JP2011116878A - Near-infrared shielding adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared shielding adhesive composition useful for fabricating a near-infrared shielding material having high adhesivity and high sustainability of the near-infrared shielding power. <P>SOLUTION: The near-infrared shielding adhesive composition comprises (A) a diimonium salt, (B) a resin having a calculated glass transition point of &le;0&deg;C, (C) a crosslinking agent, and (D) a solvent. When the near-infrared shielding adhesive composition is laminated on one surface of a biaxially stretched polyethylene terephthalate film to make an adhesive tape, the adhesive force to a glass is &ge;5 N/inch. Preferably, the solubility of the diimonium salt (A) to the solvent (D) is set &lt;5 mass%. Preferably, in the near-infrared shielding adhesive composition, a dispersion (M1) in which the diimonium salt (A) is dispersed in the solvent (D) is mixed. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a near-infrared shielding adhesive composition, a near-infrared shielding dispersion used in the near-infrared shielding adhesive composition, a near-infrared shielding material containing the near-infrared shielding adhesive composition, and the like.

  In recent years, a thin liquid crystal display applicable to a large screen and a thin display such as a PDP (Plasma Display Panel) have attracted attention. The thin display generates near infrared rays having a wavelength of 800 nm to 1100 nm. There is a problem that this near infrared ray causes malfunction of the remote control for home appliances. Moreover, since the optical semiconductor element used for a CCD camera etc. has high sensitivity in the near infrared region, it is necessary to remove the near infrared ray. Therefore, there is a need for a near-infrared shielding material that has high near-infrared absorptivity and high transparency in the visible region.

  Conventionally, cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, or inorganic oxide particles are used as near infrared shielding dyes that absorb near infrared rays. Has been. Among these, diimonium dyes are frequently used because they have a high near-infrared absorption ability and high transparency in the visible light region (see, for example, 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. The phosphor is made to emit light. Therefore, electromagnetic waves unnecessary for the operation of the PDP are simultaneously emitted during this light emission process. It is necessary to shield this electromagnetic wave. Further, an antireflection film and an antiglare film (antiglare film) are also required to suppress reflected light. For this reason, an optical filter for plasma display is generally produced by laminating a near-infrared shielding film, an electromagnetic wave shielding film, and an antireflection film on glass or a shock absorber as a support. Such an optical filter for plasma display is placed on the front side of the PDP. Such an optical filter for plasma display may be used by being directly bonded onto glass or a shock absorbing material as a support using an adhesive or a pressure-sensitive adhesive.

  In recent years, attempts have been made to integrate a near-infrared shielding film and an adhesive layer by incorporating a near-infrared shielding dye into the adhesive for the purpose of thinning the optical filter and simplifying the manufacturing process of the optical filter. (Patent Document 3 and Patent Document 4).

JP 2003-96040 A JP 2000-80071 A Japanese Patent No. 3621322 International Publication WO2008 / 026786

  The diimonium dye may have poor durability, and a decrease in the near-infrared absorption ability or coloring may be a serious problem when used in an optical semiconductor device or a display application. In particular, in a resin having a low glass transition point (Tg) such as an adhesive resin, the dye is severely deteriorated.

  JP-A 2005-325292 discloses a diimonium dye having improved durability by introducing a halogen atom into an alkyl group of a diimonium cation. Certainly, the near-infrared cut-off filter using the diimonium dye and the high Tg binder resin shows improved durability as compared with the conventional diimonium dye. However, the durability tends to be insufficient when combined with a rapidly degrading low Tg adhesive resin. In the international publication WO2008 / 026786, durability of the dye in the pressure-sensitive adhesive composition is improved by appropriately limiting the diimonium dye. In the present invention, a technique capable of improving the durability of the diimonium dye in the pressure-sensitive adhesive resin has been found from a viewpoint different from the invention of International Publication WO2008 / 026786.

  Usually, in the pressure-sensitive adhesive composition in which a pigment is added to the pressure-sensitive adhesive resin for providing functions such as near-infrared shielding ability, the adhesive strength may be lowered. From the viewpoint of improving the adhesive strength, a tackifier may be further added to the pressure-sensitive adhesive composition. The addition of the tackifier affects the near infrared shielding ability of the pressure-sensitive adhesive composition. It is difficult to achieve both adhesive force and near infrared shielding ability. Furthermore, the addition of the tackifier hinders the transparency of the pressure-sensitive adhesive composition and increases the production cost.

  An object of the present invention is to provide a near-infrared shielding adhesive composition useful for producing a near-infrared shielding material having high adhesive strength and high persistence of near-infrared shielding ability.

  This inventor earnestly examined about improvement of the near-infrared shielding ability and adhesive force of a near-infrared shielding adhesive composition. As a result, when a cross-linking agent is added to the near-infrared shielding adhesive composition and the adhesive strength to glass is set to an appropriate value, the near-infrared shielding adhesive has high adhesive strength and high persistence of near-infrared shielding ability. It was found that a composition was obtained.

  The near-infrared shielding adhesive composition of the present invention comprises a diimonium salt (A), a resin (B) having a calculated glass transition point of 0 ° C. or less, a cross-linking agent (C), and a solvent (D). Yes. When this near-infrared shielding adhesive composition is laminated on one side of a biaxially stretched polyethylene terephthalate film to form an adhesive tape, the adhesive strength to glass is 5 N / inch or more.

  Preferably, in this near-infrared shielding adhesive composition, the solubility of the diimonium salt (A) in the solvent (D) is less than 5% by mass.

  Preferably, in the near-infrared shielding adhesive composition, a mixed solution in which the diimonium salt (A) is mixed at a ratio of 0.01% by mass with respect to the solvent (D) is prepared, and the mixed solution is mixed for 30 minutes. After being subjected to ultrasonic waves, the mixture was allowed to stand for 1 hour or longer, and then the supernatant of this mixed solution was put into a cell having an optical path length of 1 mm and measured with a UV-visible spectrophotometer in the range of 350 nm to 1500 nm. Absorbance (X) at λmax is 0.5 or less.

  Preferably, in the near-infrared shielding adhesive composition, a dispersion (M1) in which the diimonium salt (A) is dispersed in the solvent (D) is mixed.

  Preferably, in this near-infrared shielding adhesive composition, the acid value of the resin (B) is 0 or more and 300 or less.

  Preferably, in the near-infrared shielding adhesive composition, the calculated solubility parameter of the resin (B) is 10.2 or less.

  Preferably, in the near-infrared shielding adhesive composition, the solvent (D) is at least one selected from the group consisting of toluene, ethyl acetate and butyl acetate.

  The near-infrared shielding material of the present invention includes those obtained by crosslinking any of the above-mentioned near-infrared shielding adhesive compositions with the crosslinking agent (C). The resin (B) contains at least one kind of functional group. The crosslinking agent (C) has at least two functional groups that can react with the functional group per molecule.

  The near-infrared shielding adhesive composition of the present invention is excellent in near-infrared shielding ability and durability of a diimonium dye. In this near infrared shielding adhesive composition, the near infrared shielding ability of the diimonium dye can be maintained for a long period of time. This near-infrared shielding adhesive composition has high adhesive strength. Therefore, when this near-infrared shielding adhesive composition is used for production of an optical semiconductor element or an optical filter for a thin display, it becomes possible to make the optical filter thinner and to simplify the optical filter manufacturing process.

  In the following, embodiments of the present invention will be described.

1. Diimonium salt (diimonium dye) A
The diimonium salt (A) used in the present invention preferably has an absorbance (X) at λmax of 0.5 or less measured by the method described later.

  Examples of the diimonium cation of the diimonium dye (A) include a diimonium cation represented by the following formula (1).

A preferred dimonium dye comprises a dimonium cation represented by the above formula (1) and a dimonium anion Z ⁻ as represented by the following formula (1S).

However, in Formula (1) and Formula (1S), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkyl group having a substituent. In the formula (1S), Z ⁻ represents a diimonium anion.

When R ¹ to R ⁸ are an alkyl group or an alkyl group having a substituent, the number of carbon atoms of the alkyl group is preferably 1 to 22 and more preferably 2 to 12 for each of R ¹ to R ^8. .

The halogen atom constituting R ¹ to R ^8, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Preferable R ^{1 to} R ⁸ include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and an alicyclic alkyl group. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, an isoamyl group, Examples include 1-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, cyclohexyl group, and the like. Other preferable R ^{1 to} R ⁸ include 4,4,4-trifluorobutyl group, 2,2,2-trifluoroethyl group and perfluorobutyl group. R ^{1 to} R ⁸ may all be the same or different from each other. Note that R ^{1 to} R ⁸ include those in which a linear alkyl group or a branched alkyl group is introduced as a side chain to a part of carbon constituting the alicyclic alkyl group.

More preferably, R ^{1 to} R ⁸ are linear or branched alkyl groups having 3 to 5 carbon atoms. More preferably, R ^{1 to} R ⁸ are an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-amyl group or an isoamyl group, and more preferably an n-butyl group, an isobutyl group or an isoamyl group. An isobutyl group is particularly preferred.

Further, Examples of the substituent which may be attached to an alkyl group of R ¹ to R ^8, cyano group; a hydroxyl group; a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom; a methoxy group, an ethoxy group, n- propoxy radical, n An alkoxy group having 1 to 6 carbon atoms such as butoxy group; alkoxy having 2 to 8 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group, etc. Alkoxy group; C3-C15 alkoxyalkoxyalkoxy group such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group; allyloxy group; phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group Such as carbon number 6-12 Reeloxy group; C2-C7 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, C2-C7 alkylcarbonyloxy groups such as n-propylcarbonyloxy group and n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyloxy group and the like And an alkoxycarbonyloxy group having 2 to 7 carbon atoms. A preferred example of the alkyl group to which the substituent is bonded is a methoxyethyl group. That is, a preferred example of R ^{1 to} R ⁸ is a methoxyethyl group.

The diimonium anion is not particularly limited. Preferred diimonium anions include hexafluoroantimonate ion, tetrafluoroborate ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, bis (trifluoromethanesulfone). Acid) imide ion, tetrakis (pentafluorophenyl) borate ion, tris (trifluoromethanesulfonic acid) methide ion, and the like. More preferable diimonium anions include hexafluoroantimonate ion [SbF ₆ ⁻ ] and tris (trifluoromethanesulfonic acid) methide ion [(CF ₃ SO ₂ ) ₃ C ⁻ ].

  A preferred diimonium salt (A) is a form in which two anions are bonded to one diimonium cation.

  As the diimonium salt (A), tris (trifluoromethylsulfonyl) methidoic acid-N, N, N ′, N′-tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenediimonium and hexafluoroantimonic acid -N, N, N ', N'-tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenediimonium. These production methods will be described by the following synthesis examples. Since these have high durability in an adhesive composition, these are especially preferable.

2. Solvent (D)
The solvent (D) can be included in the pressure-sensitive adhesive composition. In this pressure-sensitive adhesive composition, the solvent (D) may disappear due to volatilization. This solvent (D) may be used as a dilution solvent for adjusting the viscosity of the pressure-sensitive adhesive composition. By the solvent (D), the viscosity of the pressure-sensitive adhesive composition is adjusted to a viscosity suitable for application to a substrate or the like. The thickness of the pressure-sensitive adhesive composition layer can be adjusted by this viscosity.

  Examples of the solvent (D) include toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether acetate and the like. In the present invention, from the viewpoint of durability of the diimonium salt, the solvent (D) is preferably at least one selected from the group consisting of toluene, ethyl acetate and butyl acetate.

3. Measurement of absorbance (X) The solvent (D) is also used when measuring the absorbance (X) of the supernatant of the dimonium salt. As the solvent (D), those in which the measured solubility (Y) of the diimonium salt is less than 5% by mass are preferable. As this solvent (D), a solvent having a solubility (Y) of diimonium salt of less than 0.01% by mass is more preferable. Details of the measurement of the solubility (Y) will be described later. Examples of the solvent (D) used for measuring the absorbance (X) include toluene, ethyl acetate, xylene, butyl acetate and methylcyclohexane. Toluene, ethyl acetate and butyl acetate are particularly preferred.

[Measurement of absorbance (X) of supernatant]
In the measurement of the absorbance (X), a mixed solution in which a diimonium salt is mixed at a ratio of 0.01% by mass with respect to the solvent (D) is prepared, and this mixed solution is subjected to ultrasonic waves for 30 minutes, and then for 1 hour or more Left to stand. Thereafter, the supernatant of this mixed solution is put into a cell having an optical path length of 1 mm, and measurement is performed. A cell having an optical path length of 1 mm is made of quartz. The measurement is performed with an ultraviolet-visible spectrophotometer. As this ultraviolet-visible spectrophotometer, UV-3100 manufactured by Shimadzu Corporation is used. The measurement range is 350 nm or more and 1500 nm or less. λmax means the wavelength at which the absorbance is maximum in the measured wavelength range. Absorbance is obtained by the following equation, where transmittance is T (%).
Absorbance = −log (T / 100)

  The mixing method and the supernatant collecting method are as follows. First, 50 ml of a mixed solution in which a diimonium salt is mixed at a ratio of 0.01% by mass with respect to the solvent (D) is produced. The mixing container used for this mixing is a screw cap bottle. The screw bottle has an outer diameter of 40 mm and a height of 75 mm. In this mixing container, the height of the liquid surface (the uppermost surface of the liquid) of the 50 ml mixed liquid is 50 mm. The mixed solution is subjected to ultrasonic waves and allowed to stand for 1 hour or longer, and then the supernatant liquid from the liquid surface (the uppermost surface of the liquid) to 5 mm is collected and used for measurement. In addition, Preferably, in the above mixed liquid after being allowed to stand for 1 hour or more, an undissolved dimonium salt is sinking on the bottom surface of the mixing container. In this measurement, the temperature of the solvent (D) is 25 ° C. For the application of ultrasonic waves, a desktop ultrasonic cleaner (trade name “Bransonic 3510J-DTH”) manufactured by BRANSON is used. Water is added to the tank of this tabletop ultrasonic cleaner, the mixing container is placed in the tank filled with water, and the tank is vibrated at a frequency of 40,000 Hz or more (42 kHz) to mix in the mixing container. Ultrasonic waves are applied to the liquid.

  In the present invention, it has been confirmed that when the absorbance (X) with respect to the solvent (D) is 0.5 or less, the durability of the diimonium salt in the resin (B) described later can be improved. From the viewpoint of durability of the dimonium salt, the absorbance (X) is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.25 or less. From the viewpoint of durability of the dimonium salt, more preferably, the solvent (D) is any one of toluene, ethyl acetate and butyl acetate, and the absorbance (X) is preferably 0.5 or less, and 0.3 or less. More preferably, 0.25 or less is more preferable, and 0.15 or less is still more preferable. From the viewpoint of the durability of the dimonium salt, it is more preferable that the absorbance (X) is 0.5 or less, regardless of whether the solvent (D) is toluene, ethyl acetate or butyl acetate. The following is more preferable, and 0.25 or less is more preferable.

4). Measurement of Solubility (Y) A preferred pressure-sensitive adhesive composition contains a solvent (D) and a diimonium salt having a solubility (Y) in the solvent (D) of less than 5% by mass. This solvent (D) is also used for measuring the solubility (Y).

  The solvent (D) can be variously selected depending on the dimonium salt used. Examples of the solvent (D) used for measuring the solubility include toluene, ethyl acetate, xylene, butyl acetate and methylcyclohexane. Toluene, ethyl acetate and butyl acetate are particularly preferred.

[Method of measuring solubility (Y)]
Five kinds of samples having a dimonium salt content of 0.01% by mass, 0.1% by mass, 1.0% by mass, 2.0% by mass, and 5.0% by mass were prepared and ultrasonically stirred. To do. The stirring time is 30 minutes or longer, and the temperature of the solvent is 25 ° C. Next, it is confirmed whether or not there is a residue for each sample. The residue is confirmed by visually observing whether there is a residue on the filter paper after filtration. The solubility (Y) is determined by the presence or absence of residues. When no residue is confirmed in the 5.0 mass% sample (and other samples), it is determined that “the solubility (Y) is 5 mass% or more”. When a residue is confirmed in a 0.01% by mass sample (and other samples), it is determined that “the solubility (Y) is less than 0.01% by mass”. When a residue is confirmed in a sample of 0.1% by mass and no residue is confirmed in a sample of 0.01% by mass, “the solubility (Y) is 0.01% by mass or more and less than 0.1% by mass” It is judged.

5). Diluting solvent The near-infrared shielding adhesive composition may further contain a diluting solvent. This diluted solvent may be the solvent (D). By the dilution solvent, the viscosity of the pressure-sensitive adhesive composition can be adjusted to a viscosity suitable for application to a substrate or the like. The thickness of the pressure-sensitive adhesive composition layer can be adjusted by this viscosity.

  Examples of the diluent solvent include toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether acetate and the like.

  From the viewpoint of durability of the dimonium salt, the diluent solvent is preferably toluene, ethyl acetate or butyl acetate.

  Note that the dilution solvent may not be used. For example, the viscosity of the near-infrared shielding adhesive composition may be appropriately adjusted only with the solvent contained in the dispersion (M1) described later.

6). Dispersion M1 (Near-infrared shielding dispersion)
In the near-infrared shielding adhesive composition of the present invention, a dispersion (M1) in which a diimonium salt (A) is dispersed in a solvent (D) may be mixed. The method for producing a near-infrared shielding adhesive composition of the present invention includes a first step in which a diimonium salt and a solvent (D) are mixed to produce a dispersion (M1), and the dispersion (M1) and a crosslinking agent. (C) (described later) preferably includes a second step mixed with resin (B) (described later). In this second step, the resin (B) may be mixed with a solution obtained by dissolving the crosslinking agent (C) in the solvent (Sm). The solvent (Sm) in this case can be appropriately selected depending on the diimonium salt used. Examples of the solvent (Sm) include toluene, ethyl acetate, xylene, butyl acetate and methylcyclohexane. From the viewpoint of durability of the dimonium salt, toluene, ethyl acetate and butyl acetate are preferred. As this solvent (Sm), the same solvent as the solvent (D) may be used. As this solvent (Sm), a solvent different from the solvent (D) may be used.

  The diimonium dye (A) is preferably in a form that is easy to disperse. Preferably, the diimonium dye is refined by pulverization or the like. Examples of the method for producing the dispersion (M1) include a method using particles for pulverizing a diimonium salt. As this manufacturing method, wet and dry methods can be employed. As a wet manufacturing method, a method of pulverizing (miniaturizing) a diimonium salt using a bead mill, a ball mill, a liquid flow, a laser, or an ultrasonic wave may be employed. As a dry method, in addition to a ball mill and an attritor, a method of refining the diimonium salt by a roll mill or air flow can be employed. More preferably, a method of pulverizing a diimonium dye using particles such as zirconia beads, glass beads, and alumina beads may be employed. For example, as a method for producing a dispersion (M1) using zirconia particles, a liquid mixture obtained by mixing a dimonium dye, a solvent (D), and zirconia beads is prepared, and the liquid mixture is shaken in a container. A method for separating zirconia beads is exemplified. Preferable examples of the solvent (D) include a solvent (D) in which the absorbance (X) measured by the above method using a diimonium salt to be ground is 0.5 or less. Another preferable solvent (D) is a solvent (D) having a solubility (Y) of less than 0.01% measured by the above method using a diimonium salt to be ground.

  Once the dispersion (M1) is prepared, the dispersion (M1) is mixed with the resin (B) described later, whereby the dispersion state of the diimonium salt in the near-infrared shielding adhesive composition is improved. This reason is considered to be because the resin (B) contributes as a dispersant.

  Various additives may be added to the dispersion (M1). Examples of the additive include anionic, cationic or nonionic surfactants and polymer dispersants.

7). Resin (B)
The resin (B) according to the present invention is not particularly limited as long as the glass transition temperature is 0 ° C. or lower. The resin (B) according to the present invention has adhesiveness. This tackiness enables direct adhesion between the near-infrared shielding adhesive composition and the adherend. A near-infrared shielding adhesive composition and a to-be-adhered body can be adhere | attached, without interposing an adhesive agent. In this application, this resin (B) is also called adhesive resin.

7-1. Glass transition temperature From the viewpoint of imparting adhesiveness to the adherend, the glass transition temperature of the adhesive resin (B) is preferably 0 ° C or lower, more preferably -10 ° C or lower, and more preferably -20 ° C or lower. More preferably, it is -30 degrees C or less. When it is higher than 0 ° C., the tackiness may be insufficient. The glass transition temperature can also be obtained by determining the maximum temperature of the loss tangent (tan δ) by a differential scanning calorimeter (Dynamic Scanning Calorimeter) or dynamic viscoelasticity measurement. Means the calculated glass transition temperature obtained by The monomer used for the polymerization of the resin (B) is not particularly limited as long as the calculated glass transition temperature Tg calculated using the Fox formula represented by the following formula satisfies a predetermined value.
1 / (Tg + 273) = Σ [Wi / (Tgi + 273)]: Fox formula Tg (° C.): calculated glass transition temperature Wi: weight fraction of each monomer Tgi (° C.): single weight of each monomer component Glass transition temperature of coalescence

7-2. The acid value resin (B) is generally copolymerized with a carboxyl group-containing monomer such as acrylic acid for the purpose of improving the adhesion to the adherend and increasing the adhesive strength. However, since a functional group such as a carboxyl group degrades the diimonium dye, the acid value of the resin (B) is preferably 300 or less, more preferably 100 or less, and still more preferably 80 or less. From the viewpoint of durability of the diimonium salt, the acid value of the resin (B) is preferably 0 or more, more preferably 5 or more, and still more preferably 10 or more. “Acid value” refers to the amount of potassium hydroxide required to neutralize 1 g of resin. Details of the acid value measurement method will be described later.

For example, when the transparent base material mentioned later is glass, it is estimated that the following (Reaction 1) has occurred on the glass surface (interface between the glass and the near-infrared shielding adhesive composition layer). It is believed that Na ⁺ ions in the glass emerge on the glass surface by diffusion. The Na ⁺ ions react with present in near-infrared shielding pressure-sensitive adhesive composition H _{2 O} (or H _{2 O} which is attached to the glass surface prior to application of the adhesive composition) and NaOH generates considered It is done.
(Reaction 1) Na ⁺ + H ₂ O → NaOH + H ⁺ (to the inside of the glass)

This NaOH degrades the diimonium salt. When a carboxyl group is present in the resin (B), this carboxyl group traps Na ⁺ . It is considered that this trap suppresses the generation of NaOH and suppresses the deterioration of the diimonium salt. In particular, in the evaluation of wet heat resistance, the reaction 1 is likely to occur because a large amount of H ₂ O is present. Therefore, in particular, from the viewpoint of heat and humidity resistance, the acid value is preferably large. Specifically, as described above, 0 or more is preferable, 5 or more is more preferable, and 10 or more is more preferable.

  On the other hand, when the acid value of the resin (B) is excessively high, the solubility of the diimonium salt in the resin (B) increases, and the aggregate (X) tends to decrease. Therefore, from the viewpoint of heat resistance for evaluating durability at high temperatures, the acid value is preferably small. Specifically, as described above, 300 or less is preferable, 100 or less is more preferable, and 80 or less is preferable. Further preferred.

7-3. Calculated solubility parameter When the calculated solubility parameter of the resin (B) is high, the durability of the diimonium dye may be inferior, so the solubility parameter is preferably 10.2 or less. The calculated solubility parameter is a value calculated by the method described on pages 147 to 154 of “POLYMER ENGINEERING AND SCIENCE” (1974, Vol. 14, No. 2). The method is outlined below.

The solubility parameter (δ) of the homopolymer is calculated by the following formula based on the evaporation energy (Δei) and molar volume (Δvi) of the structural unit forming the polymer.
δ = (ΣΔei / ΣΔvi) ^1/2
Δei: Evaporation energy of i component atom or atomic group Δvi: Molar volume of i component atom or atomic group

  The solubility parameter of the copolymer is obtained by multiplying the evaporation energy of each constituent monomer constituting the copolymer by the mole fraction (ΣΔEi) and adding it to the molar volume of each constituent monomer. Calculated by multiplying by the mole fraction and adding together (ΣΔVi) and taking the 1/2 power.

7-4. Copolymer composition The resin (B) may be a copolymer. The resin (B) is preferably a copolymer of a (meth) acrylic acid ester containing a hydroxyl group and another compound. Furthermore, from the viewpoint of durability of the diimonium dye, the resin (B) is a (meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group. Is preferably a copolymer copolymerized in an amount of 5 to 40% by mass. The reason why the durability of the diimonium dye is improved is unknown, but the alicyclic, polycyclic alicyclic, aromatic, and polycyclic aromatic cyclic alkyl groups and the diimonium dye have a stacking structure. Therefore, it is thought that heat resistance and heat-and-moisture resistance are improved.

Preferably, the resin (B) is a resin obtained by copolymerizing the following monomers (p1) to (p3).
(P1) (meth) acrylic acid ester (p2) functional group-containing monomer having an alkyl group having 1 to 12 carbon atoms
(P3) Other copolymerizable monomers

  The preferable ratio of the monomer is 60% by mass to 99.9% by mass of (meth) acrylic acid ester of (p1), and 0.1% by mass to 20% by mass of the functional group-containing monomer of (p2). The other copolymerizable monomer (p3) is 0% by mass or more and 30% by mass or less. More preferably, the ratio of the functional group-containing monomer (p2) is 0.1% by mass or more and 10% by mass or less.

  From the viewpoint of durability of the dimonium dye, more preferably, the alkyl group in the monomer (p1) is a linear, branched or alicyclic alkyl group.

  Examples of (meth) acrylic acid esters of (p1) above include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-nonyl ( Examples include meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, and n-dodecyl (meth) acrylate.

  The functional group-containing monomer (p2) is preferably a hydroxyl group or carboxyl group-containing monomer, and more preferably a hydroxyl group or carboxyl group-containing (meth) acrylic monomer. From the viewpoint of durability of the diimonium dye, a carboxyl group-containing (meth) acrylic monomer is preferable. The carboxyl group of the carboxyl group-containing (meth) acryl monomer serves as a crosslinking point. Therefore, the adhesiveness can be adjusted by the blending amount of the carboxyl group-containing (meth) acrylic monomer. For another reason, it is considered that the carboxyl group of the carboxyl group-containing (meth) acrylic monomer contributes to the improvement of durability. Details of this reason are as described above.

  As the carboxyl group-containing (meth) acrylic monomer, acrylic acid and methacrylic acid are preferably used.

  Examples of the hydroxyl group-containing (meth) acrylic monomer include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. The hydroxyl group of the hydroxyl group-containing (meth) acrylic monomer can be a crosslinking point. Therefore, the hydroxyl group-containing (meth) acrylic monomer contributes to the adjustment of the adhesive properties. When the (p2) is a hydroxyl group-containing (meth) acrylic monomer, the ratio of the hydroxyl group-containing (meth) acrylic monomer is particularly preferably 0.1% by mass or more and 10% by mass or less with respect to the total amount of the monomer.

  As other copolymerizable monomers of the above (p3), benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Examples include phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. In addition, as an example of the above (p3), (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate; α-methylstyrene, vinyltoluene, styrene, etc. Styrene monomers represented by: vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid; monoalkyl ester of fumaric acid; dialkyl ester of fumaric acid; maleic acid; Dialkyl ester of maleic acid; itaconic acid; monoalkyl ester of itaconic acid; dialkyl ester of itaconic acid; (meth) acrylonitrile; vinyl chloride; vinylidene chloride; vinyl acetate; Nirupirijin; vinyl carbazole and the like. In addition, monomers having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group, and a fluoroalkyl group may be copolymerized within a range that does not impair the object of the present invention.

A more preferable resin (B) is a resin obtained by copolymerizing the following (m1) to (m4).
(M1) A (meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group.
(M2) A (meth) acrylic acid ester having an alkyl group. However, this alkyl group is linear or branched, and the alkyl group has 1 to 10 carbon atoms.
(M3) Functional group-containing monomer (m4) Other copolymerizable monomers.

  In the copolymer resin (B), a preferable ratio of the monomer is 5% by mass or more and 40% by mass or less of (meth) acrylic acid ester of (m1), and (meth) acrylic acid ester of (m2). Is from 60% by mass to 95% by mass, the functional group-containing monomer of (m3) is from 0.1% by mass to 20% by mass, and the other monomer of (m4) is from 0% by mass to 20% by mass. % Or less.

  Examples of the (meth) acrylic ester of (m1) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth). Acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( And (meth) acrylate.

  Examples of the (m2) (meth) acrylic acid ester of (m2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth). An acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, etc. are mentioned.

  The functional group-containing monomer (m3) is preferably a hydroxyl group or carboxyl group-containing monomer, more preferably a hydroxyl group or carboxyl group-containing (meth) acrylic monomer. From the viewpoint of durability of the diimonium dye, a carboxyl group-containing (meth) acrylic monomer is preferable. The carboxyl group of the carboxyl group-containing (meth) acryl monomer serves as a crosslinking point. Therefore, the adhesiveness can be adjusted by the blending amount of the carboxyl group-containing (meth) acrylic monomer. For another reason, it is considered that the carboxyl group of the carboxyl group-containing (meth) acrylic monomer contributes to the improvement of durability. Details of this reason are as described above.

  As the carboxyl group-containing (meth) acrylic monomer, acrylic acid and methacrylic acid are preferably used.

  Examples of the hydroxyl group-containing (meth) acrylic monomer include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. The hydroxyl group of the hydroxyl group-containing (meth) acrylic monomer can be a crosslinking point. Therefore, the hydroxyl group-containing (meth) acrylic monomer contributes to the adjustment of the adhesive properties. When the (m3) is a hydroxyl group-containing (meth) acrylic monomer, the ratio of the hydroxyl group-containing (meth) acrylic monomer is particularly preferably 0.1% by mass or more and 10% by mass or less based on the total amount of the monomers.

  Examples of the monomer (m4) include (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate; α-methylstyrene, vinyltoluene, Styrenic monomers typified by styrene and the like; vinyl ether monomers typified by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like; 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; Vinyl chloride; Vinylidene chloride; Vinyl acetate; ; And the like vinyl carbazole; vinyl pyridine.

  As the initiator used for the polymerization of the resin (B), commercially available products such as peroxides and azos can be used. Peroxide-based initiators include peroxyesters such as perbutyl O and perhexyl O (both manufactured by NOF); peroxydicarbonates such as PERROYL L and PEROIL O (both manufactured by NOF); Diacyl peroxides such as BW and Nyper BMT (both manufactured by NOF); Peroxyketals such as perhexa 3M and perhexa MC (both manufactured by NOF); perbutyl P, park mill D (all manufactured by NOF) And hydroperoxides such as Park Mill P and Permenter H (both manufactured by NOF Corporation). Examples of the azo initiator include ABN-E, ABN-R, and ABN-V (all manufactured by Nippon Hydrazine Kogyo Co., Ltd.).

  In the polymerization of the resin (B), a chain transfer agent may be used as necessary. The chain transfer agent is not particularly limited, and thiol compounds such as normal dodecyl mercaptan, dithioglycol, octyl thioglycolate, and mercaptoethanol can be used.

  The polymerization of the resin (B) may be performed without a solvent or in an organic solvent. When polymerizing in an organic solvent, aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone; other known organics A solvent can be used. The type of organic solvent to be used is determined in consideration of the solubility of the obtained resin and the polymerization temperature, but the boiling point of toluene, ethyl acetate, methyl ethyl ketone, etc. is 120 ° C. or lower in terms of the difficulty of remaining the residual solvent during drying. Organic solvents are preferred. Further, from the viewpoint of durability of the diimonium dye, an organic solvent having a solubility (Y) of less than 5% by weight of the diimonium dye is preferable, and an organic solvent having a solubility (Y) of less than 0.01% by weight is more preferable.

  Further, the resin (B) may be composed of a single composition, or may be a polymer alloy or polymer blend in which polymers having different compositions are combined.

  In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, and a polyfunctional chain transfer agent can be used. As the macromonomer, AA-6, AA-2, AS-6, AB-6, AK-5 (all manufactured by Toagosei Co., Ltd.) and the like can be used. Examples of the polyfunctional monomer include LIGHT EG EG, LIGHT SEL 1,4BG, LIGHT ESTER NP, LIGHT ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the polyfunctional initiator include Pertetra A, BTTB-50 (all manufactured by NOF Corporation), Trigonox 17-40MB, Parkadox 12-XL25 (all manufactured by Explosive Akzo), and the like. As the polyfunctional chain transfer agent, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate) or the like can be used.

8). Cross-linking agent (C)
The crosslinking agent (C) according to the present invention is not particularly limited as long as it can crosslink the resin (B) contained in the pressure-sensitive adhesive composition. As this crosslinking agent (C), the compound which has 2 or more of functional groups which can react with the functional group which resin (B) contains is preferable. For example, the compound which has a functional group which can react with the hydroxyl group or carboxyl group of resin (B), such as a polyfunctional epoxy compound, a polyfunctional melamine compound, a polyfunctional isocyanate compound, a metal crosslinking agent, an aziridine compound, is mentioned preferably.

  The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups per molecule. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N ′, N′-tetraglycidyl- Examples include m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, and the like.

  The polyfunctional melamine compound is not particularly limited as long as it is a compound having two or more functional groups of methylol group, alkoxymethyl group, and imino group per molecule. Specific examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and the like.

  The polyfunctional isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups per molecule. Specifically, for example, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, Isocyanate compounds such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; Burette polyisocyanate compounds such as Sumidur N (manufactured by Sumitomo Bayer Urethane Co., Ltd.); Desmodur IL, HL (manufactured by Bayer AG) Polyisocyanate compounds having an isocyanurate ring, such as Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.); Sumidur L (Sumitomo Bayer Urethane Co., Ltd.) ), Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) adduct polyisocyanate compounds such as and the like. Moreover, the blocked isocyanate which the isocyanate group of these polyvalent isocyanate compounds reacted with the mask agent which has active hydrogen, and was inactivated can also be used.

  Although it does not specifically limit as said metal crosslinking agent, Specifically, for example, aluminum, zinc, cadmium, nickel, cobalt, copper, calcium, barium, titanium, manganese, iron, lead, zirconium, chromium And metal chelate compounds in which acetylacetone, methyl acetoacetate, ethyl acetoacetate, ethyl lactate, methyl salicylate, and the like are coordinated to a metal such as tin.

  Examples of the aziridine compound include N, N′-hexamethylene-1.6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, bisisophthaloyl-1- ( 2-methylaziridine), tri-1-aziridinyl phosphine oxide, N, N′-diphenylethane-4,4′-bis (1-aziridinecarboxamide) and the like.

  In the near-infrared shielding adhesive composition of the present invention, only one type of crosslinking agent may be used, or two or more types may be appropriately mixed and used. The amount of the crosslinking agent can be appropriately selected depending on the type and use of the crosslinking agent. When the near-infrared shielding adhesive composition of the present invention is used as a 10 to 30 μm thin film, the blending amount is preferably 0.01 to 10% by mass, more preferably 0.00%, based on the solid content of the resin. 1 to 7% by mass. For example, when an adduct polyisocyanate compound (for example, “Coronate L-55E” (manufactured by Nippon Polyurethane Co., Ltd.)) is used as a cross-linking agent, the amount of the cross-linking agent is preferably 0.00 relative to the solid content of the resin. It is 02-20 mass%, More preferably, it is 0.05-10 mass%. If it is less than 0.02% by mass, the crosslinking point becomes insufficient, so that a sufficient crosslinking density cannot be obtained and the cohesive force may be insufficient. If it exceeds 20% by mass, an effect commensurate with the addition cannot be obtained and it is not economical, and the adhesive strength is lowered, which is not preferable.

  In this pressure-sensitive adhesive composition, a polyfunctional epoxy compound and a polyfunctional isocyanate compound are preferable as the crosslinking agent (C) from the viewpoint that sufficient adhesive strength can be obtained. From the viewpoint of obtaining stable holding power, a polyfunctional epoxy compound is particularly preferable as the crosslinking agent (C).

9. Near-infrared shielding adhesive composition Since the near-infrared shielding adhesive composition of this invention contains resin which has adhesiveness, it can adhere | attach easily with a to-be-adhered body. The near-infrared shielding adhesive composition of the present invention contains a cross-linking agent, and its adhesive strength to glass is set to an appropriate value, and thus has high adhesive strength. This near-infrared shielding adhesive composition can hold an adherend stably. Preferably, the near-infrared shielding adhesive composition of the present invention uses a diimonium dye in which the absorbance (X) or the solubility (Y) is considered. This near-infrared shielding adhesive composition is excellent in durability of near-infrared shielding ability and transparency in the visible region. When this near-infrared shielding adhesive composition contains the dispersion (M1) in which the diimonium salt is dispersed in the solvent (D), the durability of the near-infrared shielding ability and the transparency in the visible region are further improved.

[Adhesive strength of near-infrared shielding adhesive composition]
When the near-infrared shielding adhesive composition of the present invention is laminated on one side of a biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) to form an adhesive tape, the adhesive strength to glass is 5 N / inch or more. This near-infrared shielding adhesive composition has high adhesive strength.

  The adhesive strength of the adhesive composition to glass is obtained as follows. The method for measuring the adhesive strength conforms to JIS Z 0237. The pressure-sensitive adhesive composition is applied on a PET film (easily adhesive-treated PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300)) with an applicator. The thickness at the time of coating is set so that the thickness of the layer made of the pressure-sensitive adhesive composition after drying is 25 μm. The layer composed of the pressure-sensitive adhesive composition is dried for 2 minutes in a 100 ° C. hot air circulating oven. After a release film (siliconized PET film) is bonded to the layer made of the pressure-sensitive adhesive composition, the layer made of the pressure-sensitive adhesive composition is cured at 23 ° C. for 7 days to form a pressure-sensitive adhesive tape. This adhesive tape consists of an adhesive composition. This adhesive tape is sandwiched between a PET film and a release film. From this adhesive tape, a specimen (width = 25 mm, length = 100 mm) to be used for measuring the adhesive strength is cut out using a sharp blade.

  Glass (Nippon Test Panel, JIS R 3202, 2 mm x 70 mm x 150 mm) is used as an adherend, and the above-mentioned test body is attached to the adherend in an atmosphere at a temperature of 23 ° C and a relative humidity of 65%. A 2 kg rubber roller is reciprocated three times, and the test specimen is pressure-bonded to the adherend and left for 24 hours. After standing, the film part (adhesive composition) of the adherend and the test specimen was applied using a tensile tester (QC tensile tester: manufactured by Tester Sangyo Co., Ltd.) in an atmosphere at a temperature of 23 ° C. and a relative humidity of 65%. The strength when the test specimen is peeled off from the adherend is measured by gripping each of the test specimens at a speed of 300 mm / min. This strength is the adhesive force to glass when the near-infrared shielding adhesive composition is laminated on one side of a PET film to form an adhesive tape.

  As described above, in the near-infrared shielding adhesive composition of the present invention, the adhesive strength to glass is 5 N / inch or more. From the viewpoint that the near-infrared shielding adhesive composition has high adhesive strength and can stably hold the adherend, the adhesive strength is preferably 7 N / inch or more, more preferably 8 N / inch or more, and 9. 2N / inch or more is more preferable, and 9.8N / inch or more is particularly preferable. Since the adhesive strength is preferably high, the upper limit of the adhesive strength is not particularly defined.

  Other near-infrared shielding dyes may be added to the near-infrared shielding adhesive composition of the present invention. Other near-infrared shielding dyes that can be used in combination include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, and the like. Can be mentioned.

  Other preferred dyes (dyes other than diimonium dyes) are dyes that can exhibit a quencher effect with respect to the diimonium dye. The quencher effect is an effect of deexciting an active molecule in an excited state. In the present invention, other dyes having an effect of de-exciting and stabilizing diimonium dye molecules, diimonium anions or diimonium cations are preferred. From the viewpoint of the quencher effect, a phthalocyanine dye is preferable as the other dye. When the pressure-sensitive adhesive resin of the near-infrared shielding pressure-sensitive adhesive composition of the present invention is a resin obtained by copolymerizing an acid-containing monomer, a phthalocyanine dye whose center metal is copper is particularly preferable.

  When the near-infrared shielding adhesive composition of the present invention is used as an optical filter for a thin display, a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm and a cyanine dye having a maximum absorption wavelength of 800 to 950 nm together with the diimonium dye. It is preferable that a dye or a metal dithiol complex dye having a maximum absorption wavelength of 800 to 950 nm is used in combination. By this combined use, near infrared rays of 800 to 1100 nm can be effectively absorbed. From the viewpoint of obtaining a near-infrared shielding adhesive composition having good durability, it is particularly preferable to use a phthalocyanine dye in combination.

  The phthalocyanine compound that can be used in the present invention is not particularly limited as long as it has an excellent near-infrared shielding ability, and a known phthalocyanine compound can be used. Preferable phthalocyanine compounds include compounds represented by the following formula (A) or compounds represented by the following formula (I).

[Phthalocyanine compound represented by the formula (a)]

In the above formula (A), A ¹ to A ¹⁶ represent functional groups. In the above formula (a), A ¹ to A ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, or an optionally substituted carbon atom having 1 to 20 carbon atoms. 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 to 20 Aryloxy groups, optionally substituted aralkyl groups having 7 to 20 carbon atoms, optionally substituted aralkyloxy groups having 7 to 20 carbon atoms, and optionally substituted carbon atoms 1-20 alkylthio groups, optionally substituted arylthio groups having 6-20 carbon atoms, optionally substituted aralkylthio groups having 7-20 carbon atoms, substituted An optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl having 7 to 20 carbon atoms A sulfonyl group, an optionally substituted acyl group having 1 to 20 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, and an optionally substituted carbon atom having 6 to 20 carbon atoms Aryloxycarbonyl group, optionally substituted aralkyloxycarbonyl group having 2 to 20 carbon atoms, optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms, optionally substituted Good arylcarbonyloxy group having 6 to 20 carbon atoms, optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, substituted It represents an optionally substituted heterocyclic group having 2 to 20 carbon atoms, an optionally substituted amino group, an optionally substituted aminosulfonyl group or an optionally substituted aminocarbonyl group. The functional groups of A ¹ to A ¹⁶ may be the same or different, and may be the same or different in the same type, and the functional groups may be connected via a linking group. M ¹ represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal. In the present specification, the “acyl group” has the same definition as that described on page 17 of the third edition of the Dictionary of Science and Technology Terms published by the Nikkan Kogyo Shimbun. It is a group from which a group has been removed, and is a group represented by the formula: RCO— (where R is an aliphatic group, an alicyclic group or an aromatic group).

(When the terminal is a functional group other than an amino group)
In the above formula (a), examples of the halogen atom of the functional groups A ¹ to A ¹⁶ 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 phenoxy group and naphthoxy group, but are not limited thereto. 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 a phenylthio group and a naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylthio group, a phenethylthio group, a diphenylmethylthio group and the like. 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, but are not limited to, a phenylsulfonyl group and a naphthylsulfonyl group. 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 aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, phenoxycarbonyl and naphthylcarbonyl groups. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like. . 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 arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted 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.

In the above formula (a), the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group of the functional groups A ¹ to A ¹⁶ An arylsulfonyl group, an aralkylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an aralkylcarbonyloxy group or a heterocyclic group As the substituents present in these functional groups A ¹ to A ¹⁶ , for example, halogen atoms, acyl groups, alkyl groups, phenyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, Archi Ruamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic group However, it is not limited to these. A plurality of these substituents may be present. When a plurality of 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)
In the above formula (a), the substituents on the optionally substituted amino group, the optionally substituted aminosulfonyl group, and the optionally substituted aminocarbonyl group of the functional groups A ¹ to A ¹⁶ are as follows: Hydrogen atom: linear, branched or cyclic such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group and cyclohexyl group Alkyl group; aryl group such as phenyl group and naphthyl group; aralkyl group 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-hexyl Linear, branched or cyclic alkylcarbonyl groups such as carbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group and n-octylcarbonyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; benzyl Examples thereof include, but are not limited to, an aralkylcarbonyl group such as a carbonyl group, 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 2 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, the substituents may be connected via a linking group.

  Alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl which is a substituent to the above-mentioned optionally substituted amino group, optionally substituted aminosulfonyl group or optionally substituted aminocarbonyl group Group, aralkylcarbonyl group and the like, which may be further present as a substituent, for example, 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, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, complex Groups including but not limited to. A plurality of these substituents may be present. When a plurality of 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 M ¹ include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and 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) and the like, but are not limited thereto. 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-C 6 H 5, Al-C 6 H 4 (CH 3), In-C _{6 H 5, In-C 6} H 4 (CH 3), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Ru-Cl, etc. is Although it is mentioned, it is not limited to these. Examples of tetravalent substituted metal atoms include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Ge (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Sn (OH) ₂ , Zr (OH) ₂ , Cr (R ₁ ) ₂ , Ge (R ₁ ) ₂ , Si (R ₁ ) ₂ , Sn (R ₁ ) ₂ , Ti (R ₁ ) ₂ {R ₁ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof} Cr (OR ₂ ) ₂ , _{Ge (OR 2) 2, Si} (OR 2) 2, Sn (OR 2) 2, Ti (OR 2) 2, {R 2 is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkyl Alkoxysilyl represents a group or a derivative _{thereof}, Sn (SR 3) 2} , Ge (SR 3) 2 {R 3 is an alkyl group, a phenyl group, a naphthyl group or a derivative thereof} to but like these It is not limited. Examples of oxymetals include, but are not limited to, VO, MnO, TiO and the like.

[Phthalocyanine compound represented by the formula (I)]

In the above formula (A), B ¹ to B ²⁴ represent functional groups. Each of B ¹ to B ²⁴ is any of the functional groups represented by A ¹ to A ¹⁶ in the above formula (a). The functional groups of B ¹ to B ²⁴ may be the same type or different types, and may be the same or different in the same type, and the functional groups may be linked via a linking group.

In the above formula (a), M ² represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal. Examples of M ² are the same as the examples of M ¹ in the above formula (a), but are not limited thereto.

  Specific phthalocyanine compounds include trade names e-ex color IR-10A, e-ex color IR-12, e-ex color IR-14, e-ex color IR-906, e-ex color IR-910, and TX-EX-820. And TX-EX-915 (both made by Nippon Shokubai).

  In addition, a cyanine dye may be used in combination with the near-infrared shielding adhesive composition of the present invention as a near-infrared shielding dye. The cyanine dye is not particularly limited as long as it has an excellent near-infrared shielding ability, but a salt composed of an indolium cation or a benzothiazolium cation and a counter anion can be preferably used. As the indolium cation or the benzothiazolium cation, cations represented by the above formulas (a) to (i) can be preferably used, but are not limited thereto.

  The counter anion of the indolium cation or benzothiazolium cation is not particularly limited, and chloride ion, bromide ion, iodide ion, perchlorate ion, nitrate ion, benzenesulfonate ion, p-toluenesulfonic acid Ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoic acid Acid ion, oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonic acid Ion, fluorosulfo Acid ion, trifluoromethanesulfonate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion, zirconate ion, sulfate ion, vanadate ion, borate ion, etc. it can.

  More specifically, as a cyanine dye containing a cation represented by the above general formula (a), ADS812MI (counter anion is an iodide ion) manufactured by American Dye Source Co .; represented by the above general formula (b) S0712 manufactured by FEW Chemical Co. (counter anion is hexafluorophosphate ion) as a cyanine dye containing a cation; S0726 manufactured by FEW Chemical Co. as a cyanine dye containing a cation represented by the general formula (c) Counter anion is chloride ion); As cyanine-based dye containing a cation represented by the above general formula (d), ADS780MT manufactured by American Dice Source (counter anion is p-toluenesulfonic acid ion); As a cyanine dye containing a cation represented by the following formula: S0006 (counter anion is FEW Chemical) Chlorate ion); as a cyanine dye containing a cation represented by the above general formula (f), S0081 (counter anion is perchlorate ion) manufactured by FEW Chemical Co .; cation represented by the above general formula (g) As a cyanine dye containing F0 Chemical Co., S0773 (counter anion is tetrafluoroborate ion); As a cyanine dye containing a cation represented by the general formula (h), trade name S0772 manufactured by FEW Chemical Co., Ltd. (Counter anion is tetrafluoroborate ion); as a cyanine dye containing a cation represented by the above general formula (i), commercially available product name S0734 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co., Ltd. Can be used. By using a cyanine dye, a near-infrared shielding adhesive composition having high transparency in the visible region can be obtained.

  The blending amount of the diimonium dye of the present invention or the total blending amount of the diimonium dye of the present invention and other near-infrared shielding dyes can be appropriately selected depending on the type and use of the dye. When the near-infrared shielding adhesive composition of the present invention is used as a 10 to 30 μm thin film, the blending amount is preferably 0.01 to 10% by mass, more preferably 0.00%, based on the solid content of the resin. 1 to 5% by mass. For example, when a diimonium dye and a phthalocyanine dye are used in combination, the total amount of these dyes is preferably 0.01 to 10% by mass, more preferably 0.1%, based on the solid content of the resin. ˜5 mass%. If the blending amount is less than 0.01% by mass, there is a possibility that sufficient near-infrared shielding ability cannot 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.

  The near-infrared shielding adhesive composition of the present invention is characterized by transparency in the visible region, persistence of near-infrared shielding ability, and good adhesiveness. If necessary, a dye that absorbs visible light may be added to the near-infrared shielding adhesive composition of the present invention. Examples of dyes that absorb visible light include cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metal dithiol complex, squarylium, azurenium, diphenylmethane, triphenylmethane, oxazine, and azine. , Thiopyrylium, viologen, azo, azo metal complex, bisazo, anthraquinone, perylene, indanthrone, nitroso, indico, azomethine, xanthene, oxanol, indoaniline, quinoline A conventionally well-known pigment | dye, such as a system and a diketopyrrolopyrrole type | system | group, can be used widely.

  When the near-infrared shielding adhesive composition of the present invention is used as an optical filter for PDP, it is preferable to use a visible absorption dye having a maximum absorption wavelength of 550 to 650 nm in order to absorb unnecessary neon light emission. The type of the dye that absorbs neon light emission is not particularly limited, and a cyanine dye and a tetraazaporphyrin dye can be used. Specifically, Adeka Arcles TY-102 (Asahi Denka Kogyo Co., Ltd.), Adeka Arcles TY-14 (Asahi Denka Kogyo Co., Ltd.), Adeka Arcles TY-15 (Asahi Denka Kogyo Co., Ltd.), TAP-2 ( Yamada Chemical Industries), TAP-18 (Yamada Chemical Industries), TAP-45 (Yamada Chemical Industries), trade names NK-5451 (Hayashibara Biochemistry Laboratories), NK-5532 (Hayashibara Biochemistry Laboratories) ), NK-5450 (manufactured by Hayashibara Biochemical Research Institute) and the like. The addition amount of the dye for absorbing neon emission varies depending on the kind of the dye, but it is preferable to add so that the transmittance at the maximum absorption wavelength is about 20 to 80%.

  Moreover, in order to adjust the color tone of the thin film which consists of a near-infrared shielding adhesive composition, you may add the visible light absorption pigment | dye for toning. There are no particular limitations on the type of coloring pigment, but 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole, and the like can be used. Specifically, Orazol Blue GN (manufactured by Ciba Specialty Chemicals), Orazol Blue BL (manufactured by Ciba Specialty Chemicals), Orazol Red 2B (manufactured by Ciba Specialty Chemicals), Orazol Red G (Ciba)・ Specialty Chemicals), Orazole Black CN (Ciba Specialty Chemicals), Orasol Yellow 2GLN (Ciba Specialty Chemicals), Orazole Yellow 2RLN (Ciba Specialty Chemicals), Microlith DPP Red BK (manufactured by Ciba Specialty Chemicals), and the like.

  The near-infrared shielding pressure-sensitive adhesive composition of the present invention may contain one or more diluents, additives, and curing agents as long as the performance is not lost.

  The dilution solvent that can be contained in the near-infrared shielding adhesive composition is not limited, and those exemplified as the solvent (S) are preferable.

  At the time of coating, the viscosity of the near-infrared shielding adhesive composition is appropriately selected depending on the type of the coating machine, but in the case of coating by a small-diameter gravure kiss reverse method such as a micro gravure coater, 1-1000 mPa · In the case of coating by extrusion method such as s or die coater, 100 to 10,000 mPa · s is generally used. The solid content of the near-infrared shielding adhesive composition is adjusted according to the viscosity of the paint.

  Moreover, as an additive which a near-infrared shielding adhesive composition can contain, the conventionally well-known additive used for the resin composition which forms a film, a coating film, etc. may be used. These additives include dispersants, leveling agents, antifoaming agents, viscosity modifiers, matting agents, tackifiers, antistatic agents, antioxidants, UV absorbers, light stabilizers, quenchers, curing agents, A blocking agent etc. are mentioned. As the curing agent, a thiol compound, an amine compound, an imine compound, an oxazoline compound, a silane coupling agent, a UV curing agent, or the like can be used.

  The near-infrared shielding adhesive composition of the present invention includes optical, agricultural, architectural or vehicle near-infrared shielding materials, image recording materials such as photosensitive paper, information recording materials such as optical disks, and dye-sensitized types. It can be used for a solar cell such as a solar cell, a photosensitive material using a semiconductor laser beam or the like as a light source, and an eye strain prevention material. The near-infrared shielding adhesive composition of the present invention is particularly preferably used in the form of a film or a sheet.

10. Near-infrared shielding material The near-infrared shielding material which concerns on this invention contains the said near-infrared shielding adhesive composition. The near-infrared shielding material of the present invention may be a film obtained by forming the near-infrared shielding adhesive composition into a film shape, and a coating film containing the near-infrared shielding adhesive composition is laminated on a transparent substrate. It may be what you did.

  The transparent substrate is generally usable for optical materials and is not particularly limited as long as it is substantially transparent. Specific examples include glass; olefin polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl polymers such as vinyl acetate and vinyl halides; polyesters such as PET; polycarbonate and butyral. Examples thereof include polyvinyl acetals such as resins; polyaryl ether resins; lactone ring-containing resin films. 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, and coating such as an anchor coating agent and a primer. May be applied. The base resin constituting the transparent base material can be blended with known additives, heat aging inhibitors, lubricants, antistatic agents, and the like. The transparent substrate is formed into a film or a sheet using a known method such as injection molding, T-die molding, calendar molding, compression molding, or a method of casting by melting in an organic solvent. The base material constituting the transparent base material may be unstretched or stretched, and may be laminated with another base material.

  A PET film is preferable as the transparent substrate when a near-infrared shielding film is obtained by a coating method, and a PET film subjected to an easy adhesion treatment is particularly preferable. Specifically, Cosmo Shine A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex 705 (manufactured by Teijin DuPont) and the like can be mentioned. Functional films such as a TAC (triacetylcellulose) film, an antireflection film, an antiglare film, an impact absorbing film, an electromagnetic wave shielding film, and an ultraviolet absorbing film can also be used as the transparent substrate. Thereby, the optical filter for thin displays and optical semiconductor elements can be produced simply. The transparent substrate is preferably a film.

  Among these, glass, PET film, lactone ring-containing resin film, easy-adhesion PET film, TAC film, antireflection film and electromagnetic wave shielding film are preferably used as the transparent substrate. When an inorganic base material such as glass is used as the transparent base material, a material having a small alkali component is preferable from the viewpoint of durability of the near-infrared shielding dye.

  The thickness of the near-infrared shielding material of the present invention is generally about 0.1 μm to 10 mm, but is appropriately determined according to the purpose. Further, the content of the near-infrared shielding dye contained in the near-infrared shielding material is also appropriately determined according to the purpose.

  Although it does not specifically limit as a method to produce the near-infrared shielding material of this invention, For example, the following method can be utilized. For example, (I) a method of kneading a resin and a near-infrared shielding adhesive composition according to the present invention and thermoforming them to produce a resin plate or film; (II) a near-infrared shielding adhesive composition according to the present invention And a method of producing a resin plate or film by casting polymerization of a monomer or an oligomer in the presence of a polymerization catalyst; (III) a method of coating the near-infrared shielding adhesive composition according to the present invention on the transparent substrate, etc. It is.

  As a production method of (I), the processing temperature, filming (resin plate) conditions, etc. are slightly different depending on the resin to be used. Usually, the near-infrared shielding adhesive composition according to the present invention is made into resin powder or pellets. Examples thereof include a method of adding and heating and dissolving at 150 to 350 ° C. and then molding to prepare a resin plate, a method of forming a film (resin plate) with an extruder, and the like.

  As a preparation method of (II), the near-infrared shielding adhesive composition according to the present invention and a monomer or oligomer are cast polymerized in the presence of a polymerization catalyst, and the mixture is injected into a mold and reacted to be cured. Or by pouring into a mold and solidifying until a hard product is formed in the mold. Many resins can be molded in this process. Specific examples of such resins include acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like. Among them, the casting method by bulk polymerization of methyl methacrylate, which can obtain an acrylic sheet excellent in hardness, heat resistance, and chemical resistance, is preferable.

  Known radical thermal polymerization initiators can be used as the polymerization catalyst, and examples thereof include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. . The amount used is generally 0.01 to 5% by mass relative to the total amount of the mixture. The heating temperature in thermal polymerization is generally 40 to 200 ° C., and the polymerization time is generally about 30 minutes to 8 hours. In addition to thermal polymerization, a method of photopolymerization by adding a photopolymerization initiator or a sensitizer can also be used.

  As the method of (III), a method of coating the near-infrared absorbing material of the present invention on a transparent substrate, a paint in which the near-infrared shielding adhesive composition of the present invention is fixed to fine particles, and the fine particles are dispersed are used. There is a method of coating on a transparent substrate.

  When applying the near-infrared shielding adhesive composition to the substrate, a 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 a drying / curing method, a known method such as hot air, far-infrared ray or UV curing can be used. You may wind up with a well-known protective film after drying and hardening.

  The drying method is not particularly limited, and hot air drying or far infrared drying can be used. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the coating amount, the residual solvent amount, the type of substrate, and the like. If the substrate is a PET film, the general drying temperature is 50 to 150 ° C. When there are a plurality of dryers in one line, each dryer may be set to a different temperature and wind speed. In order to obtain a coating film having a good coating appearance, it is preferable that the drying condition on the inlet side is mild.

  The near-infrared shielding adhesive composition of the present invention can be a constituent material of an excellent optical filter having high transparency in the visible region and high near-infrared absorption ability. Since the near-infrared shielding adhesive composition of the present invention has higher durability, particularly heat resistance and light resistance than conventional near-infrared shielding materials, the appearance and near-infrared shielding ability are maintained even during long-term storage and use. The Furthermore, since the near-infrared shielding adhesive composition of the present invention can be easily formed into a sheet or film, it is effective for thin displays and optical semiconductor elements. In addition, the near-infrared shielding adhesive composition of the present invention can also be used for filters and films that need to cut infrared rays, such as agricultural films, heat insulating films, sunglasses, optical recording materials, and the like.

  The near-infrared shielding adhesive composition of the present invention contains a crosslinking agent (C). The near-infrared shielding material is formed by crosslinking a near-infrared shielding adhesive composition with a crosslinking agent (C). This near-infrared shielding material has high adhesive strength and cohesive strength. The near-infrared shielding material can stably hold the adherend. According to this near-infrared shielding material, the function as an optical filter is stably maintained.

  A suitable application of the near-infrared shielding material is an optical filter. This optical filter is formed using the near-infrared shielding material. This optical filter is suitable as an optical filter for an optical semiconductor element or an optical filter for a thin display. 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 near-infrared transmittance of a wavelength of 800 to 1100 nm is preferably 30% or less. Is 15% or less.

  In addition to the near-infrared shielding layer comprising the above-mentioned near-infrared shielding adhesive composition, 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, and color adjustment. A support such as a layer or glass may be provided.

  What is necessary is just to select the structure of each layer of an optical filter arbitrarily. For example, an optical filter that preferably combines at least one of an antireflection layer and an antiglare layer and at least two layers of a near-infrared shielding layer is preferable, and more preferably at least 3 that further combines an electromagnetic wave shielding layer. An optical filter having a layer.

  The antireflection layer or the glare prevention layer is preferably the outermost layer on the human side. The stacking order between the near-infrared shielding 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.

  When laminating each layer, physical treatment such as corona treatment and plasma treatment may be performed, and a known high-polarity polymer such as polyethyleneimine, oxazoline-based polymer, polyester or cellulose is used as an anchor coating agent. Also good.

  In order to make the optical filter for thin display easy to see, it is preferable to provide an antireflection layer or an antiglare layer on the outermost layer on the human side.

  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. Alternatively, it may be composed of multi-layers, and as a manufacturing method in the former case, there is a method of forming an antireflection coating on a transparent substrate in the form of a single layer or a multilayer using vapor deposition or sputtering. is there. Further, as a manufacturing method in the latter case, on a transparent film, a knife coater such as a comma coater, a fountain coater such as a slot coater and a lip coater, a gravure coater, a flow coater, a spray coater, and a bar coater are used. There is a method of applying an antireflection coating to the surface.

  The glare-preventing layer is formed by converting fine powders of silica, melamine resin, acrylic resin, etc. into ink, applying it on any layer of the filter of the present invention by a conventionally known coating method, and curing it by heat or photocuring. Is done. 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 this layer, it is formed by coating, drying and photocuring.

  An optical filter having an antireflection layer or an antiglare layer and a near-infrared shielding layer has a layer made of the near-infrared shielding adhesive composition or near-infrared shielding material of the present invention on the back surface of the antireflection film or antiglare film. Obtained by laminating. As a method of laminating, the near-infrared shielding layer according to the present invention in the form of a film and the antireflection film or the anti-glare film may be directly bonded together, or the solution of the near-infrared shielding adhesive composition of the present invention is used as a solution. You may apply | coat directly on the back surface of an antireflection film or an anti-glare film. In the case where a near-infrared shielding layer is provided on the back surface of the antireflection film or antiglare film, it is preferable to use an ultraviolet absorbing film as the transparent substrate in order to suppress the deterioration of the pigment due to ultraviolet rays. The near-infrared shielding adhesive composition of the present invention has adhesiveness. Therefore, when the near-infrared shielding layer and another layer are bonded, an adhesive or an adhesive may be unnecessary. A near-infrared shielding layer is a layer containing the near-infrared shielding adhesive composition of this invention.

  The optical filter for plasma display is preferably provided with an electromagnetic wave shielding layer in order to remove electromagnetic waves generated from the panel.

  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.

  An optical filter having two layers of a near-infrared shielding layer and an electromagnetic wave shielding layer can be obtained by combining an electromagnetic wave prevention material and a near-infrared shielding adhesive composition. As a method of combining, the near-infrared shielding adhesive composition of the present invention formed into a film and the electromagnetic shielding film may be laminated, or the solution of the near-infrared shielding adhesive composition of the present invention is used as an electromagnetic shielding film. You may apply directly. Moreover, when smoothing the metal mesh on a film, the near-infrared shielding adhesive composition of this invention can also be used. Moreover, when embedding the fiber which vapor-deposited the metal, the near-infrared shielding adhesive composition of this invention can also be used.

  As an optical filter having three layers of a near-infrared shielding layer, a reflection or glare prevention layer, and an electromagnetic wave shielding layer, a near-infrared shielding film comprising the near-infrared shielding adhesive composition of the present invention, a reflection or glare prevention film, and an electromagnetic wave A laminate of three shielding films can be used. Preferably, an optical filter having a structure in which a near-infrared shielding film made of the near-infrared shielding adhesive composition of the present invention is sandwiched between a reflection or glare-preventing film and an electromagnetic wave shielding film is preferable. Since this optical filter is laminated | stacked using the adhesiveness of a near-infrared shielding film, it can manufacture by abbreviate | omitting the adhesive layer conventionally provided only for bonding of films. If necessary, a support such as glass or a functional film such as a color adjusting film may be laminated. Since the near-infrared shielding adhesive composition has a high adhesive force, the adherend can be stably held.

  In order to further simplify the optical filter manufacturing process and film configuration, it is preferable to use a composite film having a plurality of functions. A preferred optical filter is an optical filter in which a near-infrared shielding adhesive layer comprising the near-infrared shielding adhesive composition of the present invention is bonded to a composite film comprising an electromagnetic wave shielding layer and a reflection or glare prevention layer on a single film. It is.

  The thin display optical filter of the present invention may be installed away from the display device or may be directly attached to the display device. When installing away from the display device, it is preferable to use glass as the support. In the case of directly bonding to a display device, an optical filter that does not use glass is preferable.

  When the optical filter on which the near-infrared shielding adhesive composition of the present invention is laminated is mounted on a thin display, good image quality is maintained over a long period of time. The present invention relating to a thin display is a thin display comprising the near-infrared shielding adhesive composition of the present invention, the near-infrared shielding material of the present invention, or the optical filter of the present invention. A thin display in which an optical filter is directly bonded to the display body can provide clearer image quality. When the optical filter is directly attached, it is preferable to use tempered glass as the display glass or an optical filter provided with a shock absorbing layer. Since the near-infrared shielding adhesive composition of the present invention, the near-infrared shielding material of the present invention, or the optical filter of the present invention has high adhesive strength, the display body can be stably held.

  The thickness of this near-infrared shielding material layer (hereinafter also referred to as an adhesive layer) is usually 5 to 2000 μm, preferably 10 to 1000 μm. A release film is provided on the surface of the pressure-sensitive adhesive layer, and this release film protects the pressure-sensitive adhesive layer and prevents dust from adhering to the pressure-sensitive adhesive layer until the optical filter is attached to the surface of the thin display. Also good. In this case, a non-adhesive part is formed by forming a part where the adhesive layer is not provided or by sandwiching a non-adhesive film between the adhesive layer at the edge of the filter and the release film. If the part is a peeling start part, the work at the time of sticking is easy to perform.

  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 absorber, ethylene-vinyl acetate copolymer, acrylic polymer, polyvinyl chloride, urethane-based, silicon-based resin as disclosed in JP-A-2004-246365 and JP-A-2004-264416 However, it is not limited to these.

  In the following, the present invention will be specifically described by way of examples. These examples do not limit the invention in any way. In the following component ratios, unless otherwise specified, “%” means mass% and “part” means mass part. The evaluation method is as follows.

(1) Evaluation of holding power The SUS304 steel plate prescribed | regulated to JISG4305 was used as the to-be-adhered body, and the test body was affixed in the atmosphere of the temperature of 23 degreeC and the relative humidity of 65% by the affixing area 25 mm x 25 mm. A 2 kg rubber roller was reciprocated three times, and the specimen was pressure-bonded to the adherend and left for 25 minutes. Thereafter, the test piece was put into a holding power tester adjusted to 80 ° C., and the test specimen was suspended in the tester so as to hang vertically. The specimen was left for 20 minutes in the suspended state. After being allowed to stand, a weight having a mass of 1 kg was attached to the specimen. The time (min) until the weight fell after the weight was attached or the deviation width (mm) was measured. This test was performed on three specimens, and the average value was obtained. This average value is shown in the following table as the holding force for the SUS304 steel sheet specified in JIS G 4305 when laminated on one side of a biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) to be an adhesive tape. Yes. In the table, the SUS304 steel plate that did not fall for 24 hours or more and the deviation was not recognized at all was indicated as “NC”.

(2) Evaluation of near-infrared shielding ability The transmission spectrum of 350-1500 of the test body was measured. UV-3700 (manufactured by Shimadzu Corporation) was used for measurement of the transmission spectrum. From this transmission spectrum, an average transmittance of 850 to 1000 nm was determined. The results are shown in the table below. In the table, “G” indicates that the average transmittance was 30% or less, and “B” indicates that the average transmittance was higher than 30%.

(3) Evaluation of light resistance In a "SX2-75 Super Xenon Weather Meter" manufactured by Suga Test Instruments Co., Ltd., the irradiation intensity at 300 to 400 nm is 60 W / m at 63 ° C. and 50% RH. ² was irradiated for 100 hours. Before and after this test, the transmission spectrum of light of 350 to 1500 nm was measured. UV-3700 (manufactured by Shimadzu Corporation) was used for measurement of the transmission spectrum. From the obtained transmission spectra before and after the test, the dye residual ratio (%) at λmax was evaluated. In the table, “A” indicates that the residual ratio of the pigment is 80% or more, “B” indicates that the ratio is 50% or more and less than 80%, and “C” indicates that the ratio is less than 50%. It is shown.

The dye residual ratio Px (%) is calculated by the following formula when the absorbance at λmax after the test is Ax (%) and the absorbance at λmax before the test is Bx (%).
Px = (Ax / Bx) × 100

(4) Absorbance (X) of diimonium salt
It was measured by the method described above.

(5) The above-mentioned solubility (Y) of the diimonium salt
It was measured by the measurement method described above using five types of samples.

(6) Measurement of acid value 0.5 g of resin was precisely weighed, and 50 g of toluene was added and dissolved uniformly. Two to three 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 liquid did not disappear 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 necessary to neutralize 1 g of resin solids.

Synthesis example 1:
[Synthesis of Diimonium Compound a and Production of Dispersion 1]
In 36 parts of dimethylformamide (DMF), 6 parts of N, N, N ′, N′-tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenediamine was added and dissolved by heating at 60 ° C. Thereafter, 10.1 parts of a 58.4% aqueous solution of tris (trifluoromethylsulfonyl) methane was added. Next, 2.32 parts of silver nitrate dissolved in 35 parts of DMF was added and stirred with heating for 30 minutes. After filtering the insoluble matter, water was added to the reaction solution, and the precipitated crystals were filtered, washed with methanol, washed with water and dried to obtain 8.4 parts of tris (trifluoromethylsulfonyl) methidoic acid-N, N, N ′, N′-tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenediimonium (hereinafter also referred to as compound a) was obtained. This compound a is a diimonium salt in which R ^{1 to} R ⁸ in the above formula (2) are all iso-butyl groups and Z ⁻ in the above formula (2) is [(CF ₃ SO ₂ ) ₃ C ⁻ ]. It is. The absorbance (X) of this compound a is 0.138 (λmax is 1096 nm) when the solvent is toluene, 0.239 (λmax is 1081 nm) when the solvent is ethyl acetate, and the solvent is butyl acetate. In this case, it was 0.0750 (λmax was 1085 nm). When the solubility (Y) of the compound a was measured, it was less than 0.01% by mass when the solvent was toluene, less than 0.01% by mass when the solvent was ethyl acetate, and the solvent was butyl acetate. The case was less than 0.01% by mass.

  0.5 parts of the above compound a, 9.5 parts of ethyl acetate and 25 parts of zirconia beads are put into a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, and the zirconia beads are separated by filtration to contain compound a. Dispersion 1 was obtained. The zirconia beads were manufactured by Nikkato Co., Ltd., and the particle size was 300 μm.

Synthesis example 2:
[Synthesis of Diimonium Compound b and Production of Dispersions 2 to 4]
In 30 parts of DMF, 3.8 parts of N, N, N ′, N′-tetrakis (aminophenyl) -p-phenylenediamine, 21 parts of iso-butyl bromide and 15 parts of potassium carbonate were added, and the mixture was heated at 80 ° C. for 1 hour. The reaction was further carried out at 90 ° C. for 7 hours and further at 130 ° C. for 1 hour. After cooling, the mixture was filtered, 30 parts of isopropanol was added to the reaction solution (filtrate), and the mixture was stirred at 5 ° C. or lower for 1 hour. The produced crystals were washed with methanol and dried to obtain 2.5 parts of a light brown crystalline compound. 1 part of the above crystalline compound was added to 10 parts of DMF and heated to 60 ° C. to obtain a liquid A1 in which the crystalline compound was dissolved. Liquid B1 obtained by dissolving 0.78 parts of silver hexafluoroantimonate in 10 parts of DMF was added to the liquid A1 and allowed to react for 30 minutes. After cooling, the precipitated silver was filtered off. To this reaction liquid (filtrate), 10 parts of water was slowly added dropwise, followed by stirring for 15 minutes. The produced black crystals were filtered, washed with 50 parts of water, and the resulting cake (residue) was dried to give 0.5 parts of hexafluoroantimonic acid-N, N, N ′, N′-tetrakis ( p-Di (iso-butyl) aminophenyl) -p-phenylenediimonium (hereinafter also referred to as compound b) was obtained. This compound b is a dimonium salt in which R ^{1 to} R ⁸ in the above formula (2) are all iso-butyl groups and Z ⁻ in the above formula (2) is [SbF ₆ ⁻ ]. When the absorbance (X) of this compound b was measured, it was 0.070 (λmax was 1088 nm) when the solvent was toluene, and 0.113 (λmax was 1069 nm) when the solvent was ethyl acetate. Of butyl acetate was 0.0286 (λmax was 1069 nm). When the solubility (Y) of this compound b was measured, it was less than 0.01% by mass when the solvent was toluene, less than 0.01% by mass when the solvent was ethyl acetate, and the solvent was butyl acetate. The case was less than 0.01% by mass.

  0.5 parts of the above compound b, 9.5 parts of ethyl acetate and 25 parts of the above zirconia beads are put into a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, and then the zirconia beads are separated by filtration. Dispersion 2 containing was obtained.

  0.5 parts of the compound b, 9.5 parts of toluene and 25 parts of the zirconia beads are put into a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, and then filtered to remove the zirconia beads to contain the compound b. Dispersion 3 was obtained.

  0.5 part of the compound b, 9.5 parts of butyl acetate and 25 parts of the zirconia beads are put into a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, the zirconia beads are separated by filtration, and the compound b is obtained. A dispersion 4 containing was obtained.

[Preparation of Dispersion 5]
As compound c, a diimonium dye (trade name “KAYASORB IRG-022” manufactured by Nippon Kayaku Co., Ltd.) was prepared. This compound c is a diimonium salt in which R ^{1 to} R ⁸ in the above formula (2) are all normal butyl groups and Z ⁻ in the above formula (2) is [SbF ₆ ⁻ ]. 0.5 parts of compound c, 9.5 parts of ethyl acetate and 25 parts of the above zirconia beads are put into a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, and then filtered to remove the zirconia beads to contain compound c. Dispersion 5 was obtained. When the absorbance (X) of this compound c was measured, it was 0.92 (λmax was 1086 nm) when the solvent was toluene, and 0.60 (λmax was 1063 nm) when the solvent was ethyl acetate. Was butyl acetate, it was 0.1135 (λmax was 1068 nm). When the solubility (Y) of this compound c was measured, it was less than 0.01% by mass when the solvent was toluene, less than 0.1% by mass when the solvent was ethyl acetate, and the solvent was butyl acetate. The case was less than 0.01% by mass.

[Preparation of Dispersion 6]
As compound d, titanium dioxide (trade name “CR-50-2” manufactured by Ishihara Sangyo Co., Ltd.) was prepared. 10 g of this sample, 16 g of 1 mm glass beads, and 6 g of ethyl acetate were placed in a 70 ml mayonnaise bottle, shaken with a paint shaker for 30 minutes, and then the glass beads were separated by filtration to obtain dispersion 6 containing compound d.

Resin production example 1:
As monomers, 360.6 g of 2-ethylhexyl acrylate, 60 g of butyl acrylate, 156 g of cyclohexyl methacrylate, 18 g of acrylic acid and 5.4 g of hydroxyethyl acrylate are weighed and mixed thoroughly to obtain a polymerizable monomer mixture (1 )

  160 g of ethyl acetate and 300 g of the polymerizable monomer mixture (1) were put in a flask equipped with a thermometer, a stirrer, an inert gas introduction tube, a reflux condenser, and a dropping funnel. In addition, 300 g of the polymerizable monomer mixture (1), 16 g of ethyl acetate and 0.15 g of Nyper BMT-K40 (polymerization initiator, manufactured by NOF Corporation) are mixed in the dropping funnel and mixed well for dropping. It was set as the mixture (1).

  While flowing nitrogen gas at a rate of 20 ml / min, the internal temperature of the flask was raised to 95 ° C., and Niper BMT-K40 (0.15 g) as a polymerization initiator was charged into the flask to initiate the polymerization reaction. 30 minutes after charging the polymerization initiator, the dropping of the dropping mixture (1) from the dropping funnel was started. The dropping mixture (1) was dropped evenly over 90 minutes. After completion of the dropwise addition of the mixture for dripping (1), the mixture was aged for 6 hours while maintaining the reflux temperature while appropriately diluting with ethyl acetate as the viscosity increased.

  After completion of the reaction, the reaction solution is diluted with ethyl acetate so that the non-volatile content is about 45%, a resin having a calculated glass transition temperature (Tg) of −38.5 ° C. and a calculated solubility parameter of 9.08. (1) was obtained. This resin (1) was an adhesive resin. The weight average molecular weight (Mw) of the resin (1) was 430,000, and the acid value of the resin (1) was 23.4.

[Example 1]
Coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent was dissolved in an ethyl acetate solution to prepare a crosslinking agent solution having a solid content of 2.75%. Resin (1) obtained in Resin Production Example 1, Dispersion 1 obtained in Synthesis Example 1, a phthalocyanine compound as a near-infrared shielding agent (trade name “EEX Color IR-14” manufactured by Nippon Shokubai) and The cross-linking agent solution is mixed so that the solid content weight ratio becomes 100/1 / 0.3 / 0.25, diluted with ethyl acetate as a diluent solvent so that the solid content becomes 25%, and near infrared rays A shielding adhesive composition was obtained. This solid content weight ratio is expressed in the order of (resin (1) / dispersion 1 / phthalocyanine compound / crosslinking agent solution).

  The near-infrared shielding adhesive composition was coated on an easy-adhesion-treated PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300) with an applicator. The thickness at the time of coating was set so that the thickness of the pressure-sensitive adhesive composition layer after drying was 25 μm. Subsequently, it was dried in a hot air circulating oven at 100 ° C. for 2 minutes. A release film (silicone-treated PET film) was laminated to the layer made of this pressure-sensitive adhesive composition, and then cured at 23 ° C. for 7 days to obtain a near-infrared shielding material. After peeling off the release film, this near-infrared shielding material was affixed to glass to obtain a test body according to Example 1. The adhesion of this test specimen to glass was 9.8 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 2]
The crosslinking agent is 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (indicated as “X” in Table 4), and the resin (1) obtained in Resin Production Example 1 is obtained in Synthesis Example 1. The dispersion 1, the phthalocyanine compound (trade name “EEX Color IR-14” manufactured by Nippon Shokubai Co., Ltd.) and the crosslinking agent solution were made 100/1 / 0.3 / 0.1 in weight ratio of solids. Obtained the test body which concerns on Example 2 like Example 1. FIG. The adhesion of the test specimen to glass was 10.6 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 3]
A test body according to Example 3 was obtained in the same manner as in Example 1 except that the dispersion 2 was used instead of the dispersion 1. The adhesion of the test specimen to glass was 10.2 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 4]
Using Dispersion 2 instead of Dispersion 1, and using 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (indicated as “X” in Table 4) as the cross-linking agent, obtained in Resin Production Example 1 The obtained resin (1), dispersion 2, phthalocyanine compound (trade name “EEX Color IR-14” manufactured by Nippon Shokubai Co., Ltd.) and a cross-linking agent solution were mixed at a solid content weight ratio of 100/1 / 0.3 / 0. A test body according to Example 4 was obtained in the same manner as in Example 1 except that. The adhesion of the test specimen to glass was 11.4 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 5]
A test body according to Example 5 was obtained in the same manner as in Example 1 except that the dispersion 3 was used in place of the dispersion 1. The adhesion of the test specimen to glass was 9.2 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 6]
A test body according to Example 5 was obtained in the same manner as in Example 1 except that the dispersion 4 was used in place of the dispersion 1. The adhesion of the test specimen to the glass was 9.5 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 7]
A test body according to Example 5 was obtained in the same manner as in Example 1 except that Dispersion 5 was used instead of Dispersion 1. The adhesion of the test specimen to the glass was 8.8 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Example 8]
A test sample according to Example 8 was prepared in the same manner as in Example 1 except that a solution of the dimonium compound a obtained in Synthesis Example 1 in 5% by mass in methyl ethyl ketone was used, and methyl ethyl ketone was used as a diluent solvent. Obtained. The adhesion of the test specimen to the glass was 9.5 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

[Comparative Example 1]
The dispersion 6 was used in place of the dispersion 1, and the resin (1) obtained in the resin production example 1, the dispersion 6 and the cross-linking agent solution were changed to a solid content weight ratio of 100/20 / 0.25. In the same manner as in Example 1, a test body according to Comparative Example 1 was obtained. The adhesion of the test specimen to glass was 3.5 N / inch. This specimen was evaluated for holding power, near infrared shielding ability, and light resistance. The evaluation results are shown in the following table.

  The near-infrared shielding adhesive composition of the present invention is useful as an optical filter for, for example, a thin display because it has long-infrared shielding ability and high transparency in the visible region, and is excellent in heat resistance, moist heat resistance and light resistance. It is. It can also be used as an optical information recording material.

Claims (8)

A diimonium salt (A), a resin (B) having a calculated glass transition point of 0 ° C. or less, a crosslinking agent (C), and a solvent (D),
A near-infrared shielding adhesive composition having an adhesive strength to glass of 5 N / inch or more when laminated on one side of a biaxially stretched polyethylene terephthalate film to form an adhesive tape.   The near-infrared shielding adhesive composition according to claim 1, wherein the solubility of the dimonium salt (A) in the solvent (D) is less than 5% by mass.   A mixed solution in which the dimonium salt (A) was mixed at a ratio of 0.01% by mass with respect to the solvent (D) was prepared, and this mixed solution was subjected to ultrasonic waves for 30 minutes, and then allowed to stand for 1 hour or more, Then, the absorbance (X) at λmax of the supernatant measured in the range of 350 nm to 1500 nm by an ultraviolet-visible spectrophotometer after placing the supernatant of this mixed solution in a cell having an optical path length of 1 mm is 0.5 or less. The near-infrared shielding adhesive composition according to claim 1 or 2.   The near-infrared shielding adhesive composition according to any one of claims 1 to 3, wherein a dispersion (M1) in which the dimonium salt (A) is dispersed in the solvent (D) is mixed.   The near-infrared shielding adhesive composition according to any one of claims 1 to 4, wherein an acid value of the resin (B) is 0 or more and 300 or less.   The near-infrared shielding adhesive composition according to any one of claims 1 to 5, wherein the calculated solubility parameter of the resin (B) is 10.2 or less.   The near-infrared shielding adhesive composition according to any one of claims 1 to 6, wherein the solvent (D) is at least one selected from the group consisting of toluene, ethyl acetate and butyl acetate. The near-infrared shielding pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the near-infrared shielding adhesive composition is crosslinked and formed with the crosslinking agent (C).
The resin (B) contains at least one kind of functional group,
A near-infrared shielding material in which the crosslinking agent (C) has at least two functional groups capable of reacting with the functional group per molecule.