WO2007099990A1

WO2007099990A1 - Near infrared ray absorbing film and optical filter for plasma display panel using the same

Info

Publication number: WO2007099990A1
Application number: PCT/JP2007/053735
Authority: WO
Inventors: Junichi Segawa; Takaaki Kurata; Kenji Akuta; Atsuyuki Uehara
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2006-03-01
Filing date: 2007-02-28
Publication date: 2007-09-07
Also published as: TW200801594A; KR101164880B1; CN101395501B; HK1129733A1; CN101395501A; KR101050753B1; KR20110055731A; KR20080099265A; JP4553962B2; JPWO2007099990A1

Abstract

This invention provides a near infrared ray absorbing film, which contains a diimonium compound having a relatively broad near infrared ray absorbing wavelength range and has good heat resistance and resistance to moist heat and other various properties, and an optical filter utilizing the near infrared ray absorbing film for PDPs. A mixture of diimonium compounds represented by formula (1) which are different from each other in n value in formula (1), is stacked on a transparent support film, or is incorporated in a pressure-sensitive adhesive layer to prepare a near infrared ray absorbing film. An optical filter for PDPs is prepared using the near infrared ray absorbing film. (1) wherein n-Pr represents an n-propyl group; iso-Bu represents an isobutyl group; and n is an integer of 0 to 8.

Description

Specification

Near-infrared absorbing film and optical display for plasma display panel using the same

Technical field

[0001] The present invention broadly absorbs light having a wavelength in the near-infrared region, and a near-infrared absorbing film using a dimonium compound having excellent heat resistance, heat-and-moisture resistance, solvent solubility, and the like, and a plasma display panel (hereinafter referred to as a plasma display panel using the same). (Referred to as PDP). Background art

[0002] Near-infrared rays are used as a beam for remote control of electrical equipment, so equipment that emits near-infrared rays may cause electrical equipment installed in the vicinity to malfunction. It is necessary to install an optical filter or the like having a function of shielding near infrared rays in front of such devices (for example, PDP).

[0003] The principle of the PDP is that a voltage is applied to a rare gas (neon, xenon, etc.) enclosed in a cell sandwiched between two glass sheets, and ultraviolet light emitted from the rare gas in a plasma state is applied to the cell wall. It hits the coated illuminant to generate the visible light necessary for the image, but at the same time as the visible light, the wavelength near 595 nm reduces the color purity of red light due to near infrared, electromagnetic waves, and neon gas. It also emits electromagnetic waves that are harmful to humans and electrical equipment such as orange rays (hereinafter referred to as neon light), so that useful visible light is transmitted, but harmful electromagnetic waves such as near infrared rays are shielded. The PDP needs an optical filter for that purpose.

[0004] Near-infrared absorbing films used for optical filters are used for the purpose of shielding near-infrared rays, and for this, compounds having a function of absorbing near-infrared rays (near-infrared absorbing compounds) are used. That is, these near-infrared absorptive compounds are made into transparent functional films such as transparent support films (transparent substrate films and anti-reflection films, or films that shield electromagnetic waves that are harmful to the human body (hereinafter referred to as electromagnetic shielding films)). A near-infrared-absorbing film is produced by incorporating it in a layer provided on the film surface. There are several types of near-infrared absorbing compounds used here. A relatively broad dimonium compound is often used alone or in combination with one or more other near-infrared absorbing compounds on the basis thereof. However, the same is true for dimonium compounds, which have many compounds that have near-infrared absorptive heat stability and heat-and-moisture stability (hereinafter simply referred to as “thermal stability”). I can say that. As dimonium compounds, dimonium compounds having hexafluoroantimonate ions have generally been used. However, these compounds fall under the category of deleterious substances, and restrictions on the use of heavy metals are becoming strict due to environmental problems. Therefore, safer dimonium compounds have been desired. As means for solving this, a compound using an organic counter ion such as naphthalenedisulfonic acid (Patent Document 1) and a compound using trifluoromethanesulfonic acid ion (Patent Document 2) are disclosed. Stability "is still insufficient, especially in the case of near-infrared absorbing films containing these compounds in the adhesive layer, the layer containing these compounds may change color or the near-infrared absorptivity may deteriorate. There are difficulties.

[0005] The main specific method for retaining the near-infrared absorbing compound on the transparent support film is to dissolve and / or disperse it together with the binder resin in a solvent, and apply the polymer onto the transparent resin film. In the former case, “thermal stability” is easily affected by the glass transition temperature of the binder resin used and the amount of residual solvent in the resin layer. On the other hand, in the latter method, there is a concern that “thermal stability” is likely to decrease, haze value which is one of the standards of transparency, and there is a concern that it may adversely affect the transparency of visible light. .

[0006] Patent Document 3 discloses a technique for stabilizing a dimonium compound in a layer (a layer provided using a polymer resin such as an overcoat layer, an adhesive layer, or a treatment layer) provided on a transparent support film. It is disclosed that it can be stabilized by adding a dimonium compound in a state in which the amount of the solvent remaining in the layer provided on the transparent support film is controlled to a certain ratio or less, or by using a binder resin having a high glass transition temperature. However, it is difficult to say that it is a simple method because it requires time and effort to control the amount of residual solvent and the binder resin used is limited. In addition, it effectively prevents adverse effects on haze values and visible light transmittance when dimonium compounds are contained in an adhesive layer provided on a transparent support film. No method has been reported.

In any case, using a dimonium compound that is relatively excellent in near-infrared absorption ability, it does not impair near-infrared absorption ability, its "thermal stability", and as an optical filter without restrictions on the binder resin used. The establishment of simple manufacturing technology for near-infrared absorbing films with excellent performance was requested.

Literature list

Patent Document 1: JP-A-10-316633 (Page 5)

Patent Document 2: Japanese Patent Publication No. 7-51555 (2nd page)

Patent Document 3: Japanese Patent Laid-Open No. 2000-227515

Patent Document 4: Japanese Patent Publication No. 43-25335 (Page 7_14)

Disclosure of the invention

Problems to be solved by the invention

[0007] In dimonium compounds having a relatively wide absorption wavelength range in the near-infrared region, the glass transition temperature (hereinafter referred to as Tg) of the binder resin that can be used easily due to good solvent solubility is wide. In addition, even when included in the adhesive layer, excellent `` thermal stability '' can be maintained, efficient absorption of near infrared rays, haze value can be kept low, and a dimonium compound that can be synthesized at low cost can be found. It is an object of the present invention to provide an optical filter having excellent performance used.

Means for solving the problem

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a mixture of dimonium compounds having a specific substituent on the cation side and a specific one selected as an anion is the above. The present invention has been completed by finding out that it solves the problem.

[0009] That is, the present invention provides

(1) A near-infrared absorbing film characterized in that a mixture of two or more dimonium compounds represented by the following formula (1) and having different n is contained in a layer formed on a transparent support film

[0010] [Chemical 1] 2 C (S0 ₂ CF ₃ ) ₃ )

(In the formula (1), n_Pr represents a normal propyl group, iso_Bu represents an isobutyl group, and n represents an integer of 0 to 8.)

(2) Mixture force of two or more dimonium compounds with different n in formula (1) Contains 70% (calculated from mass spectrum) or more and 98% or less of dimonium compounds of n force ¾ to 6 in formula (1). The near infrared ray absorbing film according to (1),

(3) The near-infrared absorbing film according to (1) or (2), wherein the layer formed on the transparent support film is an adhesive layer,

(4) The layer formed on the transparent support film contains a mixture of two or more kinds of dimethyl compounds having different n in formula (1) and a compound having a maximum absorption at a wavelength of 550 to 620 nm. (3) The near-infrared absorbing film according to any one of

(5) The near-infrared absorbing film according to any one of (1) to (4), wherein the transparent support film is a film having a reduced reflection function or an electromagnetic wave shielding function,

(6) An optical filter for a plasma display panel, comprising the near-infrared absorbing film according to any one of (1) to (5),

(7) The plasma display according to (6), comprising the near-infrared absorbing film according to any one of (1) to (5), a film having an electromagnetic wave shielding ability and / or a film having a function of reducing reflection. Optical filters for panels,

(8) Mixture of two or more kinds of dimonium compounds represented by formula (1) and different n

[Chemical 2]

) ₃

(In formula (1), n-Pr represents a normal propyl group, iso- Bu represents an isobutyl group, and n represents an integer of 0 to 8)

About.

The invention's effect

The mixture of dimonium compounds used in the present invention can be synthesized at a low cost by a simple method, does not contain heavy metals such as antimony, is not a deleterious substance, and has good solvent solubility. The near-infrared absorbing film obtained by using this material absorbs near-infrared light in the wavelength range of 800 ~: lOOnm well, and even when it is included in the adhesive layer, it has excellent haze value and "thermal stability". This optical filter for PDP that combines this near-infrared absorbing film with other functional films, which has no deterioration in near-infrared absorptivity, discoloration of the layer, and deterioration in surface quality, shows excellent performance and is sufficient for the above problems. It can respond.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The near-infrared absorbing film of the present invention comprises a mixture of two or more kinds of dimethylum compounds having different numbers of normal propyl groups and isobutyl groups, which are substituents of the dimonium compound represented by the above formula (1) (hereinafter referred to as “this” Is a near-infrared absorption film containing a binder resin layer or adhesive layer provided on a transparent support film, and has various physical properties as an optical film. 800 ~: 11 OOnm wavelength range Absorbs near infrared rays well.

[0014] Near-infrared absorbing film having a layer containing "this dimonium mixture" has good near-infrared absorptivity and excellent "thermal stability", and when incorporated in the adhesive layer, All of the substituents are characterized by better near-infrared absorption ability and lower haze value than dimonium compounds which are S isobutyl groups (n = 0), and all substituents of formula (1) are It was found that the solvent solubility was better than that of a normal propyl group (n = 8) dimonium compound, and coating was easy. In addition, the present dimonium mixture is easy to produce, and can be easily produced by a conventionally known method by adjusting the proportion of the alkylating agent added in the precursor production process as described below. .

In the present invention, “the present dimonium mixture” is, for example, one described in Patent Document 4. It can be obtained according to the law. That is, the amino compound represented by the following formula (2) obtained by the Ullmann reaction and the reduction reaction is preferably dimethylformamide (DMF), dimethylimidazolidinone (DMI), N-methylpyrrolidone (NMP) in an organic solvent. In a water-soluble polar solvent such as 30-160 ° C, preferably 50-140 ° C, a halogenated normal propyl compound and isobutyl compound are mixed in an arbitrary ratio and reacted to be represented by the formula (3). The ability to obtain a mixture of compounds In order to control the ratio of normal propyl group to isobutyl group, the compound corresponding to normal propyl group (or isobutyl group) is reacted first and then the compound corresponding to isobutyl group (or normal propyl group). It is also possible to synthesize a mixture of a certain proportion of compounds.

[0016] [Chemical 3]

(In Formula (3), n represents the same meaning as in Formula (1).)

The mixture of formula (3) synthesized above is in an organic solvent, preferably a water-soluble polar solvent such as dimethylformamide (DMF), dimethylimidazolidinone (DMI), N_methylpyrrolidone (NMP), 0 to: 100 ° C, preferably 5-70. The oxidation reaction is carried out by adding 2 equivalents of tris (trifluoromethylsulfonyl) carboxylic acid at C to obtain “the present dimonium mixture” used in the present invention.

[0018] Next, how to determine the composition ratio of each dimonium compound in "the present dimonium mixture" will be described. Mass spectrometer for measuring the molecular ion peak intensity of each dimonium compound (9 kinds of dimonium compounds in which n is 0, 1, 2, 3, 4, 5, 6, 7 or 8 in formula (1)) The LCT manufactured by Micromass was used. The sample for measurement to calculate the composition ratio of each dimonium compound depended on the compound of the formula (3) before cationization (hereinafter referred to as the precursor), which is the cation mixture of the present dimonium mixture. This is due to the fact that direct measurement is difficult, the measurement values are not reliable, and the composition ratio of each precursor can be judged to be highly correlated with the composition ratio of each component after cationization. Specifically, the electrospray (ESI) ionization mass spectrum of the measurement sample was measured, the molecular ion peak intensity [M] ⁺ of each precursor was determined, and the composition ratio was calculated. As the composition ratio A of each component, A (%) = 1 00 X [M] so (total of [M] ⁺ of each precursor having n = 0 to 8) and force were also estimated and calculated. Also, for example, the sum B of the composition ratios of the respective components having n of 3 to 6 is B (%) = 100 X (the sum of [M] + of each precursor having n of 3 to 6) / (n is 0 The total of [M] ⁺ of each precursor of ˜8).

[0019] The sum of the composition ratios of n = 3-6 dimonium compounds calculated from the peak intensity force of the mass spectrum as described above is 98% or more of 70% or more of the total (total of each dimonium compound where n is 0-8) The following mixture is a more preferred mixture for the purposes of the present invention. Such a composition can be easily prepared by adjusting the amount of the alkylating agent added, the reaction temperature, and the reaction time.

[0020] "The present dimonium mixture" used in the present invention may be used alone, but in order to adjust the desired near-infrared absorption wavelength region and absorption ratio, one or more other near red Specific examples of other near-infrared absorbing compounds that can be used in combination with an external absorption compound include dimonium compounds other than "this dimonium mixture", nitroso compounds and their metal salts, cyanine compounds, and scuryllium compounds. Thiol nickel complex compounds, phthalocyanine compounds, naphthalocyanine compounds, triallylmethane compounds, naphthoquinone compounds or anthraquinone compounds. In the present invention, it is preferable to select and use a compound having a maximum absorption at a wavelength of 800 to lOOnm from these compounds.

Hereinafter, a method for producing a near-infrared absorbing film by forming a layer containing “the present dimonium mixture” on a transparent support film will be described. In addition, "this dimonium mixture" When using a near infrared absorbing compound other than the above, it is advantageous to apply the mixture by mixing it with the same coating liquid as the present dimonium mixture. It can also be held.

[0022] As a method of holding the present dimonium mixture on a transparent support film, a coating layer (hereinafter referred to as a binder resin layer) is formed using a binder resin, and a method of containing the adhesive layer and an adhesive are included therein. A preferable method is a method of containing the layer.

[0023] The type and thickness of the transparent support film used in the present invention are not particularly limited as long as it can withstand use as an optical film with high transparency and resistance to scratches. 10 to 500 xm is a workable film with good workability. Polyester-based, polycarbonate-based, triacetate-based, norbornene-based, acrylic-based, cellulose-based, polyolefin-based or urethane-based polymer resin Polyethylene terephthalate (hereinafter referred to as PET) is preferable from the viewpoint of physical properties as an optical film such as transparency and easy availability. In order to absorb the ultraviolet rays from the outside and stabilize the function of the internal members, it is possible to use a transparent support film containing an ultraviolet absorbing substance, and the film surface is in close contact with the coating film. In order to improve the property, the adhesive property may be improved by applying corona discharge treatment, plasma treatment, glow discharge treatment, surface roughening treatment, chemical treatment, anchor coating agent or primer coating. In addition, the transparent support film has a function of having one or more functions such as anti-reflection, anti-glare and anti-reflection, antistatic, antifouling, neon light absorption, electromagnetic shielding or color adjustment. In particular, when `` This dimonium mixture '' is contained in the adhesive layer of these functional transparent support films, an optical film having both these functions and near-infrared absorptivity can be obtained. As a result, a rational and excellent optical filter is possible, and the use of a functional transparent support film is an advantageous choice. As the functional transparent support film, a transparent support film having a low reflection function or an electromagnetic wave shielding function is preferred.

Next, examples of the preferred functional transparent support film described above will be described, but the type of the transparent support film having functionality is not limited thereto.

Transparent support film with low reflection function (anti-reflection film) is a transparent support film such as PET. On the surface of the film, a low refractive index agent is coated together with a binder resin and other additives to suppress reflection of light from the outside or a transparent support film and a low refractive index layer between a hard coat layer and a high refractive index layer. The film is provided with a refractive index layer and controlled so that the reflected light from each layer cancels each other out. The anti-glare 'anti-reflection film is a low-reflection film with fine particles in the high-refractive index layer and hard coat layer. It is a film that improves visibility by irregularly reflecting external light. These films can be easily obtained from the market as ARK Top Series (Asahi Glass), Kyacoat ARS series (Nippon Kayaku), Kyacoat AGRS series (Nippon Kayaku), Realak series (Nippon Yushi). It is possible.

[0025] Next, a transparent support film (electromagnetic wave shielding film) having an electromagnetic wave shielding function is used. As a method of shielding an electromagnetic wave, a fine wire of metal such as copper is transparent in a geometric pattern like a mesh. There are a mesh type held on a support film and a thin film type where an ultra-thin metal film is held on a transparent base film within a range that allows light transmission. Near infrared rays are reflected and not transmitted), and no near infrared absorbing film is required. Therefore, in the present invention, when an electromagnetic wave shielding film is used, it is preferable to use a mesh type electromagnetic wave shielding film as the transparent support film. In addition, when a film having a low reflection property and an electromagnetic wave shielding property obtained by applying a conductive ink on the opposite surface of the reduced reflection surface of the reduced reflection film and applying an electromagnetic wave shielding layer in a mesh shape by screen printing or the like is used as a transparent support film. This is convenient for producing an optical filter for PDP.

[0026] The transparent support film having other functionalities that can be used in the present invention has a single function such as neon light absorption, ultraviolet light absorption, antistatic property, antifouling property, and color adjustment. There are a plurality of transparent support films, which can be prepared according to a method known per se by a method of molding from a binder resin composition containing each compound having these properties. .

[0027] First, a method for incorporating the present dimonium mixture into the adhesive layer will be described. If the resin that is the main component of the adhesive layer can disperse the present dimonium mixture uniformly, forms a transparent layer on the surface of the transparent support film, and does not impair the function as an optical film. Although not particularly limited, adhesive materials such as acrylic-based, polyester-based, polyamide-based, polyurethane-based, polyolefin-based, polycarbonate-based, rubber-based, or silicon-based resin can be mentioned. Excellent in transparency, adhesiveness, heat resistance, etc. In view of this, an acrylic resin adhesive is suitable. Acrylic resin adhesives are mainly composed of acrylic acid alkyl esters that do not have functional groups (excluding double bonds), and other than acrylic acid alkyl esters or acrylic acid alkyl esters having functional groups. 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 per 100 parts by weight of the acrylic acid alkyl ester component having no functional group. :! ~ 20 parts by weight, more preferably 1 ~: 10 parts by weight.

[0028] Examples of the acrylic acid alkyl ester having no functional group include methyl (meth) acrylate,

Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) aryl Acrylic acid having 1 to 12 carbon atoms in the alkyl group, such as octyl acid, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate or dodecyl (meth) acrylate Forces including alkyl esters or alkyl methacrylates. These may be used in combination of two or more.

[0029] As the 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 thereof is not particularly limited. Although there are no 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.

[0030] 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 according to the type of the above-mentioned monomer. For example, hexamethylene diisocyanate, aliphatic diisocyanate such as hexamethylene diisocyanate with trimethylolpropane, and tolylene diisocyanate. Such as aromatic diisocyanates such as cyanate or trimethylolpropane adduct of trilene diisocyanate. Polyisocyanate compounds, melamine compounds such as butyl etherified styrene melamine and trimethylol melamine, diamine compounds such as hexamethylene diamine and triethylene diamine, bisphenol A, and epichlorhydride Epoxy resin compounds such as phosphorus, urea resin compounds, metal salts such as aluminum chloride, ferric chloride, or aluminum sulfate are used, and the amount is usually 0 per 100 parts by weight of acrylic resin adhesive. 005-5 parts by weight, preferably 0.01-3 parts by weight.

[0031] The above-mentioned acrylic resin-based pressure-sensitive adhesive is excellent in adhesive strength and cohesive strength and has high stability to light and oxygen because there is no unsaturated bond in the crosslinked polymer. Also, the monomer type and molecular weight In order to maintain the adhesion to the transparent support film, which is also preferred because of the high degree of freedom in selecting the polymer, the polymer with a high molecular weight (degree of polymerization), that is, the weight average molecular weight (Mw) of the main polymer is 60 About 10,000 to 2,000,000 is preferable, and preferably about 800,000 to 1.8 million.

[0032] In PDP, orange neon light having a wavelength of 550 to 620 nm derived from neon gas generated at the time of applied voltage needs to be applied to the front of the display to some extent in order to reduce the color purity of red light. A neon light absorbing filter in which an absorbing compound is held on a transparent support film is usually used. By incorporating a compound having a neon light absorbing ability into a layer having a near infrared absorbing ability, a near infrared ray and a neon light can be simultaneously emitted. A method of obtaining an absorbable layer is advantageous. Examples of neon light-absorbing compounds that can be used here include, for example, compounds such as azaporphyrin-based, cyanine-based, squarylium-based, azomethine-based, xanthene-based, oxonol-based, or azo-based compounds. In the case of inclusion in the composition, it is necessary to give due consideration to the “thermal stability” of the “dimonium mixture” used. For example, tetraazaporphyrin compounds are relatively stable, and other compounds can be used if they are stabilized.

[0033] The present dimonium mixture is mixed with the adhesive, which is the main component of the adhesive, the polymerization initiator, the crosslinking agent, the ultraviolet absorber, the color adjusting dye, and other necessary additives such as an electromagnetic wave shielding mesh. In the case of discoloration due to contact with the metal used in the coating, it is sufficiently dissolved or dispersed in a solvent such as methyl ethyl ketone (MEK) together with an antioxidant, an antifungal agent, etc. to form an adhesive solution, and the surface of the transparent support film And the layer thickness after drying is 5 to: 100 zm, preferably 10 Apply to ~ 50 / m. The coating method is not particularly limited, and a method of applying with a bar coater, reverse coater, comma coater or gravure coater and drying to adhere the adhesive layer, or applying an adhesive solution onto the release film Examples thereof include a method in which a pressure-sensitive adhesive layer is transferred onto a transparent support film after being applied by a coater, reverse coater, comma coater, gravure coater, and the like and dried. The amount of solvent used depends on the coating method, but when using an acrylic resin adhesive with a main polymer weight average molecular weight of around 1 million and applying with a comma coater, the adhesive should be 10-25% by weight. It is preferable to dilute with a solvent so that The near-infrared absorbing film of the present invention is preferably designed so that the transmittance of near-infrared light having a wavelength of 800 to 1100 ηm is 10% or less. If it is used, it should be contained so as to be approximately 1 to 20% by weight with respect to a good adhesive layer.

[0034] "This dimonium mixture" is a mixture of two or more kinds of dimonium compounds. A single product of dimonium compounds having 8 normal propyl groups (n = 8 in formula (1)) is a solvent for coating. Therefore, the solubility in solvents such as MEK, which are frequently used, is insufficient, and aggregates are formed on the coated surface and the near-infrared absorptivity tends to be poor. As the mixture with a large n, that is, a dimonium compound having a large number of normal propyl groups, becomes poorer in solvent solubility, the coating becomes easier. In addition, when all of the eight are isobutyl groups (n = 0 in the formula (1)), the near-infrared absorption ability is slightly inferior to that of `` this dimonium mixture '', the haze value is higher, and `` this dimonium mixture '' Among them, the haze value tends to increase as the content ratio of the dimonium compound having a small n, that is, a large number of isobutyl groups, increases. Based on the above, the `` dimonium mixture '' is superior in terms of physical properties and ease of handling than using a single product having 8 normal propyl groups and 8 isobutyl groups. However, a mixture of compounds that are not too biased is more suitable, and the sum of the composition ratios of the dimonium compounds with n of 3 to 6 calculated from the peak intensity of the mass spectrum described above is the total (the composition with n of 0 to 8). A mixture that is 70% or more and 98% or less of the total ratio) is more preferable.

[0035] Next, a method for holding the present dimonium mixture as a binder resin layer on the transparent support film will be described. This dimonium mixture is mixed with a binder resin and, if necessary, neon light absorbing dyes, color adjusting dyes, leveling agents, antistatic agents, antioxidants, dispersants, flame retardants, lubricants, plasticizers, UV absorbers. A method of dissolving and / or dispersing in a solvent together with an agent and other additives to form a coating liquid, coating with a coating machine, and drying can be employed. In addition, when a binder resin such as thermosetting or active energy line curable is used, it is necessary to have a curing process after drying S, a compound that absorbs near infrared rays or neon light with curing heat or active energy rays. It is desirable to use a thermoplastic binder resin unless there are special circumstances.

[0036] The binder resin is not particularly limited as long as there is no problem in the surface quality and the like, which is easy to apply and immediately has good adhesion to a transparent support film, and has good visible light transmittance. It is preferably selected from thermoplastic resins such as acrylic resins, polyamide resins, polyurethane resins, polyolefin resins or polycarbonate resins. After coating and scraping into a roll, it has a glass transition temperature and other physical properties that do not cause problems such as blocking during storage, and the `` thermal stability '' of the `` dimonium mixture '' used The choice of the material that does not adversely affect ", is preferred.

[0037] Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, diacetone alcohole, ethyl acetate sorb, and methyl solvosolve, and ketones such as acetone, methyl ethyl ketone (MEK), cyclopentanone, and cyclohexanone. Amides such as N, N-dimethylformamide or N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane or ethylene glycol monomethyl ether, methyl acetate, ethyl acetate or Esters such as butyl acetate, aliphatic hydrocarbons such as chlorophenol, methylene chloride, dichloroethylene or trichloroethylene, aromatics such as benzene, toluene, xylene, monochlorobenzene or dichlorobenzene, or n-hexa , N_heptane and other aliphatic hydrocarbons, fluorinated solvents such as tetrafluoropropyl alcohol or pentafluoropropyl alcohol, etc. can be used. There are no inconveniences, safety, no problems, and it is preferable to select a solvent.

[0038] Of the additives used as necessary, the neon light absorbing compound is contained in the adhesive layer. The same compounds as those used are used, and other additives are used in the solution in consideration of the `` thermal stability '' of the `` dimonium mixture '' used and the desired quality performance. Is done.

[0039] The coating of the coating liquid is a well-known method such as a flow coating method, a spray method, a bar coating method, a gravure coating method, a single nozzle coating method, a blade coating method, an air knife coating method, a lip coating method or a die coater method. In this coating method, the finished layer thickness is usually 0.:! To 30 xm, preferably 0.5 to 10 zm, and the treatment layer is fixed by drying. If separate curing is required, after drying, a curing treatment is performed to fix the treatment layer. The near-infrared shielding property is preferably designed so that the near-infrared transmittance at a wavelength of 800 to l lOOnm is 10% or less, similar to the case where the present dimonium mixture is contained in the adhesive layer. . The amount of solvent used varies depending on the coating method. When using a thermoplastic acrylic resin binder with a main polymer weight average molecular weight of around 300,000 and coating with a micro gravure coater, it should be 15 to 30% by weight. It is preferable to dilute with a solvent.

[0040] When the dimonium compound is contained in the binder resin layer, the most commonly used dimonium compound having an anion of hexafluoroantimonate ion, such as Cyasolv IRG-022 (trade name; Nippon Kayaku Co., Ltd.) ) And many dimonium compounds, as described in Patent Document 3, if a binder resin with a low Tg of 85 ° C or less is used, the “thermal stability” is inferior, but the present dimonium compound has a temperature of 85 ° C or less. There is no problem even if a binder resin is used. Also, there is no need to manage the amount of residual solvent in the binder resin layer as disclosed in Patent Document 3, and it can be used without any problem even when drying under normal drying conditions. In addition, “this dimonium mixture” in the above formula (1) has superior solvent solubility compared to a single product in which all substituents are normal propyl groups (n = 8). An excellent near-infrared absorbing film can also be obtained by adding the “mixture” to the binder resin layer.

[0041] Next, the optical filter of the present invention includes the near-infrared absorbing film of the present invention in which a layer containing "the present dimonium mixture" is provided on a transparent support film as a minimum component and the following components: It is obtained by laminating or bonding together a transparent support film having such a function. The preferred use of these optical filters is for PDP, and the optical filter of the present invention. Can be attached to the front of the PDP by pasting it on a transparent glass plate or plastic plate in advance, or it can be used by pasting directly on the front of the PDP.

[0042] Examples of configurations of various films in the optical filter of the present invention include the following (1) to (: 13).

In the following description, NIRA represents near infrared absorptivity, NeA represents neon light absorptivity, and the part enclosed in braces ({}) encloses the near infrared absorbing film of the present invention in parentheses (()). A part shows each functional film other than this invention. As is clear from these structural examples, for example, by adding “this dimonium mixture” or a neon light absorbing compound to the adhesive layer of a transparent support film having functionality such as a low-reflection transparent support film. An optical filter for PDP can be produced by simply bonding two types of films. Furthermore, by using a film with electromagnetic shielding of the mesh on the back of the anti-reflection film as a transparent support film, a binder resin layer or an adhesive layer containing "this dimonium mixture" and a neon light absorber is provided on the mesh surface. It is also possible to produce optical filters for PDP with one kind of film. As an optical filter of the present invention, an embodiment including the near-infrared absorbing film of the present invention and a film having an electromagnetic wave shielding ability or a film having a reduced reflection function is preferable.

[0043] (1) {Non-reflective film / NIRA 'NeA' color adjusting adhesive layer} / (electromagnetic wave shielding film / adhesive layer),

(2) {Non-reflective film / NIRA * color adjustment adhesive layer} / (Electromagnetic wave shielding film / NeA adhesive layer),

(3) (Non-reflective film / adhesive layer) / {Electromagnetic wave shielding film / NIRA-NeA-color adjustment adhesive layer},

(4) {Anti-glare · Non-reflection film ZNIRA 'NeA' color adjustment adhesive layer} / (electromagnetic wave shielding film / adhesive layer),

(5) (Non-reflective film Z adhesive layer) Z {NIRA'NeA binder resin layer / PET / color tone adhesive layer} / (electromagnetic wave shielding film Z adhesive layer),

(6) (Non-reflective film Z adhesive layer) / {NeA film / NIRA · Color adjustment adhesive layer} Z (Electromagnetic wave shielding film Z adhesive layer), (7) (Non-reflection film / Adhesive layer) / (Electromagnetic wave shielding film / Adhesive layer) / {Ne A film / NIRA * color adjustment adhesive layer}

(8) (Non-reflection film / Adhesive layer) / (Electromagnetic wave shielding film) / {NIRA'NeA absorption adhesive layer / PET color adjustment adhesive layer},

(9) (Non-reflective film Z adhesive layer) Z {NIRA'NeA binder resin layer / PET / Color adjustment adhesive layer} / (Electromagnetic wave shielding film Z adhesive layer),

(10) {Non-reflective film ZNIRA · NeA binder resin layer / Color adjustment adhesive layer} / (Electromagnetic wave shielding film Z adhesive layer)

(11) {Non-reflective film ZNIRA · NeA binder resin layer / Color adjustment adhesive layer} / (Electromagnetic wave shielding film Z adhesive layer)

(12) {Non-reflection film Z Electromagnetic wave shielding layer ZNIRA binder resin layer / NeA adhesive layer}

(13) {Non-reflection film Z Electromagnetic wave shielding layer ZNIRA · NeA adhesive layer}

Example

[0044] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to such examples. In Examples, “part” means “part by weight” and “%” means “% by weight”.

[0045] Synthesis Example 1

(Substitution reaction)

In 100 parts of DMF, N, N, N, N, 1 tetrakis (aminophenol) 1 p-phenylene diamine 7 parts, potassium carbonate 27 parts, potassium iodide 14.8 parts, isoptyl bromide 32 parts, 1 -3 parts of bromopropane was added and reacted at 90 ° C for 2 hours, then at 110 ° C for 6 hours. After cooling, the precipitated crystals are filtered off, and the obtained crystals are dissolved in hot DMF. After removing the insoluble matter, methanol is added to the solution, and the precipitated crystals are separated by filtration, washed with water, dried, and a precursor of light green crystals (see formula (3) above) 6.8 Got a part.

(Oxidation reaction)

5 parts of the above precursor crystals are placed in 40 parts of DMF, heated and dissolved at 60 ° C., then 9 parts of a 58% aqueous solution of tris (trifluoromethanesulfonyl) carbonic acid is added, and then silver nitrate dissolved in 30 parts of DMF 1 9 parts were added and stirred with heating for 30 minutes. After filtering out the insoluble matter, Water was added to the reaction solution, and the resulting crystals were filtered, washed with water and dried to obtain 5.2 parts of a mixture of dimonium compounds. The composition ratio of each component in this mixture was calculated by the above method, and the results are shown in Table 1. The maximum absorption wavelength of this mixture was 1107 nm (dichroic methane).

[0046] Synthesis Example 2

(Substitution reaction)

A substitution reaction and purification were carried out in the same manner as in Synthesis Example 1 except that 3 parts of 1_bromopropane in Synthesis Example 1 were replaced with 7.3 parts to obtain 6.5 parts of a light green crystal precursor.

(Oxidation reaction)

An oxidation reaction and purification were carried out in the same manner as in Synthesis Example 1 except that the precursor obtained in Synthesis Example 1 was replaced with the above precursor to obtain 4.5 parts of a mixture of dimonium compounds. Calculation of the composition ratio of each component in this mixture was performed according to the above method, and the results are shown in Table 1. The maximum absorption wavelength of this mixture was 1092 nm (dichloromethane).

[0047] Synthesis Example 3

(Substitution reaction)

A substitution reaction and purification were carried out in the same manner as in Synthesis Example 1 except that 3 parts of 1-bromopropane in Synthesis Example 1 were replaced with 10 parts to obtain 6.2 parts of a light green crystal precursor.

(Oxidation reaction)

Oxidation reaction and purification were carried out in the same manner as in Synthesis Example 1 except that the precursor of Synthesis Example 1 was replaced with the above precursor to obtain 6.1 parts of a mixture of dimonium compounds. The composition ratio of each component in this mixture was calculated by the method described above, and the results are shown in Table 1. The maximum absorption wavelength of this mixture was 1103 nm (dichloromethane).

[0048] Synthesis Example 4

(Substitution reaction)

Substitution reaction and purification were carried out in the same manner as in Synthesis Example 1 except that 3 parts of 1_bromopropane in Synthesis Example 1 was added instead of 12.7 parts to obtain 7.6 parts of a light green crystal precursor. It was.

(Oxidation reaction)

The oxidation reaction was performed in the same manner as in Synthesis Example 1 except that the precursor of Synthesis Example 1 was replaced with the above precursor. And 5.4 parts of a mixture of dimonium compounds. The composition ratio of each component in this mixture was calculated by the method described above, and the results are shown in Table 1. The maximum absorption wavelength of this mixture was 1 lOlnm (dichloromethane).

[0049] Table 1 summarizes the ratio of each component in the mixture of dimonium compounds obtained in Synthesis Examples 1 to 4.

[0050] (Solvent solubility)

The solvent solubility of the dimonium compound obtained in Synthesis Examples 1 to 4 and the dimonium compound used in Comparative Examples 1, 2, and 3 below was measured by the following method.

A 5% methyl ethyl ketone solution of the target dimonium compound was prepared at room temperature and the dissolution state was observed. As a result, the dimonium compound used in Synthesis Examples:! To 4 and Comparative Examples 2 and 3 was in a transparent state, whereas the dimonium compound used in Comparative Example 1 was not completely dissolved and sediment was observed. It was.

[0051] [Table 1]

(Table 1) B ^

Example 1

(Preparation of near-infrared absorbing film 1)

A coating solution in which the raw materials shown in Table 2 below are mixed and dissolved so as to be homogeneous is called MRF-75 (quotient (Product name, PET release film, made by Mitsubishi Chemical Polyester Film) With a comma coater, apply at a coating speed of 0.8m / min and a drying temperature of 110 ° C so that the thickness of the adhesive layer is 18 / m. Thus, an adhesive layer was formed. Next, the PET release film provided with an adhesive layer is pressure-bonded with a roll on the opposite side of the anti-reflective surface of KAYACOAT ARS-D501 (trade name, anti-reflective film, manufactured by Nippon Kayaku Co., Ltd.). Thus, a near-infrared absorbing film 1 of the present invention that absorbs neon light was obtained.

[Table 2]

(Table 2)

Materials used Mixture of dimonium compounds from Synthesis Example 1 1.0

TAP— 2 (Product name: Neon light absorber, Yamada Chemical Co., Ltd.) 0.0 9 Tinuvin 1 0 9 (Product name: UV absorber, Ciba Geigy) 0.5 7 PTR-1 0 4 (Product name: Acrylic resin Nippon Kayaku 1 0 3. 0 0 Coronet KH L (trade name Hardener Made of Enomoto Polyurethane) 0. 0 2 3

ME K 6 4 .0 0 part

[0054] (ii) TAP-2; tetraazaporphyrin compound, tinuvin 109; benzotriazole compound, coronate HL; isocyanate curing agent

[0055] Example 2

(Preparation of near-infrared absorbing film 2)

In the same manner as in Example 1, except that the mixture of the dimonium compounds in Synthesis Example 2 is used instead of the mixture of the dimonium compounds in Synthesis Example 1 and the mixture of the dimonium compounds in Example 2 is used. Thus, a near-infrared absorbing film 2 of the present invention having neon light absorption was obtained.

(Preparation of optical filter 1 for PDP)

£ 3—15341101〇0—42—02) Peel off the protective film of Eight (trade name, electromagnetic shielding film, manufactured by Hitachi Chemical Co., Ltd.), and paste the near-infrared absorbing film 2 on the adhesive layer. Thus, the optical filter for PDP of the present invention was obtained. This filter can be applied directly to the front of the PDP module, or attached to a glass plate (transparent plate) in front of the module.

The performance required as an optical filter for DP was fully demonstrated.

[0056] Example 3

(Preparation of near-infrared absorbing film 3)

Example 1 Synthetic Example 1 Dimmonium Compound in Synthesis Example 3 A near-infrared absorbing film 3 of the present invention having reduced reflection and absorbing neon light was obtained in the same manner as in Example 1 except that a mixture of sulfur compounds was used.

(Production of optical filter 2 for PDP)

The protective film of ES_1534U (HCD_42_02) A (trade name, electromagnetic wave shielding film, manufactured by Hitachi Chemical Co., Ltd.) is peeled off, and the near-infrared absorbing film 3 is bonded on the adhesive film via an adhesive layer. An optical filter for PDP was obtained. Whether this filter is directly attached to the front of the PDP module via the adhesive layer of the electromagnetic wave shielding film, or attached to the front of the module by attaching it to a glass plate, it exhibits the necessary performance as an optical filter for PDP. It was a thing.

[0057] Example 4

(Preparation of near-infrared absorbing film 4)

Except for using the mixture of the dimonium compound of Synthesis Example 4 instead of the mixture of the dimonium compound of Synthesis Example 1, it has anti-reflective properties in the same manner as in Example 1 and emits neon light. A near-infrared absorbing film 4 of the present invention that absorbs was obtained.

[0058] Example 5

(Preparation of near-infrared absorbing film 5)

Mixing 0.5 parts of dimonium compound of Synthesis Example 2 in 40 parts of MEK, 37 parts of foret PAN-1 25 (trade name, acrylic binder resin with a Tg of 70 ° C, manufactured by Soken Chemical Co., Ltd.) Obtained. This coating solution was applied onto Cosmo Shine A4300 (trade name, polyester film with a thickness of 100 microns, manufactured by Toyobo Co., Ltd.) with a micro gravure coater using a micro gravure tool at a line speed of 10 m / min. The film was dried at 70 to 130 ° C. to obtain a near-infrared absorbing film 5 of the present invention containing the mixture of the dimonium compound of Synthesis Example 2 in the binder resin layer.

[0059] Comparative Example 1

In the same manner as in Synthesis Example 1, except that 32 parts of isobutyl bromide in Synthesis Example 1 and 1_bromopropane 12.7 parts in 12.7 parts are used instead of 12.7 parts, 8 substituents in Formula (1) A dimonium compound which is all normal propyl group was prepared and used in the same manner as in Example 1 except that it was used in place of the mixed part of the dimonium compound of Synthesis Example 1. A comparative near-infrared absorbing film was obtained.

[0060] Comparative Example 2

All eight substituents in formula (1) are all isobutyl groups in the same manner as in Synthesis Example 1 except that 32 parts of isobutyl bromide from Synthesis Example 1 and 14.7 parts of 1 bromopropane are used instead of 14.7 parts of isobutyl bromide. A comparative near-infrared absorbing film was obtained in the same manner as in Example 1 except that this dimonium compound was prepared and used in place of the mixed portion of the dimonium compound in Synthesis Example 1.

[0061] Comparative Example 3

The same procedure as in Example 5 except that the same amount of Cyasolv IRG_ 022 (trade name, dimonium compound of antimony hexafluoride, Nippon Kayaku Co., Ltd.) was used instead of the mixture of the dimonium compound of Synthesis Example 2 in Example 5. The comparative near-infrared absorption film which contains a near-infrared absorber in a binder resin layer by the method was obtained.

[0062] Performance Test (1) (Near Infrared Absorbing Film Including Near Infrared Absorber in Adhesive Layer) Near Infrared Absorbing Film Obtained in Examples 1 to 4 and Comparative Examples Obtained in Comparative Examples 1 and 2 Transmittance, luminous transmittance (Y%) and chromaticity coordinates (x, y) at each maximum absorption wavelength when each test piece of near-infrared absorbing film is stored in a thermostat at 80 ° C for 500 hours ) Was measured and the heat resistance of each specimen was compared. The transmittance was measured with UV-3150 (trade name, spectrophotometer, manufactured by Shimadzu Corporation). Luminous transmittance and chromaticity coordinates (x, y) were determined based on XYZ color of JIS Z 8701 from this transmittance. Calculation was performed according to the color display method by the system. The haze value was measured by TC-H3DPK (trade name, haze meter, manufactured by Tokyo Denshoku Technology Center). Furthermore, the appearance change was observed with the naked eye.

The results of the performance test (1) are summarized in Table 3.

[0063] [Table 3] (Table 3) Performance (1) High heat resistance>

(Discussion) In Comparative Example 1 using a dimonium compound in which n is 8 in the above formula (1), an aggregate having a high haze value was also generated. Further, Comparative Example 2 using a dimonium compound in which n is 0 in the above formula (1) had a poor haze value and a poor near-infrared absorptance. In contrast, the near-infrared absorbing films of Examples 1 to 4 using a mixture of two or more kinds of dimonium compounds having different n of the present invention have a practically effective force (Equation ( In 1), the sum of components with n between 3 and 6 is 70. /. The near-infrared absorbing films of Examples 2 to 4 each having a mixture of the above dimonium compounds in the adhesive layer were superior to those having a haze value and a near-infrared shielding ratio of 70% or less (Example 1). The test results for heat and humidity resistance (60 ° C, RH90%, 500 hours) were almost the same as above. The results of moisture and heat resistance are summarized in Table 4.

[0065] [Table 4]

(Table 4) Performance test results (1) <Heat and heat resistance>

[0066] Performance test (2) (Near-infrared absorbing film in which near-infrared absorbing agent is contained in binder resin layer)

For each test piece of the near-infrared absorbing film obtained in Example 5 (present invention) and the comparative near-infrared absorbing film obtained in Comparative Example 3, a performance test similar to that in the performance test (1) (heat resistance The results shown in Table 5 were obtained.

[0067] [Table 5]

(Table 5) Performance test (2) High heat resistance>

(Discussion) In the heat resistance test, the transmittance of near infrared rays is 10% or less, but in Comparative Example 3, the change in transmittance is large. In terms of chromaticity coordinates, Example 5 has a binder resin Tg of 70 ° C. In spite of the low appearance, there was no change in appearance, but in Comparative Example 3, the appearance with a large change in y of the chromaticity coordinates was changed due to Tg, and it became yellowish. The test results for heat and humidity resistance (60 ° C, RH90%, 500 hours) were almost the same as above. The results of moisture and heat resistance are summarized in Table 6.

[Table 6]

(Table 6) Performance (2) <β «> Storage time Example 5 Comparative example 3

Wavelength 950nm 0 hr 4.69

Transmittance (%) 500 hr 5. 13

Difference 0.o 12

Luminous transmittance 0 hr 81. 09005 80. 100

Y (° / o) 500 hr 82. 090 80. 886

ο

Difference 0. 185 0. 786

Chromaticity seat 0 hr 0. 319 0. dimension 3 dimension 20

X 500 hr 0. 319 0. 323

Difference 0.000 0.003

Chromaticity seat 0 hr 0.338 0. 341

y 500 hr 0.339 0. 348

Difference 0.001 0.00

Appearance change 500 hr No change

Claims

A near-infrared absorbing film characterized in that a mixture of two or more kinds of dimonium compounds represented by the following formula (1) and different n is contained in a layer formed on a transparent support film. [Chemical 4]

(In formula (1), n_Pr represents a normal propyl group, and iso_Bu represents an isobutyl group.

, N represents an integer of 0-8. )

[2] A mixture of two or more dimonium compounds with different n in formula (1) is

2. The near-infrared absorbing film according to claim 1, comprising 70% (calculated from mass spectrum) or more and 98% or less of 3 to 6 dimonium compounds.

[3] The near-infrared absorbing film according to claim 1 or 2, wherein the layer formed on the transparent support film is an adhesive layer.

[4] The layer formed on the transparent support film contains a mixture of two or more dimonium compounds having different n in formula (1) and a compound having a maximum absorption at a wavelength of 550 to 620 nm. Item 4. The near-infrared absorbing film according to any one of Items 3 to 3.

5. The near-infrared absorbing film according to any one of claims 1 to 4, wherein the transparent support film is a film having a reduced reflection function or an electromagnetic wave shielding function.

[6] An optical filter for a plasma display panel, comprising the near-infrared absorbing film according to any one of claims 1 to 5.

[7] The plasma display panel according to claim 6, comprising the near-infrared absorbing film according to any one of claims 1 to 5, a film having an electromagnetic wave shielding ability and / or a film having a function of reducing reflection. Optical filter.

[8] A mixture of two or more dimonium compounds represented by formula (1) and different n. (

(In the formula (1), n_Pr represents a normal propyl group, iso_Bu represents an isobutyl group, and n represents an integer of 0 to 8).