KR20110137385A - Near infrared ray-absorbable adhesive composition - Google Patents

Abstract

The near-infrared absorption adhesive composition of this invention contains dimonium salt (A1), resin (B) whose calculation glass transition point is 0 degrees C or less, and solvent (S2). After adjusting the liquid mixture which mixed the said dimonium salt (A1) with respect to the solvent (S1) at the ratio of 0.01 mass%, this mixture liquid was sonicated for 30 minutes, and left still for 1 hour or more, and then the supernatant liquid of this liquid mixture was The absorbance (X) at lambda max of the supernatant liquid contained in a cell having an optical path length of 1 mm and measured in a range of 350 nm or more and 1500 nm or less by an ultraviolet visible spectrophotometer is 0.5 or less. Preferably, the solvent (S1) is toluene and / or ethyl acetate. Preferably, the solvent (S2) is toluene and / or ethyl acetate.

Description

Near infrared ray-absorbable adhesive composition

This invention relates to a near-infrared absorption adhesive composition, the near-infrared absorption mixture used for this near-infrared absorption adhesive composition, and the near-infrared absorber containing this near-infrared absorption adhesive composition.

Recently, a thin display such as a liquid crystal display or a plasma display panel (PDP) that can be applied to a large screen is attracting attention. Thin displays produce near-infrared light with a wavelength of 800 nm to 1100 nm. It is a problem that this near-infrared radiation causes malfunction of the remote controller for home appliances. In addition, since optical semiconductor elements used in CCD cameras and the like also have high sensitivity in the near infrared region, the near infrared rays need to be removed. Accordingly, there is a demand for a near infrared absorbing material having high absorption ability of near infrared rays and high transparency of visible region.

As a near-infrared absorbing pigment which absorbs near infrared rays, a cyanine dye, a polymethine dye, a squarylium dye, a porphyrin dye, a metal dithiol complex dye, a phthalocyanine dye, a dimonium dye, or an inorganic oxide particle is conventionally used. have. Especially, dimonium pigment | dye is used abundantly because it has high absorption ability of near-infrared rays, and high transparency in visible region (for example, refer patent document 1, 2).

In addition, the PDP generates a discharge in an inert gas enclosed inside the panel, particularly a gas mainly composed of neon, and the phosphors of R, G, and B provided in the cells inside the panel by the vacuum ultraviolet rays generated at that time. Emits light. Therefore, in this light emission process, electromagnetic waves unnecessary for the operation of the PDP are simultaneously emitted. This electromagnetic wave also needs to be shielded. In addition, an antireflection film and an antiglare film (antiglare film) are also required to suppress the reflected light. For this reason, it is common that the optical filter for plasma displays is produced by laminating a near-infrared absorbing film, an electromagnetic wave shielding film, and an antireflection film on glass or a shock absorber serving as a support. Such an optical filter for plasma display is mounted on the front side of a PDP. Such an optical filter for plasma display may be used by directly bonding on glass or an impact absorber which is a support body using an adhesive agent and an adhesive.

In recent years, for the purpose of thinning an optical filter and simplifying the manufacturing process of an optical filter, an attempt is made to integrate a near-infrared absorbing film and an adhesive layer by including a near-infrared absorbing dye in an adhesive (patent document 3 and patent document 4). ).

Patent Document 1: Japanese Patent Publication No. 2003-96040

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-80071

Patent Document 3: Japanese Patent No. 3621322

Patent Document 4: International Publication WO2008 / 026786

 Dimonium pigment | dye may be inferior in durability, and the fall of near-infrared absorption ability and coloring may become a serious problem when using it for an optical semiconductor element or a display use. In particular, in a resin with a low glass transition point (Tg) such as an adhesive resin, deterioration of the dye is severe.

Japanese Laid-Open Patent Publication No. 2005-325292 discloses a dimonium pigment having improved durability by introducing a halogen atom into an alkyl group of a dimonium cation. In the case of the near-infrared cut off filter using this dimonium pigment | dye and high Tg binder resin, the improvement of durability is seen compared with the conventional dimonium pigment | dye. However, in the case of the combination with the low Tg adhesive resin which is severely deteriorated, the durability tends to be insufficient. In WO2008 / 026786, the durability of the dye in the pressure-sensitive adhesive composition is improved by appropriately limiting the dimonium pigment. In the present invention, a technique which can improve the durability of the dimonium pigment | dye in adhesive resin was discovered from a viewpoint different from the invention of international publication WO2008 / 026786.

An object of the present invention is to provide a near-infrared absorbent pressure-sensitive adhesive composition useful for producing a near-infrared absorbent material having high transparency in the visible region and high persistence of near-infrared absorbing capacity, and a near-infrared absorbent mixture useful for producing the near-infrared absorbent pressure-sensitive adhesive composition.

The present inventors earnestly examined about the improvement of the durability of the dimonium pigment | dye in adhesive resin. As a result, it was found that the solubility in specific conditions or the absorbance measured under specific conditions correlated with the durability of the dimonium pigment in the adhesive resin. MEANS TO SOLVE THE PROBLEM This inventor discovered that the near-infrared absorption adhesive composition excellent in the durability of a pigment | dye is obtained when the said solubility or the said absorbance becomes an appropriate value.

The near-infrared absorption adhesive composition of this invention contains the dimonium salt (A1) whose absorbance (X) in (lambda) max of a supernatant liquid is 0.5 or less, resin (B) whose calculated glass transition point is 0 degrees C or less, and near-infrared rays containing a solvent (S2). Absorption adhesive composition. In the measurement of this absorbance (X), first, the mixed liquid which mixed the dimonium salt (A1) in the ratio of 0.01 mass% with respect to the solvent S1 is adjusted, and this mixed liquid is sonicated for 30 minutes, and left to stand for 1 hour or more. do. Then, the supernatant liquid of this liquid mixture is put into the cell of 1 mm of optical path length, and absorbance is measured in the range of 350 nm or more and 1500 nm or less with an ultraviolet visible spectrophotometer. By this measurement, the absorbance X at λmax and its λmax is determined.

Preferably, the solvent (S1) is toluene and / or ethyl acetate. Preferably, the solvent (S2) is toluene and / or ethyl acetate.

Preferably, the solvent (S1) and the solvent (S2) are the same.

Preferably, the compounding quantity of the said dimonium salt (A1) in the said near-infrared absorption adhesive composition is 0.5 mass% or more with respect to the total mass of all solid content contained in this near-infrared absorption adhesive composition.

Another near-infrared absorption adhesive composition of this invention is solvent (S3), the dimonium salt (A2) whose solubility (Y) with respect to this solvent (S3) is less than 0.01 mass%, and resin (B) whose calculation glass transition point is 0 degrees C or less. ).

Preferably, the solvent (S3) is toluene and / or ethyl acetate.

Preferably, the acid value of the said resin (B) is 0 or more and 300 or less.

Preferably, the calculated solubility parameter of the said resin (B) is 10.2 or less.

Preferably, the said resin (B) is obtained by superposing | polymerizing the monomer mixture of the following formulation.

(1) (meth) acrylic acid ester which has a C1-C12 alkyl group: 60 mass% or more and 99.9 mass% or less.

(2) Functional group containing monomer: 0.1 mass% or more and 20 mass% or less.

(3) Other copolymerizable monomers: 0 mass% or more and 30 mass% or less.

Preferably, this near-infrared absorption adhesive composition further contains a phthalocyanine type pigment | dye.

Another near-infrared absorption adhesive composition of this invention adjusts the liquid mixture which mixed the dimonium salt (A1) by 0.01 mass% with respect to the solvent (S1), and left this mixture liquid for 1 hour or more after sonicating for 30 minutes. Then, the dimonium salt whose absorbance (X) in (lambda) max of the said supernatant liquid measured in the range of 350 nm or more and 1500 nm or less by putting the supernatant liquid of this liquid mixture into the cell of 1 mm of optical path lengths by the ultraviolet-visible spectrophotometer It is a near-infrared absorption adhesive composition containing (A1), resin (B) whose calculation glass transition point is 0 degrees C or less, and a solvent (S2). The dimonium salt (A1) has a solubility (Y) in the solvent (S3) of less than 0.01% by mass.

Preferably, the solvent S1 and the solvent S2 are the same, and the solvent S3 and the solvent S1 are the same.

The near-infrared absorber of this invention contains the near-infrared absorption adhesive composition in any one of the above.

Preferably, in the near-infrared absorber, any one of the above-mentioned near-infrared absorbent pressure-sensitive adhesive compositions is laminated on a transparent substrate.

After the near-infrared absorber is applied to the transparent substrate, the solvent (S2) or the solvent (S3) may be volatilized.

Preferably, the said near-infrared absorber is laminated | stacked on the electromagnetic wave shielding material in which the near-infrared absorption adhesive composition in any one of the above can shield an electromagnetic wave. The acid value of the said resin (B) is 0 or more and 35 or less.

Preferably, the electromagnetic shielding material includes the transparent substrate.

The near-infrared absorber in any one of the above may be used for the optical filter for thin displays of this invention.

The thin display of this invention uses any of the above-mentioned near-infrared absorption adhesive compositions, any of the above-mentioned near-infrared absorbers, or the said optical filter.

The near-infrared absorption mixture of this invention is used for a near-infrared absorption adhesive composition. This near-infrared absorption mixture adjusts the liquid mixture which mixed the dimonium salt (A1) by 0.01 mass% with respect to the solvent (Sm), and left this mixture liquid for 1 hour or more after sonication for 30 minutes, after that, The supernatant of the mixed solution was placed in a cell of 1 mm of optical path length and the dimonium salt (A1) having an absorbance (X) at lambda max of λmax of the supernatant measured in the range of 350 nm or more and 1500 nm or less by an ultraviolet visible spectrophotometer and , Solvent (Sm) is contained.

Preferably, in this near infrared absorption mixture, the solvent (Sm) is toluene and / or ethyl acetate.

Another near-infrared absorption mixture of this invention is also for near-infrared absorption adhesive compositions. This near-infrared absorption mixture contains the solvent (S3) and the dimonium salt (A2) whose solubility (Y) with respect to this solvent (S3) is less than 0.01 mass%.

Preferably, in this near infrared absorption mixture, the solvent (S3) is toluene and / or ethyl acetate.

Another near-infrared absorption adhesive composition of this invention may use any of the above-mentioned near-infrared absorption mixtures.

Preferably, the said other near-infrared absorption adhesive composition uses the said near-infrared absorption mixture and resin composition (P). This resin composition (P) contains the solvent (S2) and resin (B) whose calculation glass transition point is 0 degrees C or less.

Preferably, the compounding quantity of resin (B) in the said resin composition (P) is 50 mass% or more.

The near-infrared absorption adhesive composition using the near-infrared absorption mixture of this invention is excellent in the durability of a dimonium pigment | dye. The near-infrared absorbing material using the near-infrared absorption adhesive composition of this invention can maintain the near-infrared absorption ability of a dimonium pigment | dye over a long term. Therefore, when this near-infrared absorption adhesive composition is used for manufacture of the optical filter for optical semiconductor elements or a thin display, thinning of an optical filter and simplification of the manufacturing process of an optical filter are attained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows the transmission spectrum before (initial stage) the test of the test body of Example 2. FIG.
2 is a graph showing the transmission spectrum after the heat resistance test of the test body of Example 2. FIG.
3 is a graph showing a transmission spectrum after a heat-and-moisture resistance test of the test body of Example 2. FIG.
4 is a graph showing the transmission spectrum after the light test of the test body of Example 2. FIG.
5 is a graph showing the transmission spectrum before (initial) the test body of Comparative Example 1. FIG.
6 is a graph showing the transmission spectrum after the heat resistance test of the test body of Comparative Example 1. FIG.
7 is a graph showing a transmission spectrum after a wet and heat test of the test body of Comparative Example 1. FIG.
8 is a graph showing the transmission spectrum after the light resistance test of the test body of Comparative Example 1.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described. In addition, in this application, what is distinguished from a dimonium salt (A1) and a dimonium salt (A2) is to show that both may differ. In addition, the purpose of this distinction is also to clearly describe the claims and the specification. As described below, as a result, the dimonium salt (A1) and the dimonium salt (A2) may be the same. Regarding the dimonium salt of the present application, without adding the symbols of (A1) and (A2), and simply described as "dimonium salt", both of the dimonium salt (A1) and the dimonium salt (A2) Means to apply.

In addition, in this application, the solvent is distinguished by (S1), (S2), (S3), (S4), and (Sm) in order to show that they may differ from each other. The purpose of this distinction is also to clarify the description of the claims and the specification. As described below, as a result, two or three or more selected from the solvents S1, S2, S3, S4, and Sm may be the same. In addition, all of the solvents (S1), (S2), (S3), (S4) and (Sm) may be the same.

The solvent (S1), (S2), (S3), (S4) or (Sm) may be contained in the near-infrared absorption adhesive composition of this invention. In the near-infrared absorption adhesive composition of this invention, solvent (S1), (S2), (S3), (S4) or (Sm) may be extinguished by volatilization.

Dimonium salt (dimonium pigment) A1

As for the dimonium salt (A1) used for this invention, the absorbance (X) in (lambda) max of the supernatant liquid measured by the method mentioned later is 0.5 or less.

As a dimonium cation of a dimonium pigment | dye (A1), the dimonium cation represented by following General formula (1) is illustrated.

Preferable dimonium pigment | dye becomes a dimonium cation represented by the said General formula (1), and a dimonium anion Z <^-> as represented by following General formula (1S).

[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 general formula (1S), Z ⁻ represents a dimonium anion.

When R <^1> -R <^8> is an alkyl group or an alkyl group which has a substituent, 1 or more and 2 or less are preferable and, as for carbon number of this alkyl group, each of R <^1> -R <^8> , 2 or more and 12 or less are more preferable.

As a halogen atom which comprises R <^1> -R <^8> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

As preferable R <^1> -R <^8> , a C1-C10 linear, branched and alicyclic alkyl group is mentioned. As such an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-amyl group, isoamyl group, 1 Methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, neopentyl, n-hexyl and cyclohexyl groups. 4,4,4-trifluorobutyl group, 2,2,2-trifluoroethyl group, and perfluorobutyl group are mentioned as another preferable R <^1> -R <^8> . R ¹ to R ⁸ may all be the same or different from each other.

More preferably, R <^1> -R <^8> is a C3-C5 linear or branched alkyl group. More preferably, R ¹ to R ⁸ are n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-amyl group or isoamyl group, and n-butyl group, isobutyl group or iso Amyl group is more preferable, and isobutyl group is especially preferable.

Moreover, as a substituent which can couple | bond with the alkyl group of R <^1> -R <^8> , it is a cyano group; Hydroxyl group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; Alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group; Alkoxyalkoxy groups having 2 to 8 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group and ethoxybutoxy group; An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms such as a methoxy methoxy methoxy group, a methoxy methoxy ethoxy group, a methoxy ethoxy ethoxy group, and an ethoxy ethoxy ethoxy group; Allyloxy group; C6-C12 aryloxy groups, such as a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group; Alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group and n-butoxycarbonyl group; C2-C7 alkylcarbonyloxy groups, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, n-propylcarbonyloxy group, and n-butylcarbonyloxy group; And alkoxycarbonyloxy groups having 2 to 7 carbon atoms such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyloxy group and the like. A methoxyethyl group is mentioned as a preferable example of the alkyl group which the substituent couple | bonded. That is, a methoxyethyl group is mentioned as a preferable example of R <^1> -R <^8> .

The dimonium anion is not particularly limited. Preferred dimonium anions are hexafluoroantimonate ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, trifluoromethanesulfonic acid ion, toluenesulfonic acid ion, bis (trifluoromethanesulfonic acid ) Imide ion, tetrakis (pentafluorophenyl) borate ion, tris (trifluoromethanesulfonic acid) methion ion, etc. More preferred dimonium anions include hexafluoroantimonate ion [SbF ₆ ⁻ ] and tris (trifluoromethanesulfonic acid) methion ion [(CF ₃ SO ₂ ) ₃ C ⁻ ].

The preferable dimonium salt (A1) of this invention is a form in which two anions couple | bond with one dimonium cation.

As dimonium salt (A1), tris (trifluoromethylsulfonyl) methic acid-N, N, N ', N'- tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenedi Immonium and hexafluoroantimonic acid-N, N, N ', N'-tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenedimonium. These manufacturing methods are demonstrated by the synthesis example mentioned later. Since these are high in durability in an adhesive composition, they are especially preferable.

It is preferable that a dimonium pigment | dye (A1) becomes a form which is easy to disperse. Preferably, it is preferable that the dimonium pigment | dye is refine | miniaturized by grinding | pulverization. As the method of miniaturization, either wet or dry can be employed. As a wet refinement method, besides a bead mill and a ball mill, refinement | miniaturization by liquid flow or refinement | miniaturization using a laser or an ultrasonic wave is employable. As a dry refinement method, in addition to a ball mill and an attritor, refinement | miniaturization by a roll mill and airflow is employable. More preferably, a method of pulverizing the dimonium pigment using particles such as zirconia beads, glass beads, alumina beads and the like can be employed. For example, as a grinding method using zirconia particles, a liquid mixture in which a dimonium pigment, a solvent (S4) and zirconia beads are mixed is made, and the liquid mixture is shaken in a container, followed by separation of zirconia beads. This is illustrated. As preferable solvent (S4), the solvent (S1) by which the absorbance (X) measured by the said method using the dimonium salt which is a grinding | pulverization object becomes 0.5 or less is mentioned. As another preferable solvent (S4), the solvent (S3) whose solubility (Y) measured by the said method using the dimonium salt which is a grinding | pulverization object becomes less than 0.01% is mentioned.

2. Dimonium salt (dimonium pigment) A2

The dimonium salt (A2) used for this invention is less than 0.01 mass% in solubility (Y) measured by the method mentioned later.

As a dimonium cation of a dimonium pigment | dye (A2), the dimonium cation represented by the said General formula (1) is illustrated.

Preferable dimonium pigment | dye becomes a dimonium cation represented by the said General formula (1), and the said dimonium anion Z <^-> as represented by the said General formula (1S).

In the above formula (1) or the general formula 1S, R ¹ ~ R ^{and 8} are an alkyl group having an alkyl group or a substituent, the number of carbon atoms of the alkyl group is, for each of R ¹ ~ R ^8, and is less than 1 but not more than 22 preferably, 2 12 or more are more preferable.

As a halogen atom which comprises R <^1> -R <^8> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

As preferable R <^1> -R <^8> , the C1-C10 linear, branched and alicyclic alkyl group similar to the said dimonium pigment | dye (A1) is mentioned.

The dimonium anion is not particularly limited. For example, the dimonium anion similar to the said dimonium pigment | dye (A1) is mentioned as a dimonium anion.

The preferable dimonium salt (A2) of this invention is a form in which two anions couple | bond with one dimonium cation.

As the dimonium salt (A2), tris (trifluoromethylsulfonyl) methic acid-N, N, N ', N'-tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenedi Immonium and hexafluoroantimonic acid-N, N, N ', N'-tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenedimonium. These manufacturing methods are demonstrated by the synthesis example mentioned later. Since these are high in durability in an adhesive composition, they are especially preferable.

It is preferable that a dimonium pigment | dye (A2) becomes a form which is easy to disperse. Preferably, it is preferable that the dimonium pigment | dye is refine | miniaturized by grinding | pulverization. As this method of refinement | miniaturization, both the wet and the dry method similar to the said dimonium pigment | dye (A1) are employable. Also in this dimonium pigment | dye (A2), the same method as the said dimonium pigment | dye (A1), More preferably, the method of grind | pulverizing a dimonium pigment | dye using particle | grains, such as a zirconia bead, a glass bead, an alumina bead, Adoption is possible. For example, as a grinding | pulverization method using a zirconia particle, the dimonium pigment | dye (A2), the solvent (S3) whose solubility (Y) of this dimonium pigment | dye (A2) is less than 0.01 mass%, and zirconia beads were mixed. A method of making a liquid, shaking the liquid in a container, and then separating the zirconia beads is illustrated.

3. Determination of Solvent (S1) and Absorbance (X)

The solvent (S1) is used when measuring the absorbance (X) of the supernatant of the dimonium salt. In addition, the solvent (S1) may be contained in the near-infrared absorption adhesive composition.

As solvent (S1), it is preferable that the solubility (Y) of the dimonium salt measured becomes less than 0.01 mass%. The detail of the measurement of this solubility (Y) is mentioned later. As the solvent S1, toluene, ethyl acetate, xylene, butyl acetate and methylcyclohexane are exemplified. Toluene and ethyl acetate are particularly preferred.

[Measurement of Absorbance (X) of Supernatant]

In this measurement of absorbance (X), the mixed liquid which mixed the dimonium salt in the ratio of 0.01 mass% with respect to the solvent (S1) was adjusted, this mixed liquid was sonicated for 30 minutes, and left still for 1 hour or more. Then, the supernatant liquid of this mixed liquid is put into the cell of 1 mm of optical path length, and a measurement is performed. The cell having an optical path length of 1 mm is made of quartz. The measurement is performed by an ultraviolet visible spectrophotometer. As this ultraviolet visible spectrophotometer, UV-3100 by Shimadzu Corporation is used. The measuring range is 350 nm or more and 1500 nm or less. (lambda) max means the wavelength whose absorbance becomes the largest in the measured wavelength range. An absorbance is calculated | required by the following formula, when making transmittance T (%).

Absorbance = -log (T / 100)

The mixing method and the collection method of the supernatant are as follows. First, 50 milliliters of the mixed liquid which mixed dimonium salt in 0.01 mass% with respect to the solvent (S1) is produced. The mixing vessel used for this mixing is a screw cap bottle. The outer diameter of this screw cap bottle is 40 mm and the height is 75 mm. In this mixing vessel, the height of the liquid surface (the uppermost surface of the liquid) of the 50 milliliter liquid mixture is 50 mm. After this mixed solution is sonicated and left to stand for one hour or more, the supernatant of a portion up to 5 mm from the liquid surface (top surface of the liquid) is collected and used for the measurement. Preferably, in the mixed solution after being left for 1 hour or more, an insoluble dimonium salt is precipitated on the bottom surface of the mixed container. In this measurement, the temperature of the solvent S1 is 25 ° C. A table-type ultrasonic cleaner (brand name "Bransonique 3510J-DTH") made by BRANSON was used for the provision of the ultrasonic waves. A tank of this table type ultrasonic cleaner is filled with water, the mixing vessel is placed in a tank filled with water, and the tank is vibrated at a frequency of 40000 Hz or more (42 kHz), and ultrasonic waves are applied to the mixed liquid of the mixing container. Given.

In this invention, when the said absorbance (X) with respect to the solvent (S1) is 0.5 or less, it discovered that the durability of the dimonium salt in adhesive resin (B) can improve. From the viewpoint of the 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 the durability of the dimonium salt, More preferably, the solvent (S1) in either of toluene or ethyl acetate, it is preferable that the absorbance (X) is 0.5 or less, 0.3 or less is more preferable, 0.25 The following is more preferable, and 0.15 or less are further more preferable. From the viewpoint of the durability of the dimonium salt, More preferably, even if the solvent (S1) is either toluene or ethyl acetate, it is preferable that absorbance (X) is 0.5 or less, 0.3 or less is more preferable, 0.25 or less Is more preferable.

4. Solvent (S2)

The solvent (S2) may be included in the pressure-sensitive adhesive composition. This solvent (S2) may be used as a dilution solvent for adjusting the viscosity of an adhesive composition. By solvent (S2), the viscosity of an adhesive composition is adjusted to the viscosity suitable for application | coating to a base material etc .. By this viscosity, the thickness of an adhesive composition layer can be adjusted.

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 are used as the solvent (S2). Can be mentioned.

In the present invention, from the viewpoint of the durability of the dimonium salt, it has been found that the solvent (S2) is preferably toluene and / or ethyl acetate. In the present invention, from the viewpoint of the durability of the dimonium salt, it has been found that the solvent (S2) is toluene and / or ethyl acetate, and the solvent (S1) is more preferably toluene and / or ethyl acetate. Moreover, in this invention, it turned out that it is preferable that solvent (S1) and solvent (S2) are the same.

5. Measurement method of solvent (S3) and solubility (Y)

Preferable adhesive composition contains solvent (S3) and the dimonium salt whose solubility (Y) with respect to this solvent (S3) is less than 0.01 mass%. This solvent (S3) is used for the measurement of solubility (Y).

The solvent (S3) can be variously selected by the dimonium salt used. Toluene, ethyl acetate, xylene, butyl acetate, and methylcyclohexane are illustrated as an example of the solvent (S3). Toluene and / or ethyl acetate are particularly preferred.

This solvent (S3) may be used as a diluting solvent similarly to the said solvent (S2). A solvent preferable as the solvent (S2) is also preferable as the solvent (S3). A solvent preferable as the solvent (S1) is also preferable as the solvent (S3).

[Measuring method of solubility (Y)]

Five kinds of samples whose content ratio of dimonium salt is 0.01 mass%, 0.1 mass%, 1.0 mass%, 2.0 mass%, and 5.0 mass% are adjusted, and ultrasonically stirred respectively. The stirring time is 30 minutes or more, and the temperature of the solvent is 25 ° C. Next, about each sample, it is confirmed whether there is a residue. The residue is confirmed by visually observing whether or not there is a residue on the filter paper after filtration. The solubility (Y) is determined by the presence or absence of a residue. When no residue is confirmed in a 5.0 mass% sample (and other samples), it is judged that "solubility (Y) is 5 mass% or more". When a residue is confirmed by 0.01 mass% of samples (and other samples), it is judged that "solubility (Y) is less than 0.01 mass%". When a residue is confirmed by the 0.1 mass% sample and a residue is not confirmed by the 0.01 mass% sample, it is judged that "solubility (Y) is 0.01 mass% or more and less than 0.1 mass%".

6. Diluent Solvent

The dilute solvent may be contained in the near-infrared absorption adhesive composition. The diluting solvent may be any of the solvents (solvent (S1), (S2), (S3), (S4) and (Sm)). 2 or more types chosen from said solvent (S1), (S2), (S3), (S4), and (Sm) may be sufficient as this dilution solvent. The diluent solvent may be a solvent other than the solvents (solvent (S1), (S2), (S3), (S4) and (Sm)). By dilution solvent, the viscosity of an adhesive composition can be adjusted to the viscosity suitable for application | coating to a base material etc .. By this viscosity, the thickness of an adhesive composition layer can be adjusted.

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, etc. are mentioned as a diluting solvent. have.

From the viewpoint of the durability of the dimonium salt, the diluting solvent is preferably toluene and / or ethyl acetate.

In addition, the diluent solvent does not need to be used. For example, only the solvent contained in the mixture (M1) mentioned later may adjust suitably the viscosity of a near-infrared absorption adhesive composition.

7. Near infrared absorption mixture (hereinafter also referred to as mixture M1)

The manufacturing method of the near-infrared absorption adhesive composition of this invention is the 1st process of mixing a dimonium salt and a solvent (Sm), and producing a mixture (M1), and this mixture (M1) is mixed with resin (B) (described later). It is preferable to include the 2nd process which becomes. Preferable solvent Sm is the said solvent (S1) or the said solvent (S3). In view of the durability of the dimonium salt, it was found that this solvent (Sm) is preferably toluene and / or ethyl acetate. Moreover, it is preferable that this solvent (Sm) is the same as the dilution solvent of a near-infrared absorption adhesive composition from a viewpoint of the durability of a dimonium salt.

As a manufacturing method of the mixture M1, the method using the particle | grains for grind | pulverizing a dimonium salt is illustrated. As this manufacturing method, the same wet and dry methods as those shown as the method of miniaturization of the said dimonium pigment | dye (A1) can be employ | adopted. For example, as a method for producing a mixture (M1) using zirconia particles, a liquid mixture in which a dimonium pigment, a solvent (S4) and zirconia beads are mixed is made, and the liquid mixture is shaken in a container, followed by zirconia A method of separating the beads is illustrated. As said preferable solvent (S4), the solvent (S1) by which the absorbance (X) measured by the said method using the dimonium salt which is a grinding | pulverization object becomes 0.5 or less is mentioned. As said preferable solvent (S4), the solvent (S3) by which the solubility (Y) measured by the said method using the dimonium salt which is grind | pulverization object becomes less than 0.01% is mentioned.

From the viewpoint of the near infrared absorptivity, the blending amount of the dimonium salt in this mixture (M1) is preferably 3 mass% or more, more preferably 4 mass% or more, particularly preferably 5 mass% or more. From the viewpoint of the viscosity of the handling, the blending amount of the dimonium salt in this mixture (M1) is preferably 95 mass% or less. In addition, the compounding quantity of this dimonium salt is represented by the ratio of the mass of the dimonium salt mix | blended with this mixture M1 with respect to the mass of the mixture M1.

After the mixture M1 is once formed, the mixture M1 is mixed with a resin (B) described later to improve the phase separation state of the dimonium salt in the near-infrared absorbent pressure-sensitive adhesive composition. The reason is considered that resin (B) contributes as a dispersing agent.

Moreover, anionic, cationic, or nonionic surfactant, a polymeric dispersing agent, etc. are mentioned as this additive which various additives may be added to the said mixture M1.

8. Resin (B)

Resin (B) of this invention will not be specifically limited if glass transition temperature is 0 degrees C or less. Resin (B) of this invention has adhesiveness. This adhesiveness enables direct adhesion of the near-infrared absorbent pressure-sensitive adhesive composition and the adherend. The near-infrared absorbent pressure-sensitive adhesive composition and the adherend can be adhered without interposing the adhesive. In this application, this resin (B) is also called adhesive resin.

8-1. Glass transition temperature

From a viewpoint of providing adhesiveness to a to-be-adhered body, 0 degrees C or less is preferable, as for the glass transition temperature of an adhesive resin (B), -10 degrees C or less is more preferable, -20 degrees C or less is more preferable, More preferably, It is -30 degrees C or less. When it is higher than 0 degreeC, adhesiveness may be insufficient. The glass transition temperature is also obtained by obtaining the maximum temperature of the loss tangent (tanδ) by differential scanning calorimeter or dynamic viscoelasticity measurement, but the glass transition temperature referred to herein is determined by the following Fox equation. Calculated means glass transition temperature. 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 formula of Fox represented by the following formula satisfies a predetermined value.

1 / (Tg + 273) = Σ [Wi / (Tgi + 273)]: Fox expression

Tg (° C.): Calculated glass transition temperature

Wi: weight fraction of each monomer

Tgi (° C.): glass transition temperature of homopolymer of each monomer component

8-2. Acid

It is common for adhesive resin (B) to copolymerize carboxyl group-containing monomers, such as acrylic acid, for the purpose of improving adhesiveness with a to-be-adhered body, and increasing adhesive force. However, since functional groups, such as a carboxyl group, deteriorate a dimonium pigment | dye, 300 or less are preferable, as for the acid value of adhesive resin (B), 100 or less are more preferable, and 80 or less are still more preferable. From the viewpoint of the durability of the dimonium salt, 0 or more is preferable, as for the acid value of adhesive resin (B), 5 or more are more preferable, and 10 or more are more preferable. An "acid value" means the amount of mg of potassium hydroxide required to neutralize 1 g of the adhesive resin. The detail of the acid value measuring method is mentioned later.

For example, when the transparent base material mentioned later is glass, it is inferred that the following (reaction 1) occurs on the glass surface (interface of glass and a near-infrared absorption adhesive composition layer). Na ⁺ ions in the glass are thought to come out of the glass surface by diffusion. The Na ⁺ ions, reacts with H ₂ O (or H ₂ O before applying the pressure-sensitive adhesive composition adhering to the glass surface) present in the near infrared absorbing pressure-sensitive adhesive composition, it is believed that NaOH is generated.

(Reaction 1) Na ⁺ + H ₂ O → NaOH + H ⁺ (into glass)

This NaOH degrades the dimonium salt. When a carboxyl group exists in resin (B), this carboxyl group traps Na <^+> . It is thought that this trap suppresses production of NaOH and suppresses deterioration of the dimonium salt. In particular, in the evaluation of moisture-heat resistance, since much H ₂ O exists, the reaction 1 is likely to occur. Therefore, especially from a viewpoint of moisture-and-moisture resistance, the larger the acid value is preferable, specifically, as mentioned above, 0 or more are preferable, 5 or more are more preferable, and 10 or more are more preferable.

On the other hand, when the acid value of resin (B) is excessively high, solubility of the dimonium salt with respect to resin (B) increases, and association | aggregate (X) tends to decrease. Therefore, especially from the viewpoint of the heat resistance which evaluates durability at high temperature, the said acid value is smaller one, and specifically, as mentioned above, 300 or less are preferable, 100 or less are more preferable, 80 or less is more preferable. Do.

As mentioned later, in the case of the optical filter which has a near-infrared absorption layer which becomes the near-infrared absorption adhesive composition of this invention, the electromagnetic wave shielding layer containing a metal layer may be laminated | stacked on this near-infrared absorption layer. In particular, when the metal layer is laminated on the near infrared absorbing layer, the acid value of the resin (B) is particularly preferably 35 or less from the viewpoint that deterioration of the dimonium salt can be suppressed and discoloration of the dye, the metal layer, and the adhesive can be prevented. . From the viewpoint of improving the dispersion state of the dimonium salt, this acid value is preferably zero or more.

8-3. Calculation Solubility Parameter

When the calculation solubility parameter of an adhesive resin (B) is high, since the durability of a dimonium pigment | dye may be inferior, it is preferable that a solubility parameter is 10.2 or less. The calculated solubility parameter is a value calculated by the method described in pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2). The method is outlined below.

The solubility parameter (δ) of a homopolymer is calculated by the calculation method of the following formula based on the evaporation energy (Δei) and molar volume (Δvi) of the structural unit which forms the polymer.

Δei: evaporation energy of atom or atom group of component i

Δvi: molar volume of atoms or atom groups of component i

The solubility parameter of the copolymer is a product obtained by multiplying the evaporation energy of each constituent monomer constituting the copolymer by multiplying the mole fraction (ΣΔEi) by multiplying the mole volume of each constituent monomer by the mole fraction (Σ It is calculated by dividing by ΔVi) and taking the power of 1/2.

8-4. Copolymer composition

Copolymer may be sufficient as adhesive resin (B). It is preferable that adhesive resin (B) is a copolymer of the (meth) acrylic acid ester containing a hydroxyl group, and another compound. Furthermore, from the viewpoint of the durability of a dimonium pigment | dye, adhesive resin (B) has 5-40 mass of (meth) acrylic acid ester which has an alicyclic, polycyclic alicyclic, an aromatic ring, or a polycyclic aromatic ring alkyl group. It is preferred that it is% copolymer copolymerized. Although the reason why the durability of a dimonium pigment | dye improves is unclear, these alicyclic, polycyclic alicyclic, aromatic ring, and polycyclic aromatic ring alkyl group part and dimonium pigment | dye take a stocking structure, and it is heat resistance and heat and moisture resistance It is thought to improve.

Preferably, the said resin (B) is resin which copolymerizes the following monomer (p1)-(p3).

(p1) (meth) acrylic acid esters having an alkyl group having 1 to 12 carbon atoms

(p2) Functional group containing monomer

(p3) other copolymerizable monomers

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

From the viewpoint of the durability of the dimonium pigment | dye, More preferably, the alkyl group in the said monomer (p1) is a linear, branched, and alicyclic alkyl group.

As an example of the (meth) acrylic acid ester of said (p1), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dish Clofentanil (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylic The rate etc. are mentioned.

As a functional group containing monomer of said (p2), a hydroxyl group or a carboxyl group-containing monomer is preferable, and a hydroxyl group or a carboxyl group-containing (meth) acryl monomer is more preferable. From the viewpoint of the durability of the dimonium pigment | dye, a carboxyl group-containing (meth) acryl monomer is preferable. The carboxyl group of a carboxyl group-containing (meth) acryl monomer becomes a crosslinking point. Therefore, adhesive adjustment is possible with the compounding quantity of a carboxyl group-containing (meth) acryl monomer. Moreover, it is thought that the carboxyl group of a carboxyl group-containing (meth) acryl monomer contributes to the improvement of durability for another reason. The detail of the reason is as above-mentioned.

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

Examples of hydroxyl group-containing (meth) acryl monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. The hydroxyl group of a hydroxyl-containing (meth) acryl monomer can be a crosslinking point. Therefore, a hydroxyl-containing (meth) acryl monomer contributes to adjustment of adhesive property. When said (p2) is a hydroxyl-containing (meth) acryl monomer, the ratio of this hydroxyl-containing (meth) acryl monomer is especially preferable 0.1 mass% or more and 10 mass% or less with respect to monomer whole quantity.

As the other copolymerizable monomer of (p3), benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate , Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. . In addition, as an example of said (p3), (meth) acrylates, such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxy ethoxyethyl (meth) acrylate; styrene monomers such as α-methylstyrene, vinyltoluene, styrene, and the like; Vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; Fumaric acid; Monoalkyl esters of fumaric acid; Dialkyl esters of fumaric acid; Maleic acid; Monoalkyl esters of maleic acid; Dialkyl esters of maleic acid; Itaconic acid; Monoalkyl esters of itaconic acid; Dialkyl esters of itaconic acid; (Meth) acrylonitrile; Vinyl chloride; Vinylidene chloride; Vinyl acetate; Vinyl ketones; Vinylpyridine; Vinyl carbazole and the like. Moreover, you may copolymerize the monomer which has functional groups, such as a carboxyl group, an oxazolinyl group, a pyrrolidoneyl group, and a fluoroalkyl group, in the range which does not impair the objective of this invention.

More preferable adhesive resin (B) is resin obtained by copolymerizing following (m1)-(m4).

(m1) (meth) acrylic acid ester which has an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic ring alkyl group.

(m2) (meth) acrylic acid ester which has an alkyl group. However, this alkyl group is linear or branched, and carbon number of this alkyl group is 1 or more and 10 or less.

(m3) Functional group containing monomer

(m4) Other copolymerizable monomers.

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

As an example of the (meth) acrylic acid ester of said (m1), cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. are mentioned.

As an example of the (meth) acrylic acid ester of said (m2), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, etc. are mentioned.

As a functional group containing monomer of said (m3), the thing illustrated as a functional group containing monomer of said (p2) is mentioned.

Examples of the monomer of (m4) include (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate; styrene monomers such as α-methylstyrene, vinyltoluene, styrene, and the like; Vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether; Fumaric acid; Monoalkyl esters of fumaric acid; Dialkyl esters of fumaric acid; Maleic acid; Monoalkyl esters of maleic acid; Dialkyl esters of maleic acid; Itaconic acid; Monoalkyl esters of itaconic acid; Dialkyl esters of itaconic acid; (Meth) acrylonitrile; Vinyl chloride; Vinylidene chloride; Vinyl acetate; Vinyl ketones; Vinylpyridine; Vinyl carbazole and the like.

As an initiator used for superposition | polymerization of adhesive resin (B), commercially available things, such as a peroxide type and an azo type, can be used. As an initiator of a peroxide type | system | group, peroxy ester type, such as perbutyl O and perhexyl O (all are manufactured by Japanese fats and oils); Peroxydicarbonates such as peroyl L and peroyl O (both manufactured by Japanese fats and oils); Diacyl peroxides such as Naiper BW and Naiper BMT (all manufactured by Japanese Fats and Oils); Peroxy ketal system, such as per hexa 3M and per hexa MC (all are manufactured by Japanese fats and oils); Dialkyl peroxides such as perbutyl P and Percumyl D (both manufactured by Japanese fats and oils); Hydroperoxide systems, such as Percumyl P and Permanta H (all are manufactured by Japanese fats and oils), etc. are mentioned. As an azo initiator, ABN-E, ABN-R, ABN-V (all are manufactured by Nippon Hydrazine Industry), etc. are mentioned.

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

In addition, superposition | polymerization of adhesive resin (B) may be performed in a non-solvent, and may be performed in the organic solvent. When superposing | 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 organic solvents can be used. The type of organic solvent to be used is determined in consideration of the solubility of the resin obtained and the polymerization temperature. However, an organic solvent having a boiling point of toluene, ethyl acetate, methyl ethyl ketone or the like is preferably 120 ° C. or less in view of the difficulty of remaining of the residual solvent during drying. . Moreover, from the viewpoint of the durability of a dimonium pigment | dye, the organic solvent whose solubility (Y) of a dimonium pigment | dye is less than 5 mass% is preferable, and the organic solvent whose solubility (Y) is less than 0.01 mass% is more preferable.

In addition, the adhesive resin (B) may be made into a single composition or may be a polymer alloy or a polymer blend obtained by complexing polymers of different compositions.

In order to obtain 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.), or the like can be used. Examples of the polyfunctional monomers include light SL EG, light SL 1,4BG, light ester NP, light ester TMP (all manufactured by Kyowa Chemical Co., Ltd.), and the like. Examples of the polyfunctional initiator include Pertetra A, BTTB-50 (all manufactured by Japanese fats and oils), Trigonox 17-40MB, Percadox 12-XL25 (all manufactured by Kayaku Akujo), and the like. As the polyfunctional chain transfer agent, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), and the like can be used.

9. NIR absorption adhesive composition

In the near-infrared absorption adhesive composition of this invention, since the dimonium pigment | dye which considered the said absorbance (X) or the said solubility (Y) is used, it is excellent in the sustainability of near-infrared absorption ability. Moreover, this near-infrared absorption adhesive composition is excellent in transparency of a visible region. Since the near-infrared absorption adhesive composition of this invention contains resin which has adhesiveness, it can adhere easily to a to-be-adhered body.

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

Preferred other dyes (dyes other than the dimonium dye) are dyes capable of exhibiting the quencher effect with respect to the dimonium dye. The quencher effect is an effect of de-exciting an active molecule in an excited state. In the case of the present invention, other pigments having the effect of de-exciting and stabilizing a dimonium pigment molecule, a dimonium anion or a dimonium cation are preferable. From the viewpoint of the quencher effect, as this other pigment | dye, a phthalocyanine type pigment | dye is preferable and the phthalocyanine dye whose center metal is vanadium is especially preferable.

When using the near-infrared absorption adhesive composition of this invention as an optical filter for thin displays, the phthalocyanine pigment | dye of 800-950 nm of maximum absorption wavelengths and the cyanine system of 800-950 nm of maximum absorption wavelengths are mentioned with the said dimonium pigment | dye. It is preferable to use together a pigment | dye or the metal dithiol complex system pigment | dye of 800-950 nm of maximum absorption wavelengths. By this combination, the near infrared of 800-1100 nm can be absorbed effectively. It is especially preferable that a phthalocyanine pigment is used together from a viewpoint of obtaining a durable near-infrared absorption adhesive composition. By this combination, all the near-infrared wavelength ranges which should be shielded are cut, and the durability of a dimonium salt improves. When durability of a dimonium salt is considered and resin (B) whose acid value is 0-35 is used for a near-infrared absorption adhesive composition, the phthalocyanine type compound whose core metal is copper is especially preferable as this combined phthalocyanine type pigment | dye. .

As a phthalocyanine type compound which can be used by this invention, if it is excellent in near-infrared absorption ability, it will not specifically limit, A well-known phthalocyanine type compound can be used. As a preferable phthalocyanine type compound, the compound represented by the following general formula or the compound represented by the following general formula (B) is mentioned.

[Phthalocyanine-based compound represented by the formula]

[Formula A]

In the above formula, A ¹ to A ¹⁶ represent a functional group. In the above formula (A), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxylsulfonyl group, a carboxyl group, a thiol group, an alkyl group having 1 to 20 carbon atoms which may be substituted, and substituted. An alkoxy group having 1 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, or an aralkyl group having 7 to 20 carbon atoms which may be substituted , Aralkyloxy group having 7 to 20 carbon atoms which may be substituted, alkyl group having 1 to 20 carbon atoms which may be substituted, arylthio group having 6 to 20 carbon atoms which may be substituted, or carbon atom having 7 Or 20 aralkylthio groups, optionally substituted alkylsulfonyl groups having 1 to 20 carbon atoms, optionally substituted 6 to 20 arylsulfonyl groups, and optionally substituted Aralkyl sulfonyl group having 7 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms which may be substituted, alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted, and aryloxy having 6 to 20 carbon atoms which may be substituted A carbonyl group, an aralkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted, an arylcarbonyloxy group having 6 to 20 carbon atoms which may be substituted, or a substitution An aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, an amino group which may be substituted, an aminosulfonyl group which may be substituted, or an aminocarbonyl group which may be substituted Indicates. The functional group of A <^1> -A <^16> may be any of the same kind, or different types, and may be the same or different also in the case of the same kind, and functional groups may be connected through the coupling group. M ¹ represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxymetal. In addition, in this specification, an "acyl group" is the same as the definition described on page 17 of the 3rd edition of the scientific and technical term metabolism issue of the daily industrial newspaper, and specifically, it is group which the hydroxyl group was removed from the organic acid, Formula: RCO- (R is a group represented by an aliphatic group, an alicyclic group, or an aromatic group).

(When the terminal is a functional group other than an amino group)

In the formula (A), examples of the halogen atoms 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 alkyl group having 1 to 20 carbon atoms which may be substituted include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group and n-pen Although linear, branched, or cyclic alkyl groups, such as a methyl group, n-hexyl group, a cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. are mentioned, It is limited to these. no. Examples of the alkoxy group having 1 to 20 carbon atoms which may be substituted include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, linear, branched or cyclic such as t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc. Although an alkoxy group is mentioned, It is not limited to these. Examples of the aryl group having 6 to 20 carbon atoms that may be substituted include a phenyl group and a naphthyl group, but are not limited thereto. Examples of the aryloxy group having 6 to 20 carbon atoms that may be substituted include a phenoxy group, a naphthoxy group, and the like, but are not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms that may be substituted include, but are not limited to, a benzyl group, a phenethyl group, a diphenylmethyl group, and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyloxy group, phenethyloxy group, diphenylmethyloxy group, and the like. Examples of the alkylthio group having 1 to 20 carbon atoms which may be substituted include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group and sec-butyl Straight chains, branches, such as thio group, t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, or Although cyclic alkylthio group is mentioned, It is not limited to these. Examples of the arylthio group having 6 to 20 carbon atoms that may be substituted include a phenylthio group, a naphthylthio group, and the like, 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, benzylthio group, phenethylthio group, diphenylmethylthio group, and the like. Examples of the alkylsulfonyl group having 1 to 20 carbon atoms which may be substituted include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl group and sec-butyl Linear, branched, such as sulfonyl, t-butylsulfonyl, n-pentylsulfonyl, n-hexylsulfonyl, cyclohexylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, 2-ethylhexylsulfonyl, etc. Or a cyclic alkylsulfonyl group, although not limited thereto. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include, but are not limited to, phenylsulfonyl group, naphthylsulfonyl group, and the like. Examples of the aralkyl sulfonyl group which may be substituted include, but are not limited to, benzylsulfonyl group, phenethylsulfonyl group, diphenylmethylsulfonyl group, and the like. Examples of the acyl group having 1 to 20 carbon atoms which may be substituted are methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n Arylcarbonyl groups, such as pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, such as linear, branched or cyclic alkylcarbonyl group, benzylcarbonyl group, and phenylcarbonyl group Although aralkylcarbonyl groups, such as a diary, are mentioned, It is not limited to these. Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms which may be substituted include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso-butyloxycarbonyl group, sec-butyloxy Carbonyl, t-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, etc. may be mentioned. It is not limited to. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include phenoxycarbonyl, naphthylcarbonyl group, and the like, but are not limited thereto. 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 alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted include an acetyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an iso-propylcarbonyloxy group, and an n-butylcarbonyloxy group. , iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n- Heptylcarbonyloxy group, 3-heptylcarbonyloxy group, n-octylcarbonyloxy group, etc. are mentioned, It is not limited to these. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms that may be substituted include a benzoyloxy group and the like, but are not limited thereto. 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 heterocyclic group having 2 to 20 carbon atoms which may be substituted include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, a morpholine group, and the like.

Further, in the above formula, coming functional group A ¹ ~ A ¹⁶ alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyl kilok group, alkylthio group, arylthio group, aralkyl kilti come, alkylsulfonyl group, When arylsulfonyl group, aralkyl sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group are substituted As the substituents present in these functional groups A ¹ to A ¹⁶ , for example, a 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, sia Although angi group, a heterocyclic group, etc. are mentioned, It is not limited to these. Two or more these substituents may exist, and when two or more exist, they may be the same or different types, and may be the same or different also in the case of the same types. In addition, substituents may be connected through the coupling group.

(In the case of functional group whose terminal is an amino group)

In the above formula (A), examples of the substituent to the amino group which may be substituted of the functional groups A ¹ to A ¹⁶ , the aminosulfonyl group which may be substituted, and the aminocarbonyl group which may be substituted include a hydrogen atom; Linear, branched or cyclic alkyl groups 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; Aryl groups, such as a phenyl group and a naphthyl group; Aralkyl groups such as benzyl and phenethyl; Acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, linear, branched or cyclic alkylcarbonyl groups such as n-heptylcarbonyl group, 3-heptylcarbonyl group and n-octylcarbonyl group; Aryl carbonyl groups, such as a benzoyl group and a naphthyl carbonyl group; Although aralkylcarbonyl groups, such as a benzylcarbonyl group, etc. are mentioned, These are not limited to these, These substituents may further be substituted by the substituent. 0, 1, or 2 of these substituents may exist, and when two exist, they may mutually be the same or different, and may be the same or different also in the case of the same type. In addition, when there are two substituents, substituents may be connected through the coupling group.

Substituents which may be further present in the alkyl group, the aryl group, the aralkyl group, the alkylcarbonyl group, the arylcarbonyl group, the aralkylcarbonyl group, etc. which are substituted with the above-mentioned amino group which may be substituted, the aminosulfonyl group which may be substituted, or the aminocarbonyl group which may be substituted. As the 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, alkoxy, Although carbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, and heterocyclic group are mentioned, It is not limited to these. Two or more these substituents may exist, and when two or more exist, they may be the same or different types, and may be the same or different also in the case of the same types. In addition, substituents may be connected through the coupling group.

Examples of the divalent metal as the metal M ¹ include Cu (II), Co (II), Zn (II), Fe (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 and the like. It is not limited to these. Tetravalent examples of the substituted metal _{atom, 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 (R1) ₂ , Ge (R1) ₂ , Si ( _{R1) 2, Sn (R1)} 2, Ti (R 1) 2 {R 1 is an alkyl group, a phenyl group, a naphthyl group or derivatives _{thereof}, Cr (oR 2) 2} , Ge (oR 2) 2, Si ( OR ₂ ) ₂ , Sn (OR ₂ ) ₂ , Ti (OR ₂ ) ₂ , {R ₂ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group or a derivative thereof}, Sn ( SR ₃ ) ₂ and Ge (SR ₃ ) ₂ {wherein R ₃ represents an alkyl group, a phenyl group, a naphthyl group or derivatives thereof), and the like, but is not limited thereto. Examples of the oxymetals include, but are not limited to, VO, MnO, TiO, and the like.

[Phthalocyanine-based compound represented by Formula I]

[Formula I]

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

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

As a specific phthalocyanine type compound, brand names EXcala IR-10A, EXcala IR-12, EXcala IR-14, EXcala IR-906, EXcala IR-910, TX-EX-820, and TX- EX-915 (all are the Nippon Shokubai Co., Ltd.) can be mentioned.

In addition, in the near-infrared absorption adhesive composition of this invention, a cyanine dye may be used together as a near-infrared absorption pigment. The cyanine-based dye is not particularly limited as long as it has excellent near-infrared absorptive capacity, but salts of indoleium-based or benzothiazolium-based cations and counter anions can be preferably used. Examples of the indoleium cation or the benzothiazolium cation include cations represented by the formulas (a) to (i) above, but are not limited thereto.

(A)

[Formula b]

[Formula c]

[Formula d]

[Formula e]

[Formula f]

[Formula g]

[Formula h]

[Formula i]

The counter anion of the indoleum cation or the benzothiazolium cation is not particularly limited and is not limited to chloride ions, bromide ions, iodide ions, perchlorate ions, nitrate ions, benzenesulfonic acid ions, p-toluenesulfonic acid ions, and methyl sulfate Ions, ethyl sulfate, propyl sulfate, tetrafluoroborate ions, tetraphenylborate ions, hexafluorophosphate ions, benzenesulfinic acid ions, acetate ions, trifluoroacetic acid ions, propionic acid ions, benzoic acid ions, oxalic acid ions, Succinate ion, malonic acid ion, oleic acid ion, stearic acid ion, citric acid ion, dihydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorotartrate ion, chlorosulfonic acid ion, fluorosulfonic acid ion, trifluoromethanesulfonic acid ion , Hexafluorobiate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion, zirconic acid On, it can be used such as sulfuric acid ion, a bar Nadine acid ion and boric acid ion.

More specifically, it is a cyanine pigment | dye containing the cation represented by the said general formula a, and it is ADS812MI (the relative anion is iodide ion) by American Daisos Corporation; As a cyanine pigment | dye containing the cation represented by the said Formula (b), S0712 by a FEW Chemical company (relative anion is hexafluorophosphate ion); As a cyanine pigment | dye containing the cation represented by the said Formula (c), S0726 (relative anion is a chloride ion) by FEW Chemical Company; As a cyanine pigment | dye containing the cation represented by the said Formula d, ADS780MT (As an anion is p-toluenesulfonic acid ion) by the American Daisos company; As a cyanine pigment | dye containing the cation represented by the said Formula (e), S0006 (relative anion is a perchlorate ion) by FEW Chemical Company; As a cyanine pigment | dye containing the cation represented by the said general formula f, S0081 (relative anion is a perchlorate ion) by FEW Chemical Company; As a cyanine pigment | dye containing the cation represented by the said general formula g, S0773 by a FEW Chemical company (relative anion is tetrafluoroborate ion); As a cyanine pigment | dye containing the cation represented by the said Formula (h), Brand name S0772 by a FEW Chemical company (A counter anion is tetrafluoroborate ion); As a cyanine pigment | dye containing the cation represented by the said Formula (i), what is marketed, such as brand name S0734 by a FEW Chemical company (relative anion is tetrafluoroborate ion), can be used. By using a cyanine pigment | dye, the near-infrared absorption adhesive composition with high transparency of a visible region is obtained.

The compounding quantity of the dimonium pigment | dye of this invention or the compounding quantity which totaled the dimonium pigment | dye of this invention and other near-infrared absorbing dye can be suitably selected according to the kind and use of a pigment | dye. When using the near-infrared absorption adhesive composition of this invention as a thin film of 10-30 micrometers, compounding quantity becomes like this. Preferably it is 0.01-10 mass% with respect to the total mass of all solid content contained in a near-infrared absorption adhesive composition, More preferably, Is 0.1-5 mass%. For example, when using a dimonium pigment | dye and a phthalocyanine pigment | dye together, the compounding quantity which totaled these pigment | dyes becomes like this. Preferably it is 0.01-10 mass% with respect to solid content of resin, More preferably, it is 0.1-5 mass%. to be. If the blending amount is less than 0.01% by mass, there is a possibility that sufficient near-infrared absorptivity cannot be achieved. On the contrary, when it exceeds 10 mass%, the effect suitable for addition is not obtained and it is not economical, On the contrary, transparency in the visible region may be impaired.

As will be described later, according to the near-infrared absorbent pressure-sensitive adhesive composition in which the compounding amount of the dimonium salt is set high, even if it is stored for a long time, the improved dispersion state of the dimonium salt and the excellent near-infrared absorption capacity of the dimonium salt can be stably maintained. From this viewpoint, 0.5 mass% or more is preferable, as for the compounding quantity of the dimonium salt with respect to the total mass of all solid content contained in a near-infrared absorption adhesive composition, 1.0 mass% or more is more preferable, 1.5 mass% or more is more preferable. More preferably at least 2.0 mass%, still more preferably at least 2.9 mass%, particularly preferably at least 4.7 mass%.

The near-infrared absorptive pressure-sensitive adhesive composition of the present invention is characterized by transparency of visible region, persistence of near-infrared absorptive capacity, and good adhesion. The pigment | dye which absorbs visible light may be added to the near-infrared absorption adhesive composition of this invention as needed. Examples of the dyes that absorb visible light include cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metal dithiol complexes, squarylium, azulenium, diphenylmethane, triphenylmethane and jade. Photo system, azine system, thiopyryllium system, biorogen system, azo system, azo metal complex system, bis azo system, anthraquinone system, perylene system, indanthrone system, nitroso system, indico system, azomethine system, xanthene system, Conventionally well-known pigment | dyes, such as an oxanol system, indoaniline system, quinoline system, diketopyrrolopyrrole system, can be used widely.

When using the near-infrared absorption adhesive composition of this invention as an optical filter for PDP, it is preferable to use together the visible absorption pigment | dye whose maximum absorption wavelength is 550-650 nm in order to absorb unnecessary neon light emission. Although the kind of pigment | dye which absorbs neon light emission is not specifically limited, A cyanine pigment | dye and a tetraaza porphyrin pigment | dye can be used. Specifically, Adeka Aquars TY-102 (made by Adeka Ind. Co., Ltd.), Adeca Cruise TY-14 (Adeca Ind. Co., Ltd.), Adeca cruise TY-15 (Adeka Ind. Co., Ltd.), TAP-2 (Yamada Chemical Co., Ltd.) Production), TAP-18 (manufactured by Yamada Chemical Co., Ltd.), TAP-45 (manufactured by Yamada Chemical Co., Ltd.), trade name NK-5451 (manufactured by Hayashibara Biochemistry Research Institute), NK-5532 (manufactured by Hayashibara Biochemistry Research Institute), NK-5450 ( Hayashibara Biochemical Research Institute) etc. are mentioned. Although the addition amount of the pigment | dye for absorbing neon light emission changes with kinds of pigment | dye, it is preferable to add so that the transmittance | permeability in a maximum absorption wavelength may be about 20 to 80%.

Moreover, in order to adjust the hue of the thin film which becomes a near-infrared absorption adhesive composition, you may add the coloring visible light absorbing dye. Although the kind of coloring pigment is not specifically limited, 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole, etc. can be used. Specifically, orazolblue GN (made by Ciba Specialty Chemicals), orazolblue BL (made by Ciba Specialty Chemicals), orazoled 2B (made by Ciba Specialty Chemicals), orazoled G (made by Ciba Specialty Chemicals) ), Orazolblack CN (made by Ciba Specialty Chemicals), orazol yellow 2GLN (made by Ciba Specialty Chemicals), orazol yellow 2RLN (made by Ciba Specialty Chemicals), microless DPP red BK (made by Ciba Specialty Chemicals) Etc. can be mentioned.

The near-infrared absorption adhesive composition of this invention may contain 1 type or 2 or more of diluent solvent, an additive, and a hardening agent in the range which does not lose the performance as needed.

As mentioned above, the near-infrared absorption adhesive composition of this invention, Preferably, the 1st process of mixing a dimonium salt and a solvent (Sm) and making a mixture (M1), and this mixture (M1) make resin (B) It is manufactured by the manufacturing method including the 2nd process mixed with). In the case of this manufacturing method, in this 2nd process, the resin composition (P) containing this resin (B) and the solvent (S2) mentioned above is prepared, and this resin composition (P) has mentioned the mixture ( M1) may be mixed. In this case, the near-infrared absorber as a coating film can be obtained by apply | coating the near-infrared absorption adhesive composition containing this mixture (M1) and resin composition (P) to the transparent base material mentioned later.

The resin in this resin composition (P) is a viewpoint that resin (B) contained in resin composition (P) can contribute to the improvement of the powdered state of the dimonium salt contained in a near-infrared absorption adhesive composition, and the improvement of durability. 30 mass% or more is preferable, and, as for the compounding quantity of (B), 45 mass% or more is more preferable. In addition, the compounding quantity of this resin (B) is represented by the ratio of the mass of the non volatile matter of this resin composition (P) with respect to the mass of the resin composition (P).

In the case of the said manufacturing method, when the resin composition (P) containing much resin (B) is used, the near-infrared absorption adhesive composition with a high compounding quantity of dimonium salt is obtained. In this case, even when the near-infrared absorbent pressure-sensitive adhesive composition is stored for a long time, it has been found that the improved dispersion state of the dimonium salt and the excellent near-infrared absorption capacity of the dimonium salt remain stable. Moreover, use of the near-infrared absorption adhesive composition with a high compounding quantity of dimonium salt can achieve thin film formation of the coating film formed from a near-infrared absorption adhesive composition.

From the viewpoint that the improved dispersion state of the dimonium salt in the near-infrared absorbent pressure-sensitive adhesive composition and the excellent near-infrared absorbing ability are maintained stably, the compounding amount of the resin (B) in the resin composition (P) is the value described above. It is desirable to be higher than. From this viewpoint, 50 mass% or more is preferable, as for the compounding quantity of resin (B) in this resin composition (P), 55 mass% or more is more preferable, 60 mass% or more is more preferable, 65 mass% The above is especially preferable. Moreover, from a viewpoint of the viscosity of handling, 80 mass% or less is preferable for the compounding quantity of resin (B) in this resin composition (P).

The diluting solvent which can be contained in a near-infrared absorption adhesive composition is not limited, It is preferable to illustrate as the said solvent (S2) or the said solvent (S4).

At the time of coating, the viscosity of the near-infrared absorbent pressure-sensitive adhesive composition is appropriately selected depending on the type of coating machine. However, when coating with a small diameter gravure kiss reverse method such as a microgravure coater or the like, 1 to 1000 mPa · s, a die coater, etc. When coating by extrusion method, 100-10000 mPa * s is common. Solid content of a near-infrared absorption adhesive composition is adjusted according to paint viscosity.

Moreover, as an additive which a near-infrared absorption adhesive composition can contain, the conventionally well-known additive used for the resin composition which forms a film, a coating film, etc. can be used. As this additive, a dispersing agent, a leveling agent, an antifoamer, a viscosity regulator, a gloss remover, a tackifier, an antistatic agent, antioxidant, an ultraviolet absorber, a light stabilizer, a quencher, a hardening | curing agent, an antiblocking agent, etc. are mentioned. As the curing agent, an isocyanate compound, a thiol compound, an epoxy 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 absorbent pressure-sensitive adhesive composition of the present invention is an optical, agricultural, building or vehicle near-infrared absorbing material, an image recording material such as a photosensitive paper, an information recording material such as an optical disk, a solar cell such as a dye-sensitized solar cell, a semiconductor laser light. It can be used for the photosensitive material which uses a light source etc. as a light source, and a stable fatigue prevention material. The near-infrared absorption adhesive composition of this invention is especially preferable to use in the form of a film or a sheet.

As for the compounding quantity of the dimonium salt contained in the near-infrared absorption adhesive composition of this invention, 0.4 mass% or more is preferable from a viewpoint of near-infrared absorption ability. Even when the near-infrared absorbent pressure-sensitive adhesive composition is stored for a long time, from the viewpoint that the improved dispersion state of the dimonium salt and the excellent near-infrared absorbing capacity of the dimonium salt are maintained stably, the blending amount of the dimonium salt is preferably 0.5% by mass or more. From the viewpoint of suppressing deterioration of the dimonium pigment in high temperature storage, which will be described later, the blending amount of the dimonium salt is more preferably 1.0 mass% or more, still more preferably 1.5 mass% or more, and 1.9 mass% or more. Particularly preferred. From an economic viewpoint, 50 mass% or less is preferable and, as for the compounding quantity of this dimonium salt, 30 mass% or less is preferable.

In this invention, the temperature of a near-infrared absorption adhesive composition in storage or conveyance is not limited. From a viewpoint of suppressing deterioration of near-infrared absorptivity and deterioration suppression of a dimonium salt, 40 degrees C or less is preferable, 30 degrees C or less is more preferable, 25 degrees C or less is further more preferable. However, when the compounding quantity of dimonium salt became high, it turned out that the disadvantage caused by high storage temperature is suppressed effectively. From this viewpoint, in the near-infrared absorption adhesive composition, when the compounding quantity of the dimonium salt with respect to the total mass of all the solid content contained in this near-infrared absorption adhesive composition is 0.5 mass% or more, the maximum temperature Tmax in storage or conveyance is 40 It is preferable that it is C or more, It is more preferable that it is 45 degreeC or more, It is still more preferable that it is 50 degreeC or more. In this case, refrigeration may become unnecessary, for example in storage or conveyance in summer. From a viewpoint of suppressing deterioration of near-infrared absorption ability, 80 degrees C or less is preferable and, as for the maximum temperature Tmax, 70 degrees C or less is more preferable.

From the viewpoint of further enhancing the effect due to the high concentration of the dimonium pigment, when the compounding amount is 0.5% by mass or more, the minimum temperature Tmin in storage or transport is preferably 30 ° C or more, more preferably 35 ° C or more. It is preferable, it is more preferable that it is 40 degreeC or more, It is more preferable that it is 45 degreeC or more, It is more preferable that it is 50 degreeC or more.

In addition, the said maximum temperature Tmax means the highest temperature in the whole period of storage or conveyance. When the temperature of the dimonium pigment | dye containing composition changes in the range of T1 degreeC-T2 degreeC (T1 <T2) during the preservation or transfer period, the said maximum temperature Tmax is the said temperature T2.

It is preferable that the said compounding ratio Rp becomes the range mentioned above from a viewpoint of suppressing deterioration of the dimonium pigment | dye in high temperature storage.

In addition, the said minimum temperature Tmin means the minimum temperature in the whole period of storage or conveyance. When the temperature of the dimonium pigment | dye containing composition changes in the range of T1 degreeC-T2 degreeC (T1 <T2) during the preservation or transfer period, the said minimum temperature Tmin is said temperature T1.

10. NIR absorber

The near-infrared absorber of this invention contains the said near-infrared absorption adhesive composition. The near-infrared absorptive material of this invention may shape | mold the said near-infrared absorptive pressure-sensitive adhesive composition in the form of a film, or may laminate the coating film containing the near-infrared absorptive pressure-sensitive adhesive composition on a transparent substrate.

As a transparent base material, generally, it can be used for an optical material, and if it is substantially transparent, there will be no restriction | limiting in particular. Specific examples include glass; Olefin polymers such as cyclopolyolefins and amorphous polyolefins; Methacryl-based polymers such as polymethyl methacrylate; Vinyl polymers such as vinyl acetate and vinyl halide; Polyesters such as PET; Polyvinyl acetals such as polycarbonate and butyral resin; Polyaryl ether resins; Lactone ring containing resin film, etc. are mentioned. In addition, the transparent base material includes surface treatment by conventionally known methods such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, and chemical treatment, and an anchor coat agent and a primer. Coating may be performed. Moreover, the base resin which comprises the said transparent base material can mix | blend a well-known additive, a heat resistant aging agent, a lubricating agent, an antistatic agent, etc .. The transparent base material is molded into a film or sheet shape using known injection molding, T-die molding, calendar molding, compression molding, or the like by melting in an organic solvent and casting. The base material constituting such a transparent base material may be unstretched or stretched, or may be laminated with another base material.

As a transparent base material in the case of obtaining a near-infrared absorbing film by a coating method, PET film is preferable and especially the PET film which carried out the easily adhesive process is preferable. Specifically, Cosmoshine A4300 (made by Toyo Boseki), Lumila U34 (made by Toray), Merinex 705 (made by Teijin Dupont), etc. are mentioned. Moreover, functional films, such as a TAC (triacetyl cellulose) film, an antireflection film, an anti-glare film, an impact absorption film, an electromagnetic wave shielding film, and an ultraviolet absorbing film, can also be used as a transparent base material. Thereby, the optical filter for thin display and optical semiconductor element can be manufactured simply. It is preferable that a transparent base material is a film.

Among them, glass, PET film, lactone ring-containing resin film, easily adhesive PET film, TAC film, antireflection film, and electromagnetic wave shielding film are preferably used as the transparent substrate. When using inorganic base materials, such as glass, as a transparent base material, it is preferable from a viewpoint of the durability of a near-infrared absorbing dye that there are few alkali components.

Although the thickness of the near-infrared absorber of this invention becomes about 0.1 micrometer-about 10 mm generally, it determines suitably according to the objective. Moreover, content of the near-infrared absorbing pigment contained in a near-infrared absorber is also suitably determined according to the objective.

Although it does not specifically limit as a method of manufacturing the near-infrared absorber of this invention, For example, the following method can be used. For example, (I) the method of kneading a resin and the near-infrared absorption adhesive composition of this invention, heat-molding, and producing a resin plate or a film; (II) a method of cast polymerizing the near-infrared absorbent pressure-sensitive adhesive composition and monomer or oligomer of the present invention in the presence of a polymerization catalyst to produce a resin plate or film; (III) The method of coating the near-infrared absorption adhesive composition of this invention on the said transparent base material.

As the manufacturing method of (I), although processing temperature, film forming (resin engraving) conditions, etc. differ somewhat with the resin to be used, Usually, the near-infrared absorption adhesive composition of this invention is added to the resin powder or pellet, and it is 150- After heating and dissolving at 350 degreeC, the method of shaping | molding and producing a resin plate, the method of film-forming (resin engraving) by an extruder, etc. are mentioned.

As the method for producing (II), the near-infrared absorbent pressure-sensitive adhesive composition and monomer or oligomer of the present invention are cast-polymerized in the presence of a polymerization catalyst, and a mixture thereof is injected into a mold, reacted and cured or flowed into a mold. And molding by solidifying the mold until it becomes a solid product in the mold. Many resins can be molded in this process. Specific examples of such resins include acrylic resins, diethylene glycol bis (allylcarbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, silicone resins, and the like. Especially, the casting method by the bulk polymerization of methyl methacrylate from which the acrylic sheet excellent in hardness, heat resistance, and chemical resistance is obtained is preferable.

A well-known radical thermal polymerization initiator can be used as a polymerization catalyst, For example, Azo compounds, such as peroxides, such as a benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, and azobisisobutyronitrile, are mentioned. Can be. The usage-amount is generally 0.01-5 mass% with respect to the total amount of a mixture. The heating temperature in thermal polymerization is generally 40-200 degreeC, and polymerization time is generally about 30 minutes-about 8 hours. Moreover, in addition to thermal polymerization, the method of photopolymerizing by adding a photoinitiator and a sensitizer can also be used.

As the method of (III), the method of coating the near-infrared absorbent material of this invention on a transparent base material, the method of immobilizing the near-infrared absorption adhesive composition of this invention to microparticles | fine-particles, and coating the coating material which disperse | distributed the microparticles | fine-particles on a transparent base material Etc.

A well-known coating machine can be used when apply | coating a near-infrared absorption adhesive composition to a base material. For example, a knife coater such as a comma coater, a fountain coater such as a slot die coater, a lip coater, a kiss coater such as a microgravure coater, a roll coater such as a gravure coater, a reverse roll coater, a flow coater, a spray coater, a bar coater Can be mentioned. You may surface-treat a base material by well-known methods, such as a corona discharge process and a plasma process, before application | coating. As a drying and hardening method, well-known methods, such as hot air, near-infrared, and UV hardening, can be used. After drying and hardening, you may wind up with a well-known protective film.

The drying method is not particularly limited, but 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 remaining solvent amount, the kind of the substrate, and the like. When a base material is a PET film, general drying temperature is 50-150 degreeC. When there are a plurality of dryers in one line, each dryer may be set to different temperature and wind speed. In order to obtain a favorable coating film of coating appearance, it is preferable to make mild the inlet side drying conditions.

The near-infrared absorbent pressure-sensitive 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 absorption ability in the near infrared. Since the near-infrared absorption adhesive composition of this invention has high durability, especially heat resistance and light resistance compared with the conventional near-infrared absorbing material, external appearance and near-infrared absorption ability are maintained by long term storage and use. Moreover, since the near-infrared absorption adhesive composition of this invention is easy to make into a sheet | seat or a film form, it is effective for a thin display and an optical semiconductor element. In addition, the near-infrared absorption adhesive composition of this invention can be used also for the filter and film which need to cut infrared rays, for example, an agricultural film, a heat insulation film, a sunglass, an optical recording material.

11. Optical filter

An optical filter is mentioned as a preferable use of a near-infrared absorber. This optical filter should use the said near-infrared absorber. 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 of 40% or more, preferably 50% or more, more preferably 60% or more in the visible region, and a transmittance of near infrared rays having a wavelength of 800 to 1100 nm is 30% or less, preferably 15%. Hereinafter, More preferably, it is 5% or less.

The optical filter of the present invention may be provided with an electromagnetic wave shielding layer, an antireflection layer, an antiglare (antiglare) layer, a scratch prevention layer, a color adjustment layer, a support such as glass, or the like, in addition to the near infrared absorption layer of the near infrared absorption adhesive composition. do.

What is necessary is just to select the structure of each layer of an optical filter arbitrarily. For example, the optical filter which preferably combined at least one layer of an anti-reflective layer and an anti-glare layer, and at least 2 layers of a near-infrared absorption layer is preferable, More preferably, at least 3 layer which combined the electromagnetic wave shielding layer furthermore It is an optical filter which has.

It is preferable that the antireflection layer or the antiglare layer be the outermost layer on the human side. The order of lamination between the near-infrared absorbing layer and the electromagnetic shielding layer is arbitrary. In addition, other layers, such as a scratch prevention layer, a color adjustment layer, an impact absorption layer, a support body, and a transparent base material, may be inserted between three layers.

When bonding each layer, physical treatments, such as corona treatment and a plasma treatment, may be performed, and well-known high polar polymers, such as polyethyleneimine, an oxazoline type polymer, polyester, and cellulose, may be used as an anchor coat agent.

In the optical filter for thin display, in order to make a screen easy to see, it is preferable to provide an antireflection layer or an anti-glare layer in the outermost layer of a person.

The antireflection layer is for suppressing reflection of the surface and preventing the reflection of external light such as a fluorescent lamp onto the surface. The antireflection layer is a thin film of an inorganic material such as a metal oxide, a fluoride, a silicide, a boride, a carbide, a nitride, a sulfide, or a laminate of a resin having a different refractive index such as an acrylic resin or a fluorine resin in a single layer or a multilayer. As the manufacturing method in the former case, there is a method of forming an antireflective coating on a transparent substrate in the form of a single layer or a multilayer by using vapor deposition or sputtering. Further, in the latter case, a transparent base material is used on a transparent film by using a knife coater such as a comma coater, a slot coater, a lip coater, a fountain coater, a gravure coater, a flow coater, a spray coater or a bar coater. There is a method of applying an antireflective coating to the surface.

The anti-glare layer is formed by incorporating fine powders such as silica, melamine resins, acrylic resins, and the like by applying a conventionally known coating method onto any one of the filters of the present invention and heat or photocuring them. Moreover, you may affix the film which carried out antiglare on the filter.

In addition, the scratch prevention layer is any one of the filters of this invention which apply | coated the coating liquid which melt | dissolved or disperse | distributed the acrylate, such as a urethane acrylate, an epoxy acrylate, and polyfunctional acrylate, and a photoinitiator to the organic solvent, by a conventionally well-known coating method. It is formed by applying, drying and photocuring on the layer of.

The optical filter which has an antireflection layer or an anti-glare layer and a near-infrared absorption layer is obtained by laminating | stacking the layer which becomes the near-infrared absorption adhesive composition or near-infrared absorber of this invention on the back surface of an anti-reflection film or an anti-glare film. As a method of laminating | stacking, the near-infrared absorption layer of this invention made into the film form, an anti-reflective film, or an anti-glare film may be directly stuck together, and the near-infrared absorptive adhesive composition of this invention which liquefied was made into the back surface of an anti-reflection film or an anti-glare film. You may apply directly to. When providing a near-infrared absorption layer on the back surface of an antireflection film or an anti-glare film, it is preferable to use an ultraviolet absorption film as a transparent base material, in order to suppress deterioration of the pigment | dye by an ultraviolet-ray. The near-infrared absorption adhesive composition of this invention has adhesiveness. Therefore, when a near-infrared absorption layer and another layer adhere | attach, an adhesive or an adhesive agent may become unnecessary. The near-infrared absorption layer is a layer containing the near-infrared absorption adhesive composition of this invention.

It is preferable to provide an electromagnetic wave shielding layer in the optical filter for plasma displays in order to remove the electromagnetic wave which generate | occur | produces from a panel.

As the electromagnetic wave shielding layer, a film obtained by smoothing a pattern of a metal mesh on a film by etching or printing, or a film embedded in a resin by depositing a metal on a fiber mesh is used. These films are called electromagnetic wave shielding films or electromagnetic shielding films.

The optical filter which has two layers of a near-infrared absorption layer and an electromagnetic wave shielding layer is obtained by compounding an electromagnetic wave prevention material and a near-infrared absorption adhesive composition. As a method of compounding, the near-infrared absorption adhesive composition of this invention made into the film form, and an electromagnetic wave shielding film may be stuck together, and the near-infrared absorption adhesive composition of this invention which was made into solution may be directly apply | coated to an electromagnetic wave shielding film. Moreover, when smoothing the metal mesh on a film, it is also possible to use the near-infrared absorption adhesive composition of this invention. In addition, when embedding the metal vapor deposited, it is also possible to use the near-infrared absorbent pressure-sensitive adhesive composition of the present invention.

As an optical filter which has three layers of a near-infrared absorption layer, a reflection or an anti-glare layer, and an electromagnetic wave shielding layer, three sheets of the near-infrared absorption film, a reflection or an anti-glare film, and an electromagnetic wave shielding film which consist of the near-infrared absorption adhesive composition of this invention were bonded together. Can be used. Preferably, the optical filter which has a structure in which the near-infrared absorption film which becomes the near-infrared absorption adhesive composition of this invention is sandwiched between a reflection or the anti-glare film, and an electromagnetic wave shielding film is preferable. Since this optical filter is laminated | stacked using the adhesiveness of a near-infrared absorbing film, it can be manufactured omitting the adhesive layer provided conventionally only for bonding of films. As needed, you may paste together support bodies, such as glass, and functional films, such as a color adjustment film.

In particular, the optical filter in which the near-infrared absorbing layer is laminated on the electromagnetic wave shielding layer is such that the near-infrared absorbent pressure-sensitive adhesive composition is laminated on an electromagnetic wave shielding material capable of shielding electromagnetic waves. In the case of this optical filter, the electromagnetic wave shielding layer should just be formed so that it may have electromagnetic wave shielding property and the image permeability, and the structure, composition, etc. of this electromagnetic wave shielding layer are not specifically limited. As an electromagnetic wave shielding material which can comprise this electromagnetic wave shielding layer, the transparent conductive thin film containing the thin-film metal layer formed by vapor deposition, plating, etc. of metals, such as gold, copper, aluminum, and an electroconductive substance, is illustrated. In the case where the electromagnetic wave shielding layer has a metal layer, from the viewpoint of electromagnetic wave shielding property and image permeability, one formed in a mesh shape (hereinafter, referred to as a metal mesh layer) is more preferable.

The electromagnetic wave shielding material which can comprise an electromagnetic wave shielding layer also contains the electromagnetic wave shielding film as a transparent base material mentioned above. As the electromagnetic shielding film, when a metal mesh is patterned on a film by a method such as etching or printing, the metal mesh patterned on the film such as etching or printing constitutes the metal mesh layer described above. .

In the optical filter in which the near infrared absorbing layer is laminated on the electromagnetic wave shielding layer, when the electromagnetic shielding layer has a metal mesh layer, the metal mesh layer is in contact with the near infrared absorbing layer. In the case of such an optical filter, a metal mesh may be directly bonded to a near-infrared absorption layer, and the metal mesh layer used as a mesh may be formed on a near-infrared absorption layer. By plating the near-infrared absorbing layer with a metal such as copper and then etching it, a metal mesh layer serving as the etched plating layer may be formed on the near-infrared absorbing layer. By printing a mesh pattern with a paste ink having a catalyst such as palladium on the near infrared absorbing layer and plating with the metal, a metal mesh layer serving as a plating layer formed in a mesh shape may be formed on the near infrared absorbing layer. In addition, an optical filter in which a metal mesh layer is laminated on the near infrared absorbing layer may be formed by directly bonding the metal mesh layer to the near infrared absorbing layer using an electromagnetic wave shielding film having a metal metal mesh layer formed on the outside thereof. In addition, from the viewpoint of electromagnetic shielding properties, the thickness of the metal mesh layer is preferably 1 µm or more. From the viewpoint of narrowing of the viewing angle and deterioration of visibility, the thickness of the metal mesh layer is preferably 10 m or less.

When a metal mesh layer is laminated directly on a near-infrared absorption layer like the optical filter mentioned above, it is preferable that the near-infrared absorption adhesive composition containing resin (B) whose acid value is 0-35 is used. In this case, since a good dispersion state of the dimonium salt is maintained, and deterioration of the dimonium salt can be suppressed and discoloration of the dye, the metal layer and the adhesive can be prevented, an optical filter with high persistence of near infrared absorption ability can be obtained. Can be.

In order to simplify the manufacturing process and film structure of an optical filter further, it is good to use the composite film which has several functions. A preferable optical filter is an optical filter which pasted the near-infrared absorption adhesive layer which becomes the near-infrared absorption adhesive composition of this invention to the composite film containing an electromagnetic wave shielding layer and a reflection or anti-glare layer in one film.

The optical filter for thin displays of this invention may be installed away from a display apparatus, or may be directly affixed on a display apparatus. It is preferable to use glass as a support body when installing away from a display apparatus. In the case of directly adhering to the display device, an optical filter using no glass is preferable.

12. Thin display

When the optical filter which laminated | stacked the near-infrared absorption adhesive composition of this invention is mounted on a thin display, favorable image quality will be maintained over a long period of time. This invention regarding a thin display is a thin display using the near-infrared absorption adhesive composition of this invention, the near-infrared absorber of this invention, or the optical filter of this invention. A thin display in which an optical filter is directly bonded to a display body has a clearer picture quality. When directly attaching an optical filter, it is preferable to use tempered glass for the glass of a display body, or to use the optical filter which provided the impact absorption layer.

As an adhesive when affixing the optical filter of this invention to a display apparatus, rubbers, such as styrene butadiene rubber, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene rubber, chloroprene rubber, butyl rubber, methyl polyacrylate, poly Polyacrylic-acid alkylesters, such as ethyl acrylate and butyl polyacrylate, etc. are mentioned, These may be used independently, Furthermore, what added the picolite, polyber, rosin ester, etc. may be used as a tackifier. Moreover, although the adhesive which has a shock absorbing ability can be used as shown by Unexamined-Japanese-Patent No. 2004-263084, it is not limited to this. The optical filter of this invention may be affixed on a display apparatus using the adhesiveness of a near-infrared absorption layer, without using an adhesive.

The thickness of this adhesion layer is 5-2000 micrometers normally, Preferably it is 10-1000 micrometers. A peeling film may be provided on the surface of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer may be protected by the release film until the optical filter adheres to the surface of the thin display to prevent dust or the like from adhering to the pressure-sensitive adhesive layer. . In this case, a non-adhesive part is formed between a pressure-sensitive adhesive layer of the functional part of the filter and a release film by forming a portion without providing the pressure-sensitive adhesive layer or sandwiching a non-adhesive film, thereby forming the non-adhesive portion. When it sets as a peeling start part, the work at the time of sticking is easy to do.

The shock absorbing layer is for protecting the display device from an impact from the outside. It is preferable to use it in the optical filter which does not use a support body. As the shock absorber, ethylene-vinyl acetate copolymers, acrylic polymers, polyvinyl chloride, urethanes, silicone resins, etc., as shown in Japanese Patent Laid-Open No. 2004-246365 and Japanese Patent Laid-Open No. 2004-264416 Can be used, but is not limited to these.

Example

 In the following, the present invention is specifically described by way of examples. These examples do not limit the present invention in any way. In addition, in the following component ratios, unless otherwise indicated, "%" means the mass%, and "part" shall mean the mass part. The evaluation method is as follows.

(1) Heat test

The test body was allowed to stand for 1000 hours in an 80 degreeC constant temperature and humidity chamber, and the transmission spectrum of 350-1500 nm before and behind a test was measured. UV-3700 (manufactured by Shimadzu Corporation) was used for the measurement of the transmission spectrum. The pigment | dye persistence (%) in (lambda) max was evaluated from the transmission spectrum before and behind the obtained test. In addition, the color difference was calculated from the transmission spectrum before and after the obtained test, and the change of b * was evaluated. In addition, (lambda) max was determined based on the measurement result before a test. This evaluation result is shown in the following table | surface. Moreover, ΔT was calculated based on the transmission spectrum before and after the test. ΔT is a value (%) obtained by subtracting the transmittance (%) before the heat resistance test from the transmittance (%) after the heat resistance test. This ΔT is a change in transmittance at a wavelength of 1000 nm. This ΔT is shown in the following table.

(2) Evaluation of heat and humidity resistance

The test body was allowed to stand for 1000 hours in a constant temperature and humidity chamber of 60 degreeC and 90% RH, and the transmission spectrum of 350-1500 nm before and behind a test was measured. UV-3700 (manufactured by Shimadzu Corporation) was used for the measurement of the transmission spectrum. The pigment | dye persistence (%) in (lambda) max was evaluated from the transmission spectrum before and behind the obtained test. In addition, the color difference was calculated from the transmission spectrum before and after the obtained test, and the change of b * was evaluated. In addition, (lambda) max was determined based on the measurement result before a test. This evaluation result is shown in the following table | surface. Moreover, ΔT was calculated based on the transmission spectrum before and after the test. This (DELTA) T is the value (%) which subtracted the transmittance | permeability (%) before the moisture-resistant heat test from the transmittance | permeability (%) after a moisture-resistant heat test. This ΔT is a change in transmittance at a wavelength of 1000 nm. This ΔT is shown in the following table.

(3) evaluation of light resistance

In "SX2-75 super xenon weather meter" made by Suga Test Co., Ltd., the test piece was irradiated with light having a irradiation intensity of 60 W / m 2 at 300 to 400 nm for 100 hours under an environment of 63 ° C. and 50% RH. . In each before and after this test, the transmission spectrum of 350-1500 nm light was measured. UV-3700 (manufactured by Shimadzu Corporation) was used for the measurement of the transmission spectrum. The pigment | dye persistence (%) in (lambda) max was evaluated from the transmission spectrum before and behind the obtained test. In addition, the color difference was calculated from the transmission spectrum before and after the obtained test, and the change of b * was evaluated. In addition, (lambda) max was determined based on the measurement result before a test. This evaluation result is shown in the following table | surface. Moreover, ΔT was calculated based on the transmission spectrum before and after the test. ΔT is a value (%) obtained by subtracting the transmittance (%) before the light resistance test from the transmittance (%) after the light resistance test. This ΔT is a change in transmittance at a wavelength of 1000 nm. This ΔT is shown in the following table.

As mentioned above, in evaluation of heat resistance, heat-and-moisture resistance, and light resistance, the pigment | dye persistence (%) was measured. When the absorbance at lambda max after the test is Ax (%) and the absorbance at lambda max before the test is Bx (%), the dye residual ratio Px (%) is calculated by the following equation.

(4) the absorbance (X) of the dimonium salt

It was measured by the method described above.

(5) the solubility (Y) of the dimonium salt

It measured by the above-mentioned measuring method using five types of samples.

(6) measurement of acid value

0.5 g of the resin was accurately weighed and 50 g of toluene was added to dissolve uniformly. As an indicator, 2-3 drops of a phenolphthalein / alcohol solution were added, titrated with 0.1 N potassium hydroxide / alcohol solution, and the end point was set when the red group of the solution disappeared in about 30 seconds. The acid value was calculated | required from the appropriate amount at this time and solid content of resin. The acid value is expressed in mg of potassium hydroxide required to neutralize 1 g of the resin solid content.

Synthesis Example 1:

[Synthesis of Dimonium Compound a1 and Preparation of Near-infrared Absorption Mixture 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 it melt | dissolved at 60 degreeC. It was. Thereafter, 10.1 parts of a 58.4% aqueous solution of tris (trifluoromethylsulfonyl) methane was added. Next, 2.32 parts of nitric acid dissolved in 35 parts of DMF was added, and the mixture was heated and stirred for 30 minutes. After insoluble fractions were separated by filtration, water was added to the reaction solution, and the precipitated crystals were filtered, washed with methanol, washed with water and dried to give 8.4 parts of tris (trifluoromethylsulfonyl) methic acid-N, N, N ', N'-tetrakis (p-di (iso-butyl) aminophenyl) -p-phenylenedimonium (hereinafter also referred to as compound a1) was obtained. The compound a1 is a diimonium salt of the general formula (2) in which R ¹ to R ⁸ are all isobutyl groups and Z ^- in the general formula ( ₂ ) is [(CF ₃ SO ₂ ) ₃ C ^- ] to be. The absorbance (X) of this compound a1 was 0.138 (λmax was 1096 nm) when the solvent was toluene, and 0.239 (λmax was 1081 nm) when the solvent was ethyl acetate. When the said solubility (Y) of this compound a1 was measured, it was less than 0.01 mass% when the solvent was toluene, and less than 0.01 mass% when the solvent was ethyl acetate.

0.5 parts of the compound a1, 9.5 parts of ethyl acetate and 25 parts of zirconia beads were placed in a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, and then the zirconia beads were filtered off to obtain a near infrared absorption mixture 1 containing compound a1. Got it. In addition, zirconia bead was the Nikkat company make, The particle diameter was 300 micrometers.

Synthesis Example 2:

[Production of Near Infrared Absorption Mixture 2]

A near-infrared absorption mixture 2 was obtained in the same manner as in Synthesis example 1 except that 9.5 parts of toluene was used instead of 9.5 parts of ethyl acetate.

Synthesis Example 3:

[Synthesis of Dimonium Compound b1 and Preparation of Near-infrared Absorption Mixture 3]

In 30 parts of DMF, 3.8 parts of N, N, N ', N'-tetrakis (aminophenyl) -p-phenylenediamine, 21 parts of iso-butylbromide and 15 parts of potassium carbonate were added, at 80 ° C for 1 hour, Furthermore, it was made to react at 90 degreeC for 7 hours, and also at 130 degreeC for 1 hour. After cooling, it filtered, 30 parts of isopropanol were added to this reaction liquid (filtrate), and it stirred at 5 degrees C or less for 1 hour. The resulting crystals were washed with methanol and then dried to obtain 2.5 parts of pale brown crystalline compounds. 1 part of said crystalline compounds were added to 10 parts of DMF, and it heated at 60 degreeC, and obtained liquid A1 which melt | dissolved this crystalline compound. The liquid B1 obtained by dissolving 0.78 parts of antimony hexafluoride in 10 parts of DMF was added to the said liquid A1, and it was made to react for 30 minutes. After cooling, the precipitated silver was separated by filtration. 10 parts of water was slowly dripped at this reaction liquid (filtrate), and it stirred for 15 minutes after dripping. The resulting black crystals were filtered and washed with 50 parts of water to dry the obtained cake (residue), and 0.5 parts of hexafluoroantimonic acid-N, N, N ', N'-tetrakis (p-di (iso- Butyl) aminophenyl) -p-phenylenedimonium (hereinafter also referred to as compound b1) was obtained. The compound b1 is, in the above Formula 2, R ¹ ~ R ⁸ are all the iso- butyl group, and Z in the above formula (2) ^- is a di-salt ^aunt-a [SbF _6]. The absorbance (X) of the compound b1 was measured to find that the solvent was toluene in 0.070 (λ max is 1088 nm) and the solvent in ethyl acetate was 0.113 (λ max is 1069 nm). The solubility (Y) of this compound b1 was measured, and when the solvent was toluene, it was less than 0.01 mass%, and when the solvent was ethyl acetate, it was less than 0.01 mass%.

0.5 parts of the compound b1, 9.5 parts of ethyl acetate and 25 parts of zirconia beads were placed in a 70 ml mayonnaise bottle, shaken with a paint shaker for 4 hours, and then the zirconia beads were filtered off to obtain a near infrared absorption mixture 3 containing compound b1. Got it. In addition, a zirconia bead was the Nikat company make, and the particle diameter was 300 micrometers.

Synthesis Example 4:

[Production of Near Infrared Absorption Mixture 4]

A near-infrared absorption mixture 4 was obtained in the same manner as in Synthesis example 2 except that the trade name "CIR-1085" (dimonium pigment manufactured by Carit Japan Co., Ltd.) was used instead of the compound a1.

The "CIR-1085", a in the above formula (2), R ¹ ~ R ⁸ are all the n- butyl group, and Z in the above formula (2) ^{- in-a} _{[(CF 3 SO 2) 2} N] Dimonium salt.

When the said absorbance (X) of this "CIR-1085" was measured, it was 0.808 ((lambda) max is 1084 nm) when the solvent was toluene, and 0.563 ((lambda) max was 1069 nm) when the solvent was ethyl acetate. When the said solubility (Y) of this "CIR-1085" was measured, it was 0.01 mass% or more and less than 0.1 mass% when the solvent was toluene, and 0.01 mass% or more and less than 0.1 mass% when the solvent was ethyl acetate.

Resin Preparation Example 1:

As the monomer, 360.6 g of 2-ethylhexyl acrylate, 60 g of butyl acrylate, 156 g of cyclohexyl methacrylate, 180 g of acrylic acid, and 5.4 g of hydroxyethyl acrylate are weighed and mixed sufficiently, The polymerizable monomer mixture (1) was obtained.

160 g of ethyl acetate and 300 g of a polymerizable monomer mixture (1) were placed in a flask equipped with a thermometer, a stirrer, an inert gas introduction tube, a reflux cooler, and a dropping funnel. Further, in the dropping funnel, 300 g of a polymerizable monomer mixture (1), 16 g of ethyl acetate, and 0.15 g of Naifer BMT-K40 (polymerization initiator, manufactured by Japan Oil and Fat Company) were added, mixed well, and a dropping mixture was added. It was set as (1).

While nitrogen gas was passed through at 20 mL / min, the internal temperature of the flask was raised to 95 ° C, and Naper BMT-K40 (0.15 g), which was a polymerization initiator, was charged to the flask to initiate a polymerization reaction. 30 minutes after the addition of the polymerization initiator, 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 dropwise mixture 1, aging was carried out for 6 hours while maintaining the reflux temperature while appropriately diluting with ethyl acetate as the viscosity increased.

After the completion of the reaction, the reaction solution was diluted with ethyl acetate so that the nonvolatile content was about 45% to obtain resin (1) having a calculated glass transition temperature (Tg) of -38.5 ° C and a calculated solubility parameter of 9.08. This resin (1) was adhesive resin. The weight average molecular weight (Mw) of resin (1) was 430,000, and the acid value of resin (1) was 23.4. In addition, the reaction liquid diluted with ethyl acetate so that a non volatile matter may be about 45% is also called resin composition P1.

Resin Preparation Example 2:

As the monomer, 264.6 g of 2-ethylhexyl acrylate, 150 g of butyl acrylate, 180 g of cyclohexyl methacrylate, and 5.4 g of hydroxyethyl acrylate are weighed and mixed sufficiently to form a polymerizable monomer mixture ( 2) was obtained. Instead of the polymerizable monomer mixture (1), the polymerizable monomer mixture (2) was used in the same manner as in the resin production example 1, and the calculated glass transition temperature (Tg) was -35 ° C and the calculated solubility parameter was 8.99. Phosphorus resin (2) was obtained. This resin (2) was adhesive resin. The weight average molecular weight (Mw) of resin (2) was 440,000, and the acid value of resin (2) was zero.

Resin Preparation Example 3:

As the monomer, 365.4 g of 2-ethylhexyl acrylate, 60 g of butyl acrylate, 144 g of cyclohexyl methacrylate, 30 g of acrylic acid, and 5.4 g of hydroxyethyl acrylate are weighed and mixed sufficiently, The polymerizable monomer mixture (3) was obtained. Instead of the polymerizable monomer mixture (1), the polymerizable monomer mixture (3) was used in the same manner as in the resin production example 1, and the calculated glass transition temperature (Tg) was -38.96 ° C, and the calculated solubility parameter was 9.19. Phosphorus resin (2) was obtained. This resin (2) was adhesive resin. The weight average molecular weight (Mw) of resin (2) was 470,000, and the acid value of resin (2) was 39.96.

The specifications of Synthesis Examples 1 to 4 (Near Infrared Absorption Mixtures 1 to 4) are shown in Table 1 below. The compounding and evaluation results of Resin Production Examples 1, 2 and 3 are shown in Table 2 below.

Example 1

Coronate L-55E (manufactured by Japan Polyurethane Co., Ltd.), which is a crosslinking agent, was dissolved in ethyl acetate solution to adjust the crosslinking agent solution 1 having a solid content of 2.75%. The resin (1) obtained in the resin preparation example 1, the near-infrared absorption mixture 1 obtained in the synthesis example 1, and the crosslinking agent solution 1 were mixed so that it might be set to 100/1 / 0.25 by weight ratio of solids, and ethyl acetate as a dilution solvent was made to be 25% of solids. It diluted with and obtained the near-infrared absorption adhesive composition A1. In addition, this solid content weight ratio is described in order of (resin (1) / near-infrared absorption mixture 1 / crosslinking agent solution 1).

The near-infrared absorption adhesive composition A1 was coated by the applicator on the easily adhesive PET film (Toyo Boseki Co., Cosmoshine A4300). The thickness at the time of coating was set so that the thickness of the adhesive composition layer after drying might be set to 25 micrometers. Then, it dried for 2 minutes in 100 degreeC hot air circulation oven. After bonding a release film (silicone-treated PET film) to the layer which becomes this adhesive composition A1, it cured for 7 days at 23 degreeC, and obtained the near-infrared absorber B1. After peeling off a release film, this near-infrared absorber B1 was affixed on the glass plate and the test body of Example 1 was obtained. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in the following table | surface.

[Example 2]

The test body of Example 2 was obtained like Example 1 except having used the near-infrared absorption mixture 2 instead of the near-infrared absorption mixture 1, and changing the dilution solvent from ethyl acetate to toluene. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in the following table | surface.

Example 3

The test body of Example 3 was obtained like Example 1 except having used the near-infrared absorption mixture 3 instead of the near-infrared absorption mixture 1. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in the following table | surface.

Example 4

The test body of Example 4 was obtained like Example 2 except having used resin (2) instead of resin (1). This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in the following table | surface.

Example 5

The test body of Example 3 was obtained like Example 1 except having used resin (2) instead of resin (1), and used near-infrared absorption mixture 3 instead of near-infrared absorption mixture 1. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in the following table | surface.

Comparative Example 1

The near-infrared absorption mixture 4 was used instead of the near-infrared absorption mixture 1, and the test body of the comparative example 1 was obtained like Example 1 except having changed the dilution solvent from ethyl acetate to toluene. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in the following table | surface.

The transmission spectrum before the test (initial stage) of the test body of Example 2 is shown in FIG. The transmission spectrum after the heat resistance test of the test body of Example 2 is shown in FIG. The transmission spectrum after the moisture-resistant heat test of the test body of Example 2 is shown in FIG. The transmission spectrum after the light test of the test body of Example 2 is shown in FIG. The transmission spectrum before (initial stage) of the test body of the comparative example 1 is shown in FIG. The transmission spectrum after the heat resistance test of the test body of Comparative Example 1 is shown in FIG. 6. The transmission spectrum after the moisture-resistant heat test of the test body of Comparative Example 1 is shown in FIG. 7. The transmission spectrum after the light test of the test body of Comparative Example 1 is shown in FIG. 8.

Example 1a

1. Synthesis of Polymerizable Polysiloxane (M-1)

In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube, 144.5 parts of tetramethoxysilane, 23.6 parts of γ-methacryloxypropyltrimethoxysilane, 19.0 parts of water, 30.0 parts of methanol and Amberlyst 15 (brand name: 5.0 parts of cation exchange resins manufactured by Organo Co., Ltd. were stirred, and stirred at 65 ° C for 2 hours to react. After the reaction mixture was cooled to room temperature, a distillation column, a cooling tube connected thereto and an outlet port were installed instead of the cooling tube, and the flask internal temperature was raised to about 80 ° C. over 2 hours under normal pressure until no methanol was released. It was kept at the same temperature. The reaction was further continued at a temperature of 90 ° C. under a pressure of 2.67 × 10 kPa until methanol did not flow out. After cooling to room temperature again, Amberlyte 15 was filtered to obtain a polymerizable polysiloxane (M-1) having a number average molecular weight of 1,800.

2. Synthesis of Organic Polymer (P-1)

Into a 1-liter flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube, and an N2 gas inlet, 260 parts of n-butyl acetate was put as an organic solvent, the N2 gas was introduced, and the flask was heated to 110 ° C while stirring. It was. Then, 12 parts of polymerizable polysiloxane (M-1), 19 parts of tert-butyl methacrylate, 94 parts of butyl acrylate, 67 parts of 2-hydroxyethyl methacrylate, and perfluorooctylethyl methacrylate (light ester FM) -108, manufactured by Kyoeisha Chemical Co., Ltd.) and 2.5 parts of 2,2'-azobis- (2-methylbutyronitrile) were added dropwise over 3 hours from the dropping port. After stirring was continued for 1 hour at the same temperature after the dropwise addition, 0.1 part of tert-butylperoxy-2-ethylhexanoate was added twice at 30 minute intervals, and further heated for 2 hours to copolymerize. As a result, the number average molecular weight was 12,000, and the solution in which the organic polymer (P-1) whose weight average molecular weight is 27,000 was dissolved in n-butyl acetate was obtained. Solid content of the obtained solution was 48.2%.

3. Synthesis of Organic Polymer Composite Inorganic Particulate Dispersion (S-1)

200 parts of n-butyl acetate and 500 parts of methanol were put into the 500 ml four-necked flask equipped with the stirrer, the two dropping ports (dropping alpha and d), and the thermometer, and internal temperature was adjusted to 40 degreeC. Subsequently, while stirring the inside of the flask, a mixed solution (raw material liquid A) of 10 g of n-butyl acetate solution, 30 parts of tetramethoxysilane and 5 parts of n-butyl acetate of organic polymer (P-1) was added dropwise from 2 ° to 2 hours. At the same time, a mixture of 5 parts of 25% aqueous ammonia, 10 parts of deionized water, and 15 parts of methanol (raw material B) was added dropwise from the dropping port β over 2 hours. After dropping, a distillation column, a cooling tube and an outlet connected thereto were installed instead of the cooling tube, and the flask internal temperature was raised to 100 ° C under a pressure of 40 kPa, and 30% of the solid content of ammonia, methanol, and n-butyl acetate was added. It distilled off until it obtained, and the dispersion (S-1) which the organic polymer composite inorganic fine particle disperse | distributed to n-butyl acetate was obtained. In this dispersion (S-1), the ratio of the inorganic fine particle and the organic polymer in the said organic polymer composite inorganic fine particle was 70/30. This ratio is weight ratio. The average particle diameter of the obtained organic polymer composite inorganic fine particle was 23.9 nm. In addition, the ratio of the inorganic fine particle and the organic polymer in an organic polymer composite inorganic fine particle performs an elemental analysis about the organic polymer composite fine particle dispersion dried at 130 degreeC for 24 hours under the pressure of 1.33x10 kPa, and the ash content is organic polymer composite It calculated | required as inorganic fine particle content. In addition, the average particle diameter photographed particle | grains by the transmission electron microscope using the solution which diluted one part of organic polymer composite inorganic fine particle dispersion (S-1) with 99 parts of n-butyl acetate, and the diameter of arbitrary 100 particle | grains Was read and the average was calculated | required as average particle diameter.

4. Anti-reflection film

8 parts of dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) and 2 parts of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed and dissolved in 40 parts of methyl ethyl ketone. A solution was made. To this solution, a solution in which 0.5 parts of a photopolymerization initiator (Irugacure 907, manufactured by Ciba-Geigy Co., Ltd.) was dissolved in 2 parts of methyl ethyl ketone was added to prepare a hard coat layer coating liquid.

9 parts of organic polymer composite inorganic fine particle dispersion (S-1), Death module N3200 (brand name, isocyanate hardener made by Sumika Bayer Urethane Co., Ltd.), 0.003 parts of dilauric acid di-n-butyltin, and methyl isobutyl ketone 110 The part was mixed and the low refractive index layer coating liquid was prepared.

The said hard-coat layer coating liquid was apply | coated to the polyethylene terephthalate film (Cosmoshine A4300, Toyo Boseki Co., Ltd.) of thickness 188 micrometers using the bar coater, and the coating layer h was obtained. After drying this coating layer h for 15 minutes at 100 degreeC, it hardened | cured by irradiating an ultraviolet-ray of 200 mJ / cm <2> with a high pressure mercury lamp, and formed the hard-coat layer of a film thickness of 5 micrometers. The said low refractive index coating liquid was apply | coated on this hard-coat layer using the bar coater, and the anti-reflective film was produced on the polyethylene terephthalate film.

The surface on the opposite side to the anti-reflection film side of the film was roughened with steel wool. This roughened side was painted black ink. The specular reflection spectrum at an incident angle of 5 ° of the surface on the antireflection film side was measured using an ultraviolet visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), and the wavelength at which the reflectance exhibited the minimum value and the reflectance at the wavelength (minimum) Reflectance) was obtained. In the obtained antireflection film, the wavelength at which the reflectance exhibited the minimum value was 550 nm, and the reflectance (minimum reflectance) at the wavelength was 0.45%.

Coating and drying were performed similarly to Example 1 about the near-infrared absorption adhesive composition A1 obtained in Example 1 on the back surface side of the said antireflection film, and the optical filter 1 was obtained. Near-infrared transmittance, total light transmittance, heat resistance, moist heat resistance, light resistance, crack resistance, and solvent resistance of the optical filter 1 were good.

Example 6

A phthalocyanine-based compound (trade name "EX-Calar IR-14" manufactured by Nippon Shokubai) was added in the same manner as in Example 1 except that the solid content was added so as to be 0.3 part with respect to 100 parts of the resin (1). A test body was obtained. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. This evaluation result is shown in following Table 5 with the result of Example 1 mentioned above.

Example 7

After peeling off a release film from the near-infrared absorption layer which becomes adhesive composition A1 obtained by carrying out similarly to Example 1, this near-infrared absorption layer is affixed on the copper foil mesh surface (henceforth a metal mesh layer) of an electromagnetic wave shielding film (made by Dainippon printing company). Then, autoclave treatment (treatment temperature: 60 ° C., treatment pressure: 4 atmospheres, treatment time: 30 minutes) was performed to obtain a test body of Example 7. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. The evaluation results are shown in Table 5 below. This metal mesh layer is formed by etching the plating layer made of copper. In this Example 7, the pressure-sensitive adhesive composition is laminated on this metal mesh layer. In the table, this electromagnetic wave shielding film is shown by the mesh.

Example 8

Resin (1) was changed to resin (3), and the phthalocyanine compound (The Nippon Shokubai make brand name "EX-COL IR-14") was added so that it might be 0.3 part with respect to 100 parts of resin (3) by weight of solid content. A test sample of Example 8 was obtained in the same manner as in Example 1 except for the above. This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. The evaluation results are shown in Table 5 below.

Example 9

The resin (1) was changed to the resin (3), the glass plate of the test body was changed to the electromagnetic wave shielding film used in Example 7, and the autoclave treatment (treatment temperature: 60 ° C, treatment pressure: 4 atm, treatment time: 30 minutes) The test body of Example 9 was obtained like Example 1 except having performed). This test body was subjected to a heat resistance test, a damp heat test and a light resistance test. The evaluation results are shown in Table 5 below. In this Example 9, the pressure-sensitive adhesive composition containing the resin 3 is laminated on the metal mesh layer of the electromagnetic wave shielding film.

[Stability of Near-infrared Absorption Adhesive Composition]

The stability of the near-infrared absorption adhesive composition was examined based on the evaluation of the retention of the near-infrared absorptive capacity and the evaluation of liquid stability shown below.

<Evaluation of Retention of Near Infrared Absorption Capacity>

Evaluation was performed using the test body mentioned later. Transmission spectrum was measured using UV-3700 (made by Shimadzu Corporation), and (lambda) max in the wavelength range of 350-1500 nm was determined. The difference between lambda max before the test and lambda max after the test was calculated, and the absolute value of the difference was obtained. Based on this absolute value, the retention of near-infrared absorptivity was evaluated in three steps of "(circle)", "(triangle | delta)", and "x" according to the following evaluation criteria. This evaluation result is shown in the following table | surface.

(Circle): The absolute value of the difference of (lambda) max before and behind a test is 10 nm or less (excellent retention of a near-infrared absorption ability.).

(Triangle | delta): The absolute value of the difference of (lambda) max before and behind a test exceeds 10 nm and is 30 nm or less (The retainability of near-infrared absorptivity is slightly excellent.).

X: The absolute value of the difference of (lambda) max before and behind a test exceeds 30 nm (retainability of near-infrared absorptivity is inferior).

<Evaluation of liquid stability>

The state of the adhesive composition before and after a storage test was visually confirmed, and the liquid stability was evaluated in three steps of "(circle)", "(triangle | delta)", and "x" according to the following evaluation criteria. This evaluation result is shown in the following table | surface.

(Circle): Comparing before and behind a test, the color of liquid is equal and a precipitate of a pigment | dye is not seen.

(Triangle | delta): The color of a liquid differs slightly before and after a test, and a deposit is seen a little at the bottom of a container.

X: Compared before and after a test, the color of a liquid differs significantly and many precipitates are seen in the bottom of a container.

In addition, the test was stopped about the rust which generate | occur | produced on the inner surface of the container which contacted with liquid until the predetermined test period passed.

Resin Preparation Example 4:

In the same manner as in the resin preparation example 1, the polymerization reaction was carried out. Only the dilution ratio after completion of the reaction was changed. After the reaction was completed, a resin composition P2 was obtained in the same manner as in the resin preparation example 1 except that the reaction solution was diluted with ethyl acetate so that the nonvolatile content became about 65%.

Example 10

The near-infrared absorption mixture 3 obtained by the said synthesis example 3, and the resin composition P1 obtained by the said resin manufacture example 1 were used. Near-infrared absorption mixture 3 and resin composition P1 are mixed by the ratio of 1: 100 (100 mass parts of resin composition P1 solid content with respect to 1 mass part of mixture 3 solid content) by solid content weight ratio, and ethyl acetate is used so that solid content may be 40 mass%. It diluted, and obtained the near-infrared absorption adhesive composition B1. 0.5 kg of near-infrared absorption adhesive composition B1 was put into laminated can A (brand name "Hybrid 1.3L can"; the Dai-ichi Co., Ltd. product), the lid was sealed, and it was stored in the 25 degreeC thermostat room. The storage period was three types of 7 days, 14 days, and 28 days. After 7 days, each of the near-infrared absorption adhesive composition B1 after 14 days and 28 days was evaluated. These evaluation results are shown in Table 6 below.

In addition, a test body was produced about each of the near-infrared absorption adhesive composition B1 after 7 days, 14 days, and 28 days. The production method of this specimen is as follows. The near-infrared absorption adhesive composition B1 after the storage period passed was diluted with ethyl acetate so that solid content might be 25 mass%, and the adhesive test liquid was obtained. Using the applicator, this adhesive test liquid was coated on an easily adhesive PET film (Toyo Boseki Co., Cosmo Shine A4300). The thickness at the time of coating was set so that the thickness of the application layer after drying might be 25 micrometers. Then, it dried for 2 minutes in 100 degreeC hot air circulation oven. The application layer after this drying was affixed on the glass plate, and the test body was obtained. Therefore, three kinds of test bodies are produced. These three types of test bodies are the test body of the adhesive composition B1 after 7 days of passage, the test body of the adhesive composition B1 after 14 days of passage, and the test body of the adhesive composition B1 after 28 days of passage. About these test bodies, the retention of the near-infrared absorptivity was evaluated. The evaluation results are shown in Table 6 below.

[Examples 11 and 12]

Except the specification shown in Table 6, it carried out similarly to Example 10, and evaluated. The specifications and evaluation results of these examples are shown in Table 6 below.

Example 13

The near-infrared absorption mixture 3 obtained by the said synthesis example 3, and the resin composition P2 obtained by the said resin manufacture example 4 were used. Near-infrared absorption mixture 3 and resin composition P2 are mixed by the ratio of 5: 100 (100 mass parts of resin composition P2 solid content with respect to 5 mass parts of mixture 3 solid content) by solid content weight ratio, and ethyl acetate is used so that solid content may be 40 mass%. It diluted, and obtained near-infrared absorption adhesive composition B2. 0.5 kg of a near-infrared absorption adhesive composition B2 was put into a coating can (brand name "T40 glossiness # 30 crown can"), the lid was covered, it was sealed, and it was stored in the constant temperature room of 25 degreeC. The storage period was three types of 7 days, 14 days, and 28 days. After 7 days, each of the near-infrared absorption adhesive composition B2 after 14 days and 28 days was evaluated. These evaluation results are shown in Table 6 below.

Example 14

The evaluation of Example 14 was carried out in the same manner as in Example 13 except that the storage temperature was changed from 25 ° C to 40 ° C. The evaluation results are shown in Table 6 below.

Example 15

The coating can was changed to Laminated can A (brand name "Hybrid 1.3L can"; manufactured by Dainippon Co., Ltd.), and the same as in Example 13 except that the storage temperature was changed from 25 ° C to 50 ° C. 15 evaluations were made. The evaluation results are shown in Table 6 below.

Example 16

The near-infrared absorption mixture 3 obtained by the said synthesis example 3, and the resin composition P2 obtained by the said resin manufacture example 4 were used. Near-infrared absorption mixture 3 and resin composition P2 are mixed by the ratio of solid content weight ratio of 3: 100 (100 mass parts of resin composition P2 solid content with respect to 3 mass parts mixture 3 solid content), and ethyl acetate is made into 40 mass% of solid content. It diluted, and obtained near-infrared absorption adhesive composition B3. 0.5 kg of a near-infrared absorption adhesive composition B3 was put into laminate can A (brand name "Hybrid 1.3L can"; Dainippon Co., Ltd. product), the lid was sealed, it was stored in the 50 degreeC thermostat room. The storage period was three types of 7 days, 14 days, and 28 days. After 7 days, each of the near-infrared absorption adhesive composition B3 after 14 days and 28 days was evaluated. These evaluation results are shown in Table 6 below.

Table 7 below shows a list of hollow bodies (containers) for storage used in the examples. Among these, modified polyolefin is used for the innermost layer of the main body of laminate can A (brand name "Hybrid 1.3L can"). The material of the inner layer of a coating can (T40 gloss varnish # 30 crown can) is epoxy resin. The epoxy resin of this inner layer is baked on the main body.

In Example 13, the concentration of dimonium pigment | dye is high compared with Example 11. This Example 13 is a higher evaluation than Example 11. In Example 14, the storage temperature is higher than that in Example 13. Even when the storage temperature is increased to 40 ° C, Example 14 is higher than Example 11.

The storage temperature of Example 15 is 50 degreeC similarly to Example 12. In Example 15, the density | concentration of a dimonium pigment | dye is high compared with Example 12. This Example 15 is evaluation higher than Example 12. FIG. Also in Example 16, the storage temperature is 50 ° C. This Example 16 is a high evaluation compared with Example 12. Compared with Example 15, Example 16 has low evaluation.

As Example 13-16 shows, it turned out that the density | concentration of a dimonium pigment | dye contributes to the retention and liquid stability of near-infrared absorptivity. Moreover, it turned out that the shelf life under high temperature improves because the density | concentration of a dimonium pigment | dye becomes high.

From these evaluation results, the superiority of this invention is clear.

The near-infrared absorptive pressure-sensitive adhesive composition of the present invention is useful as an optical filter for a thin display, for example, because of its high persistence of near-infrared absorptivity and high transparency of visible regions, and excellent heat resistance, moist heat resistance, and light resistance. It can also be used as an optical information recording material.

Claims (26)

After adjusting the liquid mixture which mixed the dimonium salt (A1) with respect to the solvent (S1) at the ratio of 0.01 mass%, this mixture liquid was sonicated for 30 minutes, and left still for 1 hour or more, and then, the supernatant liquid of this liquid mixture was made into the optical path A dimonium salt (A1) having an absorbance (X) at λmax of λmax of the supernatant liquid, measured in an ultraviolet-visible spectrophotometer in the range of 350 nm or more and 1500 nm or less and 0.5 or less, and a calculated glass transition point of 0 The near-infrared absorption adhesive composition containing resin (B) which is C or less, and a solvent (S2). The method of claim 1,
The solvent (S1) is toluene and / or ethyl acetate, and the solvent (S2) is toluene and / or ethyl acetate. The method according to claim 1 or 2,
The near-infrared absorption adhesive composition in which the said solvent (S1) and said solvent (S2) are the same. 4. The method according to any one of claims 1 to 3,
The near-infrared absorption adhesive composition whose compounding quantity of the said dimonium salt (A1) in the said near-infrared absorption adhesive composition is 0.5 mass% or more with respect to the total mass of all the solid content contained in this near-infrared absorption adhesive composition. The near-infrared absorption adhesive composition containing solvent (S3), the dimonium salt (A2) whose solubility (Y) with respect to this solvent (S3) is less than 0.01 mass%, and resin (B) whose calculation glass transition point is 0 degrees C or less. The method of claim 5,
The near-infrared absorption adhesive composition whose said solvent (S3) is toluene and / or ethyl acetate. The method according to any one of claims 1 to 6,
The near-infrared absorption adhesive composition whose acid value of the said resin (B) is 0 or more and 300 or less. The method according to any one of claims 1 to 7,
The near-infrared absorption adhesive composition whose calculation solubility parameter of the said resin (B) is 10.2 or less. The method according to any one of claims 1 to 8,
The near-infrared absorption adhesive composition obtained by the said resin (B) superposing | polymerizing the monomer mixture of the following formulation.
(1) (meth) acrylic acid ester which has a C1-C12 alkyl group: 60 mass% or more and 99.9 mass% or less.
(2) Functional group containing monomer: 0.1 mass% or more and 20 mass% or less.
(3) Other copolymerizable monomers: 0 mass% or more and 30 mass% or less. The method according to any one of claims 1 to 9,
A near-infrared absorption adhesive composition which further contains a phthalocyanine type compound. After adjusting the liquid mixture which mixed the dimonium salt (A1) with respect to the solvent (S1) at the ratio of 0.01 mass%, this mixture liquid was sonicated for 30 minutes, and left still for 1 hour or more, and then, the supernatant liquid of this liquid mixture was made into the optical path A dimonium salt (A1) having an absorbance (X) at λmax of λmax of the supernatant liquid, measured in an ultraviolet-visible spectrophotometer in the range of 350 nm or more and 1500 nm or less and 0.5 or less, and a calculated glass transition point of 0 It contains resin (B) which is C or less, and a solvent (S2),
The said dimonium salt (A1) is a near-infrared absorption adhesive composition whose solubility (Y) with respect to a solvent (S3) is less than 0.01 mass%. The method of claim 11,
The solvent (S1) and the solvent (S2) are the same,
The near-infrared absorption adhesive composition which the said solvent (S3) and this solvent (S1) are the same. The near-infrared absorber containing the near-infrared absorption adhesive composition in any one of Claims 1-12. The method of claim 13,
The near-infrared absorptive material by which the near-infrared absorption adhesive composition in any one of Claims 1-12 is laminated | stacked on a transparent base material. The method of claim 14,
The near-infrared absorber in which the said solvent (S2) or the said solvent (S3) is volatilized after apply | coating to the said transparent base material. The method of claim 13,
The near-infrared absorption adhesive composition in any one of Claims 1-12 is laminated | stacked on the electromagnetic wave shielding material which can shield an electromagnetic wave,
The near-infrared absorber whose acid value of the said resin (B) is 0 or more and 35 or less. The method of claim 16,
The near-infrared absorber which said electromagnetic wave shielding material contains the said transparent base material. The optical filter for thin displays which uses the near-infrared absorber as described in any one of Claims 13-17. The thin display which uses the near-infrared absorption adhesive composition in any one of Claims 1-12, the near-infrared absorber in any one of Claims 13-17, or the optical filter of Claim 18. As a near-infrared absorption mixture for a near-infrared absorption adhesive composition,
After adjusting the liquid mixture which mixed the dimonium salt (A1) with respect to the solvent (Sm) at the ratio of 0.01 mass%, this mixture liquid was sonicated for 30 minutes, and left still for 1 hour or more, and then, the supernatant liquid of this liquid mixture was made into the optical path The dimonium salt (A1) and the said solvent (Sm) whose absorbance (X) in (lambda) max of the supernatant liquid measured in the range of 350 nm or more and 1500 nm or less in the cell of 1 mm long, and 0.5 or less Near-infrared absorption mixture containing. The method of claim 20,
The near infrared absorption mixture of said solvent (Sm) is toluene and / or ethyl acetate. As a near-infrared absorption mixture for a near-infrared absorption adhesive composition,
The near-infrared absorption mixture containing solvent (S3) and the dimonium salt (A2) whose solubility (Y) with respect to this solvent (S3) is less than 0.01 mass%. The method of claim 22,
The near-infrared absorption mixture of said solvent (S3) is toluene and / or ethyl acetate. The near-infrared absorption adhesive composition which uses the near-infrared absorption mixture of any one of Claims 20-23. 25. The method of claim 24,
The near-infrared absorption mixture and resin composition (P) may be used,
The near-infrared absorption adhesive composition in which this resin composition (P) contains solvent (S2) and resin (B) whose calculation glass transition point is 0 degrees C or less. The method of claim 25,
The near-infrared absorption adhesive composition whose compounding quantity of resin (B) in the said resin composition (P) is 50 mass% or more.

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