KR100714734B1 - Pressure-sensitive adhesive composition - Google Patents

Abstract

The inventors of the present invention find that the near-infrared absorbing dye used is less deteriorated by ultraviolet rays, and is suitable for use in forming a pressure-sensitive adhesive layer or the like for adhering with a laminated material forming a plasma display or the like, and the plasma display front plate in the formed pressure-sensitive adhesive layer. The present invention provides a pressure-sensitive composition capable of bringing together the functions of each layer, absorbing near infrared and ultraviolet rays, and further having a color tone adjustment function.

The present invention relates to a pressure sensitive adhesive composition comprising a pressure sensitive adhesive polymer (A), a near infrared absorbing dye (B), a ultraviolet absorber (C) and / or a hindered amine light stabilizer (D).

Description

Pressure Sensitive Adhesive Composition {PRESSURE-SENSITIVE ADHESIVE COMPOSITION}

The present invention relates to a pressure sensitive adhesive composition. More specifically, the present invention provides a pressure-sensitive adhesive composition suitable for use in forming an adhesive layer for forming a plasma display by combining a layered material, and an optical filter for plasma display including the pressure-sensitive adhesive composition and a plasma including the same. Relates to a display product.

The pressure sensitive adhesive composition is tacky at room temperature and simply comprises a pressure sensitive adhesive that can adhere to the adhesive upon pressure application. These are widely used, for example, in the field of electrical and electronic components and other fields. Among the above uses of pressure sensitive adhesive compositions, when using them in plasma displays (also referred to herein as "PDPs") used in large thin televisions, thin displays and the like, several layered materials are incorporated by an adhesive layer formed of the pressure sensitive adhesive composition. .

In the PDP and the like, a filter is generally disposed in front of each PDP, for example, for the purpose of shielding electromagnetic waves emitted from the PDP, infrared rays, etc., reflecting external light, or changing the original PDP coloring to exhibit a desired color.                         

Roughly speaking, a PDP generally consists of a body (plasma emitting part) and a front plate (screen side seen by a person). The front plate is a multilayer body (laminate) consisting of the following sequence of layers (required functional layers) from the viewer to the PDP body:

[Viewer side] Anti-reflective layer / Near infrared absorbing layer / (Color tone adjusting layer) / Ultraviolet absorbing layer / Electromagnetic shielding layer [PDP main body]

Pressure sensitive adhesives are used to bond (bond) the layers together. For example, each layer material, lamination order, and lamination method are various, and drawings for various embodiments are disclosed (cf. Japanese Laid-Open Publication 2003-5663 (pages 10 and 11), Japanese Laid-Open Publications, for example). 2002-366048 (page 10), Japanese Laid-Open Publication 2002-268569 (pages 11 and 12), Japanese Laid-Open Publication 2002-323860 (page 11)).

For example, in this manner, a coating layer or film having near infrared absorptivity, which is a hot wire, is used in the PDP to perform an important function. For example, near infrared light is emitted from a screen in a PDP or the like, which is placed near the PDP and acts on a remote control device or equipment or some other electronic device using near infrared, causing their malfunction. Thus, a near infrared absorbing layer that absorbs near infrared rays and passes visible light is formed to shield the near infrared rays emitted from the screen. The film or coating layer is generally formed using a near infrared absorbing resin composition. In the production of the PDP, it is preferable that the PDP is lightweight, and the manufacturing process of the water is simplified to reduce their production cost. Therefore, in order to reduce costs, studies are being actively conducted to reduce the number of layers in the front plate.

In the meantime, as a pressure-sensitive adhesive of the prior art, a cohesive composition comprising a hydroxyl group-containing cohesive polymer and a crosslinking promoter and further comprising a volatile acid is disclosed (cf. Japanese Laid-Open Patent Publication 2002-241732 (page 1, 2)). Further, at least an ultraviolet absorber-containing surface protective layer, a pressure-sensitive adhesive layer, and a release substrate (cf. Japanese Unexamined Patent Publication No. H--09-166963 (pages 1 and 2)) and dispersed hot wire-shielding in this order A sheet for forming a display surface protective film is disclosed, comprising a heat-shielding pressure-sensitive adhesive (cf. Japanese Unexamined Patent Publication No. Hei-10-8010 (pages 1 and 2)) comprising an acrylic copolymer polymerized with fine particles. . However, the pressure sensitive adhesive composition is not designed for application to PDP. Therefore, they can be applied as a material for forming a pressure-sensitive adhesive layer in electronic equipment or devices such as PDP, and providing a function as a near infrared absorbing layer to the pressure-sensitive adhesive layer, thereby simplifying the layer structure of PDP and the like and reducing the weight. There is room for research for modification of these or other compositions so that the manufacturing process can be simplified.

Further, an optical filter (cf. Japanese Laid-Open Patent Publication No. 2001-228323 (pages 1 and 2)) provided with an adhesive layer or a pressure-sensitive adhesive layer containing a dye having a maximum absorption in the wavelength range of 570 to 600 nm, color decompression Adhesive compositions (cf. Japanese Laid-Open Publication No. H 03-03-79687 (page 1)), laser beam-absorbing thermosensitive adhesives (cf. Japanese Laid-Open Publication No. H09-95657 (pages 1, 2)), and near infrared rays Absorbent materials (cf. eg JP Publication No. Hex. 9-169849 (pages 1, 2)) are disclosed. However, also with respect to the above items, there is room for research to make them applicable as materials for forming a pressure-sensitive adhesive layer in an electronic apparatus or device such as a PDP. In addition, the water has another problem; When they are applied to the formation of pressure sensitive adhesive layers in PDPs and other electronic devices or devices, the dyes deteriorate and fail to maintain their near infrared absorption capacity for a long time.

Accordingly, there is a need for a technique in which the basic performance characteristics required for PDP and the like can be achieved, and furthermore, the number of layers in the front plate can be reduced for cost reduction.

The present invention has been made in view of the above-mentioned state of the art, and an object of the present invention is to provide a pressure-sensitive adhesive for adhering together a layered material in which the near-infrared absorbing dye used is less degraded by ultraviolet rays and forms a plasma display or the like. Suitable for use in forming layers and the like, the pressure sensitive adhesive layer formed can integrate the functions of each layer in the plasma display front plate together, absorb ultraviolet as well as near infrared rays, and also have a color tone-adjusting function. It is to provide a pressure-sensitive adhesive composition.

The inventors have conducted various studies on pressure sensitive adhesive compositions so that near-infrared absorbing dyes are incorporated into pressure sensitive adhesive compositions comprising pressure sensitive adhesive polymers as essential components, and the resulting composition is used to bond layered materials together forming plasma displays and the like. When used to form the adhesive layer (pressure-sensitive adhesive layer), it was found that it is possible to reduce the layer structure of the plasma display or the like, and to achieve weight reduction and manufacturing process simplification. In addition, near-infrared absorbing dyes in electronic devices or devices such as plasma displays are degraded by ultraviolet rays emitted from plasma emission or the like, which are readily degraded in the pressure-sensitive adhesive polymer, reducing their near-infrared absorbing capacity, but reducing the ultraviolet absorber and / or The use of hindered amine light stabilizers can prevent the deterioration caused by ultraviolet light and improve the durability of the near infrared absorbing dyes, and their application to pressure sensitive adhesive layers in electronic devices or devices such as plasma displays is desired. It has been found that it is possible to satisfactorily maintain the near infrared absorption capacity. Thus, they confirmed that the above object can be successfully achieved.

When the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition of the present invention in a plasma display or the like, they also function as a near infrared absorbing layer, thus reducing the need for providing a separate near infrared absorbing layer so that the layer structure of the plasma display or the like is reduced. Can be. Accordingly, the present invention provides a method for integrating together the functions of each layer constituting the plasma display front plate in the adhesive layer, in order to achieve a reduction in the number of layers of the front plate, and thus a cost reduction. It also proposes the use of a pressure sensitive adhesive layer that can absorb near infrared rays, thereby reducing the number of layers and also allowing the basic performance characteristics required for a plasma display front plate to be fully expressed. In addition, when the color tone-adjusting agent is incorporated therein, the pressure-sensitive adhesive layer can also function as a material having a color tone adjusting function at the same time.

The inventors also note that in the pressure sensitive adhesive composition, an antioxidant is used and / or the glass transition temperature and / or the weight average molecular weight of the pressure sensitive adhesive polymer is specified such that it satisfactorily enhances its function as a pressure sensitive adhesive, and / or In view of the compatibility of the ultraviolet absorber and / or the hindered amine light stabilizer and / or their cost, when the reactive and additive ultraviolet absorber and / or the hindered amine light stabilizer are used in combination, the effect of the present invention is more marked. It was found that it can be obtained. The above findings have now completed the present invention.

Accordingly, the present invention provides a pressure sensitive adhesive composition comprising a pressure sensitive adhesive polymer (A), a near infrared absorbing dye (B), and an ultraviolet absorbent (C) and / or a hindered amine light stabilizer (D).

The invention also relates to an optical filter for use in a plasma display comprising the above-mentioned pressure sensitive adhesive composition, or to a plasma display comprising said composition.

In the following, the present invention is described in detail.

The pressure-sensitive adhesive composition of the present invention contains, as an essential component, a ultraviolet absorbent (C) and / or a hindered amine light stabilizer (D) together with the pressure-sensitive adhesive polymer (A) and the near infrared absorbing dye (B). In a preferred embodiment, the ultraviolet absorber (C) and the hindered amine light stabilizer (D) are used in combination. In this case, the effect of inhibiting ultraviolet decomposition on the near infrared absorbing dye (B) is remarkably improved. Each of these essential ingredients may comprise one single species or two or more species. Preferably, the composition also comprises an antioxidant (E), and therefore a combination of an ultraviolet absorber (C), a hindered amine light stabilizer (D) and an antioxidant (E) is preferred. Thereby, the effect of this invention can be acquired more satisfactorily.

In the practice of the present invention, the ultraviolet absorber (C) and / or the hindered amine light stabilizer (D) may be additive and / or reactive. However, the reaction type is preferred. The use of the reactive ultraviolet absorber (C) is more preferred. When reactive ultraviolet absorbers (C) and / or reactive hindered amine light stabilizers (D) are used, preferred embodiments are reactive ultraviolet absorbers (C) and / or reactive hindered amine light stabilizers (D). ) Is used in the production process of the pressure sensitive adhesive polymer (A) for incorporation of the reactive ultraviolet absorber (C) and / or the reactive hindered amine light stabilizer (D) in the pressure sensitive adhesive polymer (A), ie ultraviolet An embodiment of the pressure sensitive adhesive polymer (A) in the form produced by reaction with an absorbent (C) and / or a hindered amine light stabilizer (D). Also in this case, the resulting composition comprises a ultraviolet absorber (C) and / or a hindered amine light stabilizer (D). When the additive ultraviolet absorber (C) and / or the additive hindered amine light stabilizer (D) are used alone, the compatibility with the pressure-sensitive adhesive polymer (A) may be poor, and when the water is used at a high addition level Crystallization (deposition) may occur in the coating film or the pressure-sensitive adhesive layer, so that in some cases permeability may not be obtained. There is also the possibility of speckling or clouding of the appearance in the coating film or pressure sensitive adhesive layer.

In addition, the pressure-sensitive adhesive polymer (A) produced by reaction with the ultraviolet absorber (C) and / or the hindered amine light stabilizer (D) is preferably an additive ultraviolet absorber (C) and / or a hindered amine light stabilizer ( It is used together with D). In this case, the compatibility between the pressure sensitive adhesive polymer (A) and the ultraviolet absorbent (C) and / or the hindered amine light stabilizer (D) can be improved, and the combination is also reactive UV absorber (C) and / Or it is advantageous in terms of cost as compared with the case of the use of the hindered amine light stabilizer (D) alone.

The pressure sensitive adhesive polymer (A) to be used in the practice of the present invention may be any polymer that exhibits adhesion or tackiness to the adhesive upon pressure application, for example hydroxyl group-containing cohesive polymers are preferred. Modified polymers such as fluorine-containing polymers, (meth) acrylic polymers, polyester polymers, polyether polymers, alkyd polymers, silicone polymers and polyester-modified acrylic polymers, and monomer (s) having ethylenically unsaturated bonds The polymer obtained is suitable for use as the polymer. Rubber polymers such as natural rubber, styrene-isoprene-styrene (SIS) block copolymers, styrene-butadiene-styrene (SBS) block copolymers and synthetic rubbers can also be used. Among them, (meth) acrylic polymers are preferred in view of their weather resistance and their easily adjustable tackiness. Acrylic polymers are more preferred.

The pressure sensitive adhesive polymer (A) can be obtained by polymerizing a monomer component comprising one or two or more monomers. The monomer species to be included in the monomer component and the ratio thereof may be appropriately selected according to the physical properties required for the pressure-sensitive adhesive polymer (A), for example, in the case of the (meth) acrylic polymer, having 4 to 12 carbon atoms on the side chain as the main component. Preference is given to those comprising a (meth) acrylate ester having an alkyl group.

As the (meth) acrylate having an alkyl group having 4 to 12 carbon atoms on the side chain, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth ) Acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, amyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate , Isobornyl (meth) acrylate and the like can be mentioned.

The monomer component mentioned above may also comprise monomers (other monomers) other than the above-mentioned (meth) acrylate (s) for adjusting the Tg and / or polarity of the pressure-sensitive adhesive polymer (A) obtained. As other monomers, the following monomers are preferred:

Vinyl esters such as vinyl acetate and vinyl butyrate; Fluorine atom-containing unsaturated monomers such as trifluoroethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate; Vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; Silicon atom-containing unsaturated monomers such as γ-methacryloxypropyltrimethoxysilane; Epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate; Polyfunctional unsaturated monomers such as ethylene glycol diacrylate, neopentyl glycol diacrylate and polypropylene glycol diacrylate.

Aromatic unsaturated monomers such as styrene, α-methylstyrene and vinyltoluene; Hydrocarbon unsaturated monomers such as butadiene and isoprene; Halogen atom-containing unsaturated monomers such as chloroprene and vinyl chloride; Nitrogen atom-containing unsaturated monomers such as N, N'-dimethylaminoethyl (meth) acrylate, (meth) acrylamide, N-isopropylacrylamide, N-butoxymethylacrylamide, N-phenylmaleimide, N Cyclohexylmaleimide, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, N-dimethylacrylamide and isopropenyloxazoline; Unsaturated cyano compounds such as (meth) acrylonitrile.

In the monomer component mentioned above, monomers having functional groups such as hydroxyl or carboxyl groups can also be used as crosslinking points (crosslinkable monomers) or for the adjustment of Tg and / or polarity. The following are suitable for use as said monomers:

Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate Mono (meth) acrylates of methyl α- (hydroxymethyl) acrylate, ethyl α- (hydroxymethyl) acrylate, and phthalic acid- and propylene glycol-derived polyester diols; Acidic functional group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, and carboxyl-terminated caprolactone-modified (meth) acrylates.

When reactive UV absorbers (C) and / or hindered amine light stabilizers (D) are used as monomers for the formation of the pressure sensitive adhesive polymer (A), the following monomers are suitable for use:

Reactive benzotriazole type ultraviolet absorbing monomer (for example, disclosed in Japanese Laid-Open Publication No. Hei-08-151415), such as 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H -Benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] -2H-benzotriazole and commercially available product RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.) ); Reactive benzophenone type ultraviolet absorbing monomers such as 2-hydroxy-4-methacryloxybenzophenone and 2-hydroxy-4- (2-hydroxy-3-methacryloyloxy) propoxybenzophenone; Reactive triazine type ultraviolet absorbing monomer; 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, Commercially available Adekastab LA-82 and LA-87 (both trade names, manufactured by Asahi Denka Kogyo), commercially available FA-711MM and FA-712HM (both trade names, manufactured by Hitachi Chemical Co., Ltd.), etc. Monomers (for example, disclosed in Japanese Laid-Open Patent Publication No. O1-26l409).

As the polymerization method for polymerizing the above-mentioned monomer composition, polymerization methods known in the art, for example, solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization methods can be used. In view of the simplicity and ease of the preparation procedure, a solution polymerization method is preferably used. The solvent usable when the solution polymerization method is used can be appropriately selected from those which are substantially inert to the pressure sensitive adhesive polymer (A), and can dissolve or disperse the pressure sensitive adhesive polymer (A). Thus, organic solvents such as aromatic hydrocarbon solvents such as toluene and xylene; Ester solvents such as ethyl acetate and butyl acetate; Ketone solvents such as acetone, methyl ethyl ketone and methyl amyl ketone; Alcohol solvents such as methanol, ethanol, n-propyl alcohol and isopropyl alcohol; Alkylene glycol monoalkyl ether solvents such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve) and propylene glycol monomethyl ether; And other solvents such as tetrahydrofuran, N, N-dimethylformamide, dimethylacetamide, dioxane and chloroform; And water are suitable for use. These may be used alone or two or more of them may be used in combination. When the pressure sensitive adhesive composition comprises a polyisocyanate compound to be mentioned later herein, solvents that show activity against isocyanato groups such as alcohol solvents, alkylene glycol monoalkyl ether solvents and water are in most cases undesirable.

The solvents mentioned above are preferably used in a solvent ratio which does not exceed 95 mass% with respect to the pressure-sensitive adhesive composition. More preferably, the said ratio is 10 mass% or more. More preferably, they are 15 mass% or more and 90 mass% or less.

In the polymerization of the above-mentioned monomer composition, a polymerization initiator may be used. Polymerization initiators to be used include, among others, azo initiators such as 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobisisobutyronitrile; And peroxide type initiators such as t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide and 1,1-bis (t-butylperoxy) -3,3, It can be any conventional radical polymerization initiator, including 5-trimethylcyclohexane. The addition level of the polymerization initiator is preferably 0.05 to 20 mass%, more preferably 0.1 to 15 mass% relative to the total mass (100 mass%) of the monomer components.

In the polymerization of the above-mentioned monomer composition, a chain transfer agent or a polymerization regulator may be used for molecular weight adjustment if necessary. Alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan and dodecyl mercaptan; Other mercaptans such as thioglycolic acid, mercaptopropionic acid, thioglycerol, 2-mercaptoethanol; α-methylstyrene dimer, disulfide, isopropyl alcohol, dioxane, carbon tetrachloride, chloroform and the like can be mentioned. The water may be used alone, or two or more thereof may be used in combination. The addition level of the product is preferably 0.01 to 10 mass% relative to the total mass (100 mass%) of the monomer components.

The reaction temperature in the polymerization of the aforementioned monomer component is preferably from room temperature to 200 ° C, more preferably from 40 to 140 ° C. The reaction time may be appropriately selected depending on the reaction temperature, the monomer composition and the polymerization initiator species, among others, so that the polymerization reaction can be completed.

The pressure-sensitive adhesive polymer (A) to be used in the practice of the present invention preferably has a glass transition temperature of -80 to -20 ° C so that, among other things, the polymer-forming monomer component is such that the glass transition temperature of the polymer falls within the above range. Preferably selected. When the glass transition temperature is lower than -80 ° C, the high temperature cohesive strength tends to be lowered, and when the glass transition temperature is higher than -20 ° C, pressure-sensitive adhesiveness may not be expressed at room temperature. In both cases, there is a possibility of failing to achieve good tack. The glass transition temperature Tg is easy according to the formula given below, based on the data for the glass transition temperature Tg (K) of various homopolymers as described in [POLYMER HANDBOOK, 3rd edition (published by John Wiley & Sons, Inc.)]. Can be calculated. It can also be determined using DSC (differential scanning calorimeter) or DTA (differential thermal analyzer).

1 / Tg (K) = w ₁ / Tg ₁ + w ₂ / Tg ₂ + ... + w _n / Tg _n

In the formula, w _n is the mass fraction of each monomer, and Tg _n is Tg (K) of the homopolymer of the monomer. For the above Tg, the value given in [POLYMER HANDBOOK (3rd edition, J. Brandrup and EH Immergut, WILEY INTERSCIENCE)] or a value given in the general published literature can be used.

The above-mentioned pressure sensitive adhesive polymer (A) preferably has a weight average molecular weight (Mw) of 250,000 or more and 2,000,000 or less. When Mw is less than 250,000, it is difficult to improve the retention force (cohesive strength) even when crosslinking is performed, and also the removability is lowered, making it difficult to balance various physical properties with each other. When it exceeds 2,000,000, polymerization stability may deteriorate. More preferably, they are 400,000 or more and 1,500,000 or less. The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).                     

The above-mentioned pressure sensitive adhesive polymer (A) preferably has an acid value or hydroxyl value which falls within a specific range. The solid acid value of the pressure-sensitive adhesive polymer (A) is preferably 30 mg KOH / g or less, more preferably 15 mg KOH / g or less, still more preferably 8 mg KOH / g or less. When the acid value is excessively high, the near-infrared absorbing dye may deteriorate or the polymer may react with the reactive ultraviolet absorber (C) or the hindered amine light stabilizer (D) to lose its tackiness. The hydroxyl value of the pressure-sensitive adhesive polymer (A) is preferably 10 mg KOH / g or less, more preferably 5 mg KOH / g or less, still more preferably 2.5 mg KOH / g or less. Higher hydroxyl values can cause degradation of the near infrared absorbing dye.

The hydroxyl value is the number of milligrams of potassium hydroxide required for the neutralization of acetic acid bound to the hydroxyl group upon acetylation of a sample of 1 g. It can be determined by the method described in JIS-K-0070 or as a theoretical value by calculation based on the filling composition. The acid value is the number of milligrams of potassium hydroxide required for neutralization of the acid contained in 1 g of the sample, and can be determined by the method described in JIS K 0070 or by calculation based on the filling composition.

The above-mentioned pressure-sensitive adhesive polymer (A) is used in an amount of preferably 3 mass% or more and 99.9 mass% or less with respect to 100 mass% of the pressure-sensitive adhesive composition. If the amount is less than 3% by mass, problems may arise, for example, sufficient adhesion may not be obtained, and the applicability will be poor. At levels above 99.9%, problems may also arise, for example, poor applicability, high viscosity, poor handleability will be obtained, dyes will not be miscible and satisfactory. Unpleasant pot cycles will not be obtained. More preferably, they are 10 mass% or more and 90 mass% or less, More preferably, they are 20 mass% or more and 85 mass% or less.

In the practice of the present invention, dyes having a maximum absorption wavelength within the range of 780 to 1200 nm are suitable for use as the near infrared absorbing dye (B). Two or more such dyes having different near infrared absorption characteristics may be used in combination. In this case, the near infrared absorption effect can be improved. As used herein, the term "near infrared absorption feature" has the same meaning as in "heat radiation absorption feature".

In the practice of the present invention, a near infrared absorbing solvent that can be dissolved in an organic solvent, that is, an organic solvent-soluble, is preferably used as the near infrared absorbing dye. When the dye is soluble in the organic solvent, it can be easily dissolved in the pressure-sensitive adhesive polymer (A), thereby facilitating coating production. In contrast, when the solubility of the dye is poor, it becomes difficult to mix the dye and the pressure-sensitive adhesive polymer (A), which makes the coating production also difficult. In solubility in an organic solvent, it is suitable to use a near-infrared absorbing dye having a solubility of 0.01% by mass or more in 100% by mass of the organic solvent. The organic solvents mentioned above with respect to solubility in organic solvents are not particularly limited but may be one of the following or a combination of two or more: aromatic solvents such as toluene and xylene; Alcohol solvents such as iso-propyl alcohol, n-butyl alcohol, propylene glycol methyl ether and dipropylene glycol methyl ether; Ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Dimethylformamide and the like.

As the above-mentioned near-infrared absorbing dyes, among others, phthalocyanine-based dyes, naphthalocyanine-based dyes, anthraquinone-based dyes, naphthoquinone-based dyes, cyanine-based dyes, aluminum-based dyes, immonium-based dyes , Polymethine-based dyes, aromatic dithiol-based dyes, and aromatic diol-based dyes may be mentioned. As specific commercial products, mention may be made of the "EX color" series of Nippon Shokubai, the "Epolight" series of US Epolin, and the "KAYASORB" series of Nippon Kayaku. Among them, phthalocyanine dyes are preferably used because of their excellent near infrared absorption capacity and organic solvent solubility.

Referenced herein to phthalocyanine-based means phthalocyanine, phthalocyanine complex, and derivatives of phthalocyanine or phthalocyanine complex having one or more substituents selected from OR, SR, NHR and NRR 'on the phthalocyanine backbone benzene ring. R and R 'are the same or different and each represents a phenyl group, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, which may optionally have a substituent. Preference is given to phthalocyanines in which one of the substituents is substituted with NHR.

Compounds represented by the following general formula (1) are preferred as the near infrared absorbing dye to be used in the practice of the present invention:                     

Wherein a plurality of α are the same or different and each represents SR ¹ , OR ² , NHR ³ or halogen atom, but at least one of them is necessarily NHR ³ ; R ¹ , R ² and R ³ Represents the same or different and each may optionally have one or more substituents, a phenyl group, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms; a plurality of βs are the same or different and each represents SR ¹ , OR ² or Represents a halogen atom, but at least one of these is required to be SR ¹ or OR ² ; at least one of the plurality of α and β is required to be a halogen atom or OR ² ; M is a nonmetal, metal, metal oxide or metal Halides.) These allow the effects of the present invention to be seen in full range.

In Formula 1, an alkyl group having 1 to 20 carbon atoms includes linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and isopentyl. , Neopentyl, 1,2-dimethylpropyl, n-hexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 1,4-dimethylpentyl, 2-methyl- 1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl and 2-ethylhexyl; Cyclic alkyl groups such as cyclohexyl. Aralkyl groups having 7 to 20 carbon atoms include benzyl and phenethyl. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, of which a fluorine atom is preferable.

For R ¹ , R ² and R ³ , a phenyl group, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms may have one or more substituent (s). As the substituent (s), for example, a halogen atom, acyl group, alkyl group, alkoxy group, haloalkoxy group, nitro group, amino group, alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, and Alkoxycarbonyl groups may be mentioned.

For M in the above-mentioned formula (1), the nonmetal means that there are atoms other than the metal, for example two hydrogen atoms. More specifically, it refers to a structure in which a hydrogen atom is bonded to each of two substituted nitrogen atoms, each of which may have a substituent, generated at the center of the phthalocyanine structure. As the metal, mention may be made, for example, of iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. As the metal oxide, mention may be made, for example, titanyl and vanadil. As the metal halide, mention may be made, for example, of aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. Metals, metal oxides, or metal halides are preferred as M. As an embodiment, nickel, cobalt, copper, zinc, iron, vanadil, and dichlorotin may be mentioned. Zinc, cobalt, vanadil, and dichlorotin are more preferred.

In a preferable embodiment of the compound represented by the formula (1), 4 to 8 of 8 β are the same or different, and each represents SR ¹ or OR ² . More preferably, all 8 βs are the same or different and each represent SR ¹ or OR ² . As the near-infrared absorbing dye, for example, a phthalocyanine compound represented by the following symbol may be mentioned: ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ (PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhNH) ₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₇ F, CuPc (PhS) ₈ (PhNH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₅ F ₃ , VOPc ( PhO) ₈ (PhCH ₂ NH) ₆ F ₂ , VOPc (PhO) ₈ (PhCH ₂ NH) ₈ , VOPc (PhS) ₈ (PhCH ₂ NH) ₈ , VOPc (2,5-Cl ₂ PhO) ₈ {2, 6- (CH ₃ ) ₂ PhO} ₄ Ph (CH ₃ ) CHNH ₃ F, VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ ( _{PhCH 2 NH) 4, VOPc (} 4-CNPhO) 8 {2,6-Br 2 -4- (CH 3) PhO} 4 Ph (CH 3) CHNH 4, and _{ZnPc (2,6-Cl 2 PhO)} 8 _{{2,6-Br 2 -4- (CH} 3) PhO} 4 Ph (CH 3) CHNH 3 F. of the above compounds, the same four of eight α or different and represent oR ^2, or a halogen atom each And, to a compound represented by the symbols may be mentioned _{specifically: ZnPc (PhS) 8 (PhNH} ) 3 F 5, ZnPc (PhS) 8 (PhNH) 4 F 4, ZnPc (PhS) 8 (PhCH 2 NH) 4 F ₄ , VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, VOPc (2,5-Cl ₂ PhO) ₈ { 2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , VOPc (4-CNPhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ { Ph (CH ₃ ) CHNH} ₄ , and ZnPc (2,6-Cl ₂ PhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F. Compound In the above-mentioned abbreviation for the name, Pc represents a phthalocyanine nucleus, Pc carries eight substituents at the β position and also eight substituents at the α position. Ph mentioned above represents a phenyl group. More specifically, each abbreviation mentioned above represents eight substituents at the central metal atom: Pc: β position: eight substituents at the α position. For example for ZnPc (PhS) ₈ (PhNH) ₃ F ₅ the scheme is illustrated by the underlined portion of Zn Pc (PhS) ₈ (PhNH) ₃ F ₅ .

As the above-mentioned infrared absorbing dyes, phthalocyanine dyes having a maximum absorption wavelength in the long wavelength region (920 to 1050 nm) and a high degree of visible light transmission compared to the currently known phthalocyanine dyes can be used, and the phthalocyanine dyes can be used. It is preferable in the implementation of the present invention. The above-mentioned phthalocyanine dyes suitably include compounds represented by the following general formula (2):

(Wherein Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are the same or different and each represent SR ¹ , SR ² , OR ³ or a halogen atom; Z _{1 , Z 4, Z 5, Z} 8, Z 9, Z 12, Z 13 and Z ₁₆ are the same or different and each ^{NHR 4, NHR 5, SR 1} , SR 2, oR 3 , or a halogen atom; R ¹ is A phenyl group which may have one or more substituents, an aralkyl group which may have one or more substituents or a C ₁ -C ₂₀ alkyl group which may have one or more substituents; R ² may have one or more C ₁ -C ₂₀ alkoxyl groups R ³ and R ⁴ are the same or different and each is a phenyl group which may have one or more substituents, an aralkyl group which may have one or more substituents, or a C ₁ -C ₂₀ alkyl group which may have one or more substituents It represents; R ⁵ is or a C ₁ -C ₂₀ alkyl group which may have one or more substituents Out; M is non-metal, metal, represents a metal oxide or metal halide by one or more _{Z 2, Z 3, Z 6} , Z 7, Z 10, Z 11, Z 14 and Z ₁₅ are SR ² is not essential and At least one of Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ is NHR ⁵ and at least four of them are OR ³ ; a number of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different.)

The compound represented by the above-mentioned formula (2) can selectively absorb near infrared rays having a wavelength of more than 920 nm and 1050 nm or less. When the compound is used as an infrared absorbing dye, the transmittance of visible light in the solution is adjusted such that the concentration of the above-mentioned compound is adjusted so that the minimum transmittance value of near infrared light having a wavelength of more than 920 nm and less than 1050 nm is 5 to 6%. It may be the above, the above embodiment is preferred. More preferably, the transmittance of visible light is 70% or more. The dyes having high visible light transmittance, excellent near infrared absorption ability, high near infrared blocking efficiency, and excellent solubility, heat resistance, light resistance, etc. are heat ray-shielding materials, near infrared absorption filters such as filters for plasma displays, non-contact fixed, such as It may be suitably used for near infrared absorbers for flash fixing toner or for heat reserving fibers. For example, when the water is used as a filter for a plasma display, long wavelength near infrared rays, which are difficult to be shielded, can be effectively absorbed, so that a performance error such as a remote controller can be more effectively prevented; Also, due to the high transmittance of at least 65%, more preferably at least 70%, a clear image can be provided.

In the above-mentioned formula (2), M represents a nonmetal, metal, metal oxide or metal halide; Base metals and metals include the same as those for base metals and metals which refer to M in Formula 1 above. As the metal oxide, mention may be made, for example, titanyl and vanadil. As the metal halide, mention may be made, for example, of aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Metals, metal oxides, or metal halides are preferred as M. As an embodiment, mention may be made of copper, zinc, cobalt, nickel, iron, vanadil, titanyl, indium chloride and tin (II) chloride. Copper, vanadil and zinc are more preferred.

In the above-mentioned formula (2), four or more Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ (these may be referred to as substituents that substitute 8 β positions of the phthalocyanine core) Is preferably SR ² . More preferably, all eight of these are SR ² . When any one or more of these are halogen atoms, a fluorine atom or a chlorine atom is preferable as the halogen atom. The fluorine atom is more preferable. When an electron donor such as SR ² is included, the absorption wavelength is longer, the transmittance is better, and the selective absorption of near infrared rays having a wavelength above 920 nm and below 1050 nm is provided. By carrying out the substitution with SR ² after the substitution with the amino compound in the production process, the substitution position can be easily controlled and a phthalocyanine compound having excellent compatibility with the resin can be obtained.

In the above-mentioned formula (2), Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ (these may be referred to as substituents replacing 8 α positions of the phthalocyanine core) In contrast, it is preferable that ^3-4 of these are NHR5, and ^4-5 of these are substituted by OR3. More preferably, 4 of these are NHR ⁵ , 4 of which are substituted by OR ³ , and more preferably 2 to 3 of them are NHR ⁵ , 4 of these are OR ³ , and the remaining 1 to Two are halogen atoms. As the halogen atom, a fluorine atom or a chlorine atom is preferable. More preferably, one or two of these are all fluorine atoms.

In the above-mentioned formula (2), when 2 to 3 of the 8 α positions of the phthalocyanine core are NHR ⁵ , 4 of them are OR ³ , and the remaining 1 to 2 are all fluorine atoms, the absorption wavelength is longer, Compared with the compound containing hydrogen atom (s) or other halogen atom (s) at the α-position of the phthalocyanine core, the compatibility with the resin is excellent, and the light resistance, heat resistance, and the like may be improved. In addition, the preparation of the compounds can be carried out easily and conveniently at low cost.

In R ¹ to R ⁵ of the above-mentioned formula (2), the aralkyl group of R ¹ , R ³ or R ⁴ preferably includes benzyl, phenethyl and diphenylmethyl groups.

The alkyl group of R ¹ , R ³ , R ⁴ or R ⁵ is preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, cyclohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1, 2-dimethylbutyl, n-heptyl, l, 4-dimethylpentyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl and 2-ethylhexyl groups are included. Among these, methyl and ethyl groups are more preferable.

The alkoxyl groups of R ² mentioned above may preferably be linear, branched or cyclic alkoxyl groups having 1 to 8 carbon atoms, and are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, Isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, 1,2-dimethylpropoxy, n-hexyloxy, cyclohexyloxy, 1,3-dimethyl Butoxy, 1-isopropylpropoxy, 1,2-dimethylbutoxy, n-heptyloxy, 1,4-dimethylpentyloxy, 2-methyl-1-isopropylpropoxy, 1-ethyl-3-methylpart Preference is given to oxy, n-octyloxy and 2-ethylhexyloxy groups. Among them, methoxy and ethoxy groups are more preferable because the effect of enhancing the selective absorption of near infrared rays having a wavelength of more than 920 nm and 1050 nm or less is particularly high. More preferred is a methoxy group. SR ² preferably includes phenylthio, 2-methoxyphenylthio and 4-methoxyphenylthio groups. The alkoxyl group may be substituted for 1 to 5 positions of the phenyl group, and when a plurality of alkoxyl groups are substituted, they may be the same species or different species, but one substitution is preferred. The position of the phenyl group to be substituted with the alkoxyl group is not particularly limited, but the 2- or 4-position is preferred.

The aforementioned unsubstituted alkyl groups of 1 to 20 carbon atoms of R ¹ , R ³ or R ⁴ include linear, branched or cyclic alkyl groups of 1 to 8 carbon atoms, specifically R ¹ , R ³ , R ⁴ and R ^The same alkyl groups as in ⁵ are included, of which methyl, ethyl, n-propyl, isopropyl and n-butyl groups are preferred.

Examples of the substituent of the alkyl group include a halogen atom, an alkoxyl group, a hydroxyalkoxyl group, an alkoxyalkoxy group, a haloalkoxyl group, a nitro group, an amino group, an alkylamino group, an alkoxycarbonyl group, an alkylaminocarbonyl group and an alkoxysulfonyl group. When a plurality of said substituents are substituted, the substituents may be the same species or different species.

When the above-mentioned phenyl group or aralkyl group of R ¹ , R ³ or R ⁴ has a substituent, the substituent includes, for example, a halogen atom, acyl group, alkyl group, phenyl group, alkoxyl group, haloalkyl group, haloalkoxy group, nitro group , Amino group, alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylamino carbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, oxyalkyl ether group and cyan Anger is included. One to five of the substituents may substitute for a phenyl or aralkyl group. When a plurality of said substituents are substituted, the substituents may be the same species or different species.

When the halogen atom substitutes the above-mentioned phenyl group or aralkyl group, the halogen atom is preferably a chlorine atom.

The acyl groups mentioned above include groups such as acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl, benzoyl, p-t-butylbenzoyl and the like, of which ethylcarbonyl is preferred.

The above-mentioned haloalkyl group is a substituent in which a part of an alkyl group having 1 to 20 carbon atoms is halogenated, and preferably includes a part in which a part of a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is halogenated; Groups, such as chloromethyl, bromomethyl, trifluoromethyl, chloroethyl, 2,2,2-trichloroethyl, bromoethyl, chloropropyl, bromopropyl, are preferable.

The above-mentioned haloalkoxy group is a substituent in which a part of the alkoxyl group having 1 to 20 carbon atoms is halogenated, and preferably includes a part of the linear, branched or cyclic alkoxyl group having 1 to 8 carbon atoms is halogenated; Groups such as chloromethoxy, bromomethoxy, trifluoromethoxy, chloroethoxy, 2,2,2-trichloroethoxy, bromoethoxy, chloropropoxy and bromopropoxy are preferable.                     

The above-mentioned alkylamino group is a substituent having a C ₁ -C ₂₀ alkyl residue, preferably including a C ₁ -C ₈ alkyl residue; Groups such as methylamino, ethylamino, n-propylamino, n-butylamino, sec-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, 2-ethylhexylamino and the like are preferable. Do. Among these, methylamino, ethylamino, n-propylamino and n-butylamino groups are more preferable.

The above-mentioned alkoxycarbonyl group is a C ₁ -C ₈ group which may have a hetero atom (s) at the alkyl moiety of the alkoxyl group, and C ₁ -C ₅ alkoxycarbonyl and C ₃ -C ₈ , which may have a hetero atom, Preferably cyclic alkoxycarbonyl of C ₅ -C ₈ is preferably included. Specifically, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbon Groups such as bonyl and the like can be mentioned preferably. Among these, methoxycarbonyl and ethoxycarbonyl groups are more preferable.

The phthalocyanine compound represented by the above-mentioned formula (2) has a substituent represented by NHR ⁵ at the α position of the phthalocyanine core. NHR ⁵ is an amino group having a strong electron donating and having a bulky substituent, and by being present at the α position of the phthalocyanine core, the selective absorption ability of near infrared rays having a wavelength of more than 920 nm and 1050 nm or less can be enhanced, and it is compatible with resins. Sex can be improved.

In the above-mentioned NHR ⁵ , R ⁵ is an unsubstituted alkyl group having 1 to 20 carbon atoms, and in addition to the embodiments of the alkyl group for R ¹ , R ³ , R ⁴ and R ⁵ mentioned above, the alkyl group is 2-heptyl , 2-methylhexyl, 2-propylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotri Decyl, n-tetradecyl, isotetradecyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n-heptadecyl, isoheptadecyl, n-octadecyl, isooctadecyl, n-nona Groups such as decyl, isononadecyl, n-icosyl, isoicosyl and the like. Among them, alkyl groups having 5 or more carbon atoms, and second branched alkyl groups or further carbon atoms from amino nitrogen atoms are preferred, and 1,2-dimethylpropyl, cyclohexyl, 2-heptyl, n-hexyl, 2 Groups, such as -ethylhexyl, n-octyl, 2-methylhexyl, n-octadecyl, 2-propylhexyl, are more preferable.

Substituents for the alkyl group of R ⁵ of NHR ⁵ mentioned above include an alkoxyl group having 1 to 20 carbon atoms and a nitrogen-containing group having 1 to 20 carbon atoms. 1,2-dimethylbutoxy, n-heptyloxy, 1,4-dimethylpentyloxy, 2-methyl-1- in addition to the specific examples of the alkoxyl group to be included as substituents for the phenyl group of R ² mentioned above as an alkoxyl group Groups such as isopropylpropoxy, 1-ethyl-3-methylbutoxy, n-octyloxy, 2-ethylhexyloxy and the like can be mentioned. Among them, ethoxy, isopropoxy, n-butoxy and 2-ethylhexyloxy group are preferable, and as the alkyl group containing the alkoxyl group having 1 to 20 carbon atoms, 3-ethoxypropyl, 3-isopropoxy Preference is given to propyl, 3-butoxypropyl and 3- (2-ethylhexyloxy) propyl groups.

The nitrogen-containing group preferably contains a monovalent group obtained by removing one hydrogen atom from a primary monoamine represented by the following formula (3) or from a secondary amino represented by the following formula (4), and a hetero atom having a nitrogen atom as a hetero atom. Monovalent groups derived from cyclic compounds (nitrogen atoms have free valences) include:

RNH ₂

R ₂ NH

(In Formulas 3 and 4, R represents an alkyl group having 1 to 20 carbon atoms, and in Formula 4, two R's may be the same or different.). As the alkyl group, the same alkyl group as the substituent of the above-mentioned phenyl and aralkyl group is included. The nitrogen-containing group may preferably be a monovalent group obtained by removing one hydrogen atom from a secondary amine.

The above-mentioned nitrogen-containing group preferably contains N, N-diethylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-diethylaminoethyl, N, N-diisopropylaminoethyl, N, N-di-n-butylaminoethyl, piperazino, piperidine, morpholino, 2-piperazinoethyl, 2-piperidinoethyl, 2-morpholi Groups, such as noethyl, are included. By having a substituent represented by NHR ⁵ having a substituent as mentioned above at the α position of the phthalocyanine core, the selective absorption ability of near infrared rays having a wavelength of more than 920 nm and 1050 nm or less can be further enhanced.

Among the phthalocyanine compounds represented by the above-mentioned formula (2), specific examples of those in which M is a nonmetal include the following. In the following compounds, each 3- and 6-position is the α position of the phthalocyanine core (Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ ), and each of 4- And the 5-position is the β-position of the phthalocyanine core (Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ ). In the abbreviation of the following compound, Pc represents a phthalocyanine core, 8 substituents of a (beta) position are shown immediately after Pc, and 8 substituents of (alpha) position are shown after a (beta) position.

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (N, N-diethylethylenediamino) phthalocyanine compounds

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {(C ₂ H ₅ ) ₂ NCH ₂ CH ₂ NH} ₄

4,5-octakis (2-methoxyphenylthio) -3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (N, N-diethylethylenediamino) phthalocyanine compounds

Abbreviation; Pc {2- (CH ₃ O) PhS} ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {(C ₂ H ₅ ) ₂ NCH ₂ CH ₂ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (N, N-diisopropylethylenediamino) phthalocyanine compounds

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ [{(CH ₃ ) ₂ CH} ₂ NCH ₂ CH ₂ NH] ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (N, N-di-n-butylethylenediamino) phthalocyanine compounds

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ [{CH ₃ (CH ₂ ) ₂ CH} ₂ NCH ₂ CH ₂ NH] ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (2-piperazinoethylamino) phthalocyanine compound

Abbreviation;

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (2-piperidinoethylamino) phthalocyanine compound

Abbreviation;

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (2-morpholinoethylamino) phthalocyanine compound

Abbreviation;

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (3-ethoxypropylamino) phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ O (CH ₂ ) ₃ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (3-isopropoxypropylamino) phthalocyanine compounds

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ Ph0} ₄ {(CH ₃ ) ₂ CHO (CH ₂ ) ₃ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (3-butoxypropylamino) phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ 0 (CH ₂ ) ₃ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis {3- (2-ethylhexyloxy) propylamino} phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ Ph0} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ O (CH ₂ ) ₃ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (1,2-dimethylpropylamino) phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ C (CH ₃ ) ₂ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (cyclohexylamino) phthalocyanine compound

Abbreviation;

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (2-heptylamino) phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₄ CH (CH ₃ ) NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (n-hexylamino) phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₅ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (2-ethylhexylamino) phthalocyanine compound

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄

4,5-octakis (4-methoxyphenylthio) -3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (2-ethylhexylamino) phthalocyanine compound

Abbreviation; Pc {4- (CH ₃ O) PhS} ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (n-octylamino) phthalocyanine compounds

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₇ NH} ₄

4,5-octakisphenylthio-3,6-tetrakis (2,6-dimethylphenoxy) -tetrakis (n-octadecylamino) phthalocyanine compounds

Abbreviation; Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₁₇ NH} ₄

Of the above-mentioned compounds, as the phthalocyanine compound in which M is a metal, a metal oxide or a metal halide, it is most preferable to have vanadil as the center metal, and in the embodiments, the above-mentioned in which M is a nonmetal, except for the following four compounds Included are those obtained by changing the phthalocyanine core (Pc) residues of the embodiments to VOPc:

,

,

Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ C (CH ₃ ) ₂ NH} ₄ ,

And Pc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₄ CH (CH ₃ ) NH} ₄ . By using what has vanadil as a center metal as a phthalocyanine compound, the selective absorption ability and light resistance characteristic of near-infrared exceeding 920 nm and 1050 nm or less are excellent. The above-mentioned phthalocyanine compound may be used in one species or in two or more species. It can be used together with the phthalocyanine compound represented by Formula 1 mentioned above. When two or more species having different wavelengths are used, heat ray absorptivity may be improved.

The near infrared absorbing dye (B) is preferably used in an amount of at least 0.005 parts by weight per 100 parts by weight of the pressure-sensitive adhesive polymer (A). If the amount is less than 0.005 parts by weight, the coating film or adhesive layer formed by the pressure sensitive adhesive composition may not exhibit its near infrared absorption capacity to a satisfactory degree. The amount is more preferably 0.025 parts by weight or more, and still more preferably 0.05 parts by weight or more. On the other hand, the amount is preferably 20 parts by weight or less. If the amount exceeds 20 parts by weight, the physical properties of the near infrared absorbing coating film may be reduced. More preferably it is 10 parts by weight or less, even more preferably 5 parts by weight or less. Preferably, it is selected according to the coating film thickness. For example, when thickness is 10 micrometers, the quantity becomes like this. Preferably it is 0.5 weight part or more and 20 weight part or less, More preferably, it is 1.0 weight part or more and 10 weight part or less. In the formation of the coating film having a thickness of 3 mm, the amount is preferably 0.002 parts by weight or more and 0.06 parts by weight or less, more preferably 0.005 parts by weight or more and 0.03 parts by weight or less. When the thickness is 10 mm, the amount is preferably 0.0005 parts by weight or more and 0.02 parts by weight or less, and more preferably 0.0010 parts by weight or more and 0.01 parts by weight or less. In addition, the weight of the dye included per unit area of the coating film is preferably, for example, 0.01 g / cm ² or more. If it is less than 0.01 g / m ² , the effect of the near infrared absorbing dye may not appear to a satisfactory degree. The weight thereof is preferably 0.05 g / m ² or more, more preferably 0.1 g / m ² or more. On the other hand, it is preferably 2.5 g / m ² or less. At levels exceeding 2.5 g / m ² , the production cost of the coating film may increase. More preferably, it is 1.0 g / m <^2> or less, More preferably, it is 0.5 g / m <^2> or less.

In the practice of the present invention, additive and / or reactive ultraviolet absorbers can be used as ultraviolet absorbers (C) as described herein, salicylate UV absorbers, benzophenone UV absorbers, benzotriazole type UV absorbers, Cyanoacrylate type ultraviolet absorbers, and benzoate type ultraviolet absorbers are suitable for use. Among these, the above-mentioned ultraviolet-absorbing monomers are suitable for use as the reactive ultraviolet absorber.

Phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate are suitable for use as the salicylate ultraviolet absorbers mentioned above. As commercial grades of phenyl salicylate, SAP (trade name, manufactured by Iwaki Seiyaku Co., Ltd.), Salol (trade name, manufactured by Dow Chem. Co.), and Salol P (trade name, manufactured by Hatsudai Pharmaceutical Co.) will be mentioned. Can be. Commercial grades of p-tert-butylphenyl salicylate include TBS (trade name, manufactured by Dow Chem. Co.), TBS (trade name, manufactured by Hatsudai Pharmaceutical Co.), Biosorb 90 (trade name, manufactured by Kyodo Chemical Co.), and Butylsalol (trade name, available from Iwaki Seiyaku Co., Ltd.) may be mentioned. As commercial grades of p-octylphenyl salicylate, OPS (trade name, manufactured by Eastman Chemical Co.) and OPS (trade name, manufactured by Hatsudai Pharmaceutical Co.) may be mentioned.

2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 '-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfobenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane are suitable for use as the above-mentioned benzophenone ultraviolet absorbers. As a commercial grade of 2,4-dihydroxybenzophenone, ASL-23 (trade name, product of Shonan Kagaku), Seesorb 100 (trade name, product of Shiraishi Calcium Kaisha, Ltd.), Zislizer 0 (trade name, Sankyo Chemical Co., Ltd.) Product), Sumisorb 100 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), DHBP (trade name, manufactured by Eastman Chemical Co.), Biosorb 100 (trade name, manufactured by Kyodo Chemical), and Uvinul 400 (trade name, manufactured by BASF Corp. ) May be mentioned. Commercial grades of 2-hydroxy-4-methoxybenzophenone include ASL-23 (trade name, manufactured by Shonan Kagaku), Cyasorb UV-9 (trade name, manufactured by Cytec Industries Inc.), Zislizer M (trade name, Sankyo Chemical Co. , Ltd.), Sumisorb 100 (trade name, product of Sumitomo Chemical Co., Ltd.), Seesorb 101 (trade name, product of Shiraishi Calcium Kaisha Ltd.), Biosorb 110 (trade name, product of Kyodo Chemical), Uvinul M-40 (trade name) , BASF Corp.), and Eusorex 4360 (trade name, available from Merck Ltd., Japan). As a commercial grade of 2-hydroxy-4-octoxybenzophenone, Cyasorb UV-531 (trade name, manufactured by Cytec Industries Lnc.), Seesorb 102 (trade name, manufactured by Shiraishi Calcium Kaisha, Ltd.), Zislizer E (trade name, Sankyo) Chemical Co., Ltd.), Sumisorb 130 (trade name, product of Sumitomo Chemical Co., Ltd.), Seesorb 130 (trade name, product of Shiraishi Calcium Kaisha, Ltd.), Biosorb 130 (trade name, product of Kyodo Chemical), Advastab 46 , And Adekastab 1413 (trade name, manufactured by Asahi Denka Kogyo) may be mentioned. As a commercial grade of 2-hydroxy-4-dodecyloxybenzophenone, DOPB (trade name, manufactured by Eastman Chemical Co.) and AM-320 (trade name) can be mentioned, and 2,2'-dihydroxy-4 As a commercial product of -methoxybenzophenone, Cyasorb UV-24 (trade name, manufactured by Cytec Industries Inc.) may be mentioned. As commercial grades of 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, ASL-40 (trade name, manufactured by Shonan Kagaku) and Uvinul D-49 (trade name, manufactured by BASF Corp.) may be mentioned. As the commercial grade of 2-hydroxy-4-methoxy-5-sulfobenzophenone, Uvinul MS-40 (trade name, available from BASF Corp.) may be mentioned. As a commercial grade of bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, Adekastab LA-51 (trade name, manufactured by Asahi Denka Kogyo) may be mentioned.                     

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5-di-tert-amylphenyl) benzotriazole, 2 -(2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- [(2H-Benzotriazol-2-yl) phenol], and 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole to be mentioned above Suitable for use as The. As a commercial grade of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, JF-77 (trade name, manufactured by Johoku Chemical), Tinuvin P (trade name, manufactured by Ciba Specialty Chemicals KK), Seesorb 701 (trade name, Shiraishi Calcium product), Sumisorb 200 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Biosorb 520 (trade name, manufactured by Kyodo Chemical), and Adekastab LA-32 (trade name, manufactured by Asahi Denka Kogyo). As a commercial grade of 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, Tinuvin PS (trade name, manufactured by Ciba Specialty Chemicals KK) may be mentioned, and 2- (2'-hydroxy Commercial grades of -3 ', 5-di-tert-butylphenyl) benzotriazole include Tinuvin 320 (trade name, manufactured by Ciba Specialty Chemicals), Biosorb 582 (trade name, manufactured by Kyodo Chemical), and JF-86 (trade name, Johoku). Chemical products) may be mentioned. As a commercial grade of 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, Tinuvin 326 (trade name, manufactured by Ciba Specialty Chemicals KK), Seesorb 703 (trade name, Shiraishi Calcium Kaisha, Ltd.), Biosorb 550 (trade name, Kyodo Chemical), Sumisorb 300 (trade name, Sumitomo Chemical Co., Ltd.), JF-79 (trade name, Johoku Chemical), and Adekastab LA-36 (Trade name, manufactured by Asahi Denka Kogyo) may be mentioned, and as a commercial grade of 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, Tinuvin 327 (Trade name, product of Ciba Specialty Chemicals KK), Seesorb 702 (trade name, product of Shiraishi Calcium Kaisha, Ltd.), Biosorb 580 (trade name, product of Kyodo Chemical), JF-78 (trade name, product of Johoku Chemical), and Adekastab LA-34 (Trade name, product of Asahi Denka Kogyo) may be mentioned. As a commercial grade of 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, Tinuvin 328 (trade name, manufactured by Ciba Specialty Chemicals), Biosorb 591 (trade name, manufactured by Kyodo Chemical) , Sumisorb 350 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and JF-80 (trade name, manufactured by Johoku Chemical) may be mentioned. As a commercial grade of 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, Biosorb 590 (trade name, Kyodo Chemical), Sumisorb 250 (trade name, product of Sumitomo Chemical Co., Ltd.), and Seesorb 706 (trade name, product of Shiraishi Calcium Kaisha, Ltd.) may be mentioned. Adekastab LA-31 as a commercial grade of 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] (Trade name, manufactured by Asahi Denka Kogyo) may be mentioned, and as a commercial grade of 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, RUVA-93 (trade name, Otsuka Chemical) Co., Ltd.) may be mentioned.

2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate for use as the above-mentioned cyanoacrylate ultraviolet absorbers Suitable. As commercial grades of 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, Uninol 3039, N539T (trade name, manufactured by BASF Corp.) and Biosorb 930 (trade name, manufactured by Kyodo Chemical) can be mentioned. As the commercial grade of ethyl 2-cyano-3,3'-diphenylacrylate, Uninol 3035 (trade name, manufactured by BASF Corp.) and Biosorb 910 (trade name, manufactured by Kyodo Chemical) may be mentioned.

Tinuvin 120 (trade name, manufactured by Ciba Specialty Chemicals K.K.) and Sumisorb 400 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) are suitable for use as benzoate ultraviolet absorbers.

In the addition amount of the ultraviolet absorber (C), the additive ultraviolet absorber and the reactive ultraviolet absorber are preferably used in a total amount of 0.1 part by weight or more and 100 parts by weight or less per 100 parts by weight of the pressure-sensitive adhesive polymer (A). If the amount is less than 0.1 part by weight, the near infrared absorbing dye may undergo significant degradation. If it exceeds 100 parts by weight, poor tack can be obtained. More preferably, the addition amount is 1 weight part or more, More preferably, it is 3 weight part or more. More preferably, it is 50 weight part or less, More preferably, it is 20 weight part or less. The above-mentioned addition amount of ultraviolet absorber (C) shows the amount containing both an addition type and a reactive type absorbent.

Additive and / or reactive materials as mentioned above can be used as hindered amine light stabilizers (D). As the light stabilizer, two kinds of light stabilizers, namely, a hindered phenol skeleton-free hindered amine light stabilizer (d-1) and a hindered phenol skeleton-containing hindered amine light stabilizer (d-2) May be mentioned. These show different effects. In the practice of the present invention, these may be used in combination. The hindered phenol skeleton-containing hindered amine light stabilizer (d-2) constitutes a kind of typical antioxidant. These trap radical species generated by ultraviolet rays, and exhibit an antidegradation effect. Therefore, the use of the hindered phenol skeleton-containing hindered amine light stabilizer (d-2) is preferable because it is effective in suppressing deterioration due to ultraviolet rays. That is, in a preferred embodiment of the present invention, the ultraviolet absorbent (C) comprises a hindered amine light stabilizer (D) comprising a hindered phenol skeleton-containing hindered amine light stabilizer (d-2) as an essential component thereof. It is used together with).

As a hindered phenol skeleton-free hindered amine light stabilizer (d-1), Sanol LS-770 (trade name, manufactured by Sankyo Co., Ltd.), Adekastab LA-77 (trade name, manufactured by Asahi Denka Kogyo), Sumisorb 577 (Trade name, product of Sumitomo Chemical Co., Ltd.), Biosorb 04 (trade name, product of Kyodo Chemical), Chimassorb 944LD (trade name, product of Ciba Specialty Chemicals KK), Tinuvin 622LD (trade name, product of Ciba Specialty Chemicals KK), Biosorb 03 ( Trade name, manufactured by Kyodo Chemical), Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63, Adekastab LA-68, Adekastab LA-82, Adekastab LA-87, Adekastab LA-52 (the above eight Trade names, products of Asahi Denka Kogyo), and Goodrite UV 3034 (trade name, Product of Goodrich Co.) may be mentioned.

TINUVIN 144 (trade name, available from Ciba Specialty Chemicals) is suitable for use as the hindered phenol skeleton-containing hindered amine light stabilizer (d-2).

In the addition amount of the hindered amine light stabilizer (D), when the water is a hindered phenol skeleton-free hindered amine light stabilizer (d-1), the water is preferably of the pressure-sensitive adhesive polymer (A) It is used in the amount of 0.1 weight part or more and 10 weight part or less per 100 weight part. If it is less than 0.1 part by weight, the near infrared absorbing dye may undergo significant deterioration, while if it is more than 10 parts by weight, poor adhesiveness may be obtained. More preferably, the addition amount is 0.3 parts by weight or more, and still more preferably 0.5 parts by weight or more. More preferably, it is 5 weight part or less, More preferably, it is 2 weight part or less. In the case of the hindered phenol skeleton-containing hindered amine light stabilizer (d-2), the water is preferably used in an amount of at least 0.1 parts by weight and at most 50 parts by weight per 100 parts by weight of the pressure-sensitive adhesive polymer (A). . In amounts below or above this range, it may be difficult to sufficiently prevent the near infrared absorbing pigment from degradation. More preferably, the said water is 0.3 weight part or more, More preferably, it is 0.5 weight part or more. More preferably, it is 20 weight part or less, More preferably, it is 10 weight part or less.

As antioxidants (E) are radical chain inhibitors (primary antioxidants) and peroxide degradants (secondary antioxidants).

As radical chain inhibitors (primary antioxidants), phenolic antioxidants and amine antioxidants may be mentioned. Monophenolic antioxidants, such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-, for use as phenolic antioxidants Ethylphenol and stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; Bisphenol antioxidants such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4 ' -Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) and 3,9-bis [1,1-dimethyl- 2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane; And high molecular weight phenolic antioxidants such as 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'- Di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3 , 5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -sim-triazine-2,4,6- (1H, 3H, 5H) -trione and tocopherol (s Is appropriate.

As the peroxide decomposer, sulfur-containing antioxidants and phosphorus antioxidants may be mentioned. Dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate are suitable for use as sulfur-containing antioxidants. . Triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl ditridecyl) phosph Fight, Cyclic Neopentanetetrayl Bis (octadecyl phosphite), Tris (nonylphenyl) phosphite, Tris (mono- and / or dinonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9,10 -Dihydro-9-oxa-10-phosphaphen anthren-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa -10-phosphaphenanthren-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, tris (2, 4-di-t-butylphenyl) Phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, And 2,2'-methylenebis (4,6-di-t-butylphenyl) The butyl phosphite are suitable.

Of these, hindered phenols are preferred in view of their good compatibility with these pressure-sensitive adhesive polymers (A), less coloring tendency, and the like.

The antioxidant (E) is preferably used in an added amount of at least 0.1 part by weight, more preferably at least 1 part by weight, even more preferably at least 3 parts by weight, per 100 parts by weight of the pressure-sensitive adhesive polymer (A). In addition, this amount is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, even more preferably 20 parts by weight or less.

If the addition amount of the antioxidant (E) is excessively low, the near-infrared absorbing dye may be easily degraded, while if the amount is excessively high, poor tackiness may occur or precipitation may occur, resulting in a loss of transparency of the coating film. Can be.

In the practice of the present invention, when the ultraviolet absorber (C) and the hindered amine light stabilizer (D) are used in combination, and the hindered phenol skeleton-free hindered amine light stabilizer (dl) is used as the latter, The ratio of is preferably such that the latter is at least 0.1 parts by weight, more preferably at least 1 part by weight, even more preferably at least 5 parts by weight per 100 parts by weight of the ultraviolet absorber (C). On the other hand, the amount of (d-1) is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, even more preferably 30 parts by weight or less. Using a hindered phenol skeleton-containing hindered amine light stabilizer (d-2), it is preferably at least 0.1 part by weight, more preferably at least 1 part by weight, more per 100 parts by weight of ultraviolet absorber (C). More preferably, it is 5 weight part or more. This amount is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, even more preferably 30 parts by weight or less.

Preferably, the pressure sensitive adhesive composition of the present invention may further comprise a color tone adjuster. In plasma displays, neon-due orange occurs at wavelengths of 580-600 nm. In order to obtain a vivid red color, the orange color scheme should be cut off and at the same time the color tone of the optical filter should be adjusted to the natural gray color. When a color tone modifier is added to the pressure sensitive adhesive composition and the resulting composition is used together to bond the plasma display optical filter-forming material, it is necessary to cut off the neon dew orange color scheme and adjust the color tone of the optical filter to natural gray. It is possible.

The color tone adjuster may be a dye or a pigment. Dyes include squarylium dyes, azomethine dyes, cyanine dyes, merocyanine dyes, phthalocyanine dyes, oxonol dyes, anthraquinone dyes, benzylidene dyes, azo dyes, and triarylmethane dyes and metal chelates derived therefrom. Preference is given to dyes such as compounds. As the pigment, organic pigments such as azo, phthalocyanine, anthraquinone and quinacridone are preferable.

The amount of color tone modifier added is preferably 0.1 to 10 times, more preferably 0.5 to 5 times, of the near infrared absorbing dye on a mass basis.

The film or coating film formed from the pressure sensitive adhesive composition of the present invention can be used in a crosslinked or non-crosslinked state.

The pressure-sensitive adhesive composition of the present invention may be cured under various curing conditions depending on the intended use thereof and the kind of curing agent, and may be used, for example, in the form of a cold curing, thermal curing, ultraviolet curing or electron beam curing type. The addition amount, dispersion and addition method of the curing agent are not particularly limited, but if the pressure-sensitive adhesive polymer (A) occurs as a polyol having a plurality of hydroxyl groups in each molecule, for example, an addition and dispersion method commonly used in curing the polyol. And addition amounts can be used.

When the pressure sensitive adhesive polymer (A) is composed of polyols, (blocked) polyisocyanate compounds and aminoplast resins are suitable for use as crosslinking agents. These may be used alone or in combination of two or more thereof.

As used herein, the term “(blocked) polyisocyanate compound” refers to a polyisocyanate compound and / or a blocked kit polyisocyanate compound.

The polyisocyanate compound may be any of compounds having at least two isocyanato groups in the molecule. Thus, this includes tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), lysine di Isocyanates, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethanetriiso cyanate, and other polyisocyanates; Adducts of these polyisocyanates, biuret forms, and isocyanurate forms and other polyisocyanate derivatives (modifications).

The above-mentioned blocky polyisocyanate compounds are usually the product of the blocking by the blocking agent of the isocyanate group of the polyisocyanate compound, so that the pressure-sensitive adhesive composition can be crosslinked in the drying step by heating, and its storage stability at normal temperature. Can be improved.

Blocking agents include compounds such as β-caprolactam, phenol, cresol, oxime, and alcohol.

Commercial grades of (blockkid) polyisocyanate compounds include Sumidur N 3200, Sumidur N 3300, Sumidur EL 3175, Desmodur N 3400, Desmodur N 3600, Desmodur VPLS 2102 (trade name, available from Sumitomo Bayer Urethane), and Duranate E-402 -90T (trade name, manufactured by Asahi Kasei Corp.) may be mentioned. In order to prevent yellowing of the coating film formed of the pressure-sensitive adhesive composition, it is preferable to use a non-yellowing polyisocyanate compound having no isocyanato group directly bonded to the aromatic ring.

(Blocked) The polyisocyanate compound is preferably used in an amount such that the isocyanate group in the (blocked) polyisocyanate compound becomes 0.01 mol or more and 5 mol or less per mole of hydroxyl groups in the pressure-sensitive adhesive composition. If it is less than 0.01 mole, unreacted hydroxyl groups remain in large amounts in the pressure sensitive adhesive composition, thereby reducing the weather resistance of the coating film formed using the resulting pressure sensitive adhesive composition. If it exceeds 5 moles, unreacted isocyanato groups remain in the coating film in a large amount, and react with moisture in the air at the stage of coating film curing, causing bubbles or whitening in the coating film. More preferably, the amount is at least 0.1 moles, even more preferably at least 0.5 moles. More preferably, it is at most 2 moles, even more preferably at most 1.2 moles.

The aforementioned aminoplast resins are addition groups derived from amino group containing compounds such as melamine or guanamine, and formaldehyde, also called "amino resins".

Examples of the aminoplast resins include dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, complete alkyl type methylated melamine, fully alkylated butylated melamine, and fully alkyl. Melamine resins such as isobutylated melamine, fully alkylated etherified melamine, methylol methylated melamine, imino methylated melamine, methylol mixed etherified melamine, imino mixed etherified melamine, and the like; And guanamine resins such as butylated benzoguanamine, methyl / ethyl mixed alkylated benzoguanamine, methyl / butyl mixed alkylated benzoguanamine, butylated glycoluril, and the like.

Commercial grades of the aforementioned aminoplast resins include Cymel 1128, Cymel 303, Mycoat 506, Cymel 232, Cymel 235, Cymel 771, Cymel 325, Cymel 272, Cymel 254, and Cymel 1170 (all trade names, manufactured by Mitsui Cytec) , Etc. may be mentioned.                     

With regard to the amount of aminoplast resin added, it is preferable that the solid mass of the aminoplast resin can be at least 0.1 parts by weight, more preferably at least 0.5 parts by weight, per 100 parts by weight of the pressure sensitive adhesive polymer (A). Introduced in quantity. It is preferably introduced at 10 parts by weight or less, more preferably at 5 parts by weight or less. The use of excess aminoplast resin can result in loss of tack, and if the amount is too small, crosslinking will not proceed and result in poor adhesion.

As the crosslinking system in the pressure-sensitive adhesive composition of the present invention, not only the aforementioned OH / isocyanate system but also acid / epoxy, acid / metal chelate, acid / oxazoline, and acid / amine system are suitably used. If the effect of the present invention is not reduced, the pressure-sensitive adhesive composition of the present invention may further comprise crosslinking agents, epoxy compounds, aziridine compounds, oxazoline compounds, melamine compounds, metal chelate compounds, carbodiimide compounds, Glycidylamine compounds, amine compounds and the like. These may be used alone or in combination of two or more thereof.

The pressure-sensitive adhesive composition of the present invention may include one or more kinds of curing catalysts in order to promote the crosslinking reaction between the pressure-sensitive adhesive polymer (A) and the crosslinking agent as necessary. Such a curing catalyst is not particularly limited, but using the aforementioned (blocked) polyisocyanate compound, a catalyst such as, for example, dibutyltin dilaurate or tertiary amine is preferably used. If the above-described aminoplast resin is used, an acidic or basic curing catalyst is preferably used.

The pressure sensitive adhesive composition of the present invention may comprise one or more solvents and additives as additional component (s). As such a solvent, the same organic solvent as mentioned above can be mentioned, As an additive, It is known in the art, Additives conventionally used in resin composition for film formation, film coating, etc., For example, Leveling agent; Inorganic fine particles such as colloidal silica and alumina sol; Antifoam; Flow inhibitors; Silane coupling agents; Titanium white, composite oxide pigments, carbon black, organic pigments, pigment intermediates, and other pigments; Pigment dispersants; Viscosity modifiers; Ultraviolet stabilizers; Metal deactivators; Peroxide degrading agents; Fillers; Adjuvant; Plasticizers; slush; Preservatives; Antirust agent; Organic and inorganic ultraviolet absorbers; Inorganic heat absorbers; Organic and inorganic flame retardants; Antistatic agent; adhesive; Nucleating agents, and the like.

The above-mentioned adhesive is an adhesive improving agent, and can adjust (improve) adhesiveness. As the pressure-sensitive adhesive, (polymerized) rosin type, (polymerized) rosin ester type, terpene type, terpene phenol type, coumarone type, coumarone-indene type, styrene resin type, xylene resin type, phenol resin type, and petroleum Mention may be made of resinous pressure-sensitive adhesives. These may be used alone or in combination of two or more thereof. In the case of introducing such an adhesive, the addition amount is not particularly limited, but may be appropriately selected so that the desired adhesive performance characteristics are obtained. Examples of nucleating agents include sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, sodium bis (4-t-butylphenyl) phosphate, bis (p-methylbenzylidene) sorbitol, alkyl Mention may be made of -substituted dibenzylidene sorbitol, and bis (p-ethylbenzylidene) sorbitol. The addition amount of the nucleating agent is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive polymer (A). At lower amounts, satisfactory effects cannot be obtained.

The pressure sensitive adhesive composition of the present invention may further include light stabilizers other than the hindered amine light stabilizer (D). Such light stabilizers include nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-tert-octylphenolrato)]-n-butylamine nickel, nickel composite-3,5-di-tert Mention may be made of -butyl-4-hydroxybenzylphosphate monoethylate, and nickel dibutyldithiocarbamate. Suitable commercial grades of nickel bis (octylphenyl) sulfide can use AM-101 (trade name, manufactured by Ferro Chemical Corp.) and AM-105 (trade name, manufactured by Ferro Chemical Corp.). A suitable commercial grade of [2,2'-thiobis (4-tert-octylphenolrato)]-n-butylamine nickel may use Cyasorb UV-084 (trade name, manufactured by Cytec Industries Inc.). As a commercial grade for nickel complex-3, 5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, Irgasorb 2002 (trade name, manufactured by Ciba Specialty Chemicals K.K.) can be used. A suitable commercial grade of nickel dibutyldithiocarbamate is NBC (trade name, manufactured by ICI or Ouchishinko Chemical Industrial Co., Ltd.).

With regard to the form of a film or coating film formed of the pressure sensitive adhesive composition of the present invention, mention may be made of a laminate comprising a film or coating film formed of the pressure sensitive adhesive composition of the invention, which is disposed on a transparent substrate or 2 It sandwiches between two substrates and acts as an adhesive layer.

As the above-mentioned transparent substrate, an organic substrate, for example, polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyethylene, among others Terephthalate resin, triacetyl cellulose resin; And inorganic substrates such as glass substrates are suitably used.

The above-described adhesive layer can be formed by applying the pressure-sensitive adhesive composition on a transparent substrate. The method of applying the pressure-sensitive adhesive composition on the substrate is not particularly limited, but a method known in the art can be used. Thus, for example, the composition may be applied directly to the substrate or in advance to a release liner (release paper, release film), and then dried and then transferred to the substrate. The pressure sensitive adhesive composition may be applied to one or both sides of the substrate. Since the film or coating film formed from the pressure-sensitive adhesive composition of the present invention is tacky, after applying the pressure-sensitive adhesive composition to a substrate to form an adhesive layer, when further forming a laminate using another substrate or pressure-sensitive adhesive When using a composition in the form of a film, it is preferable to laminate | stack an adhesive layer surface or a film surface with a release paper, and, when using, to peel off a release paper.

In forming the adhesive layer described above, the method of applying the pressure sensitive adhesive composition to the transparent substrate may be appropriately selected depending on the form and other factors of the pressure sensitive adhesive composition to be applied. Such methods include (1) a solvent-type application method comprising dissolving a pressure-sensitive adhesive composition in an organic solvent and applying the resulting uniform solution to the surface of various films or sheets (substrates), (2) pressure-sensitive adhesive composition Method of dissolving in water, and applying the resulting emulsion to the surfaces of various substrates, (3) melting and mixing the pressure-sensitive adhesive composition at elevated temperatures, and applying the resulting melt to the substrate surface. Heat melting type application method, and (4) a calendering type application method which is a solventless application method. In the case of (1) solvent type application method or (2) emulsion type application method, the above-mentioned suitable organic solvent can be mixed with the pressure-sensitive adhesive composition for its application, and with regard to the application method, various coaters and dipping, spraying Mention may be made of application methods using brushing, electrostatics and the like. Coaters include gravure coaters, such as arc gravure coaters, offset gravure coaters, pan feed gravure coaters and die feed gravure coaters; Reversors such as top feed reversator and bottom feed reversator; Comma coaters such as comma direct coater, comma reversor and U comma coater; Air knife coaters, knife coaters, fountain die coaters, lip coaters, Meyer bar coaters, curtain flow coaters, roll coaters, spin coaters, blade coaters, bar coaters, die coaters, spray coaters, and the like. The curing method of the pressure-sensitive adhesive composition may be appropriately selected depending on the kind of components and other factors, and may mention, for example, a method including heating and a method including irradiation of ultraviolet or electron beams.

The thickness of the above-described adhesive layer is not particularly limited, but may be selected at an appropriate level depending on the intended use. For example, the dry thickness is preferably at least 5 μm and at most 200 μm. More preferably, it is 15 micrometers or more and 100 micrometers or less, More preferably, it is 50 micrometers or less. If the adhesive layer is thinner than this, poor adhesiveness may occur, and disadvantageously, partial lifting or flagging occurs. If the layer is thicker than above, the adhesive may disadvantageously bulge out.

In the above-mentioned laminate, the ultraviolet absorbing layer is preferably disposed on the incident light surface of the near infrared absorbing layer. This can prevent the near-infrared absorbing dye from deteriorating more effectively. The laminated structure of such a laminate is not particularly limited, but for example, (1) in the form of a laminate comprising them in the order of the ultraviolet light absorbing layer, the adhesive layer and the substrate at the incident light surface, and (2) the ultraviolet absorbing layer, the substrate and the adhesive at the incident light surface. Included are laminate forms comprising them in layered order. In order to improve antifriction and antifouling, the laminate surface may further be provided with a surface protective layer or layers, such as a silicone or organic hard coat layer or / and photocatalytic functional layer. If desired, a primer layer may be provided between the substrate and the laminate and / or between two adjacent layers of the laminate. The composition or thickness of such ultraviolet absorbing layer, surface protective layer or primer layer is not particularly limited.

The coating film formed from the pressure-sensitive adhesive composition of the present invention is characterized in that the deterioration in the near-infrared absorptivity is slight, and the composition has adhesiveness. The beneficial physical properties of the coating film are evidenced by the fact that the decrease in near infrared absorption capacity of the near infrared absorbing dye after the photoprotective test is slight, i.e., the high residual absorption capacity. The absorbency of the film at the maximum absorption wavelength (maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm) after 96 hours of UV irradiation in the evaluation of deterioration of the near infrared absorbing dye described below is preferable when the initial value is 100%. Preferably at least 5%, more preferably at least 50%, even more preferably at least 85%, most preferably at least 95%. Absorption values after UV irradiation are relative when the initial value is 100%.

(Near Infrared Absorbing Dye Evaluation for Degradation)

The absorbance at the maximum absorption wavelength of the near infrared absorbing dye is monitored after UV irradiation.

The pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive composition to a release film (silicon treated PET film) at a dry thickness of 25 μm using an applicator. The layer is dried at 100 ° C. for 2 minutes. The adhesive layer is laminated with a 50-μm-thick or 100-μm-thick PET film (for delivery of the adhesive layer to the film). The release film is peeled off from the pressure sensitive adhesive composition and then laminated to a 50-μm-thick PET film.

Using a spectrometer (manufactured by Shimadzu Corp., trade name: UV-3100), the absorbency of the film at the maximum absorption wavelength (maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm) is measured. The film described above is UV irradiated using an ultraviolet automatic fade meter (manufactured by Suga Test Instruments Co., Ltd., trade name: FAL-AU-B). Absorption measurements are performed using a spectrometer (Shimadzu Corp., trade name: UV-3100) by irradiating UV at 48 hour intervals at the maximum absorption wavelength of the film (maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm). . Record the relative absorbency value and set the initial value to 100. Values close to 100% yield better results without substantial degradation of the dye.

Films or coating films or adhesive layers formed from the pressure-sensitive adhesive composition of the invention preferably comprise laminates comprising the coating films or films have improved transparency. Thus, for example, it has a haze value of preferably 3.0% or less, more preferably 2.0% or less, even more preferably 1.0% or less.

The pressure sensitive adhesive compositions of the present invention can be used extensively for conventional adhesive purposes, which are preferably used as materials for forming adhesive layers in electronic equipment or devices, such as plasma displays.

If such a pressure-sensitive adhesive composition functions as an adhesive layer and at the same time a near infrared absorbing layer, the layer structure of a plasma display or the like can be simplified, and radiation of near infrared or the like from the screen can be suppressed.

As a preferred embodiment of the present invention, an optical filter for plasma display forming a plasma display front plate formed using the above-described pressure-sensitive adhesive composition, that is, an optical filter for plasma display including the pressure-sensitive adhesive composition described above will be mentioned. Can be. Moreover, the plasma display containing the pressure sensitive adhesive composition mentioned above is mentioned. A preferred form of such plasma display is a plasma display comprising the aforementioned plasma display optical filter as a main component.

In such a plasma display optical filter or plasma display, the adhesive layer formed of the pressure sensitive adhesive composition of the present invention can absorb near infrared and ultraviolet rays, and when the color tone adjusting agent is added, the layer will also function as a material having a color tone adjusting function. Can be. Thus, it is possible to integrate the functions of each layer constituting the front plate of the plasma display, thereby reducing the number of layers in the front plate for cost reduction. Such plasma display optical filters and plasma displays also constitute an aspect of the present invention.

The pressure-sensitive adhesive composition of the present invention having the configuration as described above enables slight deterioration of the near-infrared absorbing dye caused by ultraviolet rays, so as to be used in the formation of an adhesive layer for sticking together with the laminating material constituting a plasma display or the like. Suitable for, it becomes possible to integrate the function of each layer in the front plate of the plasma display into the adhesive layer; Thus, the adhesive layer can act as a material capable of absorbing the near infrared layer and the ultraviolet light, which can further have a color tone adjusting function. As a result, it is possible to reduce the number of layers in the front plate for cost reduction while satisfying the basic performance characteristics required for plasma displays and the like.

Best Mode for Carrying Out the Invention

The following examples illustrate the invention in more detail. However, this is not intended to limit the scope of the present invention. Unless stated otherwise, "part (s)" means "part (s) by weight".

Synthesis Example 1 (Drop monomer polymerization method)

358.2 g of 2-ethylhexyl acrylate (2EHA), 240 g of cyclohexyl methacrylate (CHMA), and 1.8 g of 2-hydroxyethyl acrylate (HEA) were weighed and thoroughly mixed (the resulting mixture) Is later referred to as “monomer mixture (A1)”). 40% of the monomer mixture (A1) and 196.4 g of ethyl acetate were weighed and placed in a flask equipped with a thermometer, agitator, inert gas inlet tube, reflux condenser and dropping funnel. The remaining 60% portion of monomer mixture (A1), 16 g of ethyl acetate, and 0.72 g of polymerization initiator Nyper BMTK 40 (trade name, manufactured by NOF Corp.) were placed in a dropping funnel and thoroughly mixed (this mixture was then referred to as "monomer"). Mixture (B1) ”). 20 mL / min of nitrogen gas was properly passed through the flask while the flask internal temperature was raised to 85 ° C. 0.96 g of a polymerization initiator Nyper BMTK 40 (trade name, manufactured by NOF Corp.) was charged to the flask to initiate a reaction. After 15 minutes of charging the polymerization initiator, the monomer mixture (B1) was evenly added to the flask over 90 minutes to proceed with the reaction. Immediately after completion of the addition of the monomer mixture (E1), 50 g of ethyl acetate was added. Aging reactions were performed at 80% for 90 minutes. A mixed solution of 1.8 g of polymerization initiator ABN-E (trade name, manufactured by Japan Hydrazine Co, Inc.) and 39 g of ethyl acetate was divided into 5 portions and placed in a flask at 30 minute intervals (for residual monomer reaction). The aging reaction was carried out at 80 ° C. for 90 minutes, 575 g of toluene were added and the reaction was terminated. The pressure sensitive adhesive polymer (A-1) was obtained.

Synthesis Example 2 (Batchwise Monomer Polymerization Method)

209.1 g of 2EHA, 60 g of CHMA, 0.9 g of HEA, 30 g of RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.), and 245 g of ethyl acetate were weighed to obtain a thermometer, stirrer, inert gas inlet. The flask was fitted with a tube, reflux condenser and dropping funnel. 20 mL / min of nitrogen gas was properly passed through the flask while the flask internal temperature was raised to 85 ° C. 0.6 g of the polymerization initiator Nyper BMTK 40 (trade name, manufactured by NOF Corp.) was charged to the flask to initiate the reaction. The reaction was carried out for 90 minutes. A mixed solution of 0.3 g of polymerization initiator Nyper BMTK 40 (trade name, manufactured by NOF Corp.) and 15 g of ethyl acetate was added in two portions each time to the flask (for residual monomer reactions). The aging reaction was carried out at 80 ° C. for 150 minutes, and after adding 155 g of toluene, the reaction was terminated. The pressure sensitive adhesive polymer (A-2) was obtained.

Synthesis Examples 3 to 5 (batch monomer polymerization method)

A pressure-sensitive polymer (A-3), a pressure-sensitive polymer (A-4) and a pressure-sensitive polymer (A-5) were obtained in the same manner as in Synthesis Example 2, except that each monomer composition specified in Table 1 was used.

Synthesis Example 6 (Drop-type monomer polymerization method)

120 g butyl acrylate (BA), 456 g 2EHA, 6 g stearyl acrylate (STA) and 18 g HEA were weighed and thoroughly mixed (this mixture is then referred to as "monomer mixture (A2)"). Call). 40% of the monomer mixture (A2) and 293.3 g of ethyl acetate were weighed and dropped into a flask equipped with a thermometer, agitator, inert gas inlet tube, reflux condenser and dropping funnel. The remaining 60% of the monomer mixture (A2), 10 g of ethyl acetate, 60 g of toluene, and 0.36 g of polymerization initiator Nyper BMTK 40 (trade name, manufactured by NCF Corp.) were added to the dropping funnel and thoroughly mixed (this mixture) Is then referred to as "monomer mixture (B2)"). 20 mL / min of nitrogen gas was properly passed through the flask while the flask internal temperature was raised to 85 ° C. 0.48 g of a polymerization initiator Nyper BMTK 40 (trade name, manufactured by NCF Corp.) was charged to a flask to initiate a reaction. After 10 minutes of charging the polymerization initiator, the monomer mixture (B2) was evenly charged to the flask over 60 minutes to proceed with the reaction. Immediately after completion of the addition of the monomer mixture (B2), 6 g of ethyl acetate and 52.4 g of toluene were added. The aging reaction was carried out at 86 ° C. for 90 minutes. A mixed solution consisting of 0.6 g of polymerization initiator Nyper BMTK 40 (trade name, manufactured by NOF Corp.) and 30 g of toluene was added in two portions each time to the flask at 1 hour intervals (for the residual monomer reaction). The aging reaction was carried out at 86 ° C. for 90 minutes, 318.5 g of ethyl acetate and 423.4 g of toluene were added and the reaction was terminated. Finally, a mixed solution consisting of 0.15 g of crosslinking accelerator di-n-butyltin dilaurate, 3 g of acetic acid and 25 g of toluene was added, followed by sufficient mixing to obtain a pressure sensitive adhesive polymer (A-6). .

Synthesis Example 7 (Drop monomer polymerization method)

275.5 g of BA, 136.8 g of 2EHA, 36 g of acrylic acid (AA), 149.9 g of vinyl acetate (VAC) and 1.8 g of HEA were weighed and thoroughly mixed (this mixture is then referred to as "monomer mixture (A3)"). Is called). 33% of the monomer mixture (A3), 312.9 g of ethyl acetate and 3.3 g of toluene were weighed and placed in a flask equipped with a thermometer, agitator, inert gas inlet tube, reflux condenser and dropping funnel. The remaining 67% of monomer mixture (A3), 139.9 g of ethyl acetate and 0.79 g of polymerization initiator ABN-E (trade name, manufactured by Japan Hydrazine Co., Inc.) were placed in a dropping funnel and thoroughly mixed (this mixture was then " Monomer mixture (B3) "). While the flask internal temperature was raised to 82 ° C., 20 mL / min of nitrogen gas was properly passed through the flask. 0.79 g of a polymerization initiator Nyper BMTK 40 (trade name, manufactured by NCF Corp.) was charged to a flask to initiate a reaction. After 15 minutes of charging the polymerization initiator, the monomer mixture (B3) was evenly added to the flask over 90 minutes to proceed with the reaction. Immediately after the addition of the monomer mixture (B3) was completed, 151.2 g of toluene was added. The aging reaction was carried out at 80 ° C. for 90 minutes. 182.9 g of toluene was added. Subsequently, a mixed solution consisting of 1.8 g of polymerization initiator ABN-R (trade name, manufactured by Japan Hydrazine Co., Inc.) and 23.4 g of toluene was added to the flask at 30-minute intervals in five portions (residual monomer reaction for). The aging reaction was carried out at 80% for 90 minutes, 164.4 g of toluene was added and the reaction was terminated. A pressure sensitive adhesive polymer (A-7) was obtained.

Remarks related to Table 1. BA stands for butyl acrylate, 2EHA stands for 2-ethylhexyl acrylate, CHMA stands for cyclohexyl methacrylate, HEA stands for 2-hydroxyethyl acrylate, and RUVA stands for RUVA-93 (trade name, Otsuka Chemical Co., Ltd.), VAC represents vinyl acetate, AA represents acrylic acid, and STA represents stearyl acrylate.

Tg is a calculated value based on the Tg value for each homopolymer. The following values were used as homopolymer Tg values: BA: -55 ° C, 2EHA: -70 ° C, CHMA: 66 ° C, HEA: -15 ° C, RUVA: 100 ° C, VAC: 25 ° C, AA: 106 ° C and STA: -70 ° C.                     

The hydroxyl value and acid value are the values per gram of polymer solids.

Example 1

0.2 g of a near-infrared absorbing dye IR-12 (Nippon Shokubai Co., Ltd., trade name: EX Color), 0.49 g of a UV absorber TINUVIN 234 (trade name, manufactured by Ciba Specialty Chemicals KK) and toluene 22.93 g of a pressure-sensitive adhesive polymer To (A-1) solution (40.6% nonvolatile (NV)). The amount of toluene was 2 g (a quantity giving a 39% theoretical nonvolatile content). The mixture is stirred using a paint shaker until a homogeneous solution is formed; Then a resin solution was prepared. The maximum absorption wavelength (λmax) of IR-12 was 885 nm (toluene solution).

The resin solution was applied to a release film (silicone treated PET film) using an applicator to obtain a dry thickness of 25 μm to form a pressure sensitive adhesive layer. It was dried at 100 ° C. for 2 minutes. A 50-μm- or 100-μm-thick PET film was laminated to the pressure sensitive adhesive layer (to transfer the pressure sensitive adhesive layer to the film). The adhesive samples thus obtained were evaluated for tackiness and appearance and for near infrared absorption dye deterioration by the method described below. The results are shown in Table 2.

Examples 2 to 10 and Comparative Example 1

The procedure of Example 1 was followed in the same manner except that the resin solution was prepared according to the formulations specified in Tables 2-4. The obtained result is shown to Tables 2-4.

Examples 11-25                     

The procedure of Example 1 was followed in the same manner, except that the resin solution was prepared according to the formulations specified in Tables 2 and 3. Subsequently, 1.0 part of isocyanate crosslinking agent Coronate L-55E (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) was mixed with respect to 100 parts of each resin solution, followed by sufficient mixing. In this case, the pressure-sensitive adhesive sample was evaluated after aging for 1 week or longer at room temperature. The results are shown in Tables 2 and 3.

(Tackiness evaluation)

The release film was peeled from each pressure-sensitive adhesive sample, and the pressure-sensitive adhesive layer was evaluated by touching the fingertips. When stickiness was felt, it was evaluated as stickiness (0), and when there was no stickiness at all, it was evaluated as non-tackiness (X).

(Appearance evaluation)

Pressure-sensitive adhesive samples prepared in this manner were visually observed respectively. If the sample had transparency, it was evaluated as good (0) and without transparency (cloudy and / or spot and other foreign material formation) as poor (X).

(Near infrared absorption dye deterioration evaluation)

The absorbance at the maximum absorption wavelength of the near infrared absorbing dye was monitored after UV irradiation.

After the release film was peeled off from each adhesive sample, a 50-μm-thick PET film was laminated thereto. The spectrophotometer (manufactured by Shimadzu Corp., trade name: UV-3100) was used to measure the absorbency (maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm) of the above-mentioned film at the maximum absorption wavelength.

The film described above was UV irradiated using an ultraviolet automatic fade meter (manufactured by Suga Test Instruments Co., Ltd., trade name: FAL-AU-B). Absorption was carried out using a spectrometer (Shimadzu Corp., trade name: UV-3100) by irradiating UV at 48 hour intervals at the maximum absorption wavelength of the film (maximum absorption wavelength of the near infrared absorbing dye: 780 to 1200 nm). The relative absorbency value was recorded and the initial value was 100. The closer the value is to 100%, the better the result is without the actual deterioration of the dye.                     

Remarks related to Tables 2-4. Regarding the near infrared absorbing dye B, IR12 is obtained from Nippon Shokubai Co., Ltd. It is a near-infrared absorption dye (trade name: EX Color) made by Corporation. With regard to ultraviolet absorbent C, TINUVIN 234 and TINUVIN 384 (both trade names) are Ciba Specialty Chemicals K.K. It is a ultraviolet absorber of the company. With respect to the hindered amine light stabilizer d-1 and the hindered amine light stabilizer d-2, TINUVIN 765 and TINUVIN 144 (both trade names) are described in Ciba Specialty Chemicals K.K. It is a light stabilizer made by the company. With respect to antioxidant E, BHT ™ is Sumitomo Chemical Co., Ltd. It is a homemade hindered phenol antioxidant.

According to the present invention, it is possible to reduce the layer structure of the plasma display or the like, to achieve weight reduction and simplify the manufacturing process.

Claims (6)

A pressure-sensitive adhesive polymer (A) and a near infrared absorbing dye (B), and further comprising an ultraviolet absorber (C), a hindered amine light stabilizer (D), or an ultraviolet absorber (C) and a hindered amine light stabilizer. As a pressure-sensitive adhesive composition comprising (D), The pressure-sensitive adhesive polymer (A) is a (meth) acrylic polymer, The glass transition temperature of the pressure-sensitive adhesive polymer (A) is -80 to -20 ℃, The acid value of the pressure-sensitive adhesive polymer (A) is 30 mg KOH / g or less composition. The pressure sensitive adhesive composition according to claim 1, further comprising an antioxidant (E). delete The pressure sensitive adhesive composition according to claim 1 or 2, wherein the pressure sensitive adhesive polymer (A) has a weight average molecular weight of 250,000 or more. An optical filter for plasma display comprising the pressure sensitive adhesive composition according to claim 1. A plasma display comprising the pressure sensitive adhesive composition according to claim 1.