Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Definitions

• the present invention relates to an optical filter film having an adhesive layer containing a neon light-absorbing dye and excellent in heat resistance and moist heat resistance, and a plasma display panel (hereinafter referred to as PD) using the same.
• the principle of PDP is that a voltage is applied to a rare gas (neon, xenon, etc.) enclosed in a cell sandwiched between two plate-like glasses, and ultraviolet rays emitted from the rare gas in a plasma state are processed on the cell wall.
• the visible light necessary for the image is generated by hitting the illuminant, but it is caused by near infrared rays, electromagnetic waves harmful to the human body and neon gas at the same time as the visible light, and the wavelength near 595 nm lowers the color purity of red light.
• Harmful electromagnetic waves such as orange rays (hereinafter referred to as neon light) are also emitted, so that useful visible light is transmitted, but neon rays and other near-infrared rays and electromagnetic waves harmful to the human body must be shielded.
• an optical filter for this purpose.
• a neon light absorbing film in which a specific dye that absorbs neon light is added to a binder resin and applied to a transparent substrate, and near infrared and electromagnetic waves It uses an optical filter with a base material having a shielding function, an anti-glare and anti-reflection film, etc. bonded together with an adhesive.
• cyanine dyes having sufficient absorption characteristics with a small amount of addition are mainly used. (See Patent Document 4)
• a neon light absorbing dye can be contained in the adhesive layer, neon light absorbing ability can be imparted between any layers constituting the optical filter. Can be expected to improve.
• the addition of neon light-absorbing dyes typified by cyanine dyes to the pressure-sensitive adhesive differs from the addition to binder resins for coatings made of polymers such as polyester resins and acrylic resins. Or there is a problem peculiar to pressure-sensitive adhesives that the deterioration of the dye after the heat and humidity test is large and the neon light absorption function is lost. Investigation into additives is underway.
• the addition of functional dyes to the adhesive layer tends to increase the haze value, which is one of the criteria for transparency of functional films and optical filters. Pay special attention to the haze value when neon light-absorbing dyes are contained in the adhesive layer.
• Patent Document 6 describes that a pigment compound and a clay mineral are used in combination, but does not describe improving dry heat durability.
• a heat-crosslinking acrylic aliphatic resin pressure-sensitive adhesive having high versatility can be considered.
• an adhesive that gradually crosslinks with a curing agent is not a polymer with sufficient crosslink density immediately after coating and drying, so the neon light-absorbing dye is unstable, and coating and drying Neon light absorptivity before and after aging work to be performed later may change. This change in neon light absorptivity affects the transmitted color of visible light, making it impossible to achieve the target optical characteristics. Therefore, an adhesive that becomes a polymer having a sufficient crosslink density even after coating and drying is required.
• Patent Document 1 JP 2000-98131 A
• Patent Document 2 Japanese Patent No. 3753482
• Patent Document 3 Japanese Patent Laid-Open No. 10-282335
• Patent Document 4 Japanese Unexamined Patent Publication No. 2004-325532
• Patent Document 5 Japanese Unexamined Patent Publication No. 2003-82302
• Patent Document 6 W ⁇ 2006Zl37272
• the pressure-sensitive adhesive is a polymer that has a sufficient crosslink density even immediately after coating and drying.
• neon light-absorbing dyes typified by cyanine dyes are stabilized in the adhesive with additives, etc., and the excellent stability can be maintained in the heat resistance test or moist heat resistance test, with a lower haze value. It is an object of the present invention to develop a film for an optical filter having a neon light-absorbing adhesive layer that can be maintained (hereinafter also referred to as “neon light-absorbing film”), and an optical filter using the film.
• the present inventors combined a specific cyanine-based neon light-absorbing dye with a specific pressure-sensitive adhesive and clay mineral, and were excellent in a heat resistance test or a moist heat test. It has been found that the stability can be maintained and the haze value can be kept lower, and the present invention has been completed.
• the gel fraction in one hour after coating and drying is 50% or more.
• a film for an optical filter characterized in that the adhesive layer contains a neon light-absorbing dye and a swellable lamellar clay mineral,
• the neon light-absorbing dye is a cyanine dye represented by the following formula (1) (1) or the film for optical filters according to (2),
• the cyanine dye is represented by the following formula (1)
• the film for optical filters according to (3) which is a cyanine dye represented by:
• At least one layer selected from a conductive layer, an antiglare layer and an antireflection layer is laminated, and the optical filter film according to any one of (1) to (4),
• An optical filter for a plasma display panel comprising the optical filter film according to any one of (1) to (5) and a film and / or glass having a near infrared and electromagnetic wave shielding function,
• the pressure-sensitive adhesive used in the present invention is a highly versatile heat-crosslinking acrylic aliphatic resin, and has a weight average molecular weight of 1 million or more, a gel fraction of 50% or more in 1 hour after coating and drying, and a fast curing speed. Therefore, it is a polymer with sufficient crosslink density even immediately after coating and drying, and the neon light absorption capacity before and after the aging work does not change, and when this is combined with an inexpensive and easily available clay mineral
• neon light-absorbing dyes typified by cyanine dyes exhibit excellent haze values and stability in adhesives, neon light-absorbing films having the adhesive layer, and further utilizing this.
• the optical filter exhibits excellent performance and can sufficiently cope with the above problems.
• the pressure-sensitive adhesive used in the present invention comprises a thermally crosslinkable acrylic aliphatic resin and a crosslinker, and has a weight average molecular weight of 1 million or more and a gel fraction of 50% or more in 1 hour after coating and drying. It is a heat crosslinkable acrylic aliphatic resin adhesive.
• Thermally crosslinkable acrylic aliphatic resins are mainly composed of acrylic acid alkyl esters having no functional group, and acrylic acid alkyl esters having functional groups on them or other units other than acrylic acid alkyl esters. A monomer component is copolymerized.
• the copolymerization ratio of the acrylic acid alkyl ester having the functional group and other monomer components other than the acrylic acid alkyl ester is 0.:! To 100 parts by weight of the acrylic acid alkyl ester component having no functional group. 20 parts by weight, more preferably:! To 10 parts by weight.
• acrylic acid alkyl ester having no functional group examples include methyl (meth) acrylate,
• a monomer other than the acrylic acid-based alkyl ester or the acrylic acid-based alkyl ester having a functional group those functioning as a crosslinking point with a crosslinking agent described later are used, and the type of the monomer is not particularly limited.
• hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxylethyl (meth) acrylate and hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl acrylate, N-tert —Amino group-containing (meth) acrylic acid monomers such as butylaminoethyl acrylate, acrylic acid, maleic acid, etc. may be mentioned, and these may be used in combination of two or more.
• the pressure-sensitive adhesive is preferably used in a composition capable of crosslinking the acrylic resin and the like by blending a crosslinking agent.
• the cross-linking agent is appropriately used depending on the type of the above-mentioned monomer.
• aromatic diisocyanates such as cyanate or trimethylolpropane adduct of trilene diisocyanate Polyisocyanate compounds, melamine compounds such as butyl etherified styrol melamine and trimethylol melamine, diamine compounds such as hexamethylene diamine or triethyl diamine, bisphenol ⁇ -epoxychlorohydrin
• Epoxy resin compounds such as urea resin compounds, metal salts such as aluminum chloride, ferric chloride or aluminum sulfate, etc., are usually used in amounts of 0.005 to 5 per 100 parts by weight of acrylic resin. Part by weight, preferably about 0.01 to 3 parts by weight.
• the heat-crosslinking acrylic aliphatic resin pressure-sensitive adhesive is excellent in adhesive strength and cohesive strength, and has no unsaturated bond in the polymer, so it has high stability to light and oxygen. Due to the high degree of freedom in molecular weight selection, and the stability of neon light-absorbing dyes before and after the preferred aging operation, the polymer should have sufficient crosslink density even immediately after coating and drying. Therefore, it is preferable that the weight average molecular weight is 1 million or more and the gel fraction in 1 hour after coating and drying is 50% or more. The weight average molecular weight is 1.5 million or more and the gel fraction in 1 hour after coating is dried. Is more preferably 80% or more.
• the neon light-absorbing dye used in the present invention preferably has an absorption maximum at a wavelength of 580 to 600 nm and a half width of about 50 nm, for example, cyanine-based, tetraazoborphyrin-based, squarylium. , Xanthene, oxonol, and azo dyes, and the cyanine dye represented by the above formula (1), namely 1, 1-di (4 isopropoxyphenoxyl) 1, 3, 3, 3 ', 3'-tetramethyl-1,5'-dinitroindocarbocyanine' perchlorate is preferred.
• This dye is also commercially available, for example, “Ade force Arkulus' TY-102” (manufactured by Asahi Denka Kogyo Co., Ltd.) (absorption wavelength peak is 586 nm).
• the amount of the dye to be blended is suitably set so that the transmittance at the maximum value of absorption is 20 to 70%.
• smectite can be suitably used, and lipophilic synthetic smectite dispersed in an organic solvent is more preferable.
• An example is Lucentite STN (manufactured by Corp Chemical).
• the adhesive layer preferably contains the neon light-absorbing dye and the clay mineral in a weight ratio of 1: 1 to 1:20, and more preferably the weight ratio is 1: 5 to 1:10. It is. If the weight ratio of the clay mineral is less than 1: 1, the light absorption pigment of the neon is not stable. If the weight ratio is more than 1:20, the haze value becomes high and the optical properties are increased. May be problematic in practice. In the present invention, the durability of the pigment is remarkably improved by including a clay mineral in the adhesive layer. This effect is thought to be due to the intercalation between ions of the clay mineral layer and ions of the pigment molecules.
• the solvent examples include alcohols such as methanol, ethanol, isopropanol, diacetone alcohol, ethyl acetate sorb, and methyl solvate, ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone, N, N — Amides such as dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane and ethylene glycol monomethyl ether, and esters such as methyl acetate, ethyl acetate and butyl acetate , Aliphatic hydrocarbons such as chloroform, methylene chloride, dichloroethylene or trichloroethylene, aromatics such as benzene, toluene, xylene, monochlorobenzene or dichlorobenzene, or n-hexane, n-h
• the pressure-sensitive adhesive is a known coating method such as a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, an air knife coating method, a lip coating method or a die coater method.
• a coating method such as a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, an air knife coating method, a lip coating method or a die coater method.
• the adhesive layer is fixed.
• an aging process is performed thereafter.
• the conditions for aging treatment vary depending on the type of resin used and the cross-linking agent, but the adhesive is preferably stored in a thermostatic bath at 25-50 ° C for about 1 day to 1 week.
• the type and thickness of the transparent substrate used in the present invention is not particularly limited as long as it can withstand use as an optical film with high transparency and no scratches. 10 to 500 zm is a preferable range because of good workability.
• polyester hereinafter referred to as P ET
• polycarbonate-based triacetate-based, norbornene-based, acrylic-based, cellulose-based, polyolefin-based, or urethane-based polymer resin films.
• a transparent support film containing an ultraviolet absorbing material can be used.
• the surface of the film is coated with corona discharge treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, anchor coating agent, primer, etc.
• the transparent substrate is a film having one or more functions such as anti-reflection, anti-glare / anti-reflection, antistatic, antifouling, near infrared absorption, electromagnetic wave shielding or color tone adjustment
• a neon light-absorbing adhesive layer it is possible to possess these functions and the neon light-absorbing ability at the same time. Films and optical filters are obtained.
• the anti-reflective film is a film or transparent support film that has low refractive index by coating the surface of a transparent support film such as PET with a low refractive index agent together with a binder resin and other additives to suppress reflection of light from the outside. It is a film with a hard coat layer and a high refractive index layer provided between the two layers to improve visibility by controlling the reflected light from each layer to cancel, and the anti-glare / anti-reflection film is a highly reflective film. A film that contains fine particles in the rate layer and other layers to diffuse the light from the outside to improve visibility.
• the arc top series (Asahi Glass Co., Ltd.) and Kyacoat ARS series (Nippon Kayaku Co., Ltd.) , Kayacoat AG RS series (made by Nippon Kayaku), Realak series (made by Nippon Oil & Fats), etc. Can be obtained from the market.
• a mesh type in which ultrafine wires of metal such as copper are held on a transparent base material with a geometric pattern like a mesh, and an ultrathin metal film within a range having light transmittance are used.
• a thin film type held on a bright substrate or glass.
• the thin film type generally reflects and does not transmit near-infrared rays, so a separate near-infrared absorbing layer is required.
• the transparent substrate having other functionalities used in the present invention includes ultraviolet absorbing property, antistatic property and anti-static property.
• films that maintain functions such as soiling and color tone, or a plurality of such functions. These are known per se by methods such as molding from a binder resin composition containing a compound having these properties. It can be prepared according to
• the optical filter of the present invention is a transparent substrate having other functions with the neon light absorbing film of the present invention in which the present adhesive layer is provided on a transparent substrate as a minimum component. It is obtained by laminating a material and / or glass.
• the optical filter of the present invention may be attached to the front surface of the plasma display by being pasted on a glass plate or a plastic plate in advance, or directly pasted on the front surface of the PDP.
• the weight average molecular weight of the pressure-sensitive adhesive used was measured under the following conditions of the GPC (gel permeation chromatography) method.
• the gel fraction of the pressure-sensitive adhesive used was measured by the following method.
• the adhesive layer was formed by coating at a speed and a drying temperature of 110 ° C so that the thickness of the adhesive layer was 18 zm, and the adhesive layer and KAYACOAT ARS _D501 (trade name, anti-reflective film, Nippon Kayaku Co., Ltd.)
• the two films were laminated so that the opposite surface of the reduced reflection surface was contacted to obtain a neon light absorbing film having reduced reflection properties.
• the weight average molecular weight of the aliphatic acrylic pressure-sensitive adhesive PTR-104 mainly composed of butyl acrylate was 1,800,000, and the gel fraction 1 hour after coating and drying was 83%.
• the neon light-absorbing film was bonded onto a film having a metal multilayer sputtered film having an adhesive layer to obtain an optical filter for PDP.
• This filter can be applied directly to the front of the PDP module, or it can be attached to a transparent plate such as a glass plate and attached to the front of the module. .
• Neon light absorber (trade name TY- 1 0 2; manufactured by Ade force) 0.0 0 4 parts
• Viscosity ⁇ IS product (trade name SENTITE S TN; manufactured by Coop Chemical)
• a neon light-absorbing film having reduced reflectivity was obtained in the same manner as in Example 1 except that acrylic resin PTR-106 (manufactured by Nippon Kayaku) was used instead of acrylic resin PTR-104 of Example 1. .
• the weight average molecular weight of the aliphatic acrylic adhesive PTR-106 mainly composed of butyl acrylate was 1,400,000, and the gel fraction 1 hour after coating and drying was 78%.
• the above neon light absorbing film was bonded onto a metal multilayer sputtered film having an adhesive layer to obtain an optical filter for PDP.
• This filter can fully demonstrate the performance required as a PDP filter, either directly on the front of the PDP module, or attached to a transparent plate such as a glass plate in front of the module. .
• Comparative Example 1 A neon light-absorbing film having reduced reflectivity was obtained in the same manner as in Example 1 except that the acrylic resin PTR-2500T (manufactured by Nippon Kayaku) was used instead of the acrylic resin PTR-104 of Example 1. .
• the weight average molecular weight of the aliphatic talyl adhesive PTR-2500T based on butyl acrylate used at this time was 1.1 million, and the gel fraction 1 hour after coating and drying was 33%.
• a neon light-absorbing film having reduced reflectivity was obtained in the same manner as in Example 1 except that acrylic resin SK — 2094 (manufactured by Soken Chemical) was used instead of acrylic resin PTR-104 of Example 1.
• the weight average molecular weight of the aliphatic acrylic adhesive SK-2094 mainly composed of methyl methacrylate was 900,000, and the gel fraction 1 hour after coating and drying was 78%.
• UV-3150 (trade name, spectrophotometer, manufactured by Shimadzu Corporation), and luminous transmittance (Y /%) and chromaticity coordinates (x, y) are colors according to the XYZ color system of JIS Z 8701. It was calculated according to the display method.
• Haze was measured with TC—H3DPK (trade name, haze meter, manufactured by Tokyo Denshoku Technology Center).
• Table 2 shows the results before and after aging. The results of the durability test are shown in Table 3 and Table 4.
• the present invention relates to an optical filter film having an adhesive layer containing a neon light-absorbing dye and excellent in heat resistance and moist heat resistance, and a plasma display panel (hereinafter referred to as PD) using the same.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Optical Filters (AREA)
• Adhesive Tapes (AREA)
• Devices For Indicating Variable Information By Combining Individual Elements (AREA)

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• 2007
  • 2007-07-05 CN CN2007800253520A patent/CN101484832B/zh not_active Expired - Fee Related
  • 2007-07-05 WO PCT/JP2007/063438 patent/WO2008004611A1/ja active Application Filing
  • 2007-07-05 TW TW96124524A patent/TW200811263A/zh unknown
  • 2007-07-05 JP JP2008523724A patent/JPWO2008004611A1/ja active Pending
• 2009
  • 2009-11-19 HK HK09110827.9A patent/HK1133085A1/xx not_active IP Right Cessation

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