JP2007131748A - Pressure-sensitive adhesive composition comprising near infrared light absorber and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition maintaining sufficient near infrared light screening characteristics and transparency with slight deterioration of a near infrared light absorber during heat resistance tests and wet heat resistance tests and having excellent cohesive force. <P>SOLUTION: The pressure-sensitive adhesive composition comprises a pressure-sensitive adhesive polymer (A) which is a block polymer or a graft polymer obtained by carrying out radical polymerization in the presence of a polyvalent mercaptan and a near infrared light absorbing dye (B). In the pressure-sensitive adhesive composition, the pressure-sensitive adhesive polymer (A) has a polymer moiety having ≥50°C glass transition temperature and a polymer moiety having <0°C glass transition temperature in the same molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pressure sensitive adhesive composition containing a near infrared absorber. In particular, the present invention relates to a pressure-sensitive adhesive composition containing a near-infrared absorber excellent in heat resistance and heat-and-moisture resistance.

  In recent years, PDPs (plasma display panels) that are thin and applicable to large screens have attracted attention. In PDP, near infrared rays are generated during plasma discharge, and this near infrared ray causes a malfunction of remote control for home appliances. As near-infrared dyes that absorb near-infrared light generated from PDP and the like, generally there are dyes such as cyanine-based, polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, and diimonium-based pigments (Patent Documents 1 and 2). ).

  The PDP generates a discharge in a rare gas, particularly a gas mainly composed of neon, enclosed in the panel, and R, G, B provided in the cells inside the panel by vacuum ultraviolet rays generated at that time. In order to cause this phosphor to emit light, an electromagnetic wave unnecessary for the operation of the PDP is simultaneously emitted during the light emission process, and it is necessary to shield the electromagnetic wave. Moreover, in order to suppress reflected light, an antireflection film and an antiglare film are also required. For this reason, an optical filter for PDP is generally prepared by laminating a near-infrared absorbing film, an electromagnetic wave shielding film, and an antireflection film on glass or a shock absorbing material as a support. Such an optical filter for PDP may be used by being placed on the front side of the PDP or pasted using an adhesive or a pressure sensitive adhesive.

JP 2003-960040 A JP-A-2000-80071 Also, a near-infrared absorbing dye is contained in the pressure-sensitive adhesive for the purpose of thinning the optical filter mounted on the front surface of the PDP and simplifying the manufacturing process of the optical filter. Attempts have been made to integrate the near-infrared absorbing film and the pressure-sensitive adhesive layer (Patent Document 3).

Japanese Patent No. 3621322 Also, an imaging device having a CCD or a CMOS is attracting the most attention, but these imaging devices have sensitivity up to the near infrared region near 1100 nm. Therefore, if the near-infrared light above visible light is not cut, it will be different from the color when seen with the eye, so an infrared cut filter is attached to the surface of the CCD or CMOS chip. A low-pass filter for preventing color moire is also provided. Many of these infrared cut filters and low-pass filters have a multilayer structure in which almost single-function films are bonded via a transparent adhesive or the like. Since it is disadvantageous, various attempts have been made to simplify the layer structure as with the PDP. For example, a technique is disclosed in which a low-pass filter is directly bonded to a container without providing a cover glass, and an infrared cut filter is realized only by an optical thin film on the surface of the low-pass filter. However, if the infrared cut filter is composed only of an optical thin film, the cutoff wavelength changes depending on the angle of the incident light beam, resulting in inconveniences such as uneven color around the screen. On the other hand, Patent Document 4 discloses a technique in which an infrared cut 10 filter (color glass filter) is bonded to the inside of a cover glass container. However, in the technique of the publication, since a low-pass filter must be separately provided, the contribution to miniaturization of the device is small. Further, Patent Document 5 discloses a technique for bonding a color glass filter to a cover glass and further forming a diffraction grating type low-pass filter. In the diffraction grating type low-pass filter, the distance between the filter and the light receiving unit is disclosed. Must be maintained at a predetermined size, which is not only a limitation of miniaturization, but also must improve the assembly dimensional accuracy.

JP 2000-216368 A Japanese Patent No. 2998739

  As an example of including a near-infrared absorbing dye in a pressure-sensitive adhesive, Patent Document 3 describes a good adhesiveness to an adherend and a carboxyl group or a hydroxyl group-containing (meth) acrylate as a crosslinking point that reacts with a crosslinking agent. Discloses a pressure sensitive adhesive obtained by copolymerizing 0.1 to 20% by weight. However, there is a problem that the carboxyl group or hydroxyl group in the pressure-sensitive adhesive reacts with the near-infrared absorbing dye to reduce near-infrared absorption. Further, there is a problem that the crosslinking agent also reacts with the near-infrared absorbing dye to reduce near-infrared absorption.

  Since the acrylic pressure-sensitive adhesive polymer itself has insufficient cohesive force, it is common to supplement the cohesive force by adding a crosslinking agent. As a method for improving the cohesive force without performing crosslinking, it is conceivable to raise the glass transition temperature of the polymer, but there is a problem that tack and adhesive strength are reduced.

  Therefore, the inventor uses a polymer having a polymer part having a glass transition temperature of 50 ° C. or higher and a polymer part having a glass transition temperature of less than 0 ° C. in the same molecule as the pressure-sensitive adhesive polymer. As a result, it has been found that it is possible to achieve both the suppression of the decrease in near-infrared absorption and the cohesive force of the pressure-sensitive adhesive.

  Generally, polymers having different glass transition temperatures in the same molecule are known to have a microphase separation structure. A polymer portion having a high glass transition temperature has a discontinuous phase (microdomain). In order to form and take a pseudo-crosslinked structure, the cohesive force is higher than that of a general pressure-sensitive adhesive, and the heat resistance is excellent. On the other hand, a polymer portion having a low glass transition temperature forms a continuous phase and develops tackiness. Therefore, a pressure-sensitive adhesive having both a cohesive force and tackiness at a level that is not problematic in practice can be obtained without performing cross-linking with a cross-linking agent or the like.

  In addition, since the use of a crosslinking agent and the copolymerization of a carboxyl group or a hydroxyl group-containing monomer as a crosslinking point are not essential, deterioration of the near-infrared absorbing dye can be suppressed.

  The pressure-sensitive adhesive composition containing the near-infrared absorber of the invention comprises a near-infrared absorbing dye having a maximum absorption wavelength from 700 nm to 1200 nm, a polymer portion having a glass transition temperature of 50 ° C. or higher, and a temperature of less than 0 ° C. It consists of a pressure-sensitive adhesive polymer which is a polymer having a polymer portion having a glass transition temperature in the same molecule. According to the present invention, a polymer portion having a high glass transition temperature of the polymer forms a discontinuous phase (microdomain) and takes a pseudo-crosslinked structure. It is possible to obtain a pressure-sensitive adhesive having a cohesive force and tackiness with no problem level.

  In addition, since the use of a crosslinking agent and the copolymerization of a carboxyl group or a hydroxyl group-containing monomer as a crosslinking point are not essential, deterioration of the near-infrared absorbing dye can be suppressed. For this reason, a pressure-sensitive adhesive composition obtained by dispersing a near-infrared absorbing dye in such a pressure-sensitive adhesive polymer has high stability and is difficult to change its color or decolor. There is an advantage. In addition to the above advantages, it is possible to effectively cut near-infrared wavelength light derived from xenon emission, and to effectively suppress malfunction of electrical equipment over a long period of time. Therefore, optical filters and plasma displays manufactured using the pressure-sensitive adhesive composition of the present invention (especially near-infrared absorbing filters for plasma display front plates and plasma displays) have high transparency in the visible region, Since the appearance of the display is improved and the stability is excellent, it is difficult for the remote control around the plasma display to malfunction, and the appearance of the display can be hardly changed.

    Furthermore, since the pressure-sensitive adhesive layer and the near-infrared blocking layer can be manufactured as one layer, the manufacturing process of the near-infrared absorption filter for the plasma display front plate and plasma display can be simplified.

  In addition, even in an imaging device having a CCD or CMOS, by using the pressure-sensitive adhesive composition or pressure-sensitive adhesive layer of the present invention, it is possible to provide a small-sized and high-quality solid-state imaging device at a low cost. It becomes.

The first aspect of the present invention is a polymer having a near-infrared absorber, a polymer part having a glass transition temperature of 50 ° C. or higher, and a polymer part having a glass transition temperature of less than 0 ° C. in the same molecule. The present invention relates to a pressure-sensitive adhesive composition. Previously, there was a report about mixing near-infrared absorbing dyes with polymer resins, but there were few known detailed studies on resins, so polymer resins, especially pressure-sensitive adhesives. When the pressure sensitive adhesive layer is formed by mixing the resin for the agent and the near infrared absorber, the stability is often lowered, and the pressure sensitive adhesive layer and the near infrared ray blocking layer are two independent layers. It had to be formed as.
In the present invention, for the purpose of making the pressure-sensitive adhesive layer and the near-infrared shielding layer into a single layer, the near-infrared absorbing property, thermal stability (heat resistance), moisture and heat resistance and light resistance of the near-infrared absorber. As a pressure-sensitive adhesive resin excellent in cohesive force without reducing the properties such as the cross-linking agent, a polymer portion having a glass transition temperature of 50 ° C. or higher and a temperature of less than 0 ° C. It has been found that a polymer having a polymer portion having a glass transition temperature in the same molecule can be particularly preferably used. Therefore, a pressure-sensitive adhesive that is a polymer having a near-infrared absorbing dye and a polymer portion having a glass transition temperature of 50 ° C. or higher and a polymer portion having a glass transition temperature of less than 0 ° C. in the same molecule. The polymer is very useful for forming a single layer having the functions of both a pressure-sensitive adhesive layer and a near-infrared blocking layer. Therefore, the polymer is used for optical filters, plasma displays (especially for plasma display front plates and plasma displays). Near-infrared absorption filter), CCD, CMOS, etc., can be used suitably for the manufacture of an image sensor and an image pickup apparatus.

Hereinafter, the present invention will be described in detail.
(1) Pressure sensitive adhesive polymer (A)
The pressure-sensitive adhesive polymer (A) is a polymer having a polymer portion having a glass transition temperature of 50 ° C. or higher and a polymer portion having a glass transition temperature of less than 0 ° C. in the same molecule. Although not particularly limited, preferred polymers in the present invention will be described below.
The pressure-sensitive adhesive polymer (A) used in the present invention includes, in the same molecule, a polymer part having a glass transition temperature of 50 ° C. or higher, and a polymer part having a glass transition temperature of less than 0 ° C. Any material having a structure having the above may be used. Examples of such a polymer include a block polymer or a graft polymer.

  Examples of the method for producing such a block polymer or graft polymer include those in which ionic polymerization is performed using an organometallic compound as an initiator (3M, JP-A-60-8379), radical polymerization using an iniferter. What to do (Osaka City University, Otsu, “Living mono and pi radical polymerization in homogeneous synthesis of AB and ABA type block copolymers”, Polymer Bulletin, 11, 135-142 (1984), radical polymerization using polyvalent mercaptans (Patent No. 2842278, Patent No. 3385177, etc.), and those that perform radical polymerization using a macromonomer (Japanese Patent Laid-Open No. 2-167380).

  Among these, the method of producing by radical polymerization using polyvalent mercaptan is preferable because the block polymer can be synthesized at a lower cost.

As the polymerizable monomer used in the present invention, any monomer can be used as long as it forms a homopolymer or a copolymer by radical polymerization.
Specific examples of such monomers include, for example, alkyl (meth) acrylates having 1 to 30 carbon atoms, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate. -(Meth) acrylates represented by methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, etc .; α-methylstyrene, vinyl Styrene monomers typified by toluene, styrene, etc .; Maleimide monomers typified by phenylmaleimide, cyclohexylmaleimide, etc .; Vinyl ethers typified by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc. Telluromer; fumaric acid, monoalkyl ester of fumaric acid Dialkyl ester of fumaric acid; maleic acid, monoalkyl ester of maleic acid, dialkyl ester of maleic acid; itaconic acid, monoalkyl ester of itaconic acid, dialkyl ester of itaconic acid; (meth) acrylonitrile, butadiene, isoprene, vinyl chloride, Examples thereof include vinylidene chloride, vinyl acetate, vinyl ketone, vinyl pyridine, vinyl carbazole, and the like can be used alone or in combination of two or more.
The monomer used in the polymer portion having a glass transition temperature of 50 ° C. or more and the polymer portion having a glass transition temperature of less than 0 ° C. has a glass transition temperature calculated using the Fox equation represented by the following equation: There is no particular limitation as long as the predetermined value is satisfied.
1 / (Tg + 273) = Σ [Wi / (Tgi + 273)]: Fox formula Tg (° C.): glass transition temperature Wi: weight fraction of each monomer Tgi (° C.): glass transition temperature of homopolymer of each monomer component Since the first polymer portion having a glass transition temperature of 50 ° C. or higher is designed from the function of increasing the cohesive force of the pressure-sensitive adhesive polymer, the higher the glass transition temperature, the better, preferably 60 ° C. or higher. Preferably it is 70 degreeC or more.

  The second polymer portion having a glass transition temperature of less than 0 ° C is designed from the function of imparting the tackiness of the pressure-sensitive adhesive polymer, so the lower the glass transition temperature, the better, preferably less than -10 ° C More preferably, it is less than -20 ° C.

  The weight ratio of the first polymer portion to the second polymer portion is 3/97 to 50/50. If the first polymer portion is less than 3% by weight, the effect of improving the cohesive force may not be obtained, and if it is 50% by weight, the tackiness may be insufficient.

In the optical filter for plasma display in which the pressure-sensitive adhesive composition of the present invention is used, it is desirable that the transmittance in a so-called visible light region of 400 nm to 800 nm is high and the haze value (turbidity) is small.
Since the pressure-sensitive adhesive polymer used in the pressure-sensitive adhesive composition of the present invention has a micro-layer separation structure, the transmittance is low and the haze value tends to be higher than that of a normal random copolymer. There is. However, the transmittance and haze value can be improved by optimizing the composition and weight ratio of the high Tg polymer portion and the low Tg polymer portion and the synthesis method. The average transmittance of 400 nm to 800 nm is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. The haze value is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.

  One of the preferable production methods for obtaining the pressure-sensitive adhesive polymer of the present invention will be described below. The pressure-sensitive adhesive polymer of the present invention is obtained by a multi-stage polymerization process in the presence of a polyvalent mercaptan, and is a single monomer having a composition different from each other in at least the first stage and the second stage of the multi-stage polymerization process. It is preferable to obtain by performing a multistage polymerization process performed using a body component.

  That is, it is one of the preferable production forms that it is a star-shaped block polymer obtained by performing radical polymerization using different types of polymerizable monomers in each stage in the presence of polyvalent mercaptan. .

  As a production procedure, in the presence of polyvalent mercaptan, as a first step, radical polymerization of a first polymerizable monomer component that forms a polymer portion having a glass transition point of 50 ° C. or higher is performed, and the polymerization rate is After being 50% or more, preferably 60% or more, as a second step, by adding a second polymerizable monomer component that forms a polymer portion having a glass transition point of less than 0 ° C., and polymerizing, The polymer which has the polymer part which has the glass transition temperature of 50 degreeC or more of this invention, and the polymer part which has a glass transition temperature of less than 0 degreeC in the same molecule can be obtained. The rate of radical polymerization performed first is 50% or more because the second polymer portion is formed even if the next polymerization is performed without removing the polymerizable monomer remaining after the polymerization. This is to make the properties of the polymers as different as possible. Therefore, it is possible to volatilize and remove the polymerizable monomer after the first polymerization.

  As the first stage, after the radical polymerization of the first polymerizable monomer is stopped at a polymerization rate of 70%, and then the second polymerizable monomer component is added to carry out the radical polymerization, The polymer part to be formed is a copolymer of 30% monomer that has not reacted in the first stage polymerization and the monomer added as the second polymer component.

  Moreover, it is also possible to use a macromonomer as a polymer part having a glass transition point of 50 ° C. or higher in the first stage. The macromonomer may be a polymer having a glass transition temperature of 50 ° C. or higher and having a polymerizable double bond at one end. Examples of such macromonomers include polymethyl methacrylate (AA-6, manufactured by Toagosei Co., Ltd.), polystyrene (AS-6, manufactured by Toagosei Co., Ltd.), poly (acrylonitrile-styrene) (AN-6, Toagosei Co., Ltd.). Manufactured).

Further, in the presence of a polyvalent mercaptan, radical polymerization of a first polymerizable monomer component that forms a polymer portion having a glass transition point of 50 ° C. or higher is performed as a first step, and then glass having a temperature of less than 0 ° C. It is also possible to perform the second stage radical polymerization using a mixture of the second polymerizable monomer component and the macromonomer that form the polymer portion having a transition point.
In the present invention, the acid value of the pressure-sensitive adhesive resin is preferably 25 or less, preferably 0 to 20, more preferably 0 to 10, and most preferably 0. In this specification, the “acid value” refers to the amount of potassium hydroxide required to neutralize 1 g of a sample.

The pressure-sensitive adhesive resin used in the present invention preferably has a hydroxyl value of 10 or less, more preferably the pressure-sensitive adhesive resin has a hydroxyl value of 0 to 10, still more preferably 0 to 5, most preferably. Is 0.
(2) Near-infrared absorbing dye (B)
As the near-infrared absorbing dye (B) in the present invention, a dye having a maximum absorption wavelength at 700 to 1200 nm is suitable. Two or more types having different near-infrared absorption characteristics may be used in combination. In this case, the near-infrared absorption effect may be improved.
Examples of the near-infrared absorbing dye (B) include phthalocyanine, naphthalocyanine, anthraquinone, naphthoquinone, cyanine, aminium, diimonium, polymethine, aromatic dithiol, and aromatic diol. However, it is not limited to these. Specific products include “EEX Color” series manufactured by Nippon Shokubai Co., Ltd., “Epolite” series manufactured by Eporin USA, “KAYASORB” series manufactured by Nippon Kayaku Co., Ltd., “YKR” series manufactured by Yamamoto Kasei Co., Ltd., Japan Carlit's “CIR” series and so on.
Of these, the phthalocyanine compound is preferably a compound represented by the following formula (1), and the naphthalocyanine compound is preferably a compound represented by the following formula (2).

[A1-A16 in Formula (1) represents a functional group, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxylic acid group, a thiol group, or an optionally substituted carbon atom having 1 to 20 alkyl groups, optionally substituted alkoxy groups having 1 to 20 carbon atoms, optionally substituted aryl groups having 6 to 20 carbon atoms, optionally substituted carbon atoms 6 ~ 20 aryloxy groups, optionally substituted aralkyl groups having 7 to 20 carbon atoms, optionally substituted aralkyloxy groups having 7 to 20 carbon atoms, optionally substituted carbons An alkylthio group having 1 to 20 atoms, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 7 to 20 carbon atoms which may be substituted, or a substituted group A good one with 1 to 20 carbon atoms A killsulfonyl group, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, an optionally substituted aralkylsulfonyl group having 7 to 20 carbon atoms, and an optionally substituted carbon atom 1 ~ 20 acyl groups (the definition of acyl group in this specification is described in P17 of the third edition of the Science and Technology Terminology Dictionary published by Nikkan Kogyo Shimbun), 2 carbon atoms that may be substituted ~ 20 alkoxycarbonyl group, optionally substituted aryloxycarbonyl group having 6 to 20 carbon atoms, optionally substituted aralkyloxycarbonyl group having 2 to 20 carbon atoms, substituted May be an alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms that may be substituted, or 8 to 20 carbon atoms that may be substituted Aralkylcarbonyloxy group, optionally substituted heterocyclic group having 2 to 20 carbon atoms, optionally substituted amino group, optionally substituted aminosulfonyl group, optionally substituted aminocarbonyl Represents a group. The functional groups of A1 to A16 may be the same type or different types, and even in the same type, they may be the same or different, and the functional groups may be connected via a linking group. M1 represents two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal.
(When the terminal is a functional group other than an amino group)
Examples of the halogen atom as the functional groups A1 to A16 in the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. It is not limited to. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic Although an alkoxy group is mentioned, it is not limited to these. Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include, but are not limited to, a phenoxy group and a naphthoxy group. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group and the like, but are not limited thereto. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, It is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include phenylthio group and naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include a benzylthio group, a phenethylthio group, a diphenylmethylthio group, and the like, but are not limited thereto. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group and a naphthylsulfonyl group, but are not limited thereto. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the optionally substituted aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl and naphthylcarbonyl groups, but are not limited thereto. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like, but are not limited thereto. . Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned, However, It is not limited to these. Examples of the optionally substituted arylcarbonyloxy group having 7 to 20 carbon atoms include, but are not limited to, a benzoyloxy group. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.
Alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group, arylsulfonyl group of functional groups A1 to A16 in formula (1), Examples of the substituents optionally present in the aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group, and heterocyclic group include Halogen atom, acyl group, alkyl group, phenyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, alkylamino group, alkylcarbonylamino group, arylamino group, Examples include, but are not limited to, carbonylcarbonyl group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, and heterocyclic group. It is not a thing. A plurality of these substituents may be present. When a plurality of these substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.
(When the terminal is an amino group)
As the substituent for the optionally substituted amino group, the optionally substituted aminosulfonyl group, and the optionally substituted aminocarbonyl group of the functional groups A1 to A16 in the formula (1), a hydrogen atom, Linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, cyclohexyl, etc. Aryl groups such as phenyl group and naphthyl group, aralkyl groups such as benzyl group and phenethyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl Group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl , Cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group, n-octylcarbonyl group and other linear, branched or cyclic alkylcarbonyl groups, benzoyl group, naphthylcarbonyl group and other arylcarbonyl groups, benzylcarbonyl group An aralkylcarbonyl group such as, for example, is not limited thereto, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1, or 2, and when two are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, they may be connected via a linking group.
The above-mentioned amino group which may be substituted, aminosulfonyl group which may be substituted, alkyl group, aryl group, aralkyl group, alkylcarbonyl group, aryl which is a substituent to the optionally substituted aminocarbonyl group Examples of the substituent that may be further present in the carbonyl group, the aralkylcarbonyl group and the like include, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, and an amino group. , Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, complex ring Including without being limited thereto. A plurality of these substituents may be present. When a plurality of these substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.
Examples of the divalent metal as the metal M1 include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II), etc. are mentioned, but not limited to these. Examples of trivalent substituted metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F. In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C6 H5, Al-C6 H4 (CH3), In-C6 H5, In-C6 Examples include, but are not limited to, H4 (CH3), In-C6 H5, Mn (OH), Mn (OC6 H5), Mn [OSi (CH3) 3], and Ru-Cl. Examples of tetravalent substituted metal atoms include CrCl2, SiF2, SiCl2, SiBr2, SiI2, ZrCl2, GeF2, GeCl2, GeBr2, GeI2, SnF2, SnCl2, SnBr2, TiF2, TiCl2, GeBr2, TiBr (OH) 2, Si (OH) 2, Sn (OH) 2, Zr (OH) 2, Cr (R1) 2, Ge (R1) 2, Si (R1) 2, Sn (R1) 2, Ti (R1) ) 2 {R1 represents an alkyl group, a phenyl group, a naphthyl group, and derivatives thereof} Cr (OR2) 2, Ge (OR2) 2, Si (OR2) 2, Sn (OR2) 2, Ti (OR2) 2, {R2 represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and a derivative thereof}, Sn (SR3) 2, Ge (SR3) 2 {R3 represents an alkyl group, phenyl , Naphthyl group, and represent derivatives thereof} but like but is not limited thereto. Examples of oxymetals include, but are not limited to, VO, MnO, TiO and the like. ]

[B1 to B24 in Formula (2) each represent a functional group, and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxylic acid group, a thiol group, or an optionally substituted carbon atom having 1 to 20 alkyl groups, optionally substituted alkoxy groups having 1 to 20 carbon atoms, optionally substituted aryl groups having 6 to 20 carbon atoms, optionally substituted carbon atoms 6 ~ 20 aryloxy groups, optionally substituted aralkyl groups having 7 to 20 carbon atoms, optionally substituted aralkyloxy groups having 7 to 20 carbon atoms, optionally substituted carbons An alkylthio group having 1 to 20 atoms, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 7 to 20 carbon atoms which may be substituted, or a substituted group A good one with 1 to 20 carbon atoms A killsulfonyl group, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, an optionally substituted aralkylsulfonyl group having 7 to 20 carbon atoms, and an optionally substituted carbon atom 1 ~ 20 acyl groups (the definition of acyl group in this specification is described in P17 of the third edition of the Science and Technology Terminology Dictionary published by Nikkan Kogyo Shimbun), 2 carbon atoms that may be substituted ~ 20 alkoxycarbonyl group, optionally substituted aryloxycarbonyl group having 6 to 20 carbon atoms, optionally substituted aralkyloxycarbonyl group having 2 to 20 carbon atoms, substituted May be an alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms that may be substituted, or 8 to 20 carbon atoms that may be substituted Aralkylcarbonyloxy group, optionally substituted heterocyclic group having 2 to 20 carbon atoms, optionally substituted amino group, optionally substituted aminosulfonyl group, optionally substituted aminocarbonyl Represents a group. The functional groups of B1 to B24 may be the same type or different types, and even in the same type, they may be the same or different, and the functional groups may be connected via a linking group. M2 represents two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal.
(When the terminal is a functional group other than an amino group)
Examples of the halogen atom as the functional groups B1 to B24 in the formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. It is not limited to. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic Although an alkoxy group is mentioned, it is not limited to these. Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include, but are not limited to, a phenoxy group and a naphthoxy group. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group and the like, but are not limited thereto. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, It is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include phenylthio group and naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include a benzylthio group, a phenethylthio group, a diphenylmethylthio group, and the like, but are not limited thereto. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group and a naphthylsulfonyl group, but are not limited thereto. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the optionally substituted aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl and naphthylcarbonyl groups, but are not limited thereto. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like, but are not limited thereto. . Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned, However, It is not limited to these. Examples of the optionally substituted arylcarbonyloxy group having 7 to 20 carbon atoms include, but are not limited to, a benzoyloxy group. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.
The alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group, arylsulfonyl group of the functional groups B1 to B24 in the formula (2), Examples of the substituents optionally present in the aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group, and heterocyclic group include Halogen atom, acyl group, alkyl group, phenyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, alkylamino group, alkylcarbonylamino group, arylamino group, Examples include, but are not limited to, carbonylcarbonyl group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, and heterocyclic group. It is not a thing. A plurality of these substituents may be present. When a plurality of these substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.
(When the terminal is an amino group)
As the substituent for the optionally substituted amino group, the optionally substituted aminosulfonyl group, and the optionally substituted aminocarbonyl group of the functional groups B1 to B24 in the formula (2), a hydrogen atom, Linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, cyclohexyl, etc. Aryl groups such as phenyl group and naphthyl group, aralkyl groups such as benzyl group and phenethyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl Group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl , Cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group, n-octylcarbonyl group and other linear, branched or cyclic alkylcarbonyl groups, benzoyl group, naphthylcarbonyl group and other arylcarbonyl groups, benzylcarbonyl group An aralkylcarbonyl group such as, for example, is not limited thereto, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1, or 2, and when two are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, they may be connected via a linking group.
The above-mentioned amino group which may be substituted, aminosulfonyl group which may be substituted, alkyl group, aryl group, aralkyl group, alkylcarbonyl group, aryl which is a substituent to the optionally substituted aminocarbonyl group Examples of the substituent that may be further present in the carbonyl group, the aralkylcarbonyl group and the like include, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, and an amino group. , Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, complex ring Including without being limited thereto. A plurality of these substituents may be present. When a plurality of these substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.
Examples of the divalent metal as the metal M2 include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II), etc. are mentioned, but not limited to these. Examples of trivalent substituted metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F. In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C6 H5, Al-C6 H4 (CH3), In-C6 H5, In-C6 Examples include, but are not limited to, H4 (CH3), In-C6 H5, Mn (OH), Mn (OC6 H5), Mn [OSi (CH3) 3], and Ru-Cl. Examples of tetravalent substituted metal atoms include CrCl2, SiF2, SiCl2, SiBr2, SiI2, ZrCl2, GeF2, GeCl2, GeBr2, GeI2, SnF2, SnCl2, SnBr2, TiF2, TiCl2, GeBr2, TiBr (OH) 2, Si (OH) 2, Sn (OH) 2, Zr (OH) 2, Cr (R1) 2, Ge (R1) 2, Si (R1) 2, Sn (R1) 2, Ti (R1) ) 2 {R1 represents an alkyl group, a phenyl group, a naphthyl group, and derivatives thereof} Cr (OR2) 2, Ge (OR2) 2, Si (OR2) 2, Sn (OR2) 2, Ti (OR2) 2, {R2 represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and a derivative thereof}, Sn (SR3) 2, Ge (SR3) 2 {R3 represents an alkyl group, phenyl , Naphthyl group, and represent derivatives thereof} but like but is not limited thereto. Examples of oxymetals include, but are not limited to, VO, MnO, TiO and the like. ]
Specifically, the trade names EEX COLOR IR-10A, EEX COLOR IR-12, EEX COLOR IR-14, TX-EX-906B, TX-EX-910B, TX-EX-902K (all of which are Nippon Shokubai Co., Ltd.) Manufactured).

  Moreover, the near-infrared absorbing composition used in the present invention may use a cyanine dye. The cyanine dye is not particularly limited as long as it has excellent near-infrared absorption ability, but compounds having a skeleton represented by the following formulas (3) to (9) are preferably used.

具体的には、上記一般式（３）で表される色素は、林原生物化学研究所の商品名ＮＫ−１０５６、上記一般式（４）で表される色素は、林原生物化学研究所の商品名ＮＫ−２６１０、上記一般式（５）で表される色素は、林原生物化学研究所の商品名ＮＫ−６、上記一般式（６）で表される色素は、林原生物化学研究所の商品名ＮＫ−２０１４、上記一般式（７）で表される色素は、林原生物化学研究所の商品名ＮＫ−４２７、上記一般式（８）で表される色素は、林原生物化学研究所の商品名ＮＫ−１２３、上記一般式（９）で表される色素は、アメリカンダイソース社の商品名ＡＤＳ８３０ＡＴ等の市販されているものを用いることができる。
ジイモニウム塩系色素としては、下記式（１０）で示されるアニオンと、下記式（１１）で示されるカチオンからなるものである。

Specifically, the dye represented by the general formula (3) is a trade name NK-1056 of Hayashibara Biochemical Laboratories, and the dye represented by the general formula (4) is a product of Hayashibara Biochemical Laboratories. The name NK-2610, the dye represented by the above general formula (5) is the product name NK-6 of Hayashibara Biochemical Laboratories, and the dye represented by the above general formula (6) is the product of Hayashibara Biochemical Laboratories. The name NK-2014, the dye represented by the general formula (7) is a trade name NK-427 of Hayashibara Biochemical Laboratories, and the dye represented by the general formula (8) is a product of Hayashibara Biochemical Laboratories. As the dye represented by the name NK-123 and the above general formula (9), commercially available products such as the trade name ADS830AT of American Dye Source Co., Ltd. can be used.
The diimonium salt pigment is composed of an anion represented by the following formula (10) and a cation represented by the following formula (11).

上記式（１０）中、Ｒ^ｘは電子吸引性基を有するアリール基を表わし；Ｒ^ｙは有機基、ハロゲン原子または水酸基を表わし；およびｍは１〜４の整数を表わす、で示される構造を有するアニオンである。

In the above formula (10), R ^x represents an aryl group having an electron withdrawing group; R ^y represents an organic group, a halogen atom or a hydroxyl group; and m represents an integer of 1 to 4. An anion.

R ^x in the above formula (10) is not particularly limited, but preferably has an electron-withdrawing group bonded to an aryl group having 6 to 12 carbon atoms, such as a phenyl group, a naphthyl group, or biphenyl. And those having an electron-withdrawing group bonded to the group. Of the aryl groups exemplified above, those having an electron-withdrawing group bonded to a phenyl group are economical and preferable.

Further, the electron-withdrawing group possessed by R ^x is not particularly limited. Specifically, —C _p F _{2p + 1} (p is a natural number), —NO ₂ , —CN, —F, —Cl And at least one substituent selected from the group consisting of —Br, and more preferably at least one substituent selected from the group consisting of —CF ₃ , —C ₂ F ₅ and —F. , -F is particularly preferable. When the aryl group includes a plurality of electron withdrawing groups, each electron withdrawing group may be the same or different.

The substituent represented by R ^y in the above formula (10) may be an organic group, a halogen atom or a hydroxyl group, and the organic group may have an electron-withdrawing group. Examples of the organic group include an aryl group having 6 to 12 carbon atoms (for example, a phenyl group, a naphthyl group, and a biphenyl group), and an alkyl group having 1 to 12 carbon atoms that may have a substituent. There is no particular limitation. In particular, when the organic group is an alkyl group, it is more preferable to have an electron-withdrawing group. In addition, as an alkyl group which has a substituent, it is more preferable that all or one part of a hydrogen atom is substituted by the fluorine atom. Specific examples of the halogen atom include -F, -Cl, -Br, -I and the like, and -F is more preferable.

Although m in the above formula (10) is not particularly limited as long as it is 1 to 4, it preferably has a structure represented by 4, that is, [BR ^x ₄ ] ⁻ . In the present invention, when m is 2 or more, a plurality of R ^x are included in the borate anion. In this case, the plurality of R ^x may be the same or different.

Examples of the borate anion represented by the above formula (10) include [B (C ₆ F ₅ ) ₄ ] ^- (tetrakispentafluorophenyl borate), [B (C ₆ F ₄ CF ₃ ) ₄ ] ⁻ , [ _{B (C 6 F 5) 3} (C 6 H 5) ] ^-, _{[B (C 6 F 5) 2} (C 6 H 5) 2 ] ^-, _{[B (C 6 F 5) (} C 6 H 5) _3] ^-, _{[B (C 6 F 5) 3} F ] ^-, _{[B (C 6 F 5) 2} F 2 ] ^-, _{[B (C 6 F 5) 3} (CF 3) ] ^-, [B ( _{C 6 F 5) 2 (CF} 3) 2 ] ^-, _{[B (C 6 F 5) (} CF 3) 3 ] ^-, _{[B (C 6 F 5) 3} (C 6 F 4 CF 3) ] ^-, _{[B (C 6 F 5) 2} (C 6 F 4 CF 3) 2 ] ^-, _{[B (C 6 F 5) (} C 6 F 4 CF 3) 3 ] ^-, _{[B (C} 6 _{F 4} CF _{3) 3} F] ^-, _{[B (C 6 F 4 CF 3} ) 2 F 2 ] ^-, _{[B (C 6 F 4 CF 3} ) F 3 ] ^-, _{[B (C 6 F 4 CF 3} ) 3 (CF _3)] ^-, _{[B (C 6 F 4 CF 3} ) 2 (CF 3) 2 ] ^-, _{[B (C 6 F 4 CF 3} ) (CF 3) 3 ] ^-, [B _(C 6 F _{5) 3 (C 6 H 13} ) ] ^-, _{[B (C 6 F 5) 2} (C 6 H 13) 2 ] ^-, _{[B (C 6 F 5) (} C 6 H 13) 3 ] ^-, [ _{B (C 6 H 4 CF 3} ) 4 ] ^-, _{[B (C 6 H 3 F 2} ) 4 ] ^-, and the like.
R ^{1 to} R ⁸ in the formula (11) each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent. R ^{1 to} R ⁸ may be different or the same.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Linear, branched, alicyclic alkyl such as 1-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, cyclohexyl group, etc. Groups and the like.

  Examples of the substituent that can be bonded to the optionally substituted alkyl group having 1 to 10 carbon atoms include cyano group; hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom; methoxy group; C1-C6 alkoxy groups such as ethoxy group, n-propoxy group, n-butoxy group; methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group An alkoxyalkoxy group having 2 to 8 carbon atoms, such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, or the like; an allyloxy group; a phenoxy group; Tolyloxy group, xylyloxy group, naphthylo group An aryloxy group having 6 to 12 carbon atoms such as a cis group; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and an n-butoxycarbonyl group; C2-C7 alkylcarbonyloxy groups such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyl Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an oxy group and an n-butoxycarbonyloxy group. Examples of such a diimonium dye include EX-991 (manufactured by Nippon Shokubai Co., Ltd.).

  Other pigments that can be blended include cyanine, tetraazaporphyrin, azurenium, squarylium, diphenylmethane, triphenylmethane, oxazine, azine, thiopyrylium, viologen, azo, azo metal complex, Widely use conventionally known dyes such as bisazo, anthraquinone, perylene, indanthrone, nitroso, metal thiol complex, indico, azomethine, xanthene, oxanol, indoaniline, quinoline Can do. For example, Asahi Denka Kogyo Co., Ltd., trade names Adeka Arcles TW-1367, Adeka Arcles SG-1574, Adeka Arcles TW1317, Adeka Arcles FD-3351, Adeka Arcles Y944, manufactured by Hayashibara Biochemical Research Institute, trade names NK-5451, NK-5532, NK-5450, etc. are mentioned.

  The amount of the near-infrared-absorbing dye in the pressure-sensitive adhesive composition of the present invention can be appropriately selected depending on the intended use. 0.1 to 10% by mass, preferably 0.5 to 8% by mass. At this time, if the blending amount of the near-infrared absorbing dye is less than 0.1% by mass, the blending amount of the dye is too small, and even if it is used for the filter of the manufactured PDP panel, sufficient near-infrared absorbing ability is obtained. May not be achieved. Conversely, when it exceeds 10 mass%, the effect corresponding to addition cannot be acquired and it is not economical, and conversely, transparency in the visible region may be impaired.

  Furthermore, the near-infrared absorbing composition of the present invention may contain one or more solvents, additives, and cross-linking agents as long as the performance is not lost.

  The near-infrared absorbing composition of the present invention may be a composition in which a near-infrared absorbing dye is mixed in the form of a solid (for example, a powder) in a resin, but in a solvent when used by coating on a film. Further, it is preferably in a dissolved, dispersed or suspended form.

Examples of solvents that can be used in this case include aliphatic systems such as cyclohexane and methylcyclohexane, aromatic systems such as toluene and xylene, ketone systems such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester systems such as ethyl acetate and butyl acetate, Nitriles such as acetonitrile, alcohols such as methanol, ethanol and isopropyl alcohol, ethers such as tetrahydrofuran and dibutyl ether, glycol ethers such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether and propylene glycol monomethyl ether acetate System, formamide, amide systems such as N, N-dimethylformamide, and halogen systems such as methylene chloride and chloroform can be used. These may be used alone or in combination. In order to improve the durability of the dye, a solvent having a boiling point of 100 ° C. or less, such as methyl ethyl ketone and ethyl acetate, is suitable. Moreover, in order to improve the coating film appearance at the time of coating, a solvent having a boiling point of 100 to 150 ° C. such as toluene, methyl isobutyl ketone, and butyl acetate is suitable.
(3) Other additives The acrylic pressure-sensitive adhesive composition of the present invention may contain a tackifier. In the present invention, the tackifier means an additive that improves the adhesive strength of a pressure-sensitive adhesive by being blended with a (meth) acrylic resin.

As the tackifier, various known tackifiers such as rosin resin, terpene resin, petroleum resin, coumarone resin, xylene resin, styrene resin and the like can be used. These tackifiers may be used alone or in the form of a mixture of two or more.
Among these tackifiers, rosin resins, terpene resins, or petroleum resins, which are generally inexpensive, are preferably used. In addition, these resins are often highly colored and have a great significance of blending a fluorescent brightening agent. However, the tackifier used is not limited to these, and other tackifiers may be blended.

Rosin resin is gum rosin collected from pine trees, wood rosin obtained by extracting with pine stumps into chips and then extracted with petroleum solvent, rosin such as tall oil rosin obtained from cooking waste during kraft pulp production, And derivatives thereof. Rosin is composed of several isomers represented by the general formula of C ₁₉ H ₂₉ COOH and a small amount of neutral components, and the composition varies depending on the type of raw wood, the place of origin, and the purification process of rosin. The main component is usually abietic acid. A rosin derivative means a rosin that has been subjected to modifications such as hydrogenation, disproportionation, or dimerization in order to improve stability against oxidation. Examples of rosin derivatives include hydrogenated rosin, disproportionated rosin, and polymerized rosin. Rosin derivatives can be synthesized based on rosin. Commercially available rosin derivatives such as trade name “Hyper” (manufactured by Arakawa Chemical Co., Ltd.) and trade name “Poly-pale” (Hercules) may be used.

  The terpene resin is a resin made from turpentine oil obtained when rosin is obtained from pine trees. The turpentine oil includes gum turpentine oil, wood turpentine oil, sulfate turpentine oil and the like. The composition varies depending on the type of raw wood, the place of production, and the purification process of the terpene resin. The main component of the terpene resin is usually α-pinene. Other components may include β-pinene, camphene, dipentene, and the like. Specific examples of the terpene resin include terpene, terpene phenol, rosin phenol, aromatic modified terpene, hydrogenated terpene and the like. In addition, various known terpene resins can be used. The terpene resin may be synthesized, and commercially available rosin derivatives such as “Tamanor 803” (manufactured by Arakawa Chemical Co., Ltd.), “Zonac” (Arizona Chemical) may be used.

The petroleum resin means a product obtained by cationic polymerization of a fraction containing unsaturated hydrocarbons by-produced by thermal decomposition such as petroleum naphtha. Petroleum resins are roughly classified into aliphatic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins, and the like, depending on the type of monomer and molecular structure. The aliphatic petroleum resin means a resin obtained by cationic polymerization of a fraction having a boiling point of 20 to 80 ° C. among naphtha cracked oil using aluminum chloride or the like as a catalyst. Aromatic petroleum resin, a C ₉ fraction containing styrenes and indenes of naphtha cracking oil is one which has been cationically polymerized with aluminum or BF ₃ catalysts chloride. Copolymer-based petroleum resin, by mixing the C ₅ fraction and C ₉ fraction in suitable proportions, means a cationic polymerization resin.

The amount of the tackifier contained in the pressure-sensitive adhesive composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the adhesive resin. When there is too little content of a tackifier, there exists a possibility that the adhesive force improvement effect by a tackifier may not be exhibited.
On the other hand, if the content of the tackifier is too large, tack may be reduced and the adhesive strength may be reduced.

In the pressure-sensitive adhesive composition of the present invention, if necessary, conventional fillers, pigments, diluents, anti-aging agents, UVA (ultraviolet absorbers), HALS (hindered amine light stabilizers), ultraviolet stabilizers and the like. Known additives can be added. Among these, when using the composition of this invention for panel uses, such as PDP, UVA (ultraviolet absorber) and HALS (hindered amine light stabilizer) are used preferably. The UVA (ultraviolet absorber) is not particularly limited, and a known ultraviolet absorber can be used. Moreover, it does not restrict | limit especially as HALS (hindered amine light stabilizer), A well-known hindered amine light stabilizer can be used. Moreover, the addition amount of these additives is appropriately set so as to obtain the desired physical properties. For example, the addition amount when UVA is used is based on the total mass of the pressure-sensitive adhesive composition. It is 0.1-100 mass%, More preferably, it is 2-20 mass%. For example, the addition amount in the case of using HALS is 0.1-50 mass% with respect to the total mass of a pressure-sensitive adhesive composition, More preferably, it is 0.5-10 mass%.
(4) Near-infrared absorber The near-infrared absorber of this invention laminates | stacks the layer containing the said pressure-sensitive adhesive composition on a non-transparent base material or a transparent base material.

The transparent substrate is generally usable for optical materials and is not particularly limited as long as it is substantially transparent. Specific examples include olefin polymers such as glass, cyclopolyolefin and amorphous polyolefin, methacrylic polymers such as polymethyl methacrylate, vinyl polymers such as vinyl acetate and vinyl halide, polyesters such as PET, polycarbonate, Examples thereof include polyvinyl acetal such as butyral resin, polyaryl ether resin, and the like. Further, the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, or coating with an anchor coating agent or a primer. May be. Further, the base resin can be blended with known additives, heat aging inhibitors, lubricants, antistatic agents, etc., known injection molding, T-die molding, calendar molding, compression molding, and the like, It is formed into a film or a sheet using a method such as casting by melting in an organic solvent. The base material constituting the transparent substrate may be unstretched or stretched, or may be laminated with another base material.

  As a transparent substrate when using a near-infrared absorbing material as a film, glass, PET film, easy-adhesive PET film, antireflection film or electromagnetic wave shielding film is preferable, PET film is more preferable, and particularly easy-adhesion treatment was performed. A PET film is particularly preferred. Specifically, Cosmo Shine A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex 705 (manufactured by Teijin DuPont) and the like can be mentioned.

  Further, when a functional film such as an antireflection film, an antiglare film, an impact absorbing film, or an electromagnetic wave shield film is used as the transparent substrate, an optical filter for plasma display can be easily produced. It is preferable to use a film.

  The thickness of the near-infrared absorbing material of the present invention is generally about 10 μm to 10 mm, but is appropriately determined according to the purpose. Further, the content of the near-infrared absorbing dye contained in the near-infrared absorbing material is also appropriately determined according to the purpose.

  The formation method in particular on the transparent base material of the pressure sensitive adhesive layer using the pressure sensitive adhesive composition of this invention is not restrict | limited, A well-known coating machine can be used. Examples thereof include knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters and bar coaters. Prior to coating, the substrate may be surface treated by a known method such as corona discharge treatment or plasma treatment. As drying and curing methods, known methods such as hot air, far infrared rays, UV curing and the like can be used. You may wind up with a well-known protective film after drying and hardening. Moreover, the method etc. of apply | coating by the said method on a release film etc., and bonding on a transparent substrate after that may be sufficient. As the releasable base material, paper or film coated with a release agent such as silicon-based, olefin-based, oil-based, or fluorine-based material, fluorine-based substrate, olefin-based substrate and the like are used. Moreover, the above-mentioned thing can be used for a transparent base material and a coating machine.

  In the above method, the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately selected depending on a desired application (for example, a near-infrared absorption filter for a plasma display front plate or a plasma display). It is -50 micrometers, More preferably, it is 10-30 micrometers.

  The pressure-sensitive adhesive layer obtained by such a method can be firmly bonded to other members such as other substrates and plasma display panels by a known method, and also has excellent near-infrared absorption ability and transparency. At the same time, it excels in various properties such as thermal stability (heat resistance), moist heat resistance and light resistance.

  The near-infrared absorbing material of the present invention can be a constituent material of an excellent optical filter for plasma display having high durability and high near-infrared absorbing ability. Since the near-infrared absorbing material of the present invention has high stability, the appearance and near-infrared absorbing ability are maintained even during long-term storage and use. Furthermore, since it has such characteristics, it can be used not only for display applications but also for filters and films that need to cut infrared rays, such as heat insulating films, sunglasses, optical recording materials, and the like.

(5) Optical filter for plasma display The optical filter for plasma display of this invention uses the said near-infrared absorber. Such an optical filter has a total light transmittance in the visible region of 40% or more, preferably 50% or more, more preferably 60% or more, and a transmittance of near infrared light having a wavelength of 800 to 1200 nm is 30% or less, preferably 15% or less, more preferably 5% or less.

  The optical filter of the present invention includes an electromagnetic wave shielding layer, an antireflection layer, a glare prevention (antiglare) layer, a scratch prevention layer, a color adjustment layer, an impact absorption layer, in addition to the near infrared absorption layer comprising the above-mentioned near infrared absorption material. A support such as a layer or glass may be provided.

  An optical filter having a near-infrared absorbing layer and an anti-reflection layer is formed by laminating a layer made of the pressure-sensitive adhesive composition of the present invention on the back surface of an anti-reflection film or applying an anti-reflection coating agent on the near-infrared absorbing material of the present invention. It is obtained by doing.

  The antireflection layer is for suppressing reflection of the surface and preventing reflection of external light such as a fluorescent lamp on the surface. The antireflection layer consists of a single layer of a resin with a different refractive index, such as an acrylic resin or a fluororesin, when it is made of an inorganic thin film such as a metal oxide, fluoride, silicide, boride, carbide, nitride, or sulfide. Or it may consist of what was laminated | stacked in multiple layers, and in the former case, there exists the method of forming on a transparent base material with the form of a single layer or multilayer using vapor deposition or sputtering method. In the latter case, the surface of the transparent substrate is reflected on a transparent film using a knife coater such as a comma coater, a fountain coater such as a slot coater or a lip coater, a gravure coater, a flow coater, a spray coater or a bar coater. There are methods of applying a protective coating.

  The optical filter having a near-infrared absorbing layer and a glare-preventing layer is formed by laminating a layer made of the pressure-sensitive adhesive composition of the present invention on the back surface of the anti-glare film, or an anti-glare coating on the near-infrared absorbing material of the present invention. It is obtained by applying an agent.

  The anti-glare layer is formed by converting fine powders of silica, melamine resin, acrylic resin, etc. into ink, applying the ink on any layer of the filter of the present invention by a conventionally known coating method, and heating or photocuring. . An antiglare-treated film may be attached on the filter. In addition, the scratch-preventing layer is a coating solution prepared by dissolving or dispersing an acrylate such as urethane acrylate, epoxy acrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent by a conventionally known coating method, and any of the filters of the present invention. On such a layer, it is preferably formed by coating, drying, and photocuring so as to be located on the outermost layer.

  An optical filter having a near-infrared absorbing layer and an electromagnetic wave shielding layer can be obtained by laminating a layer made of a near-infrared absorbing composition on an electromagnetic wave preventing film.

  The electromagnetic wave shielding layer is a film in which a metal mesh is patterned on a film by etching, printing, etc., or a film in which a metal is deposited on a fiber mesh and embedded in a resin. used. The pressure sensitive adhesive composition can also be used as a resin for smoothing the metal mesh on the film. Moreover, the near-infrared absorption composition of this invention can also be used as resin which embeds the fiber which vapor-deposited the metal.

  The shock absorbing layer is for protecting the display device from external impact. It is preferably used in an optical filter that does not use a support. As the shock absorbing material, as shown in JP-A No. 2004-246365 and JP-A No. 2004-264416, an ethylene-vinyl acetate copolymer, an acrylic polymer, a polyvinyl chloride, a urethane type, and a silicon type are used. Although resin etc. can be used, it is not limited to these.

  The configuration of each layer of the optical filter may be arbitrarily selected, but preferably a combination of at least two layers of an antireflection layer and an antiglare layer and at least two layers of a near infrared absorbing layer, more preferably It is an optical filter having at least three layers combined with an electromagnetic wave shielding layer.

  The antireflection layer or the glare prevention layer becomes the outermost layer on the human side, and the combination of the near-infrared absorbing layer and the electromagnetic wave shielding layer is arbitrary. Moreover, other layers, such as a damage prevention layer, a color adjustment layer, a shock absorption layer, a support body, and a transparent base material, may be inserted between the three layers.

  Each layer may be bonded only with the near-infrared absorbing material of the present invention, or another pressure-sensitive adhesive or adhesive may be used in combination. By using the near-infrared absorbing material of the present invention, the configuration of the optical filter for plasma display is simplified, which is economical.

In addition, when laminating each layer, physical treatment such as corona treatment or plasma treatment may be performed, or a known anchor coating agent such as a highly polar polymer such as polyethyleneimine, oxazoline-based polymer, polyester, or cellulose may be used. May be used.
(6) Plasma display The plasma display of this invention uses the said optical filter for plasma displays. The optical filter may be installed away from the display device or may be directly attached to the display device.

  In the case of direct attachment, it is preferable to use an optical filter that does not use a support, and it is more preferable to use an optical filter provided with a shock absorbing layer.

  Pressure sensitive adhesives for pasting to display devices include styrene butadiene rubber, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene rubber, chloroprene rubber, butyl rubber and other rubbers such as methyl polyacrylate and ethyl polyacrylate. And polyacrylic acid alkyl esters such as polybutyl acrylate, and the like. These may be used alone, but may further be added with piccolite, polyvale, rosin ester or the like as a tackifier. . Further, as shown in JP-A-2004-263084, a pressure-sensitive adhesive having an impact absorbing ability can be used, but the invention is not limited to this.

The pressure-sensitive adhesive layer has a thickness of usually 5 to 2000 μm, preferably 10 to 1000 μm. A release film may be provided on the surface of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer may be protected until it is attached to the surface of the plasma display so that dust or the like does not adhere to the pressure-sensitive adhesive layer. In this case, the pressure-sensitive adhesive layer is not provided between the pressure-sensitive adhesive layer and the release film on the edge of the filter, or a non-pressure-sensitive adhesive film is sandwiched between the pressure-sensitive adhesive layer and the non-pressure-sensitive film. If an adhesive part is formed and it is set as a peeling start part, the operation | work at the time of sticking will be easy to do.
(7) Optical filter for imaging device The optical filter for imaging device of the present invention uses the above-mentioned near-infrared absorbing material.
The optical filter for an image pickup device of the present invention may be provided with a support such as a primary color filter layer, a complementary color filter layer, an optical low-pass filter layer, or glass in addition to the near-infrared absorbing layer made of the near-infrared absorbing material. Good.
Imaging devices represented by CCD and CMOS function to change the intensity of light into electrical signals. However, since it is only possible to distinguish light and dark with this alone, it is not possible to obtain a color image. Usually, these three color images are captured using red (R), green (G), and blue (B) filters. . This red, green, and blue are called three primary colors, and the three color filters are called primary color filter layers.
The complementary color filter layer uses yellow, magenta, and cyan filters other than the three primary colors. The near-infrared absorbing layer is provided to correct a difference in color tone or shape between an actual scene viewed by a person and an image reproduced on the display due to a ghost or a fog of near-infrared light.
The low-pass filter layer is used for the purpose of reducing a phenomenon in which light having a high spatial frequency enters only a single pixel and is recognized as a color different from the original color.
These filters are collectively referred to as an image sensor optical filter.
(8) Image sensor The image sensor of the present invention uses the optical filter for an image sensor.
An image sensor refers to a component that receives light from a lens and converts it into an electrical signal. Currently, components such as CCD and CMOS sensors are used, but usually they are often called CCD or CMOS sensors as they are. Furthermore, recently, there are an increasing number of cases where devices in which the above-described optical filters for the image sensor are stacked are collectively referred to as an image sensor.
(9) Imaging Device The imaging device of the present invention uses the above-described imaging element.

  An image pickup device converts light into an electrical signal by an image sensor, which is further converted into digital data by the built-in D / A converter and converted into digital data. Are collectively referred to as devices that can be output as or recorded in a memory.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all. In addition, evaluation and measurement of near-infrared absorptivity, heat resistance, heat-and-moisture resistance, adhesive force, cohesive force, acid value, hydroxyl value, visible light region transmittance, and haze value were as follows.
1. Evaluation of near-infrared absorption ability Using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3700), the transmittance at 980 nm was measured for each test piece as the wavelength in the infrared region. Further, the transmittance at 450 nm was also measured as the transmittance in the visible light region.
2. The test specimen for heat resistance was left in an oven at 100 ° C. for 120 hours, and the transmission spectrum in the visible-near infrared region before and after the test was measured. For the measurement of the spectrum, Shimadzu Corporation UV-3700 was used, and the change in transmittance was measured.
3. The test specimen for evaluation of moisture and heat resistance was left in a constant temperature and humidity chamber at 80 ° C. and 95% RH for 120 hours, and the transmission spectrum in the visible-near infrared region before and after the test was measured. For the measurement of the spectrum, Shimadzu Corporation UV-3700 was used, and the change in transmittance was measured.
4). Evaluation of adhesive strength About the adhesive film obtained by the following Example and comparative example, according to JIS-Z0237, 23 mmC, 65% RH atmosphere WHEREIN: A 25 mm width adhesive sheet is made into a glass plate (made by Nippon Test Panel Co., Ltd.). ), A 2 kg roller was reciprocated once and bonded, and after 24 hours, it was peeled off at a speed of 300 mm / min in the direction of 180 degrees and measured.
5. Measurement of cohesive force The adhesive films obtained in the following examples and comparative examples were bonded to a stainless steel plate (SUS304) so that the area to be bonded was 25 mm × 25 mm according to JIS-Z0237, and 1 kg in an atmosphere of 40 ° C. The time until falling under load was measured.
6). Measurement of acid value 0.5 g of an acrylic polymer solution was precisely weighed, and 50 g of toluene was added and dissolved uniformly. A few drops of phenolphthalein / alcohol solution was added as an indicator and titrated with 0.1N potassium hydroxide / alcohol solution. The end point was when the redness of the solution disappeared in about 30 seconds. The acid value was determined from the titration amount at this time and the solid content of the resin. The acid value is expressed in mg of potassium hydroxide required to neutralize 1 g of resin solids.
7). Measurement of hydroxyl value The hydroxyl value was measured in accordance with JIS K0070 by the following method.
(Preparation of acetylating reagent)
Pyridine / acetic anhydride was uniformly mixed at a volume ratio of 100/30 to obtain an acetylating reagent.
(Preparation of pyridine aqueous solution)
Reagent primary pyridine / ion-exchanged water was mixed at a volume ratio of 2/3 to obtain an aqueous pyridine solution.
(Preparation of KOH methanol solution)
About 70 g of reagent special grade KOH was collected and dissolved by adding about 50 ml of ion-exchanged water to which about 1 liter of reagent primary methanol was added and dissolved by shaking. After blocking the carbon dioxide gas and allowing it to stand overnight or longer, the supernatant was taken and standardized with 1 mol / liter hydrochloric acid having a known factor to determine the factor (“f” in the following formula).
(Titration)
A 10 g sample was precisely weighed and 5 ml of acetylating reagent was added with a whole pipette. After completely dissolving the sample, it was immersed in an oil bath at 100 ± 2 ° C. for 60 minutes. After adding 5 ml of a pyridine aqueous solution with a whole pipette and mixing it uniformly, it was immersed in an oil bath at 100 ° C. for 10 minutes. After cooling at room temperature, 40 ml of dioxane was added. The mixture was uniformly mixed, and 2 to 3 drops of phenolphthalein indicator were added and titrated with a KOH methanol solution. The end point was the time when the color turned light red, and the titration amount (“C” in the following formula) was determined.

Similarly, the titer (“B” in the following formula) was determined for a blank to which no sample was added.
(Calculation of hydroxyl value)
The hydroxyl value was calculated by the following formula. The hydroxyl value is expressed in mg of potassium hydroxide equimolar to the hydroxyl group contained in 1 g of resin solids.
Hydroxyl value = {[(B-C) xfx56.1] / (sxN)} + A
Where B is the blank titration (ml); C is the sample titration (ml); s is the sample collection (g) (10 g); f is 1 mol / liter A is the acid value of the resin solids; and N is the resin solids.
8). Measurement of transmittance in visible light region Pressure-sensitive adhesive solution obtained by drying the pressure-sensitive adhesive polymer solution obtained in the following production example on an easy-adhesion-treated PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300). The coating was applied to a thickness of 20 microns and dried in a hot air dryer at 150 ° C. for 3 minutes. An easy-adhesive PET film was further bonded onto this to obtain a test specimen. Using this spectrophotometer (manufactured by Shimadzu Corporation: UV-3700), the average transmittance at wavelengths of 400 nm to 800 nm was measured.
9. Measurement of haze value Pressure-sensitive adhesive layer thickness after drying on easy-adhesion-treated PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300) with an applicator using the pressure-sensitive adhesive polymer solution obtained in the following production example The coating was applied to a thickness of micron and dried in a hot air dryer at 150 ° C. for 3 minutes. An easy-adhesive PET film was further bonded onto this to obtain a test specimen. The haze value of this test specimen was measured using a haze meter (Nippon Denshoku Industries Co., Ltd .: NDH-2000).
(Production Example 1-a) Production of a polymer portion having a glass transition temperature of 50 ° C. or higher Monomer in a 2 liter four-necked flask equipped with a stirrer, a nitrogen introduction tube, a dropping funnel, a thermometer, and a cooling tube As,-297 g of methyl methacrylate, 3 g of NK ester A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 300 g of ethyl acetate as a solvent were added, and the temperature was raised to 85 ° C. in a nitrogen atmosphere. After the internal temperature reached 85 ° C., 9 g of pentaerythritol tetrakisthiopropionate as a polyvalent mercaptan, 0.45 g of azobisisobutyronitrile as a radical polymerization initiator, and 9 g of ethyl acetate as a solvent were added. Polymerization was started. 10 minutes after the start of polymerization, 693 g of methyl methacrylate, 7 g of NK ester A-200, 21 g of pentaerythritol tetrakisthiopropionate, 1.05 g of azobisisobutyronitrile and 31 g of ethyl acetate were taken over 110 minutes. Dropping was performed. When the polymerization rate reached 70.2% after 170 minutes from the start of polymerization, 0.5 g of methoxyphenol as a polymerization inhibitor and 475 g of ethyl acetate as a solvent were added and cooled to complete the first stage polymerization. I let you.
(Production Example 1-b) Production of block polymer using polymer portion having glass transition temperature of 50 ° C. or higher 2 liters equipped with stirrer, nitrogen introduction tube, dropping funnel, thermometer, cooling tube To the four-necked flask, 137.1 g of the polymer solution obtained in Production Example 1-a, 171.4 g of butyl acrylate, and 124.2 g of ethyl acetate were added, and the temperature was raised to 85 ° C. in a nitrogen atmosphere. After the internal temperature reached 85 ° C., 0.14 g of azobisisobutyronitrile and 3.5 g of ethyl acetate were added to initiate polymerization. Ten minutes after the start of the reaction, 205.7 g of the polymer solution obtained in Production Example 1-a, 257.1 g of butyl acrylate, 0.22 g of azobisisobutyronitrile, and 192.4 g of ethyl acetate were added dropwise over 110 minutes. did. 60, 90, 120, and 150 minutes after completion of dropping, 0.15 g of azobisisobutyronitrile and 9 g of ethyl acetate were added, respectively, and further reacted for 4 hours under reflux, followed by cooling to obtain a solid content concentration of 50.6. %, A pressure-sensitive adhesive polymer 1 having a weight average molecular weight of 340,000 was obtained. This pressure-sensitive adhesive polymer 1 had a visible light region transmittance of 85% and a haze value of 2.2.
(Production Examples 2 and 3)
Polymerization was carried out with the composition shown in Table 1 in the same manner as in Production Example 1-b to obtain pressure-sensitive adhesive polymers 2 and 3.
Production Example 4 Production of Graft Polymer Using Macromonomer Macromonomer AA-6 (into a 2 liter four-necked flask equipped with a stirrer, a nitrogen introduction tube, a dropping funnel, a thermometer, and a cooling tube 48 g of methacryloyl group as polymerizable unsaturated group, methyl methacrylate as monomer composition, calculated glass transition temperature 105 ° C., manufactured by Toagosei Co., Ltd.) 48 g, 192 g of butyl acrylate, 179 g of ethyl acetate, 179 g of toluene, and 85 ° C. under nitrogen The temperature was raised to. After the internal temperature reached 85 ° C., 0.14 g of azobisisobutyronitrile and 3.5 g of ethyl acetate were added to initiate polymerization. Ten minutes after the start of the reaction, 72 g of macromonomer AA-6, 288 g of butyl acrylate, 0.22 g of azobisisobutyronitrile, 120 g of ethyl acetate, and 120 g of toluene were added dropwise over 110 minutes. 60, 90, 120, and 150 minutes after completion of the dropping, 0.15 g of azobisisobutyronitrile and 9 g of ethyl acetate were added, respectively, and the reaction was further performed for 4 hours under reflux, followed by cooling to obtain a solid concentration of 49.9. %, A pressure-sensitive adhesive polymer 4 having a weight average molecular weight of 290,000 was obtained. The pressure-sensitive adhesive polymer 4 had a visible light region transmittance of 87% and a haze value of 2.9.
(Production Example 5) Production of pressure-sensitive adhesive polymer having an acid value of 25 or more In a 2 liter four-necked flask equipped with a stirrer, a nitrogen introduction tube, a dropping funnel, a thermometer, and a cooling tube, 169 g of 2-ethylhexyl acrylate, 62.4 g of butyl acrylate, 8.4 g of acrylic acid, 0.24 g of 2-hydroxyethyl acrylate, and 124 g of ethyl acetate were added, and the temperature was raised to 85 ° C. in a nitrogen atmosphere. After the internal temperature reached 85 ° C., 0.48 g of Nyper BMT-K40 (Nippon Yushi Co., Ltd.) and 5 g of ethyl acetate were added to initiate polymerization. 10 minutes after the start of the reaction, 253.4 g of 2-ethylhexyl acrylate, 93.6 g of butyl acrylate, 12.6 g of acrylic acid, 0.36 g of 2-hydroxyethyl acrylate, 0.36 g of Nyper BMT-K40, 127. 7 g was added dropwise over 90 minutes. 60, 90, 120, and 150 minutes after the completion of dropping, 0.15 g of azobisisobutyronitrile and 9 g of ethyl acetate were added, respectively, and the reaction was further performed under reflux for 4 hours. Finally, the solid concentration was 40%. The pressure-sensitive polymer 5 was obtained by diluting with toluene. The polymer obtained had a weight average molecular weight of 510,000, an acid value of 27.5, and a hydroxyl value of 0.5.
(Production Example 6) Production of pressure-sensitive adhesive polymer having no acid value Polymerization was carried out with the composition shown in Table 1 in the same manner as in Production Example 5 to obtain pressure-sensitive adhesive polymer 6.
Example 1
To the pressure-sensitive adhesive polymer 1 obtained in Production Example 1-b, EX-910B, EX-906B and IR-10A (manufactured by Nippon Shokubai Co., Ltd.), which are near-infrared absorbing dyes, are 100 / It mix | blended so that it might be set to 0.8 / 0.3 / 0.8, it mixed and stirred until it became uniform, and the resin solution was created. The maximum absorption wavelengths (λmax) of the infrared absorbing dyes EX-910B, EX-906B, and IR-10A used in this example are 968 nm, 916 nm, and 828 nm, respectively.

The above resin solution was coated on an easy-adhesion treated PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) with an applicator so that the pressure-sensitive adhesive layer thickness after drying was 20 microns, and a hot air dryer at 150 ° C. Dried in for 3 minutes. A release film (silicone-treated PET film) was bonded to this to obtain a test specimen. Using this test specimen, near-infrared absorption ability, heat resistance, moist heat resistance, adhesive strength and cohesive strength were measured, and the results are shown in Table 2.
(Examples 2 to 4)
The pressure sensitive adhesive polymers 2 to 4 were subjected to the same operations as in Example 1 to obtain test bodies, and the same evaluations were performed. The results are shown in Table 2.
(Examples 5 and 6)
Except that the pressure-sensitive adhesive polymers 1 and 3 were blended so that the near-infrared absorbing dyes EX-991 and IR-10A (manufactured by Nippon Shokubai Co., Ltd.) had a solid content ratio of 100/2/1. The same operation as in Example 1 was performed to obtain a test specimen. The maximum absorption wavelengths (λmax) of the infrared absorbing dyes EX-991 and IR-10A used in this example are 1080 nm and 828 nm, respectively.

(Comparative Example 1)
To the pressure-sensitive adhesive polymer 5 obtained in the above Production Example 5, the near-infrared absorbing dyes EX-910B, EX-906B, IR-10A (manufactured by Nippon Shokubai Co., Ltd.) at a solid content ratio of 100 / 0.8 /0.3/0.8, Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent was blended so that the solid content ratio was 100 /, and mixed and stirred until uniform to prepare a resin solution. Using this solution, the same operation as in Example 1 was performed to obtain a test body, and the same evaluation was performed. The results are shown in Table 2.
(Comparative Example 2)
To the pressure-sensitive adhesive polymer 6 obtained in Production Example 6 above, EX-910B, EX-906B, IR-10A (manufactured by Nippon Shokubai Co., Ltd.), which are near infrared absorbing dyes, are 100 / 0.8 in a solid content ratio. The resin solution was prepared by mixing and stirring until uniform / 0.3 / 0.8. Using this solution, the same operation as in Example 1 was performed to obtain a test body, and the same evaluation was performed. The results are shown in Table 2.

  From the above evaluation results, Examples 1 to 6 have high optical characteristics in which the transmittance in the near infrared region is suppressed while maintaining the transmittance in the visible light region, and further excellent in heat resistance and moist heat resistance. Yes. Moreover, it turns out that it is a pressure-sensitive adhesive composition excellent in an optical characteristic and an adhesive characteristic, without an adhesive force and cohesion force.

  On the other hand, in Comparative Example 1 in which a pressure-sensitive adhesive polymer having an acid value of 27.5 was crosslinked with an isocyanate compound, the transmittance at 980 nm was increased from before the test, and the transmittance was further increased after the heat resistance test. The result was. This is presumably because the acid group contained in the pressure-sensitive adhesive polymer and the dye compound are deteriorated by the isocyanate compound, thereby reducing the near-infrared light cutting efficiency.

  Comparative Example 2 does not contain an acid group or an isocyanate compound, and thus does not show a decrease in transmittance after the heat resistance and moist heat resistance tests. Although it has good optical properties, it is non-crosslinked and has a cohesive force. being insufficient. Insufficient cohesive force may cause problems such as the optical filter being displaced from the adherend during production and use of the PDP.

2 is a graph showing a visible-near infrared absorption spectrum of the test body obtained in Example 1. FIG. 6 is a graph showing a visible-near infrared absorption spectrum of the test body obtained in Example 5. FIG.

Claims (16)

  A pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive polymer (A) and a near-infrared absorbing dye (B), wherein (A) is a polymer portion having a glass transition temperature of 50 ° C. or higher; A pressure-sensitive adhesive composition which is a polymer having a polymer portion having a glass transition temperature of less than 0 ° C. in the same molecule.   The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive polymer (A) is a block polymer or a graft polymer.   The pressure-sensitive adhesive polymer (A) comprises a polyvalent mercaptan portion which is a remaining portion of protons of the mercapto group dissociated from the polyvalent mercaptan, and a glass transition of 50 ° C. or more extending radially from the polyvalent mercaptan portion. The pressure-sensitive adhesive composition according to claim 1 or 2, which is a polymer having a first polymer portion having a temperature and a second polymer portion having a glass transition temperature of less than 0 ° C in the same molecule.   The pressure-sensitive adhesive polymer (A) is produced by carrying out a plurality of steps of radical polymerization using different types of polymerizable monomers in each step in the presence of a polyvalent mercaptan. The pressure-sensitive adhesive composition according to any one of the above.   The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein a macromonomer that is a polymer having a polymerizable double bond at one end is used as a polymer portion having a glass transition temperature of 50 ° C or higher. .   The pressure-sensitive adhesive composition according to claim 1, wherein the acid value of the pressure-sensitive adhesive polymer (A) is less than 25.   The pressure-sensitive adhesive composition according to claim 1, wherein when the pressure-sensitive adhesive polymer (A) is a pressure-sensitive adhesive layer having a thickness of 20 μm, the average transmittance from 400 nm to 800 nm is 50% or more. object.   The pressure-sensitive adhesive composition according to claim 1, which has a haze value of 10 or less when the pressure-sensitive adhesive polymer (A) is a pressure-sensitive adhesive layer having a thickness of 20 μm.   A pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to claim 1. The near-infrared absorber which laminated | stacked the coating film containing the pressure sensitive adhesive composition in any one of Claim 1 to 8 on the transparent base material.   The near-infrared absorbing material according to claim 10, wherein the transparent substrate is glass, PET film, easy-adhesive PET film, antireflection film, or electromagnetic wave shielding film.   The optical filter for plasma displays using the near-infrared absorber of Claim 10 or 11.   A plasma display using the optical filter for plasma display according to claim 12.   An optical filter for an image sensor using the near-infrared absorbing material according to claim 10 or 11.   An image sensor using the optical filter for an image sensor according to claim 14. An imaging device using the imaging device according to claim 15.

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