcohols such as methanol, ethanol and isopropinol alcohol
- ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
- esters such as methyl acetate, ethyl acetate and butyl acetate
- Hydrogen Aromatic hydrocarbons such as toluene and xylene.
- ketones and esters are used.
- the amount of the solvent is such that each component can be uniformly dissolved and dispersed, and the light-transmitting fine particles do not aggregate even after being prepared, and do not become too dilute during coating. Adjust accordingly. It is preferable to prepare a high-concentration coating solution by reducing the amount of solvent added within the range where this condition is satisfied. By doing so, it can be stored without taking up any capacity, and can be used after diluting to an appropriate concentration during the coating process.
- the solvent is preferably 50 to 99.5 parts by weight, more preferably 3 to 3 parts by weight with respect to the total solids content of 0.5 to 50 parts by weight.
- an antiglare layer forming coating solution that is particularly excellent in dispersion stability and suitable for long-term storage can be obtained.
- Each of the above essential components and each desired component can be mixed in any order to prepare a coating solution for forming an antiglare layer.
- An antiglare layer-forming coating solution may be obtained by appropriately dispersing the obtained mixture with a paint brush or a bead mill.
- the coating solution for forming an antiglare layer is applied on a transparent substrate film or one or more other functional layers, dried, and then cured by irradiation with ionizing radiation and / or heating as necessary. .
- coating methods include spin coating, dipping, spraying, slide coating, bar coating, Miyaba coating, roll coater, gravure coating, meniscus coating, flexographic printing, and screen printing. And various methods such as a pea coater method can be used.
- a normal curing method for the ionizing radiation curable resin composition that is, the ability to be cured by irradiation with an electron beam or ultraviolet light. it can.
- electron beam curing it is emitted from various electron beam accelerators such as faucet fulton type, bande graph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc. 50
- An electron beam having energy of ⁇ 1000 KeV, preferably 100 to 300 KeV is used.
- ultraviolet curing it is preferable to use ultraviolet rays having a wavelength range of 190 to 380 nm. Curing with ultraviolet rays can be carried out by using, for example, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp, black light fluorescent lamp or the like.
- the crosslinking reaction or the polymerization reaction has an oxygen concentration of 10% by volume or less. It is preferable to carry out in an atmosphere. By forming it in an atmosphere having an oxygen concentration of 10% by volume or less, it is possible to form an antiglare layer having a hard coat property (scratch resistance) excellent in chemical strength and physical strength.
- it is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable resin composition in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably an oxygen concentration of 1% by volume or less, particularly preferably an oxygen concentration.
- the resin When the resin is cured in this way, the fine particles in the binder are fixed, and the antiglare layer is fixed. A desired uneven shape is formed on the outermost surface.
- the coating solution for forming the antiglare layer is applied on the transparent substrate film or one or more other functional layers to form a coating layer, before drying and / or curing.
- the surface of the film layer may be subjected to a forming process for imparting a concavo-convex shape to form the concavo-convex shape.
- Such a method can be suitably performed by a forming process using a mold having an uneven shape opposite to the uneven shape of the antiglare layer.
- Embossed plates, embossed rolls, and the like can be cited as molds having a reverse concavo-convex shape (hereinafter sometimes simply referred to as concavo-convex molds).
- the coating liquid for forming the antiglare layer is supplied to the transparent substrate film, or one or a plurality of other functional layers and the uneven surface, and the coating liquid for forming the antiglare layer is formed into the uneven type. It is also possible to form a concavo-convex shape in a state where fine particles are contained by drying, curing, and the like by interposing between the substrate and the light transmissive substrate. In the present invention, a flat embossed plate can be used instead of the embossed roller.
- the concavo-convex surface formed on the embossing roller or the flat embossing plate can be formed by various known methods such as a sand blast method or a bead shot method.
- the anti-glare layer formed using an embossing plate (embossing roller) by sandblasting has a shape in which a large number of concave shapes are distributed on the upper side.
- the antiglare layer formed using an embossed plate (embossing roller) by the bead shot method has a shape in which many convex shapes are distributed on the upper side.
- the antiglare layer having a shape in which the convex portions are distributed on the upper side has a large number of concave portions on the upper side. It is said that there are few reflections of indoor lighting devices, etc., compared to those having a shape.
- a mold material for forming the concavo-convex mold surface plastic, metal, wood or the like can be used, and a composite of these may be used. From the viewpoint of strength and wear resistance due to repeated use, as a mold material for forming the above-mentioned concavo-convex mold surface, from the viewpoint of economy and the like that metal chromium is preferred, chromium is applied to the surface of an iron embossing plate (embossing roller). The one with a crisp is preferred.
- the particles (beads) to be sprayed when forming the concavo-convex mold by the sand blast method or the bead shot method include metal particles, silica, alumina, or inorganic particles such as glass.
- the particle diameter (diameter) of these particles is preferably about ⁇ ⁇ m to 300 ⁇ m.
- a method of spraying these particles together with a high-speed gas can be mentioned.
- an appropriate liquid such as water may be used in combination.
- the concavo-convex mold formed with the concavo-convex shape is preferably used after being subjected to chrome plating or the like for the purpose of improving durability during use, and It is preferable for preventing corrosion.
- the antiglare layer can be formed as described above, even when the antiglare layer is a multilayer, it can be formed in the same manner as described above.
- the coating liquid for forming the antiglare layer first, the base uneven layer is formed in the same manner as in the case of a single layer using the base uneven layer forming coating liquid, and then the surface shape adjusting layer forming coating liquid. It can be formed by forming a surface shape adjusting layer on the underlying concavo-convex layer using the same method as in the case of a single layer.
- the average film thickness of the antiglare layer formed as described above is preferably:! To 25 ⁇ , more preferably 2 to 20/1111, and particularly preferably 3 to 15. ⁇ ⁇ .
- the reinforcement strength pencil hardness
- the force depends on the degree of cure shrinkage of the binder. This is not preferable in terms of handling and handling.
- said average film thickness has shown the total thickness from the coating surface of a base material to the outermost surface with an uneven
- the thickness of the antiglare layer can be measured by cross-sectional observation with a laser microscope, SEM, or TEM.
- a laser microscope for example, as a method of measuring the film thickness with a laser microscope, a confocal laser microscope (LeicaTCS-NT: manufactured by Leica Co., Ltd .: magnification: 200 to 1000 times) is used for transmission observation of the cross section of the antiglare layer.
- a wet objective lens is used for the confocal laser microscope, and the air layer between the objective lens and the antiglare layer cross section is lost.
- the average film thickness can be obtained by measuring 10 points on 5 screens and calculating the average value. Even in cross-sectional observation of SEM and TEM, as described above, 5 The average value can be obtained by observing the screen.
- the thickness of the surface shape adjusting layer (when cured) is preferably 0.6 ⁇ m or more and 20 ⁇ m or less, more preferably the lower limit is 3 / im or more and the upper limit is 12 ⁇ or less.
- the thickness of the surface shape adjustment layer is the thickness of the “antiglare layer (underlying uneven layer + surface adjustment layer)” obtained by laminating the surface shape adjustment layer by cross-sectional observation using a laser microscope, SEM, or TEM as described above. This is the value calculated by measuring the thickness A of the “underlying uneven layer” and subtracting the value of A from this B.
- the film thickness is less than 0.6 zm, the antiglare property is good. The blackness may not be improved. If the film thickness exceeds 20 zm, the darkness is very good. If the anti-glare property is not improved, it may cause problems.
- the antiglare layer of the antistatic antiglare film according to the present invention can achieve a surface resistivity of 1.0 to 10 13 ⁇ / mouth or less, which is necessary for preventing dust adhesion.
- 1. 0 ⁇ 10 13 ⁇ inlet to 1. oxio 12 ⁇ / port is charged, but static charge does not accumulate, so it can prevent dust adhesion on the film.
- static charge is charged, but decays quickly 1 ⁇ 0 ⁇ 10 12 ⁇ / port to 1 ⁇ 0 ⁇ 10 1Q Q / port, more preferably non-charged range 1.0 ⁇ 10 9 ⁇ / port to 1.0 ⁇ 10 8 ⁇ / Mouth.
- the antiglare layer according to the present invention has a transparency value as an antiglare layer, a haze value according to JIS 7105: 1981 "Testing method for optical properties of plastics" and is 10% or more and 70% or less. Ability to meet S is preferable.
- the haze value as the antiglare layer is more preferably 20% or more and 60% or less, and further preferably 30% or more and 50% or less. If it is less than 10%, sufficient antiglare property and internal scattering cannot be imparted, and if it exceeds 70%, the entire film is whitened and the display image is blurred.
- the antiglare layer according to the present invention has a haze value difference of 20% or less according to JIS K7105: 1981 before and after being left in a high-temperature and high-humidity tank at 80 ° C and 90% humidity for 500 hours, Furthermore, 10% or less, especially 5% or less, especially 3 to 1% or less, because transparency is maintained even after long-term use, especially long-term use at high temperatures and high humidity. preferable.
- the strength of the antiglare layer according to the present invention is preferably 2H or higher, more preferably 3H or higher, most preferably 3H or higher in the pencil hardness test according to JIS K5400. I like it. Further, in the taper test according to JISK5400, the smaller the amount of wear of the test piece before and after the test, the better.
- the antistatic antiglare film according to the present invention may be one in which a low refractive index layer 4 having a refractive index lower than that of the antiglare layer 3 is laminated on the antiglare layer 3 as shown in FIG. .
- the refractive index of the low refractive index layer used in the present invention is preferably 1.30 to 1.50, more preferably 1.30 to 1.45.
- the refractive index is less than 30, the strength of the low refractive index layer will be insufficient, and as an antiglare film used on the outermost surface, Preferred les.
- the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance. (m / 4) ⁇ X O. 7 ⁇ n d ⁇ (m / 4) ⁇ X I. 3 Formula (I)
- n is the refractive index of the low refractive index layer
- d is the low refractive index
- E is the wavelength, which is a value in the range of 380 to 680 nm. Satisfying the above formula (I) means that m (a positive odd number, usually 1) satisfying the formula (I) exists in the above wavelength range.
- the material for forming the low refractive index layer in the present invention is not particularly limited.
- the low refractive index layer includes, for example, 1) a resin containing low refractive index fine particles such as silica or magnesium fluoride, 2) a fluorine-based resin which is a low refractive index resin, and 3) a low refractive index such as silica or magnesium fluoride. Fluorine-based resin containing refractive index fine particles, 4) A thin film of silica or magnesium fluoride, etc.
- the fluororesin is a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof.
- the polymerizable compound is not particularly limited.
- the polymerizable compound has a curing reactive group such as a functional group that is cured by ionizing radiation (ionizing radiation curable group) and a polar group that is cured by heat (thermosetting polar group). Is preferred. Further, it may be a compound having these reactive groups at the same time.
- fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetra Fluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.).
- fluoroolefins eg, fluoroethylene, vinylidene fluoride, tetra Fluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.
- thermosetting polar group containing a fluorine atom examples include 4 fluoroethylene perfluoroalkyl vinyl ether copolymer; fluoroethylene hydrocarbon-based vinyl ether copolymer; epoxy, polyurethane, cellulose Examples thereof include fluorine-modified products of resins such as phenol and polyimide.
- thermosetting polar group examples include hydrogen bond-forming groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. These are excellent in affinity with inorganic ultrafine particles such as silica as well as adhesion to the coating film.
- Polymerizable compounds having both ionizing radiation curable groups and thermosetting polar groups include acrylic or methacrylic acid moieties and fully fluorinated alkyls, alkeninoles, aryl esters, Alternatively, partially fluorinated vinyl ethers, fully or partially fluorinated butyl esters, fully or partially fluorinated vinyl ketones and the like can be exemplified.
- Examples of the polymer of the polymerizable compound containing a fluorine atom include, for example, at least one fluorine-containing (meth) ataretoy compound of the polymerizable compound having the ionizing radiation curable group.
- a silicone-containing vinylidene fluoride copolymer in which a silicone component is contained in these copolymers can also be used as a polymer of the polymerizable compound.
- Silicone components in this case include (poly) dimethylenesiloxane, (poly) jetinosiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylolsiloxane, azo Group-containing (poly) dimethylsiloxane, dimethylsilicone, phenylmethylsilicone, alkyl'aralkyl-modified silicone, fluorosilicone, polyether-modified silicone, fatty acid ester-modified silicone, methylhydrogen silicone, silanol group-containing silicone, alkoxy group -Containing silicone, phenol group-containing silicone, methacryl-modified silicone, acrylic-modified silicone, amino-modified
- At least a fluorine-containing compound having at least one isocyanato group in the molecule and an functional group that reacts with an isocyanato group such as an amino group, a hydroxyl group or a carboxyl group in the molecule Compound obtained by reacting with one compound; fluorine-containing polyether polyol, fluorine-containing alkyl polyol, fluorine-containing polyester polyol, fluorine-containing ⁇ -force Prolataton-modified polyol, etc., and isocyanato group
- a compound obtained by reacting with a compound having it can also be used as the fluororesin.
- fluorine resins that are crosslinked by heat or ionizing radiation having a dynamic friction coefficient of 0.05 to 0.30 and a contact angle with water of 90 to 120 ° are particularly preferable.
- a perfluoroalkyl group-containing silane compound for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane
- the coating amount of the inorganic fine particles is lmgz m to 100 mgZm force, preferably 5 mgZm to 80 mg / m 2 , more preferably lOmgZm 2 to 60 mg / m 2 . If it is less than lmg / m 2, the effect of improving the scratch resistance is reduced, and if it is more than 100 mg / m 2 , fine irregularities are formed on the surface of the low refractive index layer and the appearance and reflectivity deteriorate. It is not preferable.
- the inorganic fine particles contained in the low refractive index layer are desirably low refractive index fine particles.
- Examples thereof include fine particles of magnesium fluoride and silica.
- silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
- the average particle diameter of the silica fine particles is preferably 10% to 100% of the thickness of the low refractive index layer, preferably 20% to 90%, more preferably 30% to 80%. That is, when the thickness of the low refractive index layer is lOOnm, the particle diameter of the silica fine particles is preferably 10 nm or more and lOOnm or less, more preferably 20 nm or more and 90 nm or less, and further preferably 30 nm or more and 80 nm or less.
- the silica fine particles may be either crystalline or amorphous, and may be monodispersed particles, or may be aggregated particles as long as a predetermined particle size is satisfied.
- the shape is most preferably a spherical diameter, but it may be indefinite.
- the average particle diameter of the inorganic fine particles is measured by a Coulter counter.
- fine particles having voids In the low refractive index layer, it is particularly preferable to use “fine particles having voids” as the low refractive index fine particles.
- the “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the surface shape adjusting layer.
- fine particles having voids means a structure in which fine particles are filled with gas and / or a porous structure containing gas, and the gas in the fine particles is compared with the original refractive index of the fine particles. This means fine particles whose refractive index decreases in inverse proportion to the occupation ratio.
- the present invention also includes fine particles capable of forming a nanoporous structure at least inside and / or on the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating. It is.
- the refractive index of the low refractive index layer using these fine particles can be adjusted from 1.30 to 1.45.
- Examples of the inorganic fine particles having voids include silica fine particles prepared by the method described in JP-A-2001-233611. It may be silica fine particles obtained by the production methods described in JP-A-7-133105, JP-A-2002-79616, Koyuki, JP-A-2006-106714, etc.
- Silica fine particles with voids are easy to manufacture and have high hardness themselves, so when mixed with a binder to form a low refractive index layer, the layer strength is improved and the refractive index is 1.20 to: 1 It is possible to prepare in the range of about 45.
- the organic fine particles having voids hollow polymer fine particles prepared by using the technique disclosed in Japanese Patent Application Laid-Open No. 2002-80503 are preferably exemplified.
- Fine particles capable of forming a nanoporous structure inside the coating and at least a part of Z or the surface are prepared for the purpose of enlarging the specific surface area with the silica fine particles, and are used for filling. Dispersion and aggregation of hollow particulates intended to be incorporated into column and surface release materials that adsorb various chemical substances, porous fine particles used for catalyst fixation, or heat insulating materials and low dielectric materials. A collection can be mentioned. Specifically, as a commercially available product, the product name Nipsil or Nipgel manufactured by Nippon Silica Kogyo Co., Ltd., aggregates of porous silica fine particles, and silica fine particles manufactured by Nissan Chemical Industries, Ltd. are chained. From the colloidal silica UP series (trade name) having a connected structure, it is possible to use those preferred in the present invention and within the particle diameter range.
- the average particle diameter of the “fine particles having voids” is preferably 5 nm or more and 300 nm or less, more preferably the lower limit is 8 nm or more, the upper limit is lOOnm or less, and still more preferably the lower limit is 10 nm or more. The upper limit is 80nm or less.
- the average particle diameter in the present invention is a value measured by a dynamic light scattering method.
- the “fine particles having voids” are usually about 0.:! To about 500 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the matrix resin in the low refractive index layer. The amount is preferably about 200 parts by mass.
- a known silicone type or fluorine type antifouling agent, Suitable slip agent It can also be added appropriately.
- these additives it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. And is particularly preferably in the range of 0.:! To 5% by mass.
- a heating means it is preferable to add a thermal polymerization initiator that generates radicals and starts polymerization of the polymerizable compound by heating, for example.
- the low refractive index layer in the present invention is prepared by preparing a coating solution for a low refractive index layer in the same manner as the antiglare layer, and applying and drying the low refractive index layer coating solution on the antiglare layer. If necessary, it can be obtained by curing with irradiation of ionizing radiation and Z or heating.
- the viscosity of the coating solution for the low refractive index layer can provide a preferable coating property of 0.5 to 5 cps (25 ° C), preferably 0.7 to 3 cps (25 A force in the range of ° C) S is preferable.
- An antireflection film excellent in visible light can be realized, a uniform thin film with no coating unevenness can be formed, and a low refractive index layer particularly excellent in adhesion to a substrate can be formed.
- the film thickness of the low refractive index layer is preferably 15 to 200 nm, more preferably 30 to 150 nm.
- the antistatic antiglare film according to the present invention uses a triacetyl cell mouth one film as a transparent substrate film, and is disposed on the outermost surface of the display by providing an adhesive layer on one side, or a protective film for polarizing plate as described later.
- an anti-glare anti-glare film is formed by laminating an anti-glare layer and a low refractive index layer on a triacetyl cellulose film, and then a hatching treatment is performed. It is preferable to implement.
- the hatching treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After dipping in an alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkali component by dipping in a dilute acid so that the alkali component does not remain in the film.
- the surface of the triacetyl cellulose film on the side opposite to the side having the antiglare layer is hydrophilized.
- the hydrophilized surface is mainly composed of polybulu alcohol. This is particularly effective for improving the adhesion to the deflection film.
- the hydrophilic surface makes it difficult for dust in the air to adhere to it, when adhering to the deflecting film, it prevents point defects caused by dust entering the gap between the deflecting film and the anti-glare film.
- the hatching treatment that is effective for this is carried out so that the contact angle force of water on the surface of the triacetyl cellulose film on the side opposite to the side having the outermost layer such as an antiglare layer or a low refractive index layer is S40 ° or less. It is preferable. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.
- the antistatic antiglare film according to the present invention is attached to the front surface of a display such as a liquid crystal display, a cathode ray tube display device (CRT), or a plasma display panel by providing an adhesive layer on one side, etc. To prevent reflection of external light and make the image easier to see.
- a display such as a liquid crystal display, a cathode ray tube display device (CRT), or a plasma display panel
- a cellulose silicate film without birefringence for example, a triacetyl cellulose film is used as a transparent base film of the antistatic antiglare film according to the present invention
- two sheets sandwiching the polarizing layer of the polarizing plate Can be used as at least one of these protective films.
- the antistatic antiglare film according to the present invention is used for the protective film of the polarizing layer of the polarizing plate, the antistatic and antiglare functions can be imparted to the protective film of the polarizing plate. Low price can be realized.
- the antistatic antiglare film according to the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and what has substantially the same configuration as the technical idea described in the scope of the claims of the present invention and exhibits the same function and effect is remarkable. Are also included in the technical scope of the present invention.
- compositions for the following composition were mixed to prepare a composition for forming an antiglare layer.
- Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals): 6.0 :
- Polymer type cationic antistatic agent (quaternary ammonium salt-containing acrylic resin, trade name PQ-10, manufactured by Soken Chemical Co., Ltd.): 5 parts
- Fluorine-based additive (trade name FZ2191, manufactured by Nippon Tunica Co., Ltd.): 0.04 parts
- the antiglare layer-forming composition prepared in (1) was applied to a triacetylcellulose (TAC) film with a thickness of 80 ⁇ m by the gravure reverse coating method, dried, and then exposed to an ultraviolet irradiation device (fusion UV). System Japan Co., Ltd., light source H bulb) was used to cure by irradiation to an irradiation dose of lOOmJ / cm 2 , and an antistatic antiglare film with an antiglare layer with a thickness of 6 ⁇ m was produced.
- TAC triacetylcellulose
- the antiglare film was evaluated for surface resistivity and coating transparency as follows. Further, the obtained antiglare film was left in a high-temperature and high-humidity tank at 80 ° C. and 90% humidity for 500 hours to evaluate the surface resistivity and the transparency of the coating film after the high-temperature and high-humidity test. These The results are shown in Table 1 below.
- ⁇ / port Surface resistivity ( ⁇ / port) is measured with a high resistivity meter (Hiresta UP, manufactured by Mitsubishi Chemical Corporation), and the outermost surface of the antiglare film is measured at an applied voltage of 100 V for 10 seconds. Went.
- the haze value of the outermost surface of the antiglare film was measured according to JIS K 7105: 1981 “Testing method for optical properties of plastics”.
- compositions for the following composition were mixed to prepare a composition for forming an antiglare layer.
- Binder with polymer cationic antistatic agent (trade name: ASC_EX9000, manufactured by Kyoeisha Chemical Industry Co., Ltd., containing quaternary ammonium salt-containing polymer, ionizing radiation curable resin, and photopolymerization initiator): 277 parts
- Fluorine-based additive (trade name FZ2191, made by Nippon Tunica Co., Ltd.): 0.04 parts
- An antistatic antiglare film was obtained in the same manner as in Example 1 except that the composition obtained in (1) above was used as the antiglare layer forming composition.
- the surface resistance value and the minimum reflectance before and after the high temperature and high humidity test were measured in the same manner as in Example 1. The results are shown in Table 1 below.
- compositions for the following composition were mixed to prepare a composition for forming an antiglare layer.
- 'Ionizing radiation curable resin penentaerythritol triatrate: 100 parts • Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals): 6.0 :
- Fluorine-based additive (trade name FZ2191, manufactured by Nippon Tunica Co., Ltd.): 0.04 part
- An antistatic antiglare film was obtained in the same manner as in Example 1 except that the composition obtained in (1) above was used as the antiglare layer forming composition.
- the surface resistance value and the minimum reflectance before and after the high temperature and high humidity test were measured in the same manner as in Example 1. The results are shown in Table 1 below.
- An antiglare layer containing a low molecular weight antistatic agent was formed.
- compositions for the following composition were mixed to prepare a composition for forming an antiglare layer.
- Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals): 6.0 :
- 'Low-molecular-type anionic antistatic agent (trade name: Aqualon KH-10, polyoxyethylene alkyl ether sulfate introduction type, Daiichi Kogyo Seiyaku Co., Ltd.): 5.0 parts
- Fluorine-based additive (trade name FZ2191, manufactured by Nippon Tunica Co., Ltd.): 0.04 parts
- An antistatic antiglare film was obtained in the same manner as in Example 1 except that the composition obtained in (1) above was used as the antiglare layer forming composition.
- the surface resistance value and the minimum reflectance before and after the high temperature and high humidity test were measured. The results are shown in Table 1 below.
- Examples 1 and 2 which are anti-glare and anti-glare films using a polymer anti-static agent, have a surface resistivity of 1.0 to prevent dust adhesion even after high temperature and high humidity tests. It became clear that the transparency of 9 ⁇ / mouth or less can be realized, and the change in haze value is very low, within 1%.
- the antiglare film of Comparative Example 1 that did not use an antistatic agent maintained its transparency, but its surface resistivity exceeded 1.0 ⁇ 10 14 ⁇ / mouth, and was antistatic. Sex is the power that we have.
- the antiglare film of Comparative Example 2 using a low molecular weight antistatic agent the surface resistivity and haze value before and after the high temperature and high humidity test changed greatly, and the transparency deteriorated especially after the high temperature and high humidity test. It was observed.
- An antistatic antiglare film comprising a multi-layer antiglare layer having a base irregularity layer and a surface shape adjusting layer was produced.
- composition 1 for the uneven surface layer.
- Pentaerythritol triatalylate (PETA) (refractive index 1 ⁇ 51): 2. 18 parts by weight
- DPHA Dipentaerythritol hexaatalylate
- Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals):
- Photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba 'Specialty' Chemicals): 0.03 parts
- Translucent fine particles monodisperse acrylic beads, average particle size 9.5 zm, refractive index 1.535: 0.74 parts
- Translucent fine particles amorphous silica ink, average particle size 1.5 zm, amorphous silica dispersed in PETA, solid content 60./., Silica component is 15% of total solids, solvent is toluene: 1 46 parts
- compositions having the following composition were sufficiently mixed to obtain a composition having a solid content of 45%.
- the composition was filtered through a polypropylene filter having a pore size of 10 / m to prepare a composition 1 for a surface shape adjusting layer.
- Polyfunctional urethane acrylate (trade name UV1700B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., refractive index 1.51): 31.1 parts
- Isocyanuric acid-modified triatalylate (trade name: ALONIX M315 (manufactured by Toagosei Co., Ltd.): 10.4 parts
- Photocuring initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals): 0.49 parts
- Photocuring initiator (trade name: Irgacure 907, manufactured by Ciba 'Specialty' Chemicals): 0.41 parts • Antifouling agent (UT-3971, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): 2. 07 parts
- Polymeric cationic antistatic agent polymer containing quaternary ammonium salt, polyoxyethylene group of ethylene oxide adduct, trade name Nitsuka Taibo, Nippon Kasei Co., Ltd.: 2. 08 parts
- a 100 ⁇ m thick polyethylene terephthalate film (A4300, manufactured by Toyobo Co., Ltd.) is used as a transparent substrate film, and the composition 1 for the underlying uneven layer is coated on the film. Apply using # 10, heat dry for 30 seconds in an oven at 70 ° C, evaporate the solvent, and then irradiate with UV light to a dose of 30 mJ to cure the coating film.
- a base uneven layer having a thickness of about 7.3 gZm 2 was formed.
- the surface shape adjusting layer composition 1 is applied onto the base uneven layer using a coating rod (Meyer's bar) # 18, and dried by heating in a 70 ° C oven for 1 minute. After evaporation, the film is cured by irradiating with ultraviolet rays to an irradiation dose of 80 mJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and a surface shape adjusting layer is laminated to form an antistatic antiglare film. Was made. The total thickness of the antiglare layer was about 16 ⁇ .
- An antistatic antiglare film comprising a multi-layer antiglare layer having a base irregularity layer and a surface shape adjusting layer was produced.
- Amorphous silica resin (PETA) dispersion (average particle size 2.5 zm, solid content 60%, silica component 15 /., Solvent is toluene) and UV curable resin pentaerythritol tri
- PETA attalate
- monodisperse acrylic beads (particle size 7.0 zm, refractive index)
- the ratio of 1.535) is 20 parts by mass
- the monodisperse styrene beads are 2.5 parts by mass (particle size 3.5 zm, refractive index 1.60)
- the amorphous silica is 2.0 parts by mass. Adjusted.
- compositions having the following composition were sufficiently mixed to obtain a composition having a solid content of 45%.
- the composition was filtered through a polypropylene filter having a pore size of 10 zm to prepare a composition 2 for a surface shape adjusting layer.
- Polyfunctional urethane acrylate (trade name UV1700B (Nippon Synthetic Chemical Industry Co., Ltd., refractive index 1.51): 23. 20 parts
- Isocyanuric acid-modified triatalylate Alonics M315 (manufactured by Toagosei Co., Ltd.): 7 ⁇ 73 parts • Photo-curing initiator (trade name: Irgacure 184, Ciba Specialty Chemicals Inc.): 1. 86 ⁇
- Photo-curing initiator (trade name: Irgacure 907, manufactured by Ciba 'Specialty' Chemikanorezu): 0.31)
- Antifouling agent (UT-3971, solid content 30% MIBK solution, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): 1.5 5 parts
- Polymer type cationic antistatic agent (Acrylic resin containing quaternary ammonium salt, trade name PQ-10, manufactured by Soken Chemical Co., Ltd.): 2. 07 parts
- the composition 2 for the uneven surface layer is applied onto the film using a coating rod (Meyer's bar) # 8 and heated in an oven at 70 ° C for 1 minute. After drying and evaporating the solvent, the coating was cured by irradiating with ultraviolet rays to an irradiation dose of 30 mJ to form a base uneven layer with a coating thickness of 6 g / m 2 .
- the surface shape adjusting layer composition 2 was applied onto the underlying uneven layer using a coating rod (Meyer's bar) # 12 and dried by heating in an oven at 70 ° C for 1 minute. After evaporation, the film is cured by irradiating with ultraviolet rays so that the irradiation dose is lOOmJ under a nitrogen purge (oxygen concentration of 200 ppm or less), and a surface shape adjusting layer is laminated to prevent antistatic glare. A film was obtained. The total thickness of the antiglare layer was about 11 zm.
- An antistatic antiglare film comprising a multi-layer antiglare layer having a base uneven layer and a surface shape adjusting layer and a low refractive index layer was produced.
- compositions having the following composition were sufficiently mixed to obtain a composition having a solid content of 4%.
- This composition was filtered through a polypropylene filter having a pore diameter of 10 ⁇ m to prepare a composition for a low refractive index layer. This has a refractive index of 1.40.
- Hollow silica slurry (isopropanol, methylisobutyl ketone dispersion, solid content 20%, particle size 50 nm): 9.57 parts by mass
- 'Ionizing radiation curable resin penentaerythritol tritalylate: 0.981 parts by mass' Fluoropolymer (trade name: AR110; solid content 15% methylisobutyl ketone solution; manufactured by Daikin Industries): 6.53 parts by mass
- Photocuring initiator (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals): 0.069 mass ⁇ B
- the above composition for the low refractive index layer is coated with a coating rod (Mayer's bar) # 2, and heated in an oven at 70 ° C for 1 minute. After drying and evaporating the solvent, the coating film is cured by irradiating ultraviolet rays to an irradiation dose of SlOOmJ under a nitrogen purge (oxygen concentration of 200 ppm or less), resulting in a low refractive index of about lOOnm. The layers were laminated to obtain a low refractive index antistatic antiglare film.
- the surface shape of the antistatic antiglare film provided with the multilayer antiglare layer having the surface shape adjusting layer of Examples 3 to 5 was measured. According to JIS B0601 1994, Sm, ⁇ a, and Rz were measured using a surface roughness measuring instrument (model number: SE_3400 / manufactured by Kosaka Laboratory). The measurement conditions are as follows. The results are shown in Table 3.
- Examples 3 and 4 which are antistatic antiglare films having a multilayer antiglare layer including a surface shape adjusting layer using a polymer type antistatic agent are used to prevent dust adhesion even after a high temperature and high humidity test. It is clear that the surface resistivity required for stopping the film can be 2.0 ⁇ 10 9 ⁇ / mouth or less, and the haze value changes within 1.0%, maintaining a very low transparency. I got it. Further, the antistatic antiglare film provided with a multilayer antiglare layer including a surface shape adjusting layer using a polymer type antistatic agent was excellent in the original black reproducibility.
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Abstract
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JP2007535400A JP5145938B2 (ja) | 2005-09-16 | 2006-08-11 | 帯電防止防眩フィルム |
US12/064,140 US20090142562A1 (en) | 2005-09-16 | 2006-08-11 | Antistatic anti-glare film |
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Also Published As
Publication number | Publication date |
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KR20080047466A (ko) | 2008-05-28 |
JPWO2007032170A1 (ja) | 2009-03-19 |
CN101268389A (zh) | 2008-09-17 |
JP5145938B2 (ja) | 2013-02-20 |
TW200717019A (en) | 2007-05-01 |
TWI400475B (zh) | 2013-07-01 |
US20090142562A1 (en) | 2009-06-04 |
KR101117366B1 (ko) | 2012-03-07 |
CN101268389B (zh) | 2010-12-08 |
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