JP6004566B2 - Manufacturing method of near-infrared absorbent dispersion and near-infrared absorbing laminate - Google Patents

Description

  The present invention is a method for producing a near-infrared absorbent dispersion, and a near-infrared absorbing laminate having excellent transparency can be produced by using a dispersion obtained by the method for producing a dispersion. Become.

  In recent years, plasma display panels (hereinafter, abbreviated as “PDP”) have become widespread as demands for larger and thinner displays have increased. Since near infrared rays are emitted from the PDP and an electronic device using a near infrared remote controller malfunctions, it is necessary to shield the near infrared rays with a filter containing a near infrared absorber. Moreover, since the optical semiconductor element used for a CCD camera etc. has high sensitivity in the near infrared region, it is necessary to remove the near infrared ray. Furthermore, near-infrared absorbers are used as heat-ray shielding materials that shield sunlight from the viewpoint of energy saving, and are used as heat-ray shielding agents and heat-ray shielding film materials for multilayer glass such as automotive glass and building glass. Has been. In addition, a heat ray shielding agent is a useful material for maintaining the characteristics because the temperature rise of the module in the solar cell lowers the conversion efficiency. Near-infrared absorbing laminates such as near-infrared blocking filters used for these applications are required to have high transparency and to effectively absorb near-infrared light regions.

  Conventionally, as near-infrared absorbing dyes that absorb near infrared rays, cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, inorganic oxide particles, and the like have been used. (Patent Documents 1 and 2).

  By the way, the near-infrared shielding filter used for the PDP which is a near-infrared absorbing laminate is usually provided with an electromagnetic wave shielding layer, an antireflection layer, a hard coat layer and the like in addition to the near-infrared absorbing layer. For this reason, the near-infrared shielding filter for PDP is generally produced by laminating a near-infrared absorbing film, an electromagnetic wave shielding film and an antireflection film on glass or a shock absorbing material as a support. Such a near-infrared cutoff filter for PDP is placed on the front side of the PDP. Such a near-infrared shielding filter for PDP is used by being directly bonded onto glass or a shock absorbing material as a support using an adhesive or a pressure-sensitive adhesive.

  In recent years, for the purpose of thinning near-infrared blocking filters and simplifying the manufacturing process of near-infrared blocking filters, a near-infrared absorbing layer and a pressure-sensitive adhesive layer have been incorporated by adding a near-infrared absorbing dye to the pressure-sensitive adhesive. Attempts have been made to integrate them with a hard coat layer (Patent Document 3).

  However, compounds such as cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, and phthalocyanine dyes used as near-infrared absorbing dyes are suitable for low-polar solvents and low-polar resins. There is a problem of poor solubility. In particular, the pressure-sensitive adhesive is often low in polarity, and when a near-infrared absorbing dye having a close polarity is blended with these pressure-sensitive adhesives, there is a problem that the dye precipitates with time and the appearance and transparency of the coating film are impaired.

  In Patent Document 4, red is characterized in that a near-infrared-absorbing dye is contained in a resin in a fine particle state, which seems to be effective for a resin composition or the like in which the resin has poor polarity and cannot dissolve the dye. An external light absorbing film is disclosed. However, the fine particles cause light scattering, and the transparency of the film is impaired.

  In view of the above, there has been a demand for a method for producing a near-infrared absorbing laminate having excellent transparency and a near-infrared absorbent dispersion capable of producing the same.

JP 2003-096040 A JP 2000-080071 A JP 2001-207142 A JP 2001-019898 A

  An object of the present invention is a method for producing a near-infrared absorbent dispersion capable of producing a near-infrared absorbing laminate having excellent transparency, and a near-infrared absorption produced using a dispersion obtained by the production method. To provide a near infrared absorbing laminate excellent in a resin composition and transparency.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are obtained by dispersing a compound represented by the general formula (1) capable of producing a near-infrared absorbing laminate excellent in transparency in a diluent. Finding a method for producing an infrared absorbent dispersion, and a near-infrared absorbing laminate in which a near-infrared absorbing resin composition produced using the dispersion is laminated on a transparent substrate is excellent in transparency. The present invention has been completed.

  That is, the present invention is as follows.

The first invention is a method for producing a near-infrared absorber dispersion comprising a compound represented by the following general formula (1) dispersed in a diluent:
Crushing the compound represented by the following general formula (1) in the state A by dry pulverization into a compound represented by the following general formula (1) in the state B;
The compound represented by the following general formula (1) in the state B and the diluent having a solubility of 5% by mass or less of the compound represented by the following general formula (1) are in a mass ratio of 0.01: 9. A near-infrared absorber, comprising: a step represented by the following general formula (1), which is in state A, by containing at a ratio of 99 to 2: 8 and stirring for 10 minutes or more. It is a manufacturing method of a dispersion liquid.

（式中、Ｒ_１〜Ｒ_８はそれぞれ同一でも異なっていても良い有機基を表し、Ｘ⁻はアニオンを示す。）

(Wherein R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.)

In the second invention, R _{1 to} R ₈ in the compound represented by the general formula (1) are n-propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, 3- The first invention characterized in that it is one kind selected from the group consisting of a fluoropropyl group, a cyclohexylalkyl group represented by the following general formula (2), and a phenylalkyl group represented by the following general formula (3). It is a manufacturing method of the near-infrared absorber dispersion liquid of description.

（式（２）中、Ａは炭素数１〜１０のアルキル基を示し、Ｒ_９は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (2), A represents an alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

（式（３）中、Ｂは炭素数１〜１０のアルキル基を示し、Ｒ_１０は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (3), B represents an alkyl group having 1 to ₁₀ carbon atoms, and R ₁₀ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

In the third invention, X ⁻ in the compound represented by the general formula (1) is hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imido ion, bis (fluorosulfonyl) imide. The method for producing a near-infrared absorbent dispersion according to the first or second invention, wherein the method is a kind selected from the group consisting of acid ions.

  A fourth invention is characterized in that a near-infrared absorbent dispersion obtained by the method for producing a near-infrared absorbent dispersion according to any one of the first to third inventions is mixed with a resin component. The near infrared ray absorbing resin composition.

  5th invention is produced using the near-infrared absorption resin composition as described in 4th invention, It is a near-infrared absorption laminated body characterized by the above-mentioned.

In a sixth aspect of the present invention, there is provided a near-infrared absorber dispersion liquid dispersed in a compound represented by the following general formula (1) and a diluent:
When the near-infrared absorber dispersion is diluted with ethyl acetate, the concentration of the compound represented by the general formula (1) is adjusted to 100 mg / l, and the absorbance is measured with a spectrophotometer, 1000 to 1300 nm. The near-infrared absorbent dispersion is characterized in that the molar extinction coefficient of the maximum absorption wavelength is from 6000 to 14000 mol ⁻¹ · L · cm ⁻¹ , and the half width of the maximum absorption wavelength is from 200 to 700 nm.

（式中、Ｒ_１〜Ｒ_８はそれぞれ同一でも異なっていても良い有機基を表し、Ｘ⁻はアニオンを示す。）

(Wherein R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.)

In the seventh invention, R _{1 to} R ₈ in the compound represented by the general formula (1) are n-propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, 3- A sixth invention characterized in that it is a kind selected from the group consisting of a fluoropropyl group, a cyclohexylalkyl group represented by the following general formula (2), and a phenylalkyl group represented by the following general formula (3). It is a near-infrared absorber dispersion liquid of description.

（式（２）中、Ａは炭素数１〜１０のアルキル基を示し、Ｒ_９は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (2), A represents an alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

（式（３）中、Ｂは炭素数１〜１０のアルキル基を示し、Ｒ_１０は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (3), B represents an alkyl group having 1 to ₁₀ carbon atoms, and R ₁₀ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

In an eighth aspect of the present invention, X ⁻ in the compound represented by the general formula (1) is hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imido ion, bis (fluorosulfonyl) imide. The near-infrared absorber dispersion liquid according to the sixth or seventh invention, which is a kind selected from the group consisting of acid ions.

  A ninth invention is a near-infrared absorbing resin composition comprising a mixture of the near-infrared absorber dispersion liquid described in any of the sixth to eighth inventions and a resin component.

  A tenth invention is a near-infrared absorbing laminate produced using the near-infrared absorbing resin composition described in the ninth invention.

  It is providing the manufacturing method of the near-infrared absorption laminated body which is excellent in transparency, and the near-infrared absorber dispersion liquid which can manufacture it.

  The present invention relates to a method for producing a near-infrared absorbent dispersion obtained by dispersing a compound represented by the general formula (1) in a diluent, and dry pulverizing the compound represented by the general formula (1) in the state A. Are pulverized to form a compound represented by general formula (1) in state B, a compound represented by general formula (1) in state B, and a compound represented by general formula (1) And a diluent having a solubility of 5% by mass or less in a mass ratio of 0.01: 9.99 to 2: 8, which is expressed by the general formula (1) which is the state A by stirring. A method of producing a near-infrared absorbent dispersion characterized by comprising: The near-infrared absorbing resin composition using the dispersion obtained by the production method and the near-infrared absorbing laminate produced using the same are excellent in transparency.

[Compound represented by general formula (1)]
In the present invention, a compound represented by the following general formula (1) is used as a near-infrared absorber. The near infrared ray means light having a wavelength in the range of 750 to 2000 nm.

In the general formula (1), the organic groups of R _{1 to} R ₈ may be the same or different, and preferred organic groups are linear or branched optionally substituted with a halogen atom. And a C1- _C10 alkyl group, a cyclohexylalkyl group represented by the following general formula (2), a phenylalkyl group represented by the following general formula (3), and the like.

（式（２）中、Ａは炭素数１〜１０のアルキル基を示し、Ｒ_９は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (2), A represents an alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

（式（３）中、Ｂは炭素数１〜１０のアルキル基を示し、Ｒ_１０は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (3), B represents an alkyl group having 1 to ₁₀ carbon atoms, and R ₁₀ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

As the C _1-10 alkyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, 1,1-dimethylpropyl group, n-pentyl group, neopentyl group, n-hexyl Groups and the like. Among these, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an iso-butyl group are preferable.

The C _1-10 alkyl group substituted with a halogen atom includes a 2-halogenoethyl group, a 2,2-dihalogenoethyl group, a 2,2,2-trihalogenoethyl group, a 3-halogenopropyl group, 3 , 3-dihalogenopropyl group, 3,3,3-trihalogenopropyl group, 4-halogenobutyl group, 4,4-dihalogenobutyl group, 4,4,4-trihalogenobutyl group, 5-halogenopentyl group And halogenated alkyl groups such as 5,5-dihalogenopentyl group and 5,5,5-trifluoropentyl group. Specific examples include monofluoroalkyl groups such as a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group. A 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group are more preferable, and a 3-fluoropropyl group is particularly preferable.

  The cyclohexylalkyl group can be represented by the following general formula (2).

In General Formula (2), A represents an alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. More preferably, A is an alkyl group having 1 to 4 carbon atoms.
Specifically, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, cyclohexylbutyl group, 2-methylcyclohexylmethyl group, 2-ethylcyclohexylmethyl group, 3-methylcyclohexylmethyl group, 4-methylcyclohexylmethyl group, 4 -Methylcyclohexylethyl group, 4-methylcyclohexylpropyl group, 4-methylcyclohexylbutyl group, 4-fluorocyclohexylmethyl group and the like can be mentioned, and among these, cyclohexylmethyl group is preferable.

  The phenylalkyl group can be represented by the following general formula (3).

In General Formula (3), B represents an alkyl group having 1 to ₁₀ carbon atoms, and R ₁₀ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. B is preferably an alkyl group having 1 to 4 carbon atoms.
Specific examples include a methylbenzyl group, an ethylbenzyl group, a propylbenzyl group, and a butylbenzyl group.

X ⁻ in the compound represented by the general formula (1) is an anion necessary for neutralizing the charge of the cation, and an inorganic anion, an organic acid anion, or the like can be used. Specific examples of anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, perchlorate ion, periodate ion, tetrafluoroborate ion, hexafluorophosphate ion and hexafluoroantimonate ion. Bis (trifluoromethanesulfonyl) imido ion, bis (fluorosulfonyl) imido ion, and the like.
Among these, hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imidate ion, and bis (fluorosulfonyl) imidate ion are more preferable, and hexafluorophosphate ion or bis (trifluoromethane). Particularly preferred is a sulfonyl) imido ion.

  The compound having an organic group has a strong intermolecular interaction and can exist extremely stably in the dispersion and the resin.

  The compound represented by the general formula (1) which is the state A or the state B in the present invention will be described.

First, the compound represented by General formula (1) which is the state A is demonstrated. The compound represented by the general formula (1) which is in the state A took the peak top from the baseline at the peak of the maximum intensity detected using a powder X-ray diffractometer using CuKα rays as an X-ray source. The full width at half maximum of the peak is less than 2θ = 1 °.
The measurement conditions of the diffraction peak using a powder X-ray diffractometer are as follows: tube voltage: 40 kV, tube current: 20 mA, scanning range (2θ): 3 ° to 60 °, divergence slit: 1/2 °, scattering slit: 1/2 °, light receiving slit: 0.15 mm, sampling width: 0.02 °, scan speed: 4 ° / min.

  Next, the compound represented by the general formula (1) in the state B will be described. In the compound represented by the general formula (1) which is in the state B, the half-width of the peak when the peak top is taken from the baseline at the maximum intensity detected diffraction peak is 2θ = 1 ° or more. It is. Such a solid does not include the compound represented by the general formula (1) which is substantially in the state A, and is composed only of the compound represented by the general formula (1) which is in the state B. It is.

  Examples of the method for converting the compound represented by the general formula (1) in the state A into the compound represented by the general formula (1) in the state B include a pulverizing method. Although details regarding the pulverization will be described later, a dry pulverization method is preferred because of its ease. The compound is put and dry-pulverized with a pestle 100 rpm and a mortar 6 rpm. By doing in this way, the state of the compound represented by the general formula (1) can be changed from the state A to the state B. In other words, the diffraction peak is measured with a powder X-ray diffractometer, and the peak of the maximum intensity detected is pulverized until the half width of the peak when taking the peak top from the baseline is 2θ = 1 ° or more. That's fine.

The compound represented by the general formula (1) which is the state B obtained by the above method is a compound having excellent solvent affinity and easy dispersibility, and is represented by the general formula (1) which is the state B. The compound and a diluent having a solubility of 5% by mass or less of the compound represented by the general formula (1) are contained in a mass ratio of 0.01: 9.99 to 2: 8 and stirred for 10 minutes or more. Thus, the state can be changed from the state B to the state A, and a dispersion containing the compound represented by the general formula (1) which is the state A can be produced.
In addition, after drying the compound represented by the general formula (1) taken out from the dispersion, a diffraction peak is measured with a powder X-ray diffractometer, and a peak from the baseline is detected at the maximum intensity peak detected. When the half width of the peak when taking the top is less than 2θ = 1 °, it can be confirmed that the compound represented by the general formula (1) changed from the state B to the state A is included.

Moreover, mass ratio of the compound represented by General formula (1) and the diluent whose solubility of the compound represented by General formula (1) is 5 mass% or less is 0.01: 9.99- 2: 8 is preferable, and 0.1: 9.9 to 1: 9 is more preferable.
When the mass ratio of the compound represented by the general formula (1) is less than 0.01, when mixed with a resin, the viscosity becomes low and it becomes difficult to form a laminate by a known method. There is a problem that the viscosity of the dispersion becomes high and dispersion becomes difficult.

  The stirring time is preferably 10 minutes or longer, and particularly preferably 1 hour or longer. If it is less than 10 minutes, the state A may not change to the state B.

  Moreover, the compound represented by General formula (1) which is the state A in a near-infrared absorber dispersion liquid may agglomerate compounds, and may form (pi) conjugated system.

  Dispersions prepared by this method are characterized by a sharp peak with a narrow molar absorption coefficient and half-width of absorption peak, and near-infrared absorbing laminates produced using the same also have a molar absorption coefficient and half-width of absorption peak. It has the characteristic of becoming a narrow sharp peak. Moreover, in the dispersion liquid of the compound represented by the general formula (1) in the state B, the haze value of the obtained near-infrared absorbing laminate is increased, but the general formula (1) changed from the state B to the state A is obtained. The dispersion of the compound represented by the formula is characterized by a small haze value. As a result, a transparent near-infrared absorbing laminate having no absorption in the visible light region can be produced.

  Stirring at this time is carried out using a general stirring device, and examples of the device used include, but are not limited to, a magnetic stirrer, a bladed stirrer, a homogenizer, and an ultrasonic homogenizer.

  The method for dry pulverization will be described in detail. Here, “dry grinding” is an operation of grinding without using a solvent. “Crushing” means that a solid is subdivided by applying mechanical force. The pulverization can generally be performed using a pulverizer such as a ball mill, a sand mill, a paint shaker, an attritor, a hammer mill, a roll mill, a kneader, an extruder and an automatic mortar. If necessary, grinding media such as glass beads, steel beads, zirconia beads, and alumina beads can be used. Note that when pulverizing, the powder may be moistened by adding a small amount of a solvent so that the powder does not fly.

On the other hand, in the production of the near-infrared absorbing resin composition, the amount of the compound represented by the general formula (1) added to the resin is not particularly limited, and desired properties, particularly efficient near-infrared absorbing ability, visible light region. It may be adjusted so that excellent transparency, heat resistance and heat and humidity resistance can be achieved.
For example, when the dry film thickness of the resin is set to 1 to 20 μm, the compounding ratio of the compound represented by the general formula (1) is preferably 0.1 to 100 with respect to 100 parts by mass of the solid content of the resin component. Parts by mass, more preferably 0.5 to 50 parts by mass, and most preferably 1 to 30 parts by mass. If this blending ratio is less than 0.1 parts by mass, it is difficult to obtain an excellent near-infrared absorptivity. Conversely, when the blending ratio exceeds 100 parts by mass, the above-described improvement in performance commensurate with the amount of addition is not recognized. There is a problem that is not economical. In addition, the compounding ratio of the compound represented by General formula (1) can be changed with the setting of the transmittance | permeability of visible and a near-infrared region, and the thickness of the laminated body of a near-infrared absorption composition.

[Diluent]
As the diluent used in the present invention, it is necessary to use a diluent having a solubility of the compound represented by the general formula (1) of 5% by mass or less. By using the diluent, the diluent represented by the general formula (1) is used. The resulting compound can be changed from state B to state A. Examples of the diluent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; glycol solvents such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene copolymer. Monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, 3-methoxybutanol, 3-methoxy-3- Ether alcohol solvents such as methylbutanol; dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibu Polyether solvents such as ether, methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether, ethyl propyl ether, ethyl isopropyl ether and ethyl butyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl acetate, Examples thereof include ester solvents such as ethyl acetate and butyl acetate.
Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable for converting the compound represented by the general formula (1) in the state B into the compound represented by the general formula (1) in the state A. , 3-methoxybutanol and 3-methoxy-3-methylbutanol are preferred.
These solvent may be used by 1 type and may be used as 2 or more types of mixed solvents. Desirably, the water content of the solvent is 5% by mass or less.

  Moreover, as a diluent whose solubility of the compound represented by General formula (1) is 5 mass% or less, you may use the single-tube polymerizable compound which is a reactive diluent. Specific examples of the monofunctional polymerizable compound include acrylamide, (meth) acryloylmorpholine, 7-amino-3, 7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylate, isobornyloxyethyl (meth) ) Acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N, N-dimethyl (meth) acrylami , Tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxy Ethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone Phenoxyethyl (meth) acrylate, brooxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate, and the like. And may be used.

  As for the diluent, in addition to being used as a dispersion medium for changing the state of the compound represented by the general formula (1), a diluent may be further mixed in order to adjust the viscosity of the near-infrared absorbing resin composition. Absent.

The near-infrared absorber dispersion prepared by the method described above is diluted with ethyl acetate so that the concentration of the compound represented by the general formula (1) becomes 100 mg / l. When the absorbance is measured with a spectrophotometer after adjustment, the molar absorption coefficient of the maximum absorption wavelength at 1000 to 1300 nm is 6000 to 14000 mol ⁻¹ · L · cm ⁻¹ , and the half width of the maximum absorption wavelength is 200 to 700 nm. It has the characteristic which is.

[Near-infrared absorbing resin composition]
The near-infrared absorbing resin composition according to the present invention is obtained by mixing a near-infrared absorbent dispersion and a resin component. Examples of the resin component include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and are not particularly limited as long as they can be laminated on a transparent substrate. Examples include polyester resins and acrylic resins. , Epoxy resins, melamine resins, polyurethane resins, polycarbonate resins, polyimide resins, polyamide resins and the like.
However, an adhesive for sticking to the outermost layer of the near-infrared absorbing laminate used for PDP, automobiles, and building materials, which is considered as an application, for the purpose of preventing the laminate from being scratched or adhered to the adherend The agent layer is often provided, and it is desirable that the hard coat layer or the pressure-sensitive adhesive layer and the near-infrared absorbing layer are the same from the viewpoint of economy and productivity.

The resin component used in the present invention is preferably an active energy ray curable resin-hard coat resin, and particularly a resin curable with ultraviolet rays having a carbon-carbon double bond-acryloyl group. Examples include (meth) acrylic resins and the like, but are not limited thereto. (Meth) acrylic resin refers to a (meth) acrylic polymer polymerized using (meth) acrylic acid ester as a monomer. The (meth) acrylic polymer may be polymerized using one type of (meth) acrylic acid ester as a monomer, or may be polymerized using two or more types of (meth) acrylic acid ester as a monomer. Alternatively, polymerization may be performed using (meth) acrylic acid ester and a compound copolymerizable with (meth) acrylic acid ester (hereinafter also referred to as “copolymerizable compound”) as monomers. Good. Specific examples of the (meth) acrylic acid ester used as a monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( C1-C20 alkyl (meth) acrylates such as (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like Substitution: Hydroxyl-containing (meth) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Acrylate; carboxyl group-containing (meth) acrylate such as (meth) acrylic acid; aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate and ethoxypropyl (meth) acrylate; ethoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenol ethylene oxide (EO) adduct (meth) acrylate, (Meth) acrylates of oxyalkylene adducts of alcohols such as nonylphenol propylene oxide (PO) adduct (meth) acrylate; Rohekishiru (meth) acrylates such as cycloalkyl (meth) acrylate. However, (meth) acrylic acid esters other than these compounds may be used. The said (meth) acrylic acid ester may be used independently and may be used with the form of 2 or more types of mixtures. Examples of the copolymerizable compound used as a monomer as needed include a compound having an ethylenically unsaturated bond. Here, the compound having an ethylenically unsaturated bond means a compound in which a hydrogen atom of ethylene (CH ₂ ═CH ₂ ) is substituted. Other compounds may be used as monomers as long as they can be copolymerized with (meth) acrylic acid esters and do not interfere with the effects of the present invention. Other examples of the copolymerizable compound include aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, vinyl naphthalene, and halogenated styrene; vinyl ester monomers such as vinyl acetate; vinyl chloride, Vinyl halide monomers such as vinylidene chloride; (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, etc. Examples thereof include amide group-containing vinyl monomers; nitrile group-containing monomers such as (meth) acrylonitrile; vinyl ether monomers.
These can be used alone or mixed with other resins.

In addition, a polymerization initiator is appropriately added to the ultraviolet curable resin having an acryloyl group. As the polymerization initiator, an energy ray sensitive radical polymerization initiator is preferable, for example,
2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl- Benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate and the like can be used, but are not limited thereto. is not.

  These polymerization initiators can be used alone or in combination of two or more according to the desired performance. Moreover, as a compounding quantity of a polymerization initiator, it is 0.05-20 mass% with respect to a hard-coat resin component, Preferably it is 0.1-20 mass%. When the blending amount of the polymerization initiator is less than 0.05% by mass, the composition may not be cured sufficiently. On the other hand, if the blending amount of the polymerization initiator exceeds 20% by mass, the physical properties of the cured product will not be further improved, rather adversely affected and the economy may be impaired.

  Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicon-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives, and among these, acrylic pressure-sensitive adhesives are preferably used because of transparency and cost. Examples of the acrylic pressure-sensitive adhesive include those containing an acrylic polymer mainly composed of an acrylate or methacrylate having an alkyl group having 1 to 14 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) Examples include acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate.

  When an acrylic adhesive is used, a resin layer having excellent heat resistance can be obtained by crosslinking the adhesive. As a specific means of the crosslinking method, a functional group contained in the acrylate monomer or methacrylate monomer and a curing agent exhibiting thermal reactivity are added to perform thermal crosslinking, or effective polymerization for remaining acryloyl groups. Examples include a method of adding an initiator and crosslinking with active energy rays.

  Examples of the heat-reactive curing agent include an isocyanate curing agent, an epoxy curing agent, and a curing agent.

  Examples of the isocyanate curing agent include aliphatic isocyanates such as hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, cycloaliphatic diisocyanate, methylene (biscyclohexyl isocyanate), cycloaliphatic isocyanates such as isophorone diisocyanate, and tolylene diisocyanate. An aromatic isocyanate etc. are mentioned, These adduct bodies, a burette body, an isocyanurate body etc. can be used, However It is not limited to this.

  Epoxy curing agents include bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycidin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl. A compound having two or more epoxy groups in the molecule such as ether, diglycidyl aniline, diamine diglycidyl amine, 1,3-bis (N, N′-diamine glycidylaminomethyl) cyclohexane can be used. It is not limited to.

  These heat-reactive curing agents can be used alone or in combination of two or more according to the desired performance. As a compounding quantity, it is 0.05-300 mass% with respect to a resin component, Preferably 0.5-250 mass% is good. Conversely, when the curing agent is less than 0.05% by mass, curing may be insufficient. If it exceeds 300% by mass, the curability will not be further improved, but rather adversely affected and the economy may be impaired.

  As the polymerization initiator, an energy ray-sensitive radical polymerization initiator is preferable, and examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2. -Methyl-1-phenyl-propan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), ethyl-4-dimethylaminobenzoate, 2 -Ethylhexyl-4-dimethylaminobenzoate can be used, but is not limited thereto.

  These polymerization initiators can be used alone or in combination of two or more according to the desired performance. Moreover, as a compounding quantity of a polymerization initiator, it is 0.05-20 mass% with respect to adhesive resin component whole quantity, Preferably it is 0.1-20 mass%. When the blending amount of the polymerization initiator is less than 0.05% by mass, the composition may not be cured sufficiently. On the other hand, if the blending amount of the polymerization initiator exceeds 20% by mass, the physical properties of the cured product will not be further improved, rather adversely affected and the economy may be impaired.

  In addition to the compound represented by the general formula (1) used in the present invention, the near infrared absorbing resin composition may contain another near infrared absorbing agent. Examples of the near infrared absorber include phthalocyanine dyes, cyanine dyes, anthraquinone dyes, dithiol dyes, and the like.

  The near-infrared absorbing resin composition may contain a neon cut pigment. A neon cut pigment | dye is a pigment | dye which absorbs the orange neon light which has a 580-600 nm wavelength body. Specifically, cyanine compounds, polymethine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quinone compounds, azaporphyrin compounds, azo compounds, azo chelate compounds, indonaphthol chelate compounds, dithiols Examples thereof include a metallurgy compound, an azomethine compound, and a xanthene compound.

Further, for the purpose of adjusting the color, a color correcting dye having a maximum absorption wavelength in the range of 380 to 780 nm may be contained in the near-infrared absorbing resin composition.
Examples of color correction dyes include azaporphyrin compounds, polymethine compounds, cyanine compounds, squarylium compounds, azomethine compounds, polymethine compounds, xanthene compounds, pyromethene compounds, isoindolinone compounds, quinacridone compounds, Examples include diketopyrrolopyrrole compounds, anthraquinone compounds, dioxazine compounds, and the like.

[Additive]
The near-infrared absorbing resin composition of the present invention may contain an appropriate additive depending on the purpose. Specific examples of additives include other near infrared absorbers, leveling agents, pigments, pigment dispersants, ultraviolet absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxides. Decomposing agent, filler, reinforcing material, plasticizer, lubricant, anticorrosive agent, rust inhibitor, emulsifier, mold demolding agent, fluorescent whitening agent, organic flameproofing agent, inorganic flameproofing agent, anti-dripping agent, melting Flow modifiers, antistatic agents, slipping agents, adhesion promoters, antifouling agents, surfactants, antifoaming agents, polymerization inhibitors, photosensitizers, surface modifiers, silane coupling agents, etc. Can be mentioned. In addition, when using a ultraviolet absorber, it cannot be overemphasized that this ultraviolet absorber is used in the quantity of the grade which does not inhibit the superposition | polymerization (hardening) reaction of composite microparticles and a polyfunctional polymerizable compound.

[Near-infrared absorbing laminate]
The near-infrared absorbing laminate according to the present invention is formed by laminating the near-infrared absorbing resin composition on a transparent substrate. Furthermore, in order to form a desired near-infrared absorbing performance, a laminate of the near-infrared absorbing composition by a known method, the thickness of the laminate is preferably about 1 to 50 μm, and the resin used is cured by active energy rays. In the case of a possible hard coat resin, the thickness of the laminate of the near-infrared absorbing composition is preferably 1 to 20 μm in consideration of sufficient resin hardness, scratch resistance, and curing shrinkage of the resin.

  Various known coating methods such as microgravure, gravure, die, curtain, lip, comma, and slot can be used as a known method for forming a near-infrared absorbing laminate.

  Although it does not specifically limit as a transparent base material, As a shape, a sheet-like, film-like, or plate-like transparent base material can be used. Examples of the material for the transparent substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); triacetyl cellulose (TAC); acrylic resins such as methyl methacrylate copolymers; styrene resins; polysulfone resins Polyethersulfone resin; polycarbonate resin; vinyl chloride resin; polymethacrylimide resin, glass plate and the like.

The transparent substrate may be subjected to easy adhesion treatment. For example, the PET film may be a film subjected to an easy adhesion treatment (easy adhesion PET film). The easy adhesion treatment is preferably performed on at least the surface on which the hard coat layer is provided. Examples of the easy adhesion treatment include a treatment for providing an easy adhesion layer and a treatment for applying a corona treatment to the substrate surface. Examples of the easy adhesion layer include a resin layer for easy adhesion.
Particularly preferred transparent substrates are polyethylene terephthalate (PET) films and triacetyl cellulose (TAC) films.

  In addition, if necessary, an antireflection function, an antiglare function, and an electromagnetic wave shielding function can be imparted, and this machine function forms a new laminate on the transparent base material of the near infrared absorbing film and / or Alternatively, a film having this function can be separately prepared and attached to a near-infrared absorbing film.

  Hereinafter, the present invention will be described in more detail with reference to production examples and examples. In addition, this invention is not limited at all by this manufacture example and an Example.

  The compounds (A) to (E) used in the examples are as follows.

(Production Example 1)
Production of compound (A):
To 100 parts of DMF, 10 parts of N, N, N ′, N′-tetrakis (p-aminophenyl) -p-phenylenediamine, 63 parts of cyclohexylmethyl iodide and 30 parts of potassium carbonate were added and reacted at 120 ° C. for 10 hours. . Next, the reaction solution is added to 500 parts of water, and the resulting precipitate is filtered, washed with 500 parts of methyl alcohol, dried at 100 ° C., and N, N, N ′, N′-tetrakis {p-di ( 24.1 parts of (cyclohexylmethyl) aminophenyl} -p-phenylenediamine were obtained.

  To 24.1 parts of the obtained N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine, 200 parts of acetonitrile and 7.9 parts of silver hexafluorophosphate were added. In addition, the mixture was reacted at 60 ° C. for 3 hours, and the produced silver was separated by filtration. Next, 200 parts of water was added to the filtrate, and the produced precipitate was filtered and dried to obtain 27.0 parts of compound (A).

(Production Example 2)
Production of compound (B):
18 parts of compound (B) was obtained in the same manner as in Production Example 1 except that cyclohexylmethyl iodide was replaced with 1-iodo-3-fluoropropane.

(Production Example 3)
Production of compound (C):
18 parts of Compound (C) was obtained in the same manner as in Production Example 1 except that cyclohexylmethyl iodide was replaced with isobutyl iodide.

(Production Example 4)
Production of compound (D):
23 parts of compound (D) was obtained in the same manner as in Production Example 1 except that silver hexafluorophosphate was replaced with silver bis (trifluoromethanesulfonyl) imidate.

(Production Example 5)
Production of compound (E):
10 parts of N, N, N ′, N′-tetrakis (p-aminophenyl) -p-phenylenediamine and 12 parts of cyclohexanecarboxaldehyde were added to 100 parts of toluene and reacted at 80 ° C. for 5 hours. Next, after cooling to room temperature, 3 parts of palladium carbon catalyst was added, hydrogen gas was blown in for 2 hours for hydrogenation reaction, 18 parts of 1-iodopropane and 15 parts of potassium carbonate were added, and reacted at 120 ° C. for 6 hours. It was. After filtering the above reaction solution, the filtrate was added to 500 parts of methyl alcohol, and the resulting precipitate was filtered, washed with 500 parts of methyl alcohol, dried at 100 ° C., and N, N, N ′, N′-tetrakis { 24 parts of p- (cyclohexylmethyl-n-propyl) aminophenyl} -p-phenylenediamine were obtained.

  To 24.1 parts of the obtained N, N, N ′, N′-tetrakis {p- (cyclohexylmethyl-n-propyl) aminophenyl} -p-phenylenediamine, 200 parts of acetonitrile and silver hexafluorophosphate 9 parts were added and reacted at 60 ° C. for 3 hours, and the resulting silver was filtered off. Next, 200 parts of water was added to the filtrate, and the produced precipitate was filtered and dried to obtain 27 parts of Compound (E).

(Dispersion 1)
For the compound (A) obtained in Production Example 1, a powder X-ray diffractometer (RINT2200, manufactured by Rigaku Corporation) using CuKα rays as an X-ray source was used, the tube voltage was 40 kV, the tube current was 20 mA, and the scanning range. (2θ) is 3 ° to 60 °, divergence slit is 1/2 °, scattering slit is 1/2 °, light receiving slit is 0.15 mm, sampling width is 0.02 °, and scanning speed is 4 ° / min. Measured under conditions. The measurement results are shown in FIG.
It was confirmed that the full width at half maximum taking the peak top from the baseline at the peak of the maximum intensity obtained by the measurement was 2θ = 0.21 °.

This compound (A) was dry pulverized with an automatic mortar AMN-200 (manufactured by Nissho Science Co., Ltd.) at a pestle of 100 rpm and a mortar of 6 rpm for 30 minutes to obtain a pulverized product. The obtained pulverized product was measured under the same conditions as described above using a powder X-ray diffractometer using CuKα rays as an X-ray source. The measurement results are shown in FIG.
As a result of the measurement, it was confirmed that the full width at half maximum taking the peak top of the maximum intensity from the baseline was 2θ = 9.2 °, and that the compound (A) was changed from the state A to the state B.

Next, 0.5 parts of the compound in the obtained state B, 1.9 parts of ethyl acetate, and 7.6 parts of methyl isobutyl ketone are added to a 50 ml glass container, and the mixture is stirred with a magnetic stirrer for 2 hours. Dispersion 1 was obtained. The compound (A) dispersed in the dispersion 1 was taken out and dried, and then measured using a powder X-ray diffractometer using CuKα rays as an X-ray source in the same manner as the above measurement conditions. The measurement results are shown in FIG.
As a result of the measurement, it was confirmed that the full width at half maximum taking the peak top of the maximum intensity from the baseline was 2θ = 0.25 °. From this, it was confirmed that the compound (A) was changed from the state B to the state A.

(Dispersion 2)
A dispersion 2 was obtained in the same manner as the dispersion 1, except that the compound (B) obtained in Production Example 2 was used in place of the compound (A).

(Dispersion 3)
A dispersion 3 was obtained in the same manner as the dispersion 1, except that the compound (C) obtained in Production Example 3 was used in place of the compound (A).

(Dispersion 4)
A dispersion 4 was obtained in the same manner as the dispersion 1, except that the compound (D) obtained in Production Example 4 was used in place of the compound (A).

(Dispersion 5)
A dispersion 5 was obtained in the same manner as the dispersion 1 except that the compound (E) obtained in Production Example 5 was used in place of the compound (A).

(Dispersion 6)
The compound (A) obtained in Production Example 1 was added as it was without dry grinding to 0.5 parts, 1.9 parts of ethyl acetate and 7.6 parts of methyl isobutyl ketone to a 50 ml glass container, and a magnetic stirrer. The mixture was stirred for 30 minutes to obtain a dispersion 6.

(Dispersion 7)
A dispersion 7 was obtained in the same manner as the dispersion 6 except that the compound (B) obtained in Production Example 2 was used in place of the compound (A).

(Dispersion 8)
A dispersion 8 was obtained in the same manner as the dispersion 6 except that the compound (C) obtained in Production Example 3 was used in place of the compound (A).

(Dispersion 9)
A dispersion 9 was obtained in the same manner as the dispersion 6 except that the compound (D) obtained in Production Example 4 was used in place of the compound (A).

(Dispersion 10)
A dispersion 10 was obtained in the same manner as the dispersion 6 except that the compound (E) obtained in Production Example 5 was used in place of the compound (A).

(Dispersion 11)
It was produced in the same manner as dispersion 1 except that methyl isobutyl ketone described in dispersion 1 was changed to toluene. It measured similarly using the powder X-ray-diffraction apparatus which used CuK (alpha) ray as the X-ray source, and it was confirmed that it was 2 (theta) = 0.22 and it was disperse | distributing in the dispersion liquid with the state B.

(Test Example 1)
The obtained Dispersion 1 was diluted with ethyl acetate to prepare a concentration of 100 mg / l, and the absorbance was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech).
Each dispersion prepared in the same manner was diluted with an ethyl acetate solvent, and the absorbance was measured. Table 1 shows the maximum absorption wavelength, the molar extinction coefficient and the half width at the maximum absorption wavelength.

  From Table 1, dispersions 1 to 5 obtained by the method for producing a dispersion according to the present invention exhibit a steep absorption band with a small molar absorption coefficient and a half width, and are excellent in near infrared absorption effect. It was shown that.

<Production of near-infrared absorbing laminate>
Example 1
Urethane acrylate resin UN-3320HA (Negami Kogyo Co., Ltd.-refractive index 1.493) 14.7 parts, silica fine particle dispersion ELCOM V-8802 (JGC Catalysts & Chemicals-solvent methyl isobutyl ketone-concentration 40.8% -particle diameter 12 nm-refractive index of about 1.46) 36.0 parts, dispersion 1 (dispersion 1) 40.7 parts, methyl isobutyl ketone 6.98 parts as a diluent solvent, Irgacure 184 as a photopolymerization initiator (BASF) 1.47 parts of BYK-3500 (manufactured by Big Chemie) as a leveling agent was mixed to obtain a near-infrared absorbing resin composition.
Next, the prepared near-infrared absorbing resin composition was bar-coated on a PET film A-4300 (100 μm thickness, manufactured by Toyobo Co., Ltd.) using a coating rod # 10, dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet light with a high-pressure mercury lamp to 150 mJ / Cm ^{2 was} irradiated to obtain a near-infrared absorbing laminate.

(Example 2)
A near-infrared absorbing laminate was obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was replaced with the dispersion 2.

(Example 3)
A near-infrared absorbing laminate was obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was replaced with the dispersion 3.

Example 4
A near-infrared absorbing laminate was obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was replaced with the dispersion 4.

(Example 5)
A near-infrared absorbing laminate was obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was replaced with the dispersion 5.

(Example 6)
200 parts of acrylic pressure-sensitive adhesive 1811L (manufactured by Soken Chemical Co., Ltd.), 20 parts of produced dispersion 1, 0.84 parts of isocyanate curing agent L-45 (manufactured by Soken Chemical Co., Ltd.), 30 parts of methyl isobutyl ketone as a diluent Were mixed to obtain a near-infrared absorbing resin composition.
Next, the produced near-infrared absorbing resin composition was laminated on a PET film A-4300 (100 μm thickness, manufactured by Toyobo Co., Ltd.) using an applicator and dried at 120 ° C. for 3 minutes to obtain a near-infrared absorbing laminate.

(Comparative Example 1)
A near-infrared absorbing resin composition and an infrared-absorbing resin composition laminate were obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was changed to the dispersion 6.

(Comparative Example 2)
A near-infrared absorbing resin composition and an infrared-absorbing resin composition laminate were obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was changed to the dispersion 7.

(Comparative Example 3)
A near-infrared absorbing resin composition and an infrared-absorbing resin composition laminate were obtained in the same manner as in Example 1, except that the dispersion 1 described in Example 1 was changed to the dispersion 8.

(Comparative Example 4)
A near infrared absorbing resin composition and an infrared absorbing resin composition laminate were obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was changed to the dispersion 9.

(Comparative Example 5)
A near-infrared absorbing resin composition and an infrared absorbing resin composition laminate were obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was changed to the dispersion 10.

(Comparative Example 6)
A near-infrared absorbing resin composition and an infrared-absorbing resin composition laminate were obtained in the same manner as in Example 6 except that the dispersion 1 described in Example 6 was changed to the dispersion 6.

(Comparative Example 7)
A near-infrared absorbing resin composition and an infrared absorbing resin composition laminate were obtained in the same manner as in Example 1 except that the dispersion 1 described in Example 1 was changed to the dispersion 11.

(Test Example 2)
Haze measurement was implemented as a scale which shows the transparency of the near-infrared absorption laminated body obtained in Examples 1-6 and Comparative Examples 1-7. For haze measurement, a haze meter NDH5000 (Nippon Denshoku Industries Co., Ltd.) was used. The smaller the haze value, the better the transparency. More preferably, the haze value is 2% or less.
Table 2 shows the haze values of the near-infrared absorbing laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 7.

  From Table 2, since Examples 1-6 which are the near-infrared absorption laminated bodies produced using the dispersion liquid manufactured by the method of this invention are small compared with Comparative Examples 1-7, since haze value is small, it is in transparency. It can be confirmed that it is excellent.

Before pulverization of the compound represented by the general formula (1) After dry grinding of the compound represented by the general formula (1) After dispersion of the compound represented by the general formula (1)

  The near-infrared absorbing resin composition produced by using the dispersion obtained by the method for producing a near-infrared absorbent dispersion of the present invention and the near-infrared absorbing laminate obtained by laminating this on a transparent substrate are transparent, It has excellent infrared absorption ability. Therefore, it can be used for various applications such as for PDP, automobile glass, and building glass.

Claims (2)

In the method for producing a near-infrared absorber dispersion obtained by dispersing a compound represented by the following general formula (1) in a diluent,
Crushing the compound represented by the general formula (1) in the state A by dry pulverization into a compound represented by the general formula (1) in the state B;
At least one diluent selected from the group consisting of the compound represented by the general formula (1) represented by the state B and methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3-methoxybutanol, and 3-methoxy-3-methylbutanol And a ratio of 0.01: 9.99 to 2: 8 in a mass ratio, and stirring for 10 minutes or more to form a compound represented by the general formula (1) in the state A. A method for producing a near-infrared absorbent dispersion, comprising:

(Wherein R _{1 to} R ₈ may be the same or different , n-propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, 3-fluoropropyl group, the following general formula: represents one selected from the group consisting of cyclohexyl alkyl group represented by (2), X ^- represents an anion).

(In formula (2), A represents an alkyl group having 1 to 10 carbon atoms.) X ⁻ in the compound represented by the general formula (1) is selected from the group consisting of hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imidate ion, and bis (fluorosulfonyl) imidate ion. The method for producing a near-infrared absorbent dispersion according to claim 1, which is a kind selected.

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