JP2008216568A - Antireflective/near ir light blocking laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflective/near IR light blocking laminate which produces no winding wrinkle and no struck trace or the like due to winding tightness when being wound up and has stable high quality and to provide its manufacturing method. <P>SOLUTION: When an antireflection layer and a near IR light blocking layer are formed on each of both surfaces of a transparent base material to form a laminate, the near IR light blocking layer is formed by using a near IR light absorbing dyestuff, a binder resin and also minute solid particles which have an average primary grain size of ≥1 μm and are smaller than thickness of the near IR light blocking layer. The laminate can be wound up without producing trouble. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antireflection / near-infrared shielding laminate suitably used for an optical filter disposed on a display surface of a display that emits near-infrared rays, such as a plasma display, and a method for producing the same, and more particularly In other words, when manufacturing this anti-reflection / near-infrared shielding laminate, a high-quality anti-reflection / near-infrared shielding laminate that does not cause defects due to curling or tightening and has a stable quality. And a manufacturing method thereof.

In recent years, large-screen displays such as plasma display panels have rapidly spread in place of CRTs. On the display surface of these displays, there is an antireflection layer formed of a single layer or multiple layers thin film combining a low refractive index and a high refractive index material for the purpose of preventing the reflection of outside light such as room lighting and sunlight. It is common practice to arrange stacked optical filters.
In addition, in the plasma display and liquid crystal display, in addition to visible light emission necessary for color display, unnecessary near infrared light is emitted, which causes malfunction of peripheral electronic devices such as a remote control device using the near infrared light. Therefore, an optical filter in which a near-infrared absorbing layer containing a near-infrared absorbing dye is laminated on the display surface of these displays is also performed.

In recent years, various proposals have been made on anti-reflection / near-infrared shielding laminates that combine the anti-reflection function and near-infrared shielding function to reduce the cost of the filter member and to simplify the process. Has been made.
For example, in Patent Documents 1 to 3 below, an antireflection layer is provided on one main surface of a transparent resin film, and a near-infrared absorbing dye such as a diimonium-based material and a thermoplastic resin as a binder resin on the other main surface of the transparent resin film. An antireflection / infrared shielding laminate in which a near infrared shielding layer formed by applying and drying a near infrared shielding composition containing a resin is laminated is described.
Patent Document 4 listed below describes a near-infrared shielding laminate that is formed using a specific near-infrared absorbing dye and a specific binder resin and has excellent weather resistance.

However, the surface of the antireflection layer and the surface of the near-infrared shielding layer are both highly smooth, so that they are in close contact with each other and become very slippery in the roll-up process. Costs in materials and processes are increased, such as winding up while sticking a protective film on the surface of the near-infrared shielding layer in order to prevent defects due to curling and tightening on the surface of the near-infrared shielding laminate. It was a factor.
JP 10-156991 A JP-A-11-295506 Japanese Patent Laid-Open No. 11-344935 WO2005 / 037940 International Publication Pamphlet

  The present invention has been made to solve the above-mentioned problems in the prior art, that is, the occurrence of defects due to winding and tightening during the production of a roll-up body of an antireflection / near-infrared shielding laminate. It is an object of the present invention to provide an anti-reflection / near-infrared shielding laminate capable of forming a high-quality rolled-up body having a stable quality and a method for producing the same.

〔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い。
本発明の反射防止・近赤外線遮蔽性積層体の製造方法は、透明基材の一面側に反射防止層を積層し、前記透明基材の他の面側に近赤外線遮蔽層を積層するに際し、前記近赤外線遮蔽層を、近赤外線吸収色素と、バインダー樹脂と、平均１次粒子径が１μｍ以上であって、かつ、前記近赤外線遮蔽層の膜厚よりも小さい微小固体粒子とを含有する塗料を塗布し、乾燥して形成して積層体を製造することを特徴とするものである。 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.
The antireflection / near-infrared shielding laminate of the present invention includes a transparent base material, an antireflection layer laminated on one side of the transparent base material, and a near side laminated on the other side of the transparent resin base material. Including an infrared shielding layer,
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 antireflection / 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.
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 manufacturing method of the anti-reflection / near-infrared shielding laminate of the present invention is a method of laminating an anti-reflection layer on one side of a transparent substrate and laminating a near-infrared shielding layer on the other side of the transparent substrate. The near-infrared shielding layer comprises a near-infrared absorbing dye, a binder resin, and a fine solid particle having an average primary particle diameter of 1 μm or more and smaller than the film thickness of the near-infrared shielding layer. The laminate is manufactured by coating and drying.

  According to the present invention, since the near-infrared shielding layer contains fine solid particles having a specific particle size, the adhesion between the surface of the antireflection layer and the surface of the near-infrared shielding layer is reduced, and the roll shape is reduced. It is possible to wind smoothly in the winding process, thereby preventing the occurrence of defects caused by winding wrinkles and tightening during the production of the anti-reflection / near-infrared shielding laminate, and the quality is stable. It becomes possible to provide a high-quality anti-reflection / near-infrared shielding laminate at low cost.

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

"Anti-reflection / Near-infrared shielding laminate"
The antireflection / near-infrared shielding laminate of the present invention was laminated on the transparent base, the antireflection layer laminated on one surface of the transparent base, and the other main part of the transparent resin base. The near-infrared shielding layer includes a near-infrared shielding layer, and the near-infrared shielding layer has a near-infrared absorbing dye, an average primary particle diameter of 1 μm or more, and a fine solid smaller than the film thickness of the near-infrared shielding layer. It contains particles, preferably fine solid particles having an average primary particle size of 2 μm to 10 μm, and a binder resin for fixing the near-infrared absorbing dye and the fine solid particles on the transparent substrate.

  The fine solid particles contained in the near-infrared shielding layer reduce the smoothness of the surface of the near-infrared shielding layer, and wind up the antireflection / near-infrared shielding laminate in a roll shape. In addition, the surface of the near-infrared shielding layer and the surface of the antireflection layer are prevented from coming into close contact with each other, so that defects caused by curling and tightening, for example, dents (surface irregularities) due to air entrapment are prevented. Is to do.

  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 the near infrared shielding layer. On the other hand, when the average primary particle diameter of the fine solid particle diameter is less than 1 μm, the surface of the near-infrared shielding layer and the surface of the antireflection layer are sufficiently prevented from being in close contact during the formation of the wound body. It is not possible to prevent the occurrence of defects due to curling and tightening.

  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, Organic fine solid particles such as acrylic resin can be used.

  The addition amount of the fine solid particles in the near-infrared shielding layer depends on the type and composition of the binder resin used and the fine solid particles, but is 0.01% by mass or more, preferably 0.05% by mass with respect to the binder resin. % Or more. Moreover, although the upper limit of the amount of addition depends on the haze value allowed for the formed near-infrared shielding laminate, it is generally 5% by mass or less in order to obtain a haze value of about 1.5% or less. Preferably, it is 3 mass% or less, More preferably, it is 1 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, and still more preferably. 0.01 or less.
By adjusting the difference between 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. The visibility of the optical filter using the infrared shielding laminate is improved.

The near-infrared absorbing dye may be a dye having a maximum absorption wavelength in the near-infrared (800 nm to 1100 nm) wavelength band, and is not particularly limited. It is preferable to use a near infrared absorbing dye (hereinafter sometimes 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 a useful component for obtaining a high transmittance in the visible light region because the visible light permeability is superior to other near infrared absorbing dyes.

（式中、ｎ及びｎ´は、１〜８の整数を表す）
で表され、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を用いることが好ましく、特に、一般式（Ｉ）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て、耐湿性と耐熱性が優れており、かつ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、即ち耐クラック性が良好な近赤外線吸収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を有する。
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が利用可能である。 Among the diimonium-based near-infrared absorbing dyes, the following general formula (I):

(In the formula, n and n ′ represent an integer of 1 to 8)
It is preferable to use a near-infrared absorbing dye composed of a diimonium-based compound having an anion as a counter anion, and in particular, bis (trifluoromethanesulfonyl), which corresponds to the case where n = n ′ = 1 in the general formula (I) ) Diimonium compounds with imido acid as counter anion are compared with diimonium compounds with perion acid ions, boron fluoride ions, hexafluoroarsenate ions, hexafluoroantimonate, etc. as counter anions. In addition, since the moisture resistance and heat resistance are excellent and the weather resistance is remarkably improved, a transparent resin having a glass transition temperature lower than the conventional one is used as a transparent resin component for forming a coating film. It is possible to prevent the near-infrared shielding layer from being broken or cracked by handling, and Crack resistance becomes possible to form a good near infrared ray absorbing layer, also has the effect of improving the weather resistance of the obtained near infrared ray shielding layer.
As the 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 that the average near-infrared transmittance in the near-infrared region of 900 to 1000 nm is controlled 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.

As the second near-infrared absorbing dye used in combination with the dimonium-based near-infrared absorbing dye, a phthalocyanine dye, an organometallic complex dye, cyanine having an absorption maximum at a wavelength of 750 to 950 nm and no absorption in the visible light region It is preferable to use one or more selected from the system dyes.
When a near-infrared shielding layer is formed using only a diimonium-based near-infrared absorbing dye, a large amount of addition is necessary to obtain sufficient near-infrared shielding in the wavelength region of 850 nm to 900 nm. The weather resistance of the near infrared shielding layer may be lowered.

  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. is there. When the mass ratio is less than 1/99, in order to obtain a high near-infrared shielding rate, it is necessary to increase the thickness of the near-infrared shielding layer to 20 μm or more. Formation of the layer can be difficult. On the other hand, if the mass ratio exceeds 1/4, there may be a disadvantage that the shielding performance is lowered and the haze value is increased due to segregation of the near-infrared absorbing dye in the process of forming the near-infrared shielding layer.

  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.

In the near-infrared shielding layer of the antireflective / near-infrared shielding laminate of the present invention, the selective absorptive color that further lowers the visible transmittance at a wavelength of 590 nm by 10% or more than the visible light transmittance at wavelengths of 450 nm, 525 nm, and 620 nm. By adding a material, it is possible to add a color tone correction function such as improving the contrast of a display such as a plasma 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 first infrared absorbing dye and the second near-infrared absorbing dye. For example, quinacridone pigments, 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 resin film, has good wettability to the near-infrared absorbing dye and the fine solid particles, and For example, an acrylic resin, a polyester resin, a polyurethane resin, a polyolefin resin, or a polystyrene resin can be used alone or in combination, as long as it has sufficient transparency to visible light. The resin is suitable for enhancing the stability of the diimonium compound.

一般式（ＩＩ）中のＸは炭素数６〜２５の環状炭化水素基を表し、その具体例としてシクロヘキシル基、メチルシクロヘキシル基、シクロドデシル基、ボルニル基、イソボルニル基等をあげることができる。また、式（ＩＩ）中、Ｒは水素原子またはメチル基を表す。 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 mass or more, preferably It is preferable to use a copolymer obtained by copolymerizing a monomer mixture containing 20% by mass or more, more preferably 30% by mass or more, as a binder resin.

X in the general formula (II) represents a cyclic hydrocarbon group having 6 to 25 carbon atoms, and specific examples thereof include a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group, a bornyl group, and an isobornyl group. In the formula (II), R represents a hydrogen atom or a methyl group.

  In a near-infrared shielding layer formed by dispersing a near-infrared absorbing dye, in particular, a diimonium-based near-infrared absorbing dye, in a general acrylic resin such as methyl methacrylate resin, it is used for a long time under high temperature and high humidity. When exposed, the binder resin deteriorates due to the influence of moisture in the environment, which is accompanied by alteration of near-infrared absorbing dyes, especially diimonium-based near-infrared absorbing dyes, and thereby the color of the near-infrared shielding layer. The diimonium-based near-infrared light can be obtained by using a polymer obtained by polymerizing the monomer or copolymer represented by the general formula (II) as an essential component. The durability of the absorbing dye under high temperature and high humidity can be improved.

Moreover, it is preferable that the glass transition point of the said binder resin is 60 degreeC or more and 120 degreeC or more, More preferably, it is 60 degreeC or more and 100 degrees C or less.
When the glass transition point is less than 60 ° C., when exposed to a high temperature of 80 ° C. or higher for a long time, the binder resin becomes significantly softened, and at the same time, a near-infrared absorbing dye in the near-infrared shielding layer, particularly diimonium-based near infrared rays. Absorbing dyes are susceptible to alteration, and the chromaticity of the near-infrared shielding layer may change greatly, and the near-infrared shielding properties may be affected, which may affect long-term heat resistance. 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, when the glass transition temperature exceeds 120 ° C., the near-infrared shielding layer is hard and brittle, and may cause practical problems such as easy bending due to a decrease in bending resistance or handling. Absent.

The antireflection layer uses a refractive index difference between a plurality of thin films to reduce reflection by optical interference. For example, a multilayer antireflection layer or a low refractive index thin film is used as a single layer. A single-layer type antireflection layer can be exemplified. In the multilayer antireflection layer, for example, a thin film layer such as a high refractive index layer / low refractive index layer, a middle refractive index layer / high refractive index layer / low refractive index layer, etc. is sequentially laminated in order from the transparent substrate side. There is something.
The outermost layer of the antireflection layer is preferably provided with antifouling properties. In order to impart antifouling properties, for example, an antireflection layer such as silicone oil or a coating for forming an antireflection layer containing a silane compound having a fluorine group is used. For example, an antireflection layer is formed using a sol-gel method. To do.

A hard coat layer may be provided between the transparent substrate and the antireflection layer in order to improve the hardness of the surface of the transparent substrate and to prevent scratches caused by scratching a pencil or the like.
In the hard coat layer, inorganic fine particles are preferably dispersed and mixed in order to improve adhesion to the antireflection layer. The inorganic fine particles are not particularly limited as long as they become sufficiently transparent without impairing the transparency when the hard coat layer is formed, but improve the adhesion surface with the antireflection layer. For this purpose, it is preferable to add silica-based fine particles such as silica and silica sol, and in order to impart conductivity, it is preferable to add conductive fine particles such as ATO and ITO.

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 more preferably formed on a transparent polyester-based resin film. The transparent polyester film is excellent in terms of tolerance, cost, and productivity.
In addition, in the polyester resin film, the first and second near-infrared absorbing dyes, the selective absorbing colorant, the fine solid particles, and a solvent that can dissolve or disperse the binder resin are conventionally known. In the case of applying the near infrared shielding resin composition obtained by dissolving and dispersing by the method, an adhesion improving layer composed of an organic resin component is also arranged between them in order to improve the adhesion of both considerations. It is preferable. When the adhesion improving layer is not applied, the near-infrared shielding layer may 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 preferably contains an organic resin component not containing a reactive curing agent as a main component. The organic resin component that does not contain a reactive curing agent is not particularly limited as long as practically sufficiently high adhesion between the near-infrared shielding layer and the polyester-based resin film can be obtained. For example, an acrylic resin, an acrylic-melanin Examples thereof include a simple substance such as copolymer resin, acrylic-polyester copolymer, polyester resin, or a mixture thereof. In the case where a reactive curing agent such as an isocyanate compound or a blocked isocyanate compound is contained in the adhesion improving layer, the diimonium-based near infrared ray in the near infrared ray shielding layer when exposed to a high temperature of 80 ° C. or longer for a long time. Absorbing dye may react with the reactive curing agent and undergo alteration, resulting in a significant change in chromaticity of the near-infrared shielding layer, a decrease in near-infrared shielding, and long-term weather resistance. May have an effect.

  Although there is no restriction | limiting in particular in the thickness of the said transparent base material, Usually, it is preferable that it is 25 micrometers-200 micrometers. In addition, the transparent base material may be added with an ultraviolet absorber, an antioxidant, a refractory agent or the like for suppressing the fading deterioration of the near infrared absorbing dye, and a coating process. In order to improve the winding property of the film, and to prevent the occurrence of blocking and scratching, it is possible to appropriately add fine particles such as silica fine particles and talc.

  The diimonium-based near-infrared absorbing dye prepared as described above is, for example, a diimonium compound containing an anion represented by the general formula (I) as a counter anion, and a glass transition temperature of 60 ° C. as the binder resin. The near-infrared shielding laminate formed using an acrylic resin at ˜120 ° C. contains the fine solid particles in the near-infrared shielding layer. Generation can be prevented, 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 In addition, it 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 a weather resistance. The amount of change in chromaticity x and y before and after storage in an atmosphere of 60 ° C. and 90% relative humidity for 500 hours is ± 0.010 or less, and For example, the amount of change in chromaticity x and y before and after being left for 500 hours in a dry atmosphere at 80 ° C. is ± 0.010 or less, even in a high temperature and high humidity environment and a high temperature environment. It has stable optical properties with little change in chromaticity and has excellent weather resistance.

  In the antireflection / near-infrared shielding laminate of the present invention, a functional layer such as an electromagnetic shielding layer having an electromagnetic shielding function or an ultraviolet shielding layer having an ultraviolet shielding function, for example, on the near infrared shielding layer, Or you may laminate | stack between the said near-infrared shielding layer and the said transparent base material.

"Production method of anti-reflection and near-infrared shielding laminate"
The antireflection / near-infrared shielding laminate of the present invention having the above-described configuration can be produced, for example, as follows.
First, a hard coat layer for an antireflection layer is laminated on one surface of a transparent substrate by a known method, and an antireflection layer is laminated on the hard coat layer. Next, the near-infrared shielding obtained by dissolving and dispersing the first and second near-infrared absorbing dyes, the selective absorbing colorant, the fine solid particles, and the binder resin in a solvent that can be dissolved or dispersed. The adhesive composition is coated on the other surface of the transparent substrate using a normal coating apparatus such as a bar coater, gravure reverse coater, slit die coater, etc., and the residual solvent is 5% by mass or less, preferably 1 Dry to less than mass%.

  When producing an antireflection / near infrared shielding laminate comprising an antireflection layer formed on one surface of a transparent substrate and a near infrared shielding layer coated on the other surface, In order to improve the hardness and prevent scratches due to scratches such as pencils, it is preferable to provide a hard coat layer that is cured by an active energy ray such as ultraviolet rays between the antireflection layer and the transparent substrate. In order to prevent deterioration of the near-infrared absorbing dye having low weather resistance against energy rays, it is preferable to form the antireflection layer and the near-infrared shielding layer in this order as the coating order.

As the solvent in the near-infrared shielding composition, those that can sufficiently dissolve near-infrared absorbing dyes, and those that are particularly limited if the affinity between the binder resin and the fine solid particles is good. However, for example, ketone solvents such as acetone, 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-state particles are contained in the near-infrared shielding composition. The particles can be easily dispersed.

  According to the above production method of the anti-reflection / near infrared shielding laminate of the present invention, the smoothness of the near infrared shielding layer surface is low, and thus the adhesion is low, Anti-reflective / near-infrared shielding laminate does not cause defects due to winding wrinkles or tightening, for example, dents (surface irregularities) due to air entrapment. Therefore, a protective film is bonded to the near-infrared shielding layer surface. However, since it is not necessary to wind up, it is possible to manufacture an antireflection / near-infrared shielding laminate-rolled body efficiently and inexpensively.

The present invention will be specifically described by the following examples. In addition, measurement of optical properties (visibility reflectance, spectral transmittance, haze value) of near-infrared shielding laminates in each example and comparative example, weather resistance test, appearance evaluation test of roll-shaped wound body, surface hardness The outline of the antifouling test method is as follows.
"Measurement of luminous reflectance"
The surface of the near-infrared shielding layer formed on the opposite side of the transparent substrate with the antireflection layer is roughened with sandpaper, and blackened, and then a spectrophotometer V-570 manufactured by JASCO Corporation. (Trademark) was used, the spectral reflectance of the antireflection layer of each sample was measured by regular reflection at 5 degrees, and the visibility reflectance was obtained.

"Spectral transmittance measurement"
Using a spectrophotometer V-570 (trademark) 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, and the transmittance of indoor air. Was measured as a reference for comparison.
"Measure haze value"
The haze value of the laminate was measured using a fully automatic haze meter NDH2000 manufactured by JASCO Corporation.

"Weather resistance test"
Using a color analyzer TOPSCAN TC-1800-MkII (trademark) manufactured by Tokyo Denshoku Industries Co., Ltd. (standard light; light source, two-degree field of view), chromaticity x of each sample before and after the following high-temperature and high-humidity test and heat resistance test , Y were measured respectively.
(High temperature and high humidity test)
Each sample was placed in a constant temperature fence humidity tester set to 60 ° C. and relative humidity 90% and held for 500 hours, and the change in the transmittance of light having the wavelengths shown in Table 2 was determined.
(Heat resistance test)
Each sample was put in an incubator having a dry atmosphere at 80 ° C. and held for 500 hours, and a change in transmittance of light having a wavelength shown in Table 3 was determined.

"Appearance evaluation of rolled-up rolls"
For problems due to winding and tightening during the production of a laminate having an antireflection layer and a near-infrared shielding layer, a substrate having a width of 1400 mm is used, and a continuous coating having a length of 1000 m is wound into a roll, About this roll-shaped roll-up body, the external appearance was visually observed, and the thing in which abnormality was recognized was evaluated as 1 and the thing in which it was not recognized was described as 2.

(Measurement of surface hardness)
Nippon Steel Co., Ltd. Bone Star No. The steel wool of 0000 (trademark) was reciprocated 10 times at a load of 250 g / cm ² , and the number of scratches on the surface of the antireflection layer that could be visually confirmed was observed.
(Evaluation of antifouling properties)
Anti-fouling property of the anti-reflective layer is that the human fingerprint is attached to the surface of the anti-reflective layer, the part is lightly wiped with tissue paper 5 times, and it is difficult to wipe 2 that can be easily wiped off. The thing was evaluated and displayed as 1.

Example 1
(Formation of antireflection layer)
1) Formation of transparent hard coat layer Acrylic ultraviolet curable resin UV-3701 (trademark) manufactured by Toa Gosei Co., Ltd .: 40 parts by mass of ATO with an average particle size of 5 nm to 15 nm manufactured by Sumitomo Osaka Cement Co., Ltd. A fine powder: 2 parts by mass, propylene glycol monomethyl ether: 10 parts by mass, methanol: 48 parts by mass were added and mixed, and a paint prepared by dispersing with an ultrasonic homogenizer for 10 minutes was used. Mitsubishi Chemical Polyester Film Co., Ltd. UV absorber-containing polyethylene terephthalate (hereinafter abbreviated as “PET”) resin film manufactured by the company: 0700E100 (trademark) (100 μm thickness), coated to a thickness of 3 μm after drying, and dried at 80 ° C. for 1 minute. and this by using an ultraviolet irradiation apparatus of a high pressure mercury lamp was irradiated with ultraviolet rays of 150 mJ / cm ^2, a transparent conductive hardcoat It was formed.

2) Formation of a transparent low refractive index layer TSL8233 (trademark) manufactured by Toshiba Silicone Co., Ltd., which is an alkylsilane containing a fluorine group: 4 parts by mass, tetramethoxysilane: 14 parts by mass, 0.1 N nitric acid Aqueous solution: 0.2 parts by mass, pure water: 20 parts by mass, methanol: 61.8 parts by mass of a hydrolyzed mixture of propylene glycol monomethyl ether so that the solid content in terms of SiO2 is 3%: A paint prepared with a diluting solution consisting of isopropyl alcohol (hereinafter abbreviated as IPA) = 1: 9 was applied on the transparent conductive hard coat so that the film thickness after drying was 0.1 μm. And dried at 130 ° C. for 1 minute to form an antireflection layer having a transparent low refractive index layer.

3) Preparation of composition for near-infrared shielding layer Nippon Carlit Co., Ltd. comprising diimonium salt of bis (trifluoromethanesulfonyl) imidic acid having an anion represented by chemical formula (I) as a counter anion as a diimonium-based near infrared absorbing dye ) CIR-1085 (trademark): 2 parts by mass, Nippon Catalytic EEX Color IR-10A, which is a phthalocyanine dye as the second near infrared absorbing dye, and 1 part by weight as an acrylic resin GS-1000 manufactured by Kagaku Co., Ltd. (resin solid content: 30%, glass transition temperature: 100 ° C.): 50 parts by mass and fine solid particles made of polymethyl methacrylate (hereinafter abbreviated as PMMA), Toa Gosei Chemical Co., Ltd. TM-X-1 (average primary particle size: 2 μm, spherical): 0.1 part by mass of methyl ethyl ketone 46.9 The resin composition was prepared by dissolving a mixture in an amount unit.

4) Formation of near-infrared shielding layer On the back side of the PET film with antireflection layer, the composition for infrared shielding layer is applied so that the film thickness after drying becomes 10 μm, and remains in a hot air drying furnace. While the solvent is dried to 1% by mass to form a near-infrared shielding layer, the formed laminate is continuously wound up to wind up the laminate that combines the antireflection layer and the near-infrared shielding layer. The body was made.

  Measurement results of optical properties of the antireflection / near-infrared shielding laminate of Example 1 in the initial stage and after each test, and performance and appearance of the anti-reflection / near-infrared shielding laminate raising body wound up in a roll shape Properties are shown in Tables 1-3.

Example 2
GMP-0800 manufactured by Ganz Kasei Co., Ltd. (average primary particle size: 8 μm, spherical) in the near-infrared shielding composition of Example 1 as fine solid particles mainly composed of PMMA: 0.01 parts by mass An antireflection / near-infrared shielding laminate wound body was produced in the same manner as in Example 1 except that was added.
Table 1 shows the measurement results of the optical properties of the antireflection / near-infrared shielding laminate of Example 2 in the initial stage and after each test, and the appearance properties of the antireflection / near-infrared shielding laminate wound up in a roll shape. Shown in ~ 3.

Example 3
In the near-infrared shielding composition of Example 1, 0.5 part by mass of TAP-2 (trademark) manufactured by Yamada Chemical Industry was added as a coloring material that selectively absorbs 590 nm, and the compounding amount of methyl ethyl ketone was 46. An antireflection / near-infrared shielding laminate was manufactured in the same manner as in Example 1 except that the amount was changed to 4 parts by mass.
The measurement results of the optical properties of the antireflection / near-infrared shielding laminate of Example 3 in the initial stage and after each test, and the appearance properties of the antireflection / near-infrared shielding laminate wound up in a roll shape are shown. 1-3.

Example 4
CIR-RL (trademark) manufactured by Nippon Carlit Co., Ltd., consisting of a diimonium salt of bis (trifluoromethanesulfonyl) imidic acid having an anion represented by chemical formula (I) as a counter anion as a diimonium-based near infrared absorbing dye: 2 mass Part, NK-5060 (trademark) manufactured by Hayashibara Biochemical Laboratories Co., Ltd., which is a cyanine dye as the second near-infrared absorbing dye, and 0.1 part by mass; manufactured by Toa Gosei Co., Ltd. as the acrylic resin SM-22 ((trademark) resin solid content 30%, glass transition temperature 63 ° C.): TM-X-1 (by Toa Gosei Chemical Co., Ltd.) as fine solid particles mainly composed of PMMA and 50 parts by mass (( (Trademark) average primary particle diameter: 2 μm, spherical): 0.1 parts by mass was dissolved and mixed in 47.8 parts by mass of methyl ethyl ketone to prepare a resin composition, Example 1 In the same manner as was produced an antireflection-near-infrared shielding laminate winding body.
The measurement results of the optical properties of the antireflection / near-infrared shielding laminate of Example 4 in the initial stage and after each test, and the appearance properties of the antireflection / near-infrared shielding laminate wound up in a roll shape are shown. 1-3.

Comparative Example 1
An antireflection / near-infrared shielding laminate wound body was manufactured in the same manner as in Example 1 except that the fine particles mainly containing PMMA were not added.
The measurement results of the optical properties of the anti-reflection / near-infrared shielding laminate of Comparative Example 1 in the initial stage and after each test, and the appearance properties of the anti-reflection / near-infrared shielding laminate wound up in a roll shape are shown. 1-3.

〔Evaluation results〕
The antireflection / near-infrared shielding laminates of Examples 1, 2, and 4 have good antireflection characteristics, surface hardness, and antifouling properties in initial characteristics, low haze values, and high transmittance in the visible light region. , Having a high near-infrared shielding property in the range of 850 to 1000 nm. Moreover, in any of the test items of the high-temperature and high-humidity test and the heat resistance test, the amount of change in chromaticity x and y was 0.005 points or less and had excellent durability. Further, there was no abnormality in the appearance of the antireflection / near infrared shielding laminate after winding the roll, and the antireflection / near infrared shielding laminate roll was stably manufactured.

  The antireflection / near-infrared shielding laminate of Example 3 has good antireflection characteristics, surface hardness, and antifouling properties in the initial characteristics, has a low haze value, and selective absorption at 590 nm and 450 nm and 525 nm. , Having a high transmittance of 620 nm and a high near-infrared shielding property in the region of 850 to 1000 nm. Moreover, in any of the test items of the high-temperature and high-humidity test and the heat resistance test, the amount of change in chromaticity x and y was 0.005 points or less, and the durability was excellent. Further, there was no abnormality in the appearance of the antireflection / near-infrared shielding laminate wound body after winding the roll, and stable production of the antireflection / near-infrared shielding laminate was possible.

  On the other hand, the antireflection / near-infrared shielding laminate of Comparative Example 1 has good antireflection characteristics, surface hardness, and antifouling properties in the initial characteristics, a low haze value, a high transmittance in the visible light region, and 850. It has a high near-infrared shielding property in the region of ˜1000 nm, and the change in chromaticity x and y is 0.005 points or less in any of the test items of the high-temperature and high-humidity test and the heat resistance test. Durability, but anti-reflective and near-infrared shielding laminated rolls after winding up rolls have severe dents (surface irregularities) due to air entrapment, causing defects due to curling and tightening As a result, it was impossible to stably produce a roll-up body having an antireflection / near-infrared shielding laminate.

  The anti-reflective / near-infrared shielding laminate of the present invention has stable high quality without causing problems due to curling and tightening during its production, and is excellent in practicality. .

Claims (4)

A transparent base material, an antireflection layer laminated on one side of the transparent base material, and a near infrared shielding layer laminated on the other side of the transparent base material,
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. Anti-reflective and near-infrared shielding laminate characterized by   The antireflection / near-infrared shielding laminate according to claim 1, wherein the difference between the refractive index of the binder resin and the refractive index of the fine solid particles 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.   When laminating an antireflection layer on one surface side of the transparent substrate and laminating a near infrared shielding layer on the other surface side of the transparent substrate, the near infrared shielding layer, a near infrared absorbing dye, a binder resin, Applying a coating material containing 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, and drying to form a laminate. A method for producing an antireflection / near-infrared shielding laminate, which is characterized.