JP2008213258A - Near-infrared shielding laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared shielding laminate which has a near-infrared shielding layer free from the generation of breaks or cracks even when the layer is cleaned with alcohol, in manufacturing the near-infrared shielding laminate. <P>SOLUTION: The near-infrared shielding layer formed on one surface of a transparent resin substrate, contains a near-infrared absorption coloring matter, a binder resin and a microsolid particle which has not less than 1 μm average primary particle diameter and a smaller particle diameter than the coat thickness of the near-infrared shielding layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a near-infrared shielding laminate suitably used for an optical filter disposed on the display surface of a display that emits near-infrared rays, such as a plasma display. The infrared shielding laminate relates to a high-quality near-infrared shielding laminate in which no cracks or cracks are generated in the near-infrared shielding layer when the surface of the near-infrared shielding layer is cleaned with a chemical such as alcohol. It is.

  In recent years, large screen displays represented by plasma display panels and liquid crystal display panels have been rapidly spread in place of cathode ray tubes. In these plasma displays and liquid crystal displays, in addition to visible light emission necessary for color display, unnecessary near infrared light is emitted, thereby causing malfunction of peripheral electronic devices such as remote control devices using near infrared light. There was a problem. Therefore, for example, as described in Patent Documents 1 to 3 below, a near-infrared absorbing layer containing a near-infrared absorbing pigment is bonded to a display surface of these displays on a transparent substrate such as a glass substrate. An infrared shielding filter is formed and disposed on the display surface.

However, when the near-infrared shielding filter is manufactured, the surface of the near-infrared shielding layer is contaminated by, for example, contact with an operator, and therefore the near-infrared shielding layer surface is cleaned with a chemical such as alcohol. However, the near-infrared shielding layer formed by applying and drying a resin composition containing a near-infrared absorbing dye basically applies the resin composition and evaporates the solvent such as an organic solvent contained in the applied layer. Since it is formed by drying, the solvent resistance of the obtained near-infrared shielding layer is generally low. Therefore, the near-infrared shielding layer swells with a chemical such as alcohol, and when the near-infrared shielding layer is dried, There is a problem that cracks are likely to occur, and thus the production efficiency of the near infrared absorption filter is low.
JP 2001-133624 A JP 2002-138203 A WO2005 / 037940 International Publication Pamphlet

  The present invention was made to solve the above-mentioned problems in the prior art, that is, when manufacturing a near-infrared shielding laminate for a near-infrared absorbing filter, the surface of the near-infrared shielding layer, An object of the present invention is to provide a near-infrared shielding laminate that does not generate cracks and / or cracks in the cleaned near-infrared shielding layer even if it is cleaned using a chemical such as alcohol.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be effectively solved by including specific fine solid particles in the near-infrared shielding layer, and the present invention has been completed. It came to do.

〔但し式（Ｉ）中、ｎ及びｎ′は１〜８の整数を表す〕
で表されるアニオンをカウンターアニオンとして有するジイモニウム系化合物を含み、かつバインダー樹脂は、ガラス転移温度が６０℃〜１２０℃のアクリル系樹脂を含むことが好ましく、このようにすることによって、近赤外線遮蔽層の耐候性を向上させることができる。 The near-infrared shielding laminate of the present invention includes a transparent substrate and a near-infrared shielding layer laminated on one side of the transparent substrate,
The near-infrared shielding layer contains a near-infrared absorbing dye, a binder resin, and fine solid particles having an average primary particle diameter of 1 μm or more and smaller than the film thickness of the near-infrared shielding layer. It is characterized by.
In the near-infrared shielding laminate of the present invention, the difference between the refractive index of the binder resin and the refractive index of the fine solid particles is preferably 0.03 or less.
In the near-infrared shielding laminate of the present invention, the near-infrared absorbing dye contained in the near-infrared shielding layer has the following general formula (1):

[In the formula (I), n and n ′ represent an integer of 1 to 8]
It is preferable that the binder resin contains an acrylic resin having a glass transition temperature of 60 ° C. to 120 ° C. The weather resistance of the layer can be improved.

  According to the present invention, since the near-infrared shielding layer contains fine solid particles having a specific particle diameter, when the surface of the near-infrared shielding layer is cleaned with a chemical such as alcohol, the near-infrared shielding layer Therefore, cracks and cracks do not occur. Therefore, the near-infrared shielding laminate can be bonded to a transparent substrate such as a glass substrate to increase the efficiency when producing a near-infrared filter.

  Hereinafter, embodiments of the present invention will be described in detail.

"Anti-reflection / Near-infrared shielding laminate"
The near-infrared shielding laminate of the present invention comprises a transparent substrate and a near-infrared shielding layer laminated on one surface of the transparent substrate, and the near-infrared shielding layer comprises a near-infrared absorbing dye and A fine solid particle having an average primary particle size of 1 μm or more and smaller than the film thickness of the near infrared shielding layer, preferably a fine solid particle having an average primary particle size of 2 μm to 10 μm, and the near infrared ray It contains a binder resin that fixes the absorbing dye and the fine solid particles on the transparent substrate.

In the near-infrared shielding layer configured as described above, when the near-infrared shielding layer surface is cleaned using a chemical such as alcohol, the reason why the near-infrared shielding layer does not have cracks or cracks is not necessarily clear. It is considered as follows.
That is, by adding the fine solid particles, it is considered that the near-infrared shielding layer can be prevented from swelling with a solvent such as alcohol, and cracks and cracks can be prevented from occurring.
Even if the near-infrared shielding layer swells with a solvent such as alcohol and cracks or cracks occur when it is dried, the fine solid particles contained in the near-infrared shielding layer serve as a stopper and crack. It is thought that the expansion of cracks and cracks can be prevented.

The fine solid particles are added to prevent cracking or cracking of the near-infrared shielding layer due to solvent shock. When the average primary particle diameter of the fine solid particles in the near-infrared shielding layer exceeds the film thickness of the near-infrared shielding layer, the fine solid particles easily fall off from the near-infrared shielding layer, If the average primary particle size of the fine solid particles is less than 1 μm, it is impossible to prevent cracks and cracks from occurring in the near-infrared shielding layer.
The material of such fine solid particles is not particularly limited as long as it does not hinder the transparency of the near-infrared shielding layer. For example, inorganic fine solid particles such as silica and talc, silicone resin, acrylic resin Organic fine solid particles such as can be used.

  The addition amount of the fine solid particles in the near-infrared shielding layer depends on the binder resin and fine solid particles used, but is at least 0.01% by mass, preferably 0.05% by mass or more based on the binder resin. is there. Moreover, although the upper limit which can be added is based also on the haze value accept | permitted by the near-infrared shielding laminated body formed, in order to set it as the haze value of about 1.5% or less generally, it is 5 mass% or less. Preferably, it is 3% by mass or less, more preferably 1% by mass or less.

In the near-infrared shielding laminate, the difference between the refractive index of the binder resin and the refractive index of the fine solid particles is preferably 0.03 or less, more preferably 0.02 or less. More preferably, it is 0.01 or less.
By adjusting the refractive index of the binder resin and the refractive index of the fine solid particles as described above, the transparency of the near-infrared shielding layer can be improved, thereby using the near-infrared shielding laminate. Visibility of the near-infrared shielding filter was further improved.

As long as the near-infrared absorbing dye is a dye having a maximum absorption wavelength in the near-infrared (800 nm to 1100 nm) wavelength band, its type and composition are not limited, but dimonium is excellent in near-infrared absorption performance. It is preferable to use a near-infrared absorbing dye (hereinafter referred to as a first near-infrared absorbing dye).
The diimonium-based near-infrared absorbing dye has a strong absorption with a molar extinction coefficient of about 100,000 in the near-infrared region with a wavelength of 850 to 1100 nm and a slight absorption in the visible light region with a wavelength of 400 to 500 nm. However, it is an important component for obtaining a high transmittance in the visible light region because the visible light transmittance is superior to other near infrared absorbing dyes.

（式中、ｎ及びｎ′は１〜８の整数を示す）
で表されるアニオンをカウンターアニオンとして有するジイモニウム系化合物からなる近赤外線吸収色素、特に、一般式（１）においてｎ＝ｎ′＝１の場合に該当する、ビス（トリフルオロメタンスルホニル）イミド酸をカウンターアニオンとするジイモニウム系化合物は、従来用いられてきた過塩素酸イオン、弗化硼素酸イオン、ヘキサフルオロ砒酸イオン、ヘキサフルオロアンチモン酸塩等をカウンターアニオンとして有するジイモニウム系化合物と比べ、耐湿性と耐熱性が優れ、耐候性が格段に向上しているので、塗膜形成用の透明性樹脂成分として従来のものよりもガラス転移温度が低い透明性樹脂を使用することが可能となり、ハンドリングによる近赤外線遮蔽層の折れ、割れが防止された、即ち耐クラック性が良好な近赤外線遮蔽層を形成することが可能になり、また、得られる近赤外線遮蔽層の耐候性を向上させる効果がある。
このようなジイモニウム系化合物からなる近赤外線吸収色素としては、例えば、日本カーリット社製ＣＩＲ−１０８５、ＣＩＲ−ＲＬ等の市販のジイモニウム系化合物を利用することができる。 Among the diimonium-based near infrared absorbing dyes, the following general formula (1):

(In the formula, n and n ′ represent an integer of 1 to 8)
A near-infrared absorbing dye comprising a diimonium-based compound having an anion represented by the following formula as a counter anion, in particular, bis (trifluoromethanesulfonyl) imidic acid corresponding to the case where n = n ′ = 1 in the general formula (1) The diimonium compounds used as anions are more resistant to moisture and heat than conventional diimonium compounds containing perchlorate ions, boron fluoride ions, hexafluoroarsenate ions, hexafluoroantimonate, etc. as counter anions. Excellent weatherability and markedly improved weather resistance, it is possible to use a transparent resin with a glass transition temperature lower than that of conventional ones as a transparent resin component for coating film formation. The near-infrared shield that prevents the shielding layer from being broken or cracked, that is, has good crack resistance. It is possible to form a layer, also has the effect of improving the weather resistance of the obtained near infrared ray shielding layer.
As a near-infrared absorbing dye composed of such a diimonium compound, for example, commercially available diimonium compounds such as CIR-1085 and CIR-RL manufactured by Nippon Carlit Co., Ltd. can be used.

  The amount of the first near-infrared absorbing dye added to the near-infrared shielding layer depends on the thickness of the near-infrared shielding layer, but in order to achieve practically sufficient near-infrared shielding properties, It is preferable to control the average near infrared transmittance in the near infrared region of 900 to 1000 nm to be 2 to 10%. For this purpose, when the thickness of the near-infrared shielding layer is designed to be about 5 to 20 μm, the blending amount of the first near-infrared absorbing dye with respect to 100 parts by mass of the binder resin is about 0.5 to 5 parts by mass. It is preferable to control. If the blending amount of the first near-infrared absorbing dye is less than 0.5 parts by mass, it may be difficult to make the average near-infrared transmittance in the near-infrared region with a wavelength of 900 to 1000 nm 10% or less. If it exceeds 5 parts by mass, the near-infrared absorbing dye may segregate in the near-infrared shielding layer, or the near-infrared shielding layer may have insufficient visible light transparency.

In the near-infrared shielding layer, in addition to the above-mentioned diimonium-based near-infrared absorbing dye, a phthalocyanine-based dye, an organometallic complex-based dye, a cyanine-based dye having an absorption maximum at a wavelength of 750 to 950 nm and having no absorption in the visible light region It is preferable to contain a near-infrared absorbing dye (hereinafter referred to as a second near-infrared absorbing dye) comprising at least one selected from the dyes.
When a near-infrared shielding layer is formed using only the diimonium-based first near-infrared absorbing dye, it is necessary to add a large amount in order to obtain sufficient near-infrared shielding in the wavelength region of 850 nm to 900 nm. As a result, the weather resistance of the near-infrared shielding layer is lowered, which is not preferable.

  The mass ratio of the total mass of the first and second near-infrared absorbing dyes to the binder resin is preferably in the range of 1:99 to 1: 4, more preferably 1:49 to 1:24. . If this mass ratio is less than 1/99, it is necessary to increase the film thickness of the near-infrared shielding layer to 20 μm or more in order to obtain a high near-infrared shielding rate. When the mass ratio exceeds 1/4, in the process of forming the near-infrared shielding layer, in the process of forming the near-infrared shielding layer, there is a disadvantage that the shielding performance is lowered due to segregation of the near-infrared absorbing dye and the haze value is increased. May occur.

  Moreover, it is preferable that the compounding mass ratio of a 1st near-infrared absorption pigment | dye and a 2nd near-infrared absorption pigment | dye is 3: 2-29: 1, More preferably, it is 2: 1-9: 1. If this blending ratio is less than 3/2, the transmittance in the visible light region may be insufficient, and if it exceeds 29/1, the change in chromaticity of the near-infrared shielding layer over time is large. As a result, the weather resistance may decrease.

Furthermore, by adding a selective absorptive color material that makes the visible transmittance at a wavelength of 590 nm 10% or more lower than the visible light transmittance at wavelengths of 450 nm, 525 nm, and 620 nm in the near infrared shielding layer, a plasma display, etc. It is also possible to add a color correction function such as improving the contrast of the display.
The selective absorbing colorant that selectively absorbs a wavelength of 590 nm is not particularly limited as long as it does not adversely affect the diimonium-based near infrared absorbing dye and the second near infrared absorbing dye. For example, a quinacridone pigment Azomethine compounds, cyanine compounds, porphyrin compounds and the like are preferably used.

  The binder resin fixes the near-infrared absorbing dye and the fine solid particles on the transparent substrate, and has good wettability between the near-infrared absorbing dye and the fine solid particles. What is necessary is just to have sufficient transparency with respect to visible light, for example, acrylic resins, polyester resins, polyurethane resins, polyolefin resins, polystyrene resins, etc. can be used alone or in combination. it can. Among these binder resins, acrylic resins are preferably used because they have the effect of increasing the stability of the diimonium compounds.

（式中、Ｒは水素原子またはメチル基を表し、Ｘは６〜２５個の炭素原子を有する環状炭化水素基を表す）
上記一般式（II）中のＸで表される炭素原子数６〜２５の環状炭化水素基としては、シクロヘキシル基、メチルシクロヘキシル基、シクロドデシル基、ボルニル基、イソボルニル基等が例示できる。 Among the acrylic resins, a polymer obtained by polymerizing a monomer represented by the following general formula (II), or a monomer represented by the general formula (II) is 10% by weight or more, preferably A copolymer obtained by copolymerizing a monomer mixture containing 20% by weight, more preferably 30% by weight, is preferably used as the binder resin.

(Wherein R represents a hydrogen atom or a methyl group, and X represents a cyclic hydrocarbon group having 6 to 25 carbon atoms)
Examples of the cyclic hydrocarbon group having 6 to 25 carbon atoms represented by X in the general formula (II) include a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group, a bornyl group, and an isobornyl group.

  A thermoplastic film in which a near-infrared-absorbing dye, especially a diimonium-based near-infrared absorbing dye, is dispersed in a general acrylic resin such as methyl methacrylate resin. There is a problem that the binder resin is deteriorated due to the influence of moisture in the inside, and the near-infrared absorbing dye accompanying it, particularly the dimonium-based near-infrared absorbing dye, changes the chromaticity of the near-infrared shielding layer greatly. By using a polymer or copolymer obtained by polymerizing the monomer represented by the general formula (II) as an essential component, the durability of the diimonium-based near infrared absorbing dye under high temperature and high humidity can be improved. Can be improved.

Moreover, it is preferable that the glass transition point of the said binder resin is 60 to 120 degreeC, Preferably it is 60 to 100 degreeC.
When the glass transition point is less than 60 ° C., when exposed to a high temperature of 80 ° C. or more for a long time, the binder resin becomes significantly softened, and at the same time, the near-infrared absorbing dye in the near-infrared shielding layer, especially the diimonium-based near infrared absorption. It is not preferable because the dye is susceptible to alteration and the long-term heat resistance is affected, such as the chromaticity of the near-infrared shielding layer is greatly changed or the near-infrared shielding property is lowered. When the glass transition point is 60 ° C. or higher, it is possible to suppress the deterioration of the near-infrared absorbing dye, particularly the diimonium-based near infrared absorbing dye, due to heat.
On the other hand, if the glass transition temperature exceeds 120 ° C., the near-infrared shielding layer becomes hard and brittle, and it is not preferable because it causes practical problems such as a decrease in bending resistance and easy cracking due to handling.

As the transparent substrate, various materials such as a transparent plastic plate, a transparent plastic film, and a glass plate can be used, and it is preferable to use a transparent plastic film as the transparent substrate. In particular, the near-infrared shielding layer is preferably formed on a transparent plastic film, and in particular, it is preferably formed on a transparent polyester resin film. The transparent polyester film is excellent in terms of solvent resistance, cost, productivity, and the like.
The polyester-based resin film is conventionally known in a solvent capable of dissolving or dispersing the first and second near-infrared absorbing dyes, the selective absorbing colorant, the fine solid particles, and the binder resin. When a near-infrared shielding resin composition obtained by dissolving and dispersing by the method is applied, in order to impart practically high adhesion, an adhesive improvement layer comprising an organic resin component is applied. preferable. When the adhesion improving layer is not applied, the near-infrared shielding layer may easily peel off at the interface between the polyester resin film and the near-infrared shielding layer.

In order to suppress the chromaticity change of the near-infrared shielding layer, the adhesion improving layer is preferably composed mainly of an organic resin component that does not contain a reactive curing agent. The organic resin component that does not contain a reactive curing agent is not particularly limited as long as high practical adhesion between the near-infrared shielding layer and the polyester-based resin film is obtained. For example, an acrylic resin and an acrylic-melanin co-polymer Examples thereof include a simple substance such as a polymer resin, an acrylic-polyester copolymer, a polyester resin, or a mixture thereof. When a reactive curing agent such as an isocyanate compound or a blocked isocyanate compound is contained in the adhesion improving layer, the diimonium compound in the near infrared shielding layer is exposed to a high temperature of 80 ° C. or longer for a long time. This is not preferable because it reacts with the reactive curing agent and is susceptible to alteration, and the chromaticity of the near-infrared shielding layer is greatly changed, or the near-infrared shielding properties are affected.
Moreover, in order to prevent the film winding property improvement, blocking and scratching in the coating process, fine particles such as silica fine particles and talc may be appropriately added.

  The near-infrared shielding laminate is a conventional solvent that can dissolve or disperse the first and second near-infrared absorbing dyes, the selective absorbing colorant, the fine solid particles, and the binder resin. A near-infrared shielding composition obtained by dissolving and dispersing by a known method is applied onto the transparent substrate using a normal coating apparatus such as a bar coater, a gravure reverse coater, or a slit die coater. The solvent is dried and evaporated so that the residual solvent is 5% by mass or less, preferably 1% by mass or less.

The organic solvent is capable of sufficiently dissolving near-infrared absorbing dyes and is not particularly limited as long as the affinity between the binder resin and the fine solid particles is good. For example, acetone, A ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, toluene, ethyl acetate, butyl acetate and the like are preferably used, and can be used alone or in combination as appropriate.
In preparing the near-infrared shielding composition, the fine solid particles preferably have a spherical shape, preferably a true spherical shape. In this way, the fine solid-particle particles are contained in the near-infrared shielding composition. Is preferable because it can be easily dispersed.

  A diimonium compound having such a structure and having an anion represented by the general formula (I) as a counter anion as the diimonium-based near infrared absorbing dye has a glass transition temperature of 60 ° C. to 120 ° C. as the binder resin. When the near-infrared shielding laminate using an acrylic resin at 0 ° C. contains the fine solid particles in the near-infrared shielding layer, the near-infrared shielding layer surface is cleaned using a chemical such as alcohol. No cracks or cracks are generated, and since a specific near-infrared absorbing dye is contained in a specific binder resin, the average transmittance at a wavelength of 850 to 1000 nm is 10% or less, and a high transmittance in the visible light region. And has a high near-infrared shielding property with an average transmittance of 10% or less at a wavelength of 850 to 1000 nm, and also has good weather resistance. For example, when stored for 500 hours in an atmosphere of 60 ° C.-90% relative humidity, the amount of change in chromaticity x and y before and after storage is both ± 0.010 or less, and 80 ° C.-dry atmosphere The amount of change in chromaticity x and y before and after storage for 500 hours below is ± 0.010 or less, and stable under little high-temperature and high-humidity environment and high-temperature environment. It has optical properties and excellent weather resistance.

  Further, the near-infrared shielding laminate according to this embodiment is applied to a transparent hard substrate such as a glass plate or a transparent hard resin substrate when used as an optical filter for plasma display or a near-infrared shielding filter for optical products. In order to be used by pasting, an adhesive layer made of a transparent adhesive composition or a transparent adhesive composition is appropriately formed on the near-infrared shielding layer or on the transparent resin film on the back side thereof. It may be.

  The near-infrared shielding laminate of the present invention includes a hard coat layer, an antireflection layer having an antireflection function, an electromagnetic wave shielding layer having an electromagnetic wave shielding function, an ultraviolet ray, in addition to the near infrared shielding layer and the adhesive layer. A functional layer such as an ultraviolet shielding layer having a shielding function is formed in multiple layers, for example, on the near infrared shielding layer, between the near infrared shielding layer and the transparent resin film, or on the other surface of the transparent resin film (the near It can be laminated on the surface opposite to the surface on which the infrared shielding layer is laminated.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the outline | summary of the measurement of the optical characteristic (spectral transmittance) of the near-infrared shielding laminated body which concerns on each Example and a comparative example, a weather resistance test, and a knick-proof test is as follows.
"Measurement of optical characteristics (spectral transmittance)"
Using a spectrophotometer V-570 manufactured by JASCO Corporation, the transmittance of each sample at wavelengths of 450 nm, 525 nm, 590 nm, 620 nm, 850 nm, 900 nm, 950 nm, and 1000 nm was measured using the indoor air transmittance as a comparative control. did. Moreover, the haze value of the laminated body was measured using JASCO Corporation full automatic haze meter NDH2000.
"Weather resistance test"
Using a color analyzer TOPSCAN TC-1800-Mk II manufactured by Tokyo Denshoku Industries Co., Ltd. (standard light; light source, 2 degree field of view), the chromaticity x, y of each sample before and after the following high temperature and high humidity test and heat resistance test Was measured.
(High temperature and high humidity test)
Each sample was placed in a constant temperature and humidity tester set to 60 ° C. and a relative humidity of 90% and held for 500 hours.
(Heat resistance test)
Each sample was placed in a thermostat set to 80 ° C.-dry atmosphere and held for 500 hours.
"Alcohol resistance test"
Alcohol resistance of each sample was prepared by applying a transparent adhesive layer to the back side of the near-infrared shielding laminate coated with a near-infrared shielding layer, and pasting it on soda lime glass having a thickness of 2 mm. After storing for 30 minutes in a dryer set to 1 and leaving it to stand at room temperature for 1 hour, 20 μl of ethanol is dropped onto the surface of the near-infrared shielding layer, and the number of cracks in the coating film formed on the dropping mark is visually observed. evaluated.

Example 1
(Preparation of near-infrared shielding composition)
2 parts by mass of CIR-1085 manufactured by Nippon Carlit Co., Ltd., which is a diimonium salt having bis (trifluoromethanesulfonyl) imidic acid, which is one of anions represented by chemical formula (1), as a counter anion 1 part by mass of Exex IR-10A manufactured by Nippon Shokubai Co., Ltd., which is a phthalocyanine-based dye as the second near-infrared absorbing dye, and IR-G205 manufactured by Nippon Shokubai Co., Ltd. (resin solid content: 30%) TM-X-1 (average primary particle size: 2 μm, spherical) made by Toagosei Chemical Co., Ltd. as fine solid particles mainly composed of PMMA and glass transition temperature of 100 ° C. Part was dissolved and mixed in 46.9 parts by mass of methyl ethyl ketone to prepare a near-infrared shielding composition.

(Preparation of near-infrared shielding laminate)
Using O-320E100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd. as the polyester resin film, the near infrared shielding composition is applied on one side so that the film thickness after drying is 10 μm, The near-infrared shielding laminate was produced by evaporating in a drying oven so that the residual solvent amount was 1% by mass to form a near-infrared shielding layer.
Tables 1 to 3 show the measurement results of the optical properties of the near-infrared shielding laminate at the initial stage and after each test, and the results of the alcohol resistance test.

Example 2
In the near-infrared shielding composition of Example 1, 0.5 part by mass of TAP-2 manufactured by Yamada Chemical Industry was added as a coloring material that selectively absorbs 590 nm, and methyl ethyl ketone was changed to 46.4 parts by mass. Except for this, a near-infrared shielding laminate was produced in the same manner as in Example 1.
Tables 1 to 3 show the measurement results of the optical properties of the near-infrared shielding laminate at the initial stage and after each test, and the results of the alcohol resistance test.

Example 3
2 parts by mass of CIR-RL manufactured by Nippon Carlit Co., Ltd., which is a diimonium salt having bis (trifluoromethanesulfonyl) imidic acid, which is one of anions represented by chemical formula (1), as a counter anion 0.1 part by mass of NK-5060 manufactured by Hayashibara Biochemical Laboratories Co., Ltd., which is a cyanine dye as the second near-infrared absorbing dye, and IR-G207 manufactured by Nippon Shokubai Co., Ltd. (resin solid content) 30%, glass transition temperature 75 ° C.) 50 parts by mass, TM-X-1 (average primary particle diameter: 2 μm, spherical) manufactured by Toagosei Chemical Co., Ltd. as fine solid particles mainly composed of PMMA 01 parts by mass is dissolved and mixed in 47.89 parts by mass of methyl ethyl ketone to prepare a near-infrared shielding resin composition. A near-infrared shielding laminate was produced in the same manner as in Example 1 except that O-320E100 manufactured by Reester Film Co., Ltd. was used.
The measurement results of the optical properties of the near-infrared shielding laminate of Example 3 at the initial stage and after each test, and the results of the alcohol resistance test are shown in Tables 1 to 3.

Comparative Example 1
A laminate of Comparative Example 1 was produced in the same manner as in Example 1 except that fine solid particles containing PMMA as a main component were not added.
Tables 1 to 3 show the measurement results of the optical properties of the near-infrared shielding laminate of Comparative Example 1 at the initial stage and after each test, and the results of the alcohol resistance test.

〔Evaluation results〕
The near-infrared shielding laminates of Examples 1 to 3 had excellent alcohol resistance without causing cracks or cracks in the near-infrared shielding layer in the alcohol resistance test.
Moreover, it has a high visible light region transmittance before and after the weather resistance test and a high near-infrared shielding property in the region of 850 to 1000 nm. In any of the test items of the high temperature and high humidity test and the heat resistance test, chromaticity, x , Y were both 0.005 points or less, and had excellent durability.
On the other hand, the near-infrared shielding laminate of Comparative Example 1 showed excellent durability equivalent to that of Examples 1 to 3, but in the alcohol resistance test, the near-infrared absorbing layer had many cracks and cracks. Produced and inferior in alcohol resistance.

  The near-infrared shielding laminate of the present invention is a crack in the near-infrared shielding layer that occurs when a stain on the near-infrared shielding layer produced in the process of producing a near-infrared absorption filter using this is cleaned with a chemical such as alcohol. Generation of cracks and cracks can be prevented, and a near-infrared absorption filter can be produced stably and efficiently, and has high practicality.

Claims (3)

Including a transparent substrate and a near-infrared shielding layer laminated on one side of the transparent substrate,
The near-infrared shielding layer contains a near-infrared absorbing dye, a binder resin, and fine solid particles having an average primary particle diameter of 1 μm or more and smaller than the film thickness of the near-infrared shielding layer. A near infrared shielding laminate.   The near-infrared shielding laminated body of Claim 1 whose difference of the refractive index of the said binder resin and the refractive index of the said fine solid particle is 0.03 or less. The near-infrared absorbing dye contained in the near-infrared shielding layer has the following general formula (1):

[In the formula (I), n and n ′ represent an integer of 1 to 8]
The near-infrared shielding laminate according to claim 1, wherein the binder resin contains an acrylic resin having a glass transition temperature of 60 ° C. to 120 ° C. body.