JP4857187B2 - Laminated sheet manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a laminated sheet, and more specifically, there is no coating unevenness of the laminated sheet, no discoloration of the laminated sheet, and excellent alkali resistance, stain resistance, average visible light transmittance, and near infrared absorption. The present invention relates to a method for producing a laminated sheet.

  In recent years, the progress of optoelectronic components and equipment has been remarkable, and among them, the demand for displays for displaying images has been increasing for computer monitors and the like in addition to conventional television devices. In particular, the market demand for larger and thinner displays is increasing. Recently, a plasma display panel (PDP) has attracted attention as a display that can be made large and thin. In principle, the PDP emits strong near infrared rays to the outside of the device. This near infrared ray causes a malfunction of a cordless telephone or an infrared remote controller. Therefore, a near infrared (NIR) cut film is used for the plasma display panel in order to block near infrared rays.

  On the other hand, a display such as a personal computer, a television, a car navigator, or a mobile phone is one in which a person views an image and reads information, and visibility is required as an important function. However, in reality, there are many situations in which the contrast due to the reflection of the background decreases and the screen becomes difficult to see. In order to prevent this, a device for suppressing the surface reflection of the screen, which causes a reduction in visibility, is made, and the display surface is subjected to an antiglare treatment or an antireflection treatment.

The anti-glare process is a process of forming fine irregularities on the surface of the display and scatter the reflected image by scattering light to blur the outline. When the substrate is plastic, inorganic fine particles such as silica and organic fine particles such as polystyrene are coated on the surface, but the resolution of the image is lowered. In the antireflection treatment, a thin film having a thickness of about the wavelength of light is formed on the surface, and the reflectance is reduced by the light interference effect. When the refractive index of the incident medium is n ₁ , the refractive index of the film is n ₂ , and the reflectance is R,
R = [(n ₂ −n ₁ ) / (n ₂ + n ₁ )] ²
Where d is the film thickness and λ is the wavelength of the light.
d = λ / (4n ₂ )
In this case, the light interference effect is maximized.

In Patent Document 1, as an antireflection film having near infrared absorption characteristics, an antireflection layer is formed on one surface of a transparent resin film, and a near infrared absorber is added to the other surface of the transparent resin film. An antireflective film obtained by laminating an adhesive layer containing 0.005 to 0.3 wt% · mm is disclosed.
However, the antireflection film described in Patent Document 1 has a problem that uneven coating of the laminated sheet and discoloration of the laminated sheet occur. In addition, there is room for improvement in characteristics such as alkali resistance, stain resistance, average visible light transmittance, and near infrared absorptivity.
Japanese Patent Laid-Open No. 10-156991

  Therefore, the object of the present invention is to solve the conventional problems as described above, and there is no coating unevenness of the laminated sheet, no discoloration of the laminated sheet, and excellent in alkali resistance, stain resistance, visible light average transmittance, and near infrared absorption. Another object of the present invention is to provide a method for producing a laminated sheet.

The present invention is as follows.
1. Forming a low refractive index layer (B) on one surface of the transparent substrate film (A), forming a near infrared absorbing layer (C) on the other surface of the transparent substrate film (A), and A method for producing a laminated sheet comprising:
The following composition for forming a low refractive index layer is applied to one surface of the transparent substrate film (A) with a first coater and dried by heating to form the low refractive index layer (B). Without winding, the following composition for forming a near-infrared absorbing layer is applied to the other surface of the transparent substrate film (A) with a second coater, followed by drying by heating to form the near-infrared absorbing layer (C). A method for producing a laminated sheet, comprising:
Low refractive index layer forming composition: Contains a graft copolymer having a repeating unit formed using a radical polymerizable monomer as a trunk and silicone as a branch.
Near-infrared absorbing layer forming composition: containing an acrylic resin binder and a near-infrared absorbing dye, and containing 5-50 parts by weight of the near-infrared absorbing dye with respect to 100 parts by weight of the acrylic resin binder.
2. The low refractive index layer forming composition is a matrix component mainly composed of a disilane compound having a divalent organic group containing one or more fluorine atoms or a (partial) hydrolyzate thereof; hollow silica particles; and 2. The graft copolymer as described above, which contains 20 to 120 parts by mass of the hollow silica particles and 5 to 40 parts by mass of the graft copolymer with respect to 100 parts by mass of the matrix component. A method for producing a laminated sheet.
3. 2 or more types of the said near-infrared absorption pigment | dye are used, The manufacturing method of the laminated sheet of said 1 or 2 characterized by the above-mentioned.
4). 4. The method for producing a laminated sheet according to 3 above, wherein the near-infrared absorbing dye is at least two kinds selected from diimonium dyes, cyanine dyes, and phthalocyanine dyes.
5. 2. The method for producing a laminated sheet according to 1 above, wherein the acrylic resin is a polymethyl methacrylate resin.
6). 2. The method for producing a laminated sheet according to 1 above, wherein the transparent substrate film (A) is a biaxially stretched polyethylene terephthalate film.
7). 2. The method according to 1 above, further comprising a step of forming a pressure-sensitive adhesive layer (D) on the surface of the near-infrared absorbing layer (C) opposite to the surface on the transparent base film (A) side. A method for producing a laminated sheet.

The low refractive index layer having the composition specified in the present invention has the advantages of being excellent in alkali resistance, coating property, stain resistance, scratch resistance, transparency and low minimum reflectance. When an attempt is made to produce a laminated sheet by applying conventional methods, the components of the composition for forming a low refractive index layer, particularly the above graft copolymer, is present on the other surface of the transparent substrate film (A). There was a problem in that the film was transferred and uneven coating of the near-infrared absorbing layer (C) occurred. Here, the conventional method means that a low refractive index layer is formed on a substrate, wound up into a long roll, and then rolled up again to be the target layer on the other surface of the substrate. It is a method of forming.
Therefore, in the production method of the present invention, a low refractive index layer-forming composition having a specific composition is applied to one surface of the transparent substrate film (A) with a first coater, and then dried by heating. ), The composition for forming a near-infrared absorbing layer having a specific composition is applied to the other surface of the transparent base film (A) with a second coater without winding up the sheet, and is dried by heating and near. An infrared absorption layer (C) is formed. According to this method, after forming the low refractive index layer (B), the near infrared absorption layer (C) is formed without winding up the sheet. The component of the product is not transferred to the other surface of the transparent substrate film (A). Therefore, uneven coating of the near infrared absorbing layer (C) does not occur. Further, in order to form the low refractive index layer (B) in the present invention, it is necessary to dry at a high temperature of about 140 ° C. Such a high temperature is caused by the near infrared absorbing dye contained in the near infrared absorbing layer (C). Cause discoloration. In the production method of the present invention, since the heat drying for forming the low refractive index layer (B) is performed before the formation of the near infrared absorbing layer (C) as described above, the near infrared absorbing dye is discolored. There is nothing to do.
As described above, according to the present invention, there is provided a method for producing a laminated sheet having no coating unevenness of the laminated sheet and no discoloration of the laminated sheet, and excellent in alkali resistance, stain resistance, visible light average transmittance, and near infrared absorption. be able to.

Hereinafter, the present invention will be described in more detail. The near infrared ray as used in the present invention means an infrared ray having a wavelength region of about 800 to 1100 nm, but this product was evaluated particularly with a near infrared transmittance of 850 nm and 950 nm. It is required that the near infrared transmittance at 850 nm is 10% or less and the near infrared transmittance at 950 nm is 5% or less.

(Transparent substrate film (A))
The transparent substrate film (A) used in the present invention is not particularly limited, and can be appropriately selected from various transparent plastic films depending on the situation. Examples of the transparent plastic film include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1, and polybutene-1, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resins, and polyvinyl chloride resins. Film made of cellulose resin such as polyphenylene sulfide resin, polyether sulfone resin, polyethylene sulfide resin, polyphenylene ether resin, styrene resin, acrylic resin, polyamide resin, polyimide resin, cellulose acetate These laminated films are exemplified. Among these, a biaxially stretched polyethylene terephthalate film is preferable. The biaxially stretched polyethylene terephthalate film has good mechanical strength and dimensional stability and can be adjusted to a desired thickness.
As thickness of a transparent base film (A), it is 10-300 micrometers, for example, Preferably it is 20-200 micrometers.
The transparent substrate film (A) may be blended with known additives such as an antioxidant and an ultraviolet absorber as desired.
Moreover, in order to improve adhesiveness with another layer, the transparent base film (A) can also provide an easily bonding agent layer.

(Hard coat layer)
The laminated sheet in the present invention preferably has a hard coat layer provided between the transparent base film (A) and the low refractive index layer (B).
Such a hard coat layer preferably has a thickness of 0.5 to 10 μm.
If thickness is less than 0.5 micrometer, pencil hardness will fall and steel wool resistance will also fall. When the thickness exceeds 10 μm, curling is strongly generated, which is not preferable. A preferred thickness is 0.6 to 4.0 μm, and a more preferred thickness is 0.7 to 3.0 μm.

  In the present invention, the hard coat layer also has a role of the high refractive index layer, and a simple structure in which the low refractive index layer is provided thereon, and the high refractive index layer and the low refractive index layer are provided on the hard coat layer. The provided structure is mentioned. In the former configuration, that is, in a simple configuration in which the high refractive index layer serves as a hard coat layer and a low refractive index layer is provided on the hard coat layer (hereinafter referred to as a simple configuration), the hard coat layer is formed in the molecule. 100 parts by mass of ionizing radiation curable resin containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, 20 to 600 parts by mass of antimony pentoxide, and optionally unsaturated double copolymerizable at the terminal A form formed by blending 5 to 20 parts by mass of a polymer having a bond and curing the polymer is preferable.

  As polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and epoxy acrylate. Preferable examples include pentaerythritol triacrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol pentaacrylate. Among them, dipentaerythritol hexa (meth) acrylate is particularly preferable. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Antimony pentoxide preferably has an average particle size of 5 to 100 nm. By having this average particle diameter, transparency is enhanced.
The more preferable average particle size is 10 to 70 nm, and the particularly preferable average particle size is 15-50 nm.
Antimony pentoxide preferably has a pyrochlore structure. What has such a pyrochlore structure has the property that the electroconductivity by proton conduction is high. The pyrochlore structure is an octahedron formed of six oxygen atoms and OH groups centered on antimony atoms, as described in Journal of Chemical Society of Japan, No. 4, P. 488, 1983. A skeleton structure formed by sharing the vertices of these octahedrons.

  Examples of the polymer having an unsaturated double bond copolymerizable at the terminal include terminal methacrylate polymethyl methacrylate, terminal styryl polymethacrylate, terminal methacrylate polystyrene, terminal methacrylate polyethylene glycol, terminal methacrylate acrylonitrile-styrene copolymer, terminal methacrylate styrene. -A methyl methacrylate copolymer etc. can be mentioned, The mass mean molecular weight has preferable 5000-10000. Examples of commercially available polymers having an unsaturated double bond copolymerizable at the terminal include macromonomers AA-6, AS-6S, AN-6S, AW-6S (manufactured by Toagosei Co., Ltd.), and the like. Can do.

In a simple configuration, the hard coat layer is composed of 20 to 600 parts by mass of antimony pentoxide, 100 parts by mass of ionizing radiation curable resin containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. It is formed using the composition which mix | blended 5-20 mass parts of polymers which have an unsaturated double bond copolymerizable at the terminal. When the blending ratio of antimony pentoxide is 20 to 600 parts by mass, the effect of reducing the minimum reflectance is improved. In addition, an antistatic effect is exhibited. When the polymer having an unsaturated double bond copolymerizable at the terminal is 5 to 20 parts by mass, the adhesion to the low refractive index layer is enhanced, and as a result, the effect of excellent alkali resistance and scratch resistance is obtained. Demonstrated. Further, the curl resistance is improved.
Further preferable blending ratio is 45 to 140 parts by mass of antimony pentoxide and copolymerizable to the terminal with respect to 100 parts by mass of ionizing radiation curable resin containing polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. 5 to 15 parts by mass of a polymer having an unsaturated double bond.

In the configuration in which the high refractive index layer and the low refractive index layer are provided on the hard coat layer (hereinafter referred to as a three-layer configuration), it is not necessary to add antimony pentoxide to the hard coat layer. However, it is preferable to blend a polymer having an unsaturated double bond copolymerizable at the terminal.
Thereby, the adhesiveness with a high refractive index layer increases, As a result, the effect that it is excellent in alkali resistance and scratch resistance is exhibited.
In the three-layer configuration, preferred types and blending ratios of the ionizing radiation curable resin and the polymer having an unsaturated double bond copolymerizable at the terminal are the same as those in the above-described simple configuration.

  A hard-coat layer can be formed by apply | coating said each component as a coating material on a transparent base film, drying, and making it harden | cure by ionizing radiation irradiation. There is no particular limitation on the ionizing radiation, and examples thereof include an electron beam, radiation, and ultraviolet rays. Among ionizing radiations, ultraviolet rays are particularly suitable because they are simple in equipment and easy to handle. By irradiating with ionizing radiation and crosslinking, a coating film having a pencil hardness of H or higher as defined in JIS K 5400 can be formed.

  When the ionizing radiation is ultraviolet, a photopolymerization initiator is usually added. There is no restriction | limiting in particular as a photoinitiator, For example, Irgacure 184,907,651,1700,1800,819,369 (made by Ciba Specialty Chemicals), Darocur 1173 (made by Ciba Specialty Chemicals), Ezacure KIP150, TZT (made by Nippon Shibel Hegner), Lucyrin TPO (made by BASF), Kayacure BMS (made by Nippon Kayaku), etc. are mentioned.

  Of course, the composition can be used in combination with various additives as required.

(Easily adhesive layer)
In the present invention, an easy-adhesive layer may be provided between the transparent substrate film and the hard coat layer for the purpose of improving the adhesion between them. The easy adhesive layer is particularly effective when a biaxially stretched polyethylene terephthalate film is employed as the transparent substrate film.
The material of the easy-adhesive layer is not particularly limited as long as it is transparent and improves the adhesion between the transparent base film and the hard coat layer. For example, acrylic resin, polyester resin, urethane resin, and those A polymer etc. are mentioned. Although the thickness of an easily adhesive layer is not specifically limited, 0.03-0.30 micrometer is preferable and 0.05-0.20 micrometer is more preferable. The easy adhesive layer can be provided on the transparent substrate film by a known coating technique.

(Low refractive index layer)
The low refractive index layer in the present invention uses a composition for forming a low refractive index layer containing a graft copolymer having a repeating unit formed using a radical polymerizable monomer as a trunk and a silicone as a branch. It is formed. Among them, the composition for forming a low refractive index layer is a matrix component mainly composed of a disilane compound having a divalent organic group containing one or more fluorine atoms or a (partial) hydrolyzate thereof; hollow silica particles; While containing a graft copolymer, the form containing 20-120 mass parts of said hollow silica particles and 5-40 mass parts of said graft copolymers with respect to 100 mass parts of said matrix components is preferable.
In the present invention, the (partial) hydrolyzate indicates that it may be a partial hydrolyzate or a complete hydrolyzate. The main component in the matrix component means that it is contained in an active ingredient excluding the solvent in a proportion of 50% by mass or more, particularly 70% by mass or more.

The matrix component is mainly composed of a disilane compound having a divalent organic group containing at least one fluorine atom or a (partial) hydrolyzate thereof.
The disilane compound has the following formula (I)
^{_{X m R 1 3-m Si}} -Y-SiR 1 3-m X m (I)
Wherein R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, and m is 1, 2 or 3. .)
Or a (partial) hydrolyzate thereof (hereinafter also referred to as component (i)).

Here, Y represents a divalent organic group containing 1 or more, preferably 4 to 50, particularly preferably 8 to 24, fluorine atoms. Specific examples thereof include the following. However, the present invention is not limited to this.
_{-C 2 H 4 - (CF 2} ) n -C 2 H 4 -
_{-C 2 H 4 -CF (CF 3} ) - (CF 2) n -CF (CF 3) -C 2 H 4 -
_{-C 2 H 4 -CF (C 2} F 5) - (CF 2) n -CF (C 2 F 5) -C 2 H 4 -
_{-C 2 H 4 -CF (CF 3} ) CF 2 -O (CF 2) n O-CF 2 CF (CF 3) -C 2 H 4 -
(However, n is 2-20.)
_{-C 2 H 4 -C 6 F 10} -C 2 H 4 -
_{-C 2 H 4 -C 6 F 4} -C 2 H 4 -

In order to express various functions such as antifouling properties and water repellency in addition to antireflection properties, it is preferable to contain a large amount of fluorine atoms. In addition, since the perfluoroalkylene group is rigid, it is preferable to contain as many fluorine atoms as possible for the purpose of obtaining a film having high hardness and high scratch resistance. If it contains a large amount of fluorine atoms, the alkali resistance is improved. Therefore, Y represents the following structure: —CH ₂ CH ₂ (CF ₂ ) _n CH ₂ CH ₂ —
_{-C 2 H 4 -CF (CF 3} ) - (CF 2) n -CF (CF 3) -C 2 H 4 -
(However, n is 2-20.)
In particular, —CH ₂ CH ₂ (CF ₂ ) _n CH ₂ CH ₂ — (n = 2 to 20)
Is preferred.

  Although it is necessary to satisfy | fill the value of 2-20 as n, More preferably, it is good to satisfy | fill the range of 4-12, Most preferably, 4-10. If it is less than this, various functions such as antireflection, alkali resistance, stain resistance and water repellency may not be obtained sufficiently, and if it is too much, sufficient crosslinking resistance will be obtained because the crosslink density will decrease. There are cases where it is not possible.

R ¹ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, a phenyl group, and the like can be exemplified. A methyl group is preferred for obtaining good scratch resistance.

  m is 1, 2 or 3, preferably 2 or 3, and in order to obtain a particularly hard film, m = 3 is preferable.

X represents a hydrolyzable group. Specific examples include halogen atoms such as Cl, organooxy groups represented by OR ² (R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms), particularly methoxy group, ethoxy group, propoxy group, isopropoxy group, Examples include alkoxy groups such as butoxy groups, alkenoxy groups such as isopropenoxy groups, acyloxy groups such as acetoxy groups, ketoxime groups such as methylethyl ketoxime groups, and alkoxyalkoxy groups such as methoxyethoxy groups. Among these, an alkoxy group is preferable, and a silane compound having a methoxy group or an ethoxy group is particularly preferable because it is easy to handle and the reaction during hydrolysis is easily controlled.

Specific examples of the disilane compound satisfying the above include the following.
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 8 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 10 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 16 -C 2 H 4 -Si (OCH 3) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 2 H 5) 3
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (CH 3) (OCH 3) 2
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (CH 3) (OCH 3) 2
_{(CH 3 O) (CH 3} ) 2 Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (CH 3) 2 (OCH 3)
_{(C 2 H 5 O) (} CH 3) 2 Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (CH 3) 2 (OC 2 H 5)
_{(CH 3 O) 3 Si-} C 2 H 4 -CF (CF 3) - (CF 2) 4 -CF (CF 3) -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 -CF (CF 3) - (CF 2) 8 -CF (CF 3) -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 -CF (CF 3) - (CF 2) 12 -CF (CF 3) -C 2 H 4 -Si (OCH 3) 3
Among these, preferably,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 8 -C 2 H 4 -Si (OCH 3) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 2 H 5) 3
These disilane compounds are preferably used.

The disilane compound of the above formula (I) can be used in combination with an organosilicon compound containing a fluorine atom-substituted organic group represented by the following formula (II) or its (partial) hydrolyzate (component (ii)). .
Rf-SiX ₃ (II)
(In the formula, Rf is a monovalent organic group containing one or more fluorine atoms, and X is a hydrolyzable group.)

Here, Rf represents a monovalent organic group containing one or more fluorine atoms, preferably 3 to 25, particularly preferably 3 to 17, and specific examples thereof include the following.
CF ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₅ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₉ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₁₁ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₇ CONHC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ CONHC ₂ H ₄ NHC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCOC ₂ H ₄ SC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCONHC ₃ H ₆ −
CF ₃ (CF ₂ ) ₇ SO ₂ NHC ₃ H ₆ −
_{C 3 F 7 O (CF (} CF 3) CF 2 O) p CF (CF 3) CONHC 3 H 6 -
(However, p is p ≧ 1, especially 1 to 3.)
Among these,
CF ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ −
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ −
Is preferable because it does not contain a polar part. X is as described above.

Specific examples of the organosilicon compound containing a fluorine atom-substituted organic group that satisfies the above are exemplified below.
CF ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₅ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₉ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₁₁ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONHC ₃ H ₆ —Si (OCH ₃ ) _{3
CF 3 (CF 2) 7 CONHC} 2 H 4 NHC 3 H 6 -Si (OCH 3) 3
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCOC ₂ H ₄ SC ₃ H ₆ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ OCONHC ₃ H ₆ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ SO ₂ NHC ₃ H ₆ —Si (OCH ₃ ) _{3
C 3 F 7 O (CF (} CF 3) CF 2 O) p CF (CF 3) CONHC 3 H 6 -Si (OCH 3) 3
(However, p is p ≧ 1.)
Among these, the following are preferable.
CF ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ C ₂ H ₄ —Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OCH ₃ ) ₃

In the present invention, the component (i) can be used alone without being used in combination with the component (ii). However, when the component (i) and the component (ii) are mixed and used, the component (i) It is necessary that the content be 60% by mass or more and less than 100% by mass. When the content of the component (i) is less than 60% by mass, the crosslinking density is lowered, and good scratch resistance cannot be obtained, so that the function as a protective film becomes insufficient, which is not preferable. More preferably, the content of component (i) is 95% by mass or more. Moreover, it is preferable that the content rate of (i) component is 99.5 mass% or less from the point of the addition effect of (ii) component.
Moreover, in this invention, you may use what cohydrolyzed the mixture of the said (i) component and (ii) component.

  The preferred composition for forming a low refractive index layer in the present invention is mainly composed of component (i), a mixture of component (i) and component (ii), or a co-hydrolyzate thereof, but has an effect on various properties required. The following organosilicon compound or a (partial) hydrolyzate thereof can be used within the range not giving the above.

  Examples of the organosilicon compounds that can be used in combination with the components (i) and (ii) include silicates such as tetraethoxysilane, alkylsilanes such as methyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, phenyl Silane coupling agents such as phenylsilanes such as trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane And various compounds. In particular, tetraalkoxysilane is effective when used in combination with the purpose of improving scratch resistance because it has the effect of increasing the crosslink density, but it tends to make the coating hydrophilic, alkali resistance, and stain resistance. In addition, since various functions such as water repellency may be deteriorated, it is better to avoid using a large amount, and it is 5 for the total amount of (i) component or (i), (ii) component being 100 parts by mass. It is preferable that the amount is not more than part by weight, particularly not more than 2 parts by weight, particularly not more than 1 part by weight.

The compounds of the above formulas (I) and (II), or the organosilicon compounds that can be used in combination with the above components (i) and (ii) may be used as they are, or (partially) in a hydrolyzed form, or You may use in the form hydrolyzed in the following solvent. From the viewpoint of increasing the curing rate after coating, it is preferable to use the (partly) hydrolyzed form. The amount of water used for the hydrolysis is preferably such that the molar ratio of (H ₂ O / Si—X) is 0.1 to 10.

  For the hydrolysis, a conventionally known method can be applied. As this hydrolysis catalyst or hydrolysis / condensation curing catalyst, acids such as hydrochloric acid, acetic acid, maleic acid, sodium hydroxide (NaOH), ammonia, triethylamine Amine compounds such as dibutylamine, hexylamine, octylamine and dibutylamine, salts of amine compounds, bases such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, potassium fluoride, fluorine Organic compounds such as fluorides such as sodium fluoride, solid acidic catalysts or solid basic catalysts (eg ion exchange resin catalysts), iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate Metal salts of carboxylic acids, tetrabutoxy titanium, Organic titanium esters such as la-i-propoxytitanium, dibutoxy- (bis-2,4-pentanedionate) titanium, di-i-propoxy (bis-2,4-pentanedionate) titanium, tetrabutoxyzirconium, tetra Organic zirconium esters such as i-propoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di-i-propoxy (bis-2,4-pentanedionate) zirconium, aluminum triisopropoxide, etc. Alkoxy aluminum compounds, organometallic compounds such as aluminum chelate compounds such as aluminum acetylacetonate complex, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyl bird Aminoalkyl-substituted alkoxysilanes such as methoxysilane and N- (β-aminoethyl) -γ-aminopropyltriethoxysilane are exemplified, and these may be used alone or in combination.

  The addition amount of this catalyst is 0.01 to 10 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the (partial) compound to be hydrolyzed. If this amount is less than 0.01 parts by mass, it may take too long to complete the reaction or the reaction may not proceed. Moreover, when it exceeds 10 mass parts, it is disadvantageous in cost, and the obtained composition or hardened | cured material may color, or a side reaction may increase.

  The hollow silica particles are particles having an outer shell layer mainly composed of silica and having a porous or hollow interior. The average particle diameter of the hollow silica particles is preferably 5 to 100 nm, and more preferably 10 to 80 nm. The average particle diameter was determined by a dynamic light scattering method.

  The graft copolymer having a repeating unit formed from a radically polymerizable monomer as a trunk and a silicone as a branch is preferably a comb-shaped acrylic graft copolymer in which the trunk portion composed of the repeating unit is an acrylic polymer. It is a polymer. Examples of the graft copolymer include products obtained by condensing a silicone represented by the following formula (III) and an acrylsilane compound represented by the following formula (IV).

(In the formula, R ⁶ and R ^{7 each} represent a monovalent aliphatic hydrocarbon group, phenyl group or monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms. Q is a positive number of 1 or more.)

(Wherein R ⁸ represents a hydrogen atom or a methyl group. R ⁹ represents a methyl group, an ethyl group or a phenyl group, and two R ^{9 s} may be the same or different from each other. Z represents a chlorine atom or a methoxy group. Or represents an ethoxy group.)

The silicone represented by the formula (III) used here can be obtained as a commercial product, and those suitable for the purpose can be used. R ⁶ and R ⁷ in the formula (III) are monovalent aliphatic hydrocarbon groups, phenyl groups or monovalent halogenated hydrocarbons having 1 to 10 carbon atoms, and monovalent fatty acids having 1 to 10 carbon atoms. Examples of the group hydrocarbon group include a methyl group, an ethyl group, and an acyl group. Examples of the monovalent halogenated hydrocarbon include a 3,3,3-trifluoropropyl group and a 4,4,4-tri group. A fluoro-3,3-difluorobutyl group, a 2-chloroethyl group, etc. are mentioned. Particularly preferred as R ⁸ and R ⁹ is a methyl group.

  In the formula (III), q is a positive number of 1 or more, but generally when a high molecular weight silicone having a number of q of 100 or more is used, the resulting graft copolymer is often oily. . When a low molecular weight silicone having a q number of 100 or less is used, the resulting graft copolymer can be obtained in various forms such as oil, jelly, and solid depending on the type of monomer.

  Next, examples of the acrylic silane compound represented by the formula (IV) include γ-methacryloxypropyldimethylchlorosilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldiphenylchlorosilane, γ-acryloxypropyldimethylchlorosilane, Examples include γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, and the like. These acrylic silane compounds can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid according to the method described in JP-B-33-9969.

  For radical copolymerization in the production of the graft copolymer, a conventionally known method can be used, and a radiation irradiation method or a method using a radical polymerization initiator can be used. Furthermore, when copolymerizing by the ultraviolet irradiation method, a known sensitizer is used as a radical polymerization initiator, and when copolymerizing by electron beam irradiation, it is not necessary to use a radical polymerization initiator. The radical copolymer thus obtained is a comb-shaped graft copolymer having a repeating unit formed using a radical polymerizable monomer as a trunk and silicone as a branch. In addition, you may use together the monomer containing a hydroxyl group like 2-hydroxyethyl (meth) acrylate as a radically polymerizable monomer.

  Moreover, the graft copolymer in this invention can also utilize a commercial item, for example, Cymac US-150, US-270, US-350, US-450, Reseda GP-700 (above, Toagosei Co., Ltd.) Manufactured).

  As described above, in a preferred embodiment of the composition for forming a low refractive index layer in the present invention, 20 to 120 parts by mass of the hollow silica particles and 5 to 40 of the graft copolymer are used with respect to 100 parts by mass of the matrix component. It is formed by blending parts by mass. When the blending amount of the graft copolymer is less than 5 parts by mass, the effect of improving alkali resistance is not exhibited. On the other hand, when the amount exceeds 40 parts by mass, uneven coating occurs when the low refractive index layer is applied. A more preferable blending ratio is 40 to 100 parts by mass of hollow silica particles and 10 to 30 parts by mass of the graft copolymer with respect to 100 parts by mass of the matrix component.

  Furthermore, various additives can be blended in the composition for forming a low refractive index layer in the present invention for the purpose of adjusting physical properties such as hardness, scratch resistance, and conductivity of the film.

  Examples of the organic solvent suitable for use in the coating material for forming the low refractive index layer include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, Aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate and γ-butyrolactone, ethers such as tetrahydrofuran and 1,4-dioxane And β-diketones such as acetylacetone and ethyl acetoacetate, and β-ketoesters.

  The refractive index of the low refractive index layer is preferably 1.28 to 1.50, more preferably 1.30 to 1.45. The thickness of the low refractive index layer is preferably 40 to 300 nm, and more preferably 60 to 150 nm.

(High refractive index layer)
The high refractive index layer in the present invention is not particularly limited, and a known high refractive index layer can be appropriately employed. For example, in the present invention, the high refractive index layer includes, for example, a matrix component that can form a high refractive index layer, titanium oxide, zinc oxide, indium oxide, tin oxide, zirconium oxide, aluminum oxide, which are high refractive index materials, and these. The metal oxide fine particles may be a layer formed by dispersing fine particles doped with a different element such as antimony or tin in a matrix for forming a high refractive index layer to form a paint, which is formed by coating or the like.
In the present invention, the matrix for forming the high refractive index layer can be selected and used from a resin or the like that meets conditions such as adhesion to the hard coat layer and coating properties. Specifically, the hard coat layer can be used. An ionizing radiation curable resin, a thermosetting resin, or the like used for forming the film can be used. Among these, in the present invention, an ionizing radiation curable resin containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule is preferable. The ionizing radiation curable resin preferably has the same components as those used for the hard coat layer.

In the present invention, a particularly preferred form as the high refractive index layer is that the high refractive index layer contains 100 parts by mass of an ionizing radiation curable resin containing a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule. In addition, 100 to 600 parts by mass of zinc antimonate is blended and cured.
Zinc antimonate is known and disclosed, for example, in JP-A-6-219743, JP-A-9-212221 and the like. The publication discloses a powder of conductive anhydrous zinc antimonate having a ZnO / Sb ₂ O ₅ molar ratio of 0.8 to 1.2 and a primary particle size of 5 to 200 nm. Can be used for The zinc antimonate is composed of a zinc compound that produces zinc oxide by firing at a molar ratio of ZnO / Sb ₂ O ₅ of 0.8 to 1.2, and an antimony compound that produces antimony oxide by firing. Can be produced by firing the mixture. The firing temperature is, for example, 500 to 680 ° C.

Zinc antimonate can be obtained as an anhydrous zinc antimonate sol having a primary particle size of 0.5 microns or less. For example, it can be obtained as an organosol of methanol (CELNAX CX-Z603M-F2, CELNAX CX-Z400, manufactured by Nissan Chemical Co., Ltd.) or methanol / isopropanol (CELNAX CX-Z300IM, manufactured by Nissan Chemical Co., Ltd.).
The anhydrous zinc antimonate sol is stable and does not aggregate in methanol and does not increase in particle size. However, it is unstable and aggregates in ionizing radiation curable resin to increase particle size or disperse. It is destroyed and separated and settled. Therefore, when an ionizing radiation curable resin is used as the matrix of the high refractive index layer, it is preferable to uniformly disperse the zinc antimonate in the matrix using a dispersant. As the dispersant in this case, a cationic, weakly cationic, nonionic or amphoteric surfactant is effective, and in particular, an alkylamine EO / PO adduct (for example, Solsperse 20000, manufactured by Nippon Lubrizol), alkylamine EO. Adducts (for example, TAMNO-15, TAMNS-10 and TAMNO-5, manufactured by Nikko Chemical Co., Ltd.) and ethylenediamine PO-EO condensates (for example, Pluronic TR-701, TR-702 and TR-704, Asahi Denka Kogyo Co., Ltd.) And the like) are preferred. The addition amount is 0.1 to 5 parts by mass with respect to 100 parts by mass of zinc antimonate. In addition, examples of the alkyl group of the alkylamine include a methyl group, an ethyl group, a lauryl group, and a stearyl group. The number of moles of EO (ethylene oxide) or PO (propylene oxide) added is suitably from several moles to about 100 moles per mole of amine, but is not limited thereto.

  As described above, zinc antimonate is blended in an amount of 100 to 600 parts by mass with 100 parts by mass of ionizing radiation curable resin containing polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule. It is preferable to add 200 to 500 parts by mass.

  Furthermore, various additives can be blended in the high refractive index layer in the present invention for the purpose of adjusting physical properties such as hardness, scratch resistance and conductivity of the coating.

  Organic solvents suitable for use in the coating material for forming the high refractive index layer include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, Aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, esters such as ethyl acetate, butyl acetate and γ-butyrolactone, ethers such as tetrahydrofuran and 1,4-dioxane And β-diketones such as acetylacetone and ethyl acetoacetate, and β-ketoesters.

  The refractive index of the high refractive index layer is preferably 1.60 or more. A more preferable refractive index is 1.70 to 1.80. Moreover, 30-500 nm is preferable and, as for the thickness of a high refractive index, 50-250 nm is more preferable.

(Near-infrared absorbing layer (C))
The near-infrared absorbing layer (C) in the present invention contains an acrylic resin binder and a near-infrared absorbing dye, and contains 5 to 50 parts by mass of the near-infrared absorbing dye with respect to 100 parts by mass of the acrylic resin binder. It is formed of a composition for forming a near infrared absorption layer.

(Acrylic resin binder)
Examples of the acrylic resin binder used in the present invention include homopolymers of alkyl esters of acrylic acid or methacrylic acid, and copolymers with ethylenically unsaturated monomers that can be copolymerized with the monomers. Although not particularly limited, a polymethyl methacrylate resin is preferred in the present invention. Above all, polymethylmethacrylate resins can improve the heat resistance and light resistance without causing deterioration of near-infrared absorbing dyes, as long as they have a sharp molecular weight distribution with low molecular weight components eliminated as much as possible. it can. The low molecular weight component tends to destroy the structure of the near infrared absorbing dye, changes the absorption performance of the near infrared absorbing dye, and deteriorates the heat resistance and light resistance. Therefore, the molecular weight distribution of the polymethyl methacrylate resin particularly suitable in the present invention is preferably such that Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) is 1.5 to 2.1. More preferably, it is 6 to 1.9. The molecular weight distribution referred to in the present invention is measured by GPC (polymethyl methacrylate equivalent value) using chloroform as a developing solvent.

(Near-infrared absorbing dye)
The near-infrared absorbing dye used in the present invention is not particularly limited as long as it is a dye that can absorb infrared rays in the near-infrared wavelength region defined above, but in the present invention, the near-infrared absorbing dye is a diimonium-based dye, Two or more kinds selected from a cyanine dye and a phthalocyanine dye are preferable.

  Examples of the diimonium dye include those having a structure represented by the following general formula (1).

In the general formula (1), R _{16 to} R ₂₃ may be the same or different from each other, and are a hydrogen atom, a hydroxy group, an optionally substituted alkyl group, a cycloalkyl group, an aryl group, or a phenylalkyl. Indicates a group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -C1-C20 alkyl groups, such as an octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, are mentioned. Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, and 2-pentenyl group. Examples of the aryl group include aryl groups having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

  Examples of substituents bonded to these groups include: cyano group; nitro group; hydroxy group; tetrahydrofuryl group; halogen atom such as fluorine atom, chlorine atom, bromine atom; methoxy group, ethoxy group, n-propoxy group, isopropoxy group Group, n-butoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group, n-octyloxy group, n-decyloxy group and the like, alkoxy group having 1 to 10 carbon atoms; methoxymethoxy group, ethoxymethoxy Group, propoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxypropoxy group, ethoxypropoxy group, methoxybutoxy group, ethoxybutoxy group, etc., alkoxyalkoxy group having 2 to 12 carbon atoms; methoxymethoxymethoxy group, methoxy Methoxyethoxy group, methoxy An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms such as a toximethoxy group, a methoxyethoxyethoxy group, an ethoxymethoxymethoxy group, an ethoxymethoxyethoxy group, an ethoxyethoxymethoxy group, an ethoxyethoxyethoxy group; an allyloxy group; a phenoxy group, a tolyloxy group, Aryloxy groups having 6 to 12 carbon atoms such as xylyloxy group and naphthyloxy group; methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group, isopropylsulfonylamino group, n-butylsulfonylamino group, tert A C1-C6 alkylsulfonylamino group such as -butylsulfonylamino group, sec-butylsulfonylamino group, n-pentylsulfonylamino group, n-hexylsulfonylamino group; Nyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc. An alkoxycarbonyl group having 2 to 7 carbon atoms: methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, tert-butylcarbonyloxy group, n-pentyl C2-C7 alkylcarbonyloxy groups such as carbonyloxy group and n-hexylcacarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopoxy 2 to 7 carbon atoms such as a lopoxycarbonyloxy group, an n-butoxycarbonyloxy group, a tert-butoxycarbonyloxy group, a sec-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, and an n-hexyloxycarbonyloxy group An alkoxycarbonyloxy group etc. are mentioned.

Of these R _{16 to} R ₂₃ , a linear or branched alkyl group having 1 to 8 carbon atoms, a halogen-substituted alkyl group, or a cyano-substituted alkyl group is preferable, and a linear or branched group having 2 to 6 carbon atoms. Alkyl groups having are particularly preferred. Specific examples of the alkyl group having a linear or branched group having 2 to 6 carbon atoms include, for example, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an iso-propyl group, and an iso-butyl group. Group, iso-amyl group and the like.

Other preferable examples of R ₁₆ to R _23, may be mentioned phenyl alkylene group. The alkylene group of such a phenylalkylene group preferably has 1 to 8 carbon atoms. Further, the phenyl group in the phenylalkylene group may not have a substituent, but an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, a halogen-substituted alkyl group, and a halogen atom. It may have at least one substituent selected from the group consisting of A phenyl group having no substituent is preferable.

  Examples of the phenylalkylene group include benzyl group, phenethyl group, phenylpropylene group, phenyl-α-methylpropylene group, phenyl-β-methylpropylene group, phenylbutylene group, phenylpentylene group, and phenyloctylene group. A benzyl group and a phenethyl group are preferred.

Rings A and B in the general formula (1) may or may not have 1 to 4 substituents in addition to the 1,4-position.
Examples of the substituent that can be bonded include a halogen atom, a hydroxy group, a lower alkoxy group, a cyano group, and a lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include C1-C5 alkoxy groups such as methoxy group and ethoxy group, and examples of the lower alkyl include C1-C5 alkyl groups such as methyl group and ethyl group. Preferably, A and B do not have a substituent or are substituted with a halogen atom (especially a chlorine atom or a bromine atom), a methyl group or a cyano group. In addition, when B has a substituent, all of the four B rings are the same, and further, the position of the substituent is m-position with respect to the nitrogen atom bonded to the phenylenediamine skeleton. preferable. Further, rings A and B preferably have no substituent other than the 1,4-position in terms of synthesis.

  X in the general formula (1) is an anion necessary for neutralizing the charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. These anions are selected from, for example, organic acid anions or inorganic anions. Specifically, examples of the organic acid anion include organic carboxylate ions such as acetate ion, lactate ion, trifluoroacetate ion, propionate ion, benzoate ion, oxalate ion, succinate ion and stearate ion; Acid ion, toluenesulfonate ion, naphthalene monosulfonate ion, naphthalene disulfonate ion, chlorobenzenesulfonate ion, nitrobenzenesulfonate ion, dodecylbenzenesulfonate ion, benzenesulfonate ion, ethanesulfonate ion, trifluoromethanesulfonate ion Organic sulfonate ions such as tetraphenylborate ion, butyltriphenylborate ion, bis (trifluoromethanesulfone) imido ion, bis (penta Fluoroethane) imide acid ion, pentafluoroethanesulfone trifluoromethanesulfonimidate ion, trifluoromethanesulfone heptafluoropropanesulfonimidate ion, nonafluorobutanesulfone trifluoromethanesulfonimidate ion, 1,3-disulfonylhexafluoropropylimidate Examples thereof include sulfonimidate ions such as ions, preferably alkyl sulfonate ions such as trifluoromethane sulfonate ions and toluene sulfonate ions, alkylaryl sulfonate ions, and sulfonimidate ions.

  Examples of inorganic anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion; thiocyanate ion, hexafluoroantimonate ion, perchlorate ion, periodate ion, nitrate ion and tetrafluoroborate ion. Hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, vanadate ion, phosphate ion, borate ion, etc., and preferable ones include perchlorate ion, iodine ion, tetrafluoro Examples thereof include borate ion, hexafluorophosphate ion and hexafluoroantimonate ion.

  Among these anions, preferred are, for example, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion and sulfone. Examples include imido ion.

  A method of synthesizing the diimonium dye represented by the general formula (1) is known, and for example, a method disclosed in Japanese Patent Publication No. 43-25335 can be employed. The diimonium dye represented by the general formula (1) has a near infrared absorption ability in the range of 850 to 1200 nm, particularly has a strong near infrared absorption around 1000 nm, and has a near infrared wavelength light used for a remote control or the like. In addition to this, light of the wavelength of the computer communication that is expected to be used in the future can also be blocked, and an effect can be expected to prevent this malfunction.

  A particularly preferred diimonium dye in the present invention is represented by the following general formula (2).

(In the general formula (2), R _{1 to} R ₈ may be the same or different, and a hydrogen atom, a hydroxy group, a substituted or unsubstituted alkyl group, a cycloalkyl group, a halogenated alkyl group, It is a cyanoalkyl group, an aryl group, or a phenylalkyl group, and rings A and B may have a substituent, and R ₉ and R ₁₀ may be the same or different, Represents a fluoroalkyl group or represents a fluoroalkylene group formed by them together.)

  Among the diimonium dyes represented by the general formula (2) in the present invention, particularly preferred compounds are exemplified below.

Bis (trifluoromethanesulfone) imidic acid N, N, N ′, N′-tetrakis {p-di (n-butyl) aminophenyl} -p-phenylenediimonium represented by the formula (20),
Formula (20)

Bis (pentafluoroethanesulfone) imidic acid N, N, N ′, N′-tetrakis {p-di (n-butyl) aminophenyl} -p-phenylenediimonium represented by the formula (21),
Formula (21)

Bis (trifluoromethanesulfone) imidic acid N, N, N ′, N′-tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenediimonium represented by the formula (22),
Formula (22)

Bis {bis (trifluoromethanesulfone) imidic acid} N, N, N ′, N′-tetrakis (p-dibenzylaminophenyl) -p-phenylenediimonium represented by formula (23),
Formula (23)

Bis {bis (trifluoromethanesulfone) imidic acid} N, N, N ′, N′-tetrakis (p-diphenethylaminophenyl) -p-phenylenediimonium represented by the formula (24),
Formula (24)

Bis {bis (trifluoromethanesulfone) imidic acid} N, N, N ′, N′-tetrakis {(p-di (4-fluorinated) benzylaminophenyl) -p-phenylenediimonium represented by the formula (25) ,
Formula (25)

Bis (1,3-disulfonylhexafluoropropylimidic acid) N, N, N ′, N′-tetrakis (p-diphenethylaminophenyl) -p-phenylenediimonium represented by the formula (26)
Formula (26)

Examples thereof include bis (1,3-disulfonylhexafluoropropylimidic acid) N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium represented by the formula (27).
Formula (27)

The diimonium dye represented by the general formula (2) used in the present invention can be obtained by the following method disclosed in, for example, Japanese Patent Publication No. 43-25335. That is, an amino compound represented by the following general formula (28) obtained by reducing a product obtained by subjecting p-phenylenediamine and 1-chloro-4-nitrobenzene to Ullmann reaction is preferably used in an organic solvent. Corresponds to the desired R _{1 to} R ₈ in a water-soluble polar solvent such as dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone at 30 to 160 ° C., preferably 50 to 140 ° C. A halogenated compound (for example, BrC ₄ H ₉ when R ₁ is n-C ₄ H ₉ ), and all the substituents (R _{1 to} R ₈ ) are the same (hereinafter, all substituted) Can be obtained). In the case of synthesizing a compound other than all substituents, for example, previously reacted with a predetermined number of moles reagent (formula (20 amine compound per mole 7 moles)) (BrC ₄ H ₉₎ with R ₁ After introducing an n-butyl group into seven of ˜R _8, the number of moles necessary for introducing the remaining substituent (iso-butyl group) (1 mole per mole of amine compound of the general formula (28)) ) Reagent (BrC ₄ H ₉ BrCH ₂ CH (CH ₃ ) ₂ ).
Formula (28)

(Wherein rings A and B are as defined above.)

Thereafter, the compound synthesized above is heated in an organic solvent, preferably in a water-soluble polar solvent such as dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, acetonitrile, preferably 0 to 100 ° C. Is an oxidation reaction by adding a silver sulfonidate derivative represented by the general formula (29) at 5 to 70 ° C., and after filtering the precipitated silver, a solvent such as water, ethyl acetate or hexane is added, The resulting precipitate is filtered to obtain a diimonium dye represented by the general formula (2) of the present invention.
Formula (29)

(Wherein R ₉ and R ₁₀ are as defined above.)

  Examples of commercially available diimonium dyes represented by the general formula (2) include “CIR-RL”, “CIR-1085” (all manufactured by Nippon Carlit Co., Ltd.), and “K-1032” (Nipponization). Yakuhin Co., Ltd.).

The phthalocyanine dye is a phthalocyanine, a phthalocyanine complex, or a phthalocyanine and a phthalocyanine complex, and has one or more of OR, SR, NHR, or NRR ′ on the benzene ring of the phthalocyanine skeleton. R and R ′ are the same or different and each represents a phenyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In addition, it is preferable that one of the substituents is phthalocyanine substituted with NHR.
The phthalocyanine dye is preferably a compound represented by the following general formula (3).

(In the formula, α is the same or different and represents SR ²⁸ , OR ²⁹ , NHR ³⁰ or a halogen atom, and NHR ³⁰ is essential. R ²⁸ , R ²⁹ and R ³⁰ are the same or different and are each a substituent. a phenyl group which may have a, .Beta represents an alkyl group or an aralkyl group having 7 to 20 carbon atoms having 1 to 20 carbon atoms, which may be the same or different, represent SR ^28, oR ²⁹ or halogen atom, SR ²⁸ OR ²⁹ is essential, and M represents a metal-free, metal, metal oxide or metal halide.)

  In the general formula (3), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group A linear or branched alkyl group such as 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group; cyclohexyl group And the like, and the like. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The phenyl group, the alkyl group having 1 to 20 carbon atoms or the aralkyl group having 7 to 20 carbon atoms in R ²⁸ , R ²⁹ and R ³⁰ may have one or more substituents. Examples of such substituents include halogen atoms, acyl groups, alkyl groups, alkoxy groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkylcarbonylamino groups, arylamino groups, arylcarbonylamino group carbonyls. Group, alkoxycarbonyl group and the like.

  In M in the above general formula (3), metal-free means an atom other than a metal, for example, two hydrogen atoms. Specifically, a structure in which a hydrogen atom is bonded to two opposing nitrogen atoms that may have a substituent and exist in the central portion of the phthalocyanine structure. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. M is preferably a metal, metal oxide or metal halide, and specific examples include nickel, cobalt, copper, zinc, iron, vanadyl, dichlorotin and the like. More preferred are zinc, copper, cobalt, vanadyl and dichlorotin.

As a preferred form of the phthalocyanine dye represented by the general formula (3), 4 to 8 of 8 βs are the same or different and are SR ²⁸ or OR ²⁹ . More preferably, all eight βs are the same or different and are SR ²⁸ or OR ²⁹ . Examples of such phthalocyanine compounds include ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ (PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhNH) ₅ F ₃ , ZnPc (PhS). ) ₈ (PhCH ₂ NH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₇ F, CuPc (PhS) ₈ (PhNH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₆ F ₂ , VOPc (PhO) ₈ (PhCH ₂ NH) ₈ , VOPc (PhS) ₈ (PhCH ₂ NH) ₈ , VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (2,5-Cl _{2 PhO) 8 {2,6- (CH} 3) 2 PhO} 4 (PhCH 2 NH) 4, CuPc (PhS) 8 {2,6- (CH 3) 2 PhO} 4 (PhCH 2 NH) 4, VOPc (4-CNPhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₄ , ZnPc (2,4-Cl ₂ PhO) ₈ {2,6-Br _And a phthalocyanine compound represented by an abbreviation of 2-4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F.

Among these compounds, 4 of 8 α's are the same or different and represent NHR ³⁰ or a halogen atom. For example, ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ ( PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₄ F ₄ , VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (2,5-Cl ₂ PhO) ₈ {2, 6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , VOPc (4-CNPhO) ₈ { _{2,6-Br 2 -4- (CH 3} ) PhO} 4 {Ph _{CH 3) CHNH} 4, ZnPc} (2,4-Cl 2 PhO) 8 {2,6-Br 2 -4- (CH 3) PhO} 4 {Ph (CH 3) CHNH} represented by abbreviation ₃ F Preferred are phthalocyanine compounds.

In the abbreviations of the above compounds, Pc represents a phthalocyanine nucleus, and after Pc, represents eight substituents substituted at the β-position, and then represents eight substituents substituted at the α-position. Moreover, said Ph represents a phenyl group. More specifically, the above abbreviations represent central metal: Pc: 8 substituents at β-position: 8 substituents at α-position. For example, in VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, the central metal is 2 at the VO: phthalocyanine nucleus: β position. , 5-Cl ₂ PhO is substituted: represents a phthalocyanine compound in which α is substituted with 4,6- (CH ₃ ) ₂ PhO, ₃ Ph (CH ₃ ) CHNH, and 1 F.

  The method for producing the phthalocyanine dye represented by the general formula (3) is not particularly limited, and a conventionally known method can be appropriately used. For example, the phthalonitrile compound is produced by a cyclization reaction with one selected from metal salts, metal oxides, metal carbonyls, metal halides, and organic acid metals, followed by reaction with an amino compound.

  Examples of commercially available phthalocyanine dyes represented by the general formula (3) include “EX color IR10A”, “EX color IR12”, “EX color IR14”, and “EX color HA-1”. , "EX Color HA-14" (all made by Nippon Shokubai Co., Ltd.), etc. are opened and used as a near-infrared absorbing filter from the viewpoint of solvent solubility of phthalocyanine compounds and compatibility with copolymer (A). From the viewpoint of visible light transmittance and near infrared absorption efficiency, “EX color IR10A”, “EX color IR12”, and “EX color IR14” are preferable.

These phthalocyanine dyes represented by the general formula (3) are characterized by having an absorption maximum in the near infrared region of 800 to 900 nm and a small absorption in the visible light region. Thus, by combining with a diimonium dye, the near-infrared region of 800 to 1000 nm is efficiently absorbed and shielded by the synergistic effect of both, so that unnecessary near-infrared rays emitted from the plasma display can be absorbed.
In addition, since phthalocyanine dyes are generally excellent in heat resistance, there is no problem in reducing heat resistance when used alone or when mixed with other dyes.

  The cyanine dye is preferably, for example, the following general formula (4).

(In the general formula (4), R ^{31 to} R ³⁵ each independently represents an alkyl group which may have a substituent, and specific examples thereof are the same as those described above. Represents an integer of 0 or more, and is usually ¹ to ^3. Z ¹ and Z ² are each independently an S atom, an O atom, NR ³⁶ , or CR ³⁷ R ^38, where R ^{36 to} R ³⁸ are Each independently represents an optionally substituted alkyl group or an optionally substituted phenyl group, specific examples of which are the same as those described above, L ¹ and L ² are each independently (It forms a 5- to 7-membered ring, and is preferably an aromatic ring such as a benzene ring or a pyridine ring.)

  Specific examples of cyanine dyes include, for example, cyanine compounds such as CY17 manufactured by Nippon Kayaku Co., Ltd., SD50 manufactured by Sumitomo Seika Co., Ltd., NK-5706, NK-5060, and NK-9028 manufactured by Hayashibara Biochemical Laboratories. Can be used. The above is an example, and the present invention is not limited to these.

  These cyanine dyes represented by the general formula (4) are characterized by having an absorption maximum in the near infrared region of 800 to 950 nm and a small absorption in the visible light region. Thus, by combining with a diimonium dye, the near-infrared region of 800 to 1000 nm is efficiently absorbed and shielded by the synergistic effect of both, so that unnecessary near-infrared rays emitted from the plasma display can be absorbed.

As described above, in the present invention, only one kind of near-infrared absorbing dye can be used, but it is preferable to use two or more kinds selected from diimonium dyes, cyanine dyes and phthalocyanine dyes. When two or more types are used in combination, the ratio of each dye used is arbitrary. For example, when a diimonium dye and a cyanine dye are used in combination, the mass ratio of the former 1 to the latter 0.01 to 0.5. Is preferred. Moreover, when using a diimonium pigment | dye and a phthalocyanine pigment | dye together, 0.02-2.0 of the latter is preferable with respect to the former 1 as mass ratio. Moreover, when using together a cyanine dye and a phthalocyanine dye, the latter 1.0-100 is preferable with respect to the former 1 as mass ratio. When all three are used, the cyanine dye 0.01 to 0.5 and the phthalocyanine dye 0.02 to 2.0 are preferable with respect to the diimonium dye 1 as the mass ratio.
If necessary, for example, a dithiol-based metal complex-based dye that absorbs light in a wavelength region other than near-infrared light may be added to the near-infrared absorbing layer (C).

(Silica fine particles)
In the present invention, the near-infrared absorbing layer (C) preferably contains silica fine particles. Examples of such silica fine particles include silica fine particles having an average particle diameter (primary particle diameter) of 5 to 50 nm. A preferable average particle diameter is 10 to 40 nm.

The shape of the silica fine particles in the present invention is spherical, hollow, porous, rod-like, plate-like, fiber-like, or indefinite, and preferably spherical. The specific surface area of the silica fine particles is 0.1 to 3000 m ² / g, preferably 10 to 1500 m ² / g.
These silica fine particles can be used in a dry state or dispersed in water or an organic solvent, and a dispersion of fine silica particles known as colloidal silica can be used directly. In particular, the use of colloidal silica is preferable for improving the particle feeling. When the dispersion solvent of colloidal silica is water, the hydrogen ion concentration is in the range of 2 to 10 as a pH value, and acidic colloidal silica having a pH of 3 to 7 is preferably used. When the colloidal silica dispersion solvent is an organic solvent, methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene are used as the organic solvent. In addition, a solvent such as xylene and dimethylformamide, an organic solvent compatible with these solvents, or a mixture with water may be used. Preferred dispersing solvents are methanol, isopropyl alcohol, methyl ethyl ketone, and xylene. Examples of commercially available silica fine particles include, as colloidal silica, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST and ST-UP manufactured by Nissan Chemical Industries, Ltd. ST-20L, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. Further, as the silica powder, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600 and Aerosil OX50 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122, manufactured by Asahi Glass Co., Ltd., Examples include E220A manufactured by Nippon Silica Kogyo Co., Ltd., E220 Silicia 470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like. Examples of fumed silica include Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.

  In the near-infrared absorbing layer (C) of the present invention, it is necessary to set the blending ratio of the near-infrared absorbing dye to 5 to 50 parts by mass with respect to 100 parts by mass of the acrylic resin binder. Moreover, when using a silica particle, it is necessary to set the said mixture ratio to 0.1-2.0 mass part. If the blending ratio of the near-infrared absorbing dye is less than 5 parts by mass, the near-infrared absorbing effect is not exhibited. Conversely, if it exceeds 50 parts by mass, the visible light transmittance is adversely affected. Moreover, the winding property of a film will deteriorate that the compounding ratio of a silica particle is less than 0.1 mass part. On the other hand, if the amount exceeds 2.0 parts by mass, the haze and particle feeling deteriorate. As a more preferable form, 10 to 40 parts by weight of the front infrared absorbing dye and 0.2 to 1.5 parts by weight of silica fine particles are used with respect to 100 parts by weight of the acrylic resin binder.

  In addition, the thickness after drying of a near-infrared absorption layer (C) is 0.5 micrometer-5.0 micrometers, for example, Preferably they are 1.0 micrometer-3.0 micrometers.

Moreover, the manufacturing method of this invention apply | coats the said composition for low-refractive-index layer formation to one side of a transparent base film (A) with a 1st coater, heat-drys, and forms a low-refractive-index layer (B). After forming, the near-infrared absorbing layer is formed by applying the near-infrared absorbing layer-forming composition to the other surface of the transparent base film (A) with a second coater without heating up the sheet, and drying by heating. (C) is formed.
An example will be described. First, a long roll-shaped transparent base film (A) is prepared. At the time of manufacture, this long roll-shaped transparent substrate film (A) is continuously unwound and provided to the first coater. The coating material which consists of a composition for low refractive index layer formation is continuously apply | coated to one side of a transparent base film (A) by a 1st coater. Subsequently, the paint is dried by a known drying furnace. The drying temperature is, for example, around 140 ° C., specifically about 120 to 150 ° C. After the low refractive index layer (B) is formed on one surface of the transparent substrate film (A), the sheet is used for the second coater without being wound. By the second coater, the paint composed of the composition for forming a near-infrared absorbing layer is continuously formed on the other surface of the transparent base film (A), that is, the surface opposite to the surface on which the low refractive index layer (B) is formed. Applied. Subsequently, the paint is dried by a known drying furnace. The drying temperature is, for example, around 80 ° C., specifically about 60 to 110 ° C.
In this way, the laminated sheet is manufactured without winding up the sheet in the same manufacturing line. Therefore, the component of the composition for forming a low refractive index layer is not transferred to the other surface of the transparent base film (A), and the coating unevenness of the near infrared absorption layer (C) does not occur. Moreover, since the heat drying for forming the low refractive index layer (B) is performed before the formation of the near-infrared absorbing layer (C), the near-infrared absorbing dye is not discolored.
The first coater and the second coater used in the present invention are not particularly limited, and various types of known coaters can be used. Examples thereof include a gravure coater, a die coater, a reverse roll coater, a knife coater, a bar coater, and a lip coater.

Moreover, in this invention, you may provide the process of laminating | stacking an adhesive layer (D) further. The pressure-sensitive adhesive layer (D) is usually provided on the surface of the near-infrared absorbing layer (C) opposite to the surface on the transparent substrate film (A) side. Moreover, after forming a near-infrared absorption layer (C), you may provide an adhesive layer (D), without winding up a sheet | seat, and after winding up a sheet | seat, you may wind up and provide again. The laminated sheet having the pressure-sensitive adhesive layer (D) is suitably used for a plasma display panel. For example, from the front glass plate of the plasma display panel to the viewing side, the front glass plate, the pressure-sensitive adhesive layer (D), the near-infrared absorbing layer (C), the transparent substrate film (A), and the low refractive index layer (B) Can be applied.
The pressure-sensitive adhesive layer (D) is for optical use, and can be appropriately selected from known ones such as acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. The thickness of this pressure-sensitive adhesive layer (D) is usually in the range of 5 to 40 μm.
In the present invention, a contamination prevention layer having a contamination prevention function may be used in place of the low refractive index layer (B).

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited to these examples.

Example 1
A hard coat layer having the following composition is formed on a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm (A-1540 manufactured by Toray Industries, Inc., an easy-adhesive layer is formed on both sides, referred to as biaxial PET (1)). The composition B was applied to a dry film thickness of 2.5 μm and dried. Subsequently, the coating was cured by irradiating ultraviolet rays with a high-pressure mercury lamp to form a hard coat layer (refractive index 1.57), and wound into a long roll.
Next, the long roll-like material is continuously unwound, and a low refractive index layer-forming composition A having the following composition is applied on the hard coat layer so as to have a dry film thickness of 70 nm, and a drying furnace at 140 ° C. And a low refractive index layer was formed (refractive index 1.39 of the low refractive index layer). A gravure coater was used as the first coater for applying the low refractive index layer forming composition A. Subsequently, the composition C for forming a near-infrared absorbing layer having the following composition is applied to the other surface of the biaxial PET (1), that is, the surface opposite to the surface on which the low refractive index layer is formed, without winding up the sheet. It applied continuously so that it might become a dry film thickness of 1.5 micrometers, and let it pass through a 80 degreeC drying furnace, and formed the near-infrared absorption layer. In addition, the gravure coater was used as a 2nd coater for apply | coating the composition C for near-infrared absorption layer formation. After the formation of the near infrared absorption layer, the sheet was again wound into a long roll.

(Hardcoat layer forming composition B)
・ Ionizing radiation curable resin 100 parts by mass Dipentaerythritol hexaacrylate (DPHA)
(Nippon Kayaku 6 functional acrylic UV curable resin, solid content 100%, refractive index 1.48)
・ 333 parts by mass of antimony pentoxide sol
(Solid content 100 parts by mass)
(Catalytic Chemical Industries, ELCOM RK-1022SBV, solid content 30%, solvent is denatured alcohol, refractive index 1.70)
-Polymer having an unsaturated double bond copolymerizable at the terminal 20 parts by mass
(9 mass parts solid content)
(Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd., terminal methacrylate polymethyl methacrylate, molecular weight 6000, solid content 45%, diluted with toluene)
・ 7 parts by weight of photopolymerization initiator (Irgacure (IR) 184, manufactured by Ciba Specialty Chemicals)
-Photopolymerization initiator 1 part by mass (Irgacure (IR) 907 manufactured by Ciba Specialty Chemicals)
・ Solvent 120 parts by mass (methyl ethyl ketone (MEK) / propylene glycol monomethyl ether (PGM))

(Low refractive index layer forming composition A)
・ The following matrix component A 3333 parts by mass
(Solid content 100 parts by mass)
・ Hollow silica dispersion sol 250 parts by mass
(Solid content 50 parts by weight)
(Catalytic Chemical Industries, ELCOM RK-1018 SIV, solid content 20%, solvent is methyl isobutyl ketone (MIBK), hollow silica average particle size is 40 nm)
・ Graft copolymer 67 parts by mass
(Solid content 20 parts by mass)
(Toagosei Co., Ltd., Cymac US-270, solid content 30%, comb-shaped graft polymer in which the trunk portion is an acrylic polymer and the branch portion is made of silicone)
・ Solvent 4850 parts by mass (Methyl isobutyl ketone (MIBK))

(Preparation of matrix component A)
A 1 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 29.9 g (0.05 mol) of the following disilane compound (1) and 125 g of t-butanol and stirred at 25 ° C. .10 g of 1N aqueous acetic acid was added dropwise over 10 minutes. The mixture was further stirred at 25 ° C. for 20 hours to complete hydrolysis. To this, 2 g of aluminum acetylacetonate as a condensation catalyst and 1 g of polyether-modified silicone as a leveling agent were added, and the mixture was further stirred for 30 minutes. Paint prepared by diluting and adding 40 g of propylene glycol monomethyl ether and 40 g of diacetone alcohol. (Solid content 3%)
_{(CH 3 O) 3 Si-} C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (OCH 3) 3 (1)

(Near-infrared absorbing layer forming composition C)
-Binder resin (1) 333 parts by mass
(Solid content 100 parts by mass)
Polymethylmethacrylate resin (manufactured by Soken Chemical Co., Ltd., GS1000, solid content 30%, weight average molecular weight (Mw) 111,000, and has a molecular weight distribution of Mw / Mn = 1.68)
The molecular weight distribution was measured by GPC (polymethyl methacrylate conversion value) using chloroform as a developing solvent. The GPC measurement conditions were as follows: Column type: Shodex K806L × 2 + K800P, sample concentration: 0.2% (w / v), injection volume: 100 μL, flow rate: 1.0 ml / min, measurement temperature: 35 ° C., detector: differential Measured with a refractometer.
・ Diimonium dye (1) 200 parts by mass
(Solid content 20 parts by mass)
(Nippon Carlit Co., Ltd., CIR-RL, solid content 10%, solvent is methyl ethyl ketone (MEK))
・ Cyanine dye (1) 100 parts by mass
(1.0 mass part of solid content)
(Manufactured by Hayashibara Biochemical Research Institute, NK-5060, maximum absorption wavelength is 864 nm, solid content is 1%, MEK dilution)
-Colloidal silica dispersion (1) 2 parts by mass
(Solid content 0.6 parts by mass)
(Nissan Chemical Co., Ltd., MEK-ST, methyl ethyl ketone dispersion colloidal silica, average particle size 15 nm, silica concentration 30%)
・ Solvent MEK 317 parts by mass

The following evaluation was performed about the obtained lamination sheet.
(1) Coat unevenness of laminated sheet The coat unevenness of the laminated sheet was visually observed and evaluated according to the following criteria.
・ Evaluation criteria for coat unevenness ○: No coat unevenness.
Δ: Slight coat unevenness.
X: Coat unevenness is large.

(2) Discoloration of laminated sheet After measuring the obtained near-infrared cut film with a spectrophotometer [manufactured by Shimadzu Corporation, Solid Spec 3700] according to JIS Z8701-1999 (Y, x, y) The (Y, x, y) after standing in a constant temperature layer at 80 ° C. for 500 hours was measured in the same manner as described above. The amount of change in (Y, x, y) before and after the test was determined and evaluated according to the following criteria.
-Evaluation criteria for discoloration ◯: All of the numerical values of (Y, x, y) are less than 1%.
Δ: All the numerical values of (Y, x, y) are less than 2%, but at least one is 1% or more.
X: At least one change amount of each numerical value of (Y, x, y) is 2% or more.

(3) Alkali resistance A 2% NaOH aqueous solution is dropped on the surface of the low refractive index layer, wiped off after standing for 20 minutes, and the state of contamination is visually determined according to the following criteria.
○: No contamination is seen.
Δ: Contaminated.
×: Significantly contaminated.

(4) Contamination resistance After writing letters on the surface using Sakura Crepas, Sakura Myname (oil), and wiping with tissue paper [Crecia Co., Ltd., “Kimwipe”]. Evaluation was made by observation.
○: Wipe clean within 10 round trips.
Δ: Cleanly wiped within 11 to 20 round trips.
X: It cannot wipe off by 20 reciprocations.

(5) Visible light (400 to 700 nm) average transmittance Measured according to JIS A5759.

(6) Near infrared transmittance (850 nm)
The light transmittance at a wavelength of 850 nm was measured using a spectrophotometer [manufactured by Shimadzu Corporation, Solid Spec 3700].
(7) Near-infrared transmittance (950 nm)
The light transmittance at a wavelength of 950 nm was measured using a spectrophotometer [manufactured by Shimadzu Corporation, Solid Spec 3700].

  The results are shown in Table 1.

Comparative Example 1
In Example 1, after forming the low refractive index layer, Example 1 was repeated except that the sheet was once wound and the sheet was wound again to form a near-infrared absorbing layer.

Comparative Example 2
In Comparative Example 1, the graft copolymer was omitted from the low refractive index layer forming composition A to form a low refractive index layer forming composition D, and the composition D was used as the low refractive index layer forming composition. Except that, Comparative Example 1 was repeated.

Comparative Example 3
A hard coat layer is formed on biaxial PET (1) in the same manner as in Example 1 and wound into a long roll, and then the long roll is continuously wound to form a hard coat layer. The composition C for forming a near-infrared absorbing layer used in Example 1 was continuously applied to the side opposite to the surface so as to have a dry film thickness of 1.5 μm, and passed through a drying furnace at 80 ° C. A layer was formed and wound into a long roll. Subsequently, the long roll-shaped product was continuously unwound again, and the low refractive index layer forming composition A used in Example 1 was applied on the hard coat layer so as to have a dry film thickness of 70 nm, and 140 ° C. The low refractive index layer was formed by passing through a drying oven. The first coater and the second coater used in Comparative Example 3 are the same as those in Example 1.

Comparative Example 4
In Comparative Example 3, the diimonium dye (1) and the cyanine dye (1) were omitted from the composition C for forming a near-infrared absorbing layer. 200 parts by weight of a solid content) and 6 boride compound fine particles (a dispersion of hexaboride fine particles having a concentration of 1.85% dispersed in toluene, an average particle size of 0.02 μm (manufactured by Sumitomo Metal Mining Co., Ltd., “KHF -7A ")) was used as 2 parts by weight of solid content to make composition E for forming a near infrared absorbing layer, and Comparative Example 3 was repeated except that composition E was used as a composition for forming a near infrared absorbing layer. It was.

  The results of Comparative Examples 1 to 4 are shown in Table 2.

Example 2
On the biaxial PET (1) used in Example 1, a hard coat layer-forming composition G having the following composition was applied to a dry film thickness of 2.5 μm and dried. Subsequently, the coating was cured by irradiating ultraviolet rays with a high pressure mercury lamp to form a hard coat layer (refractive index 1.49).
Next, on the hard coat layer, a composition F for forming a high refractive index layer having the following composition was applied so as to have a dry film thickness of 80 nm (refractive index 1.70 of the high refractive index layer), dried, and then subjected to high pressure. The paint was cured by irradiating ultraviolet rays with a mercury lamp, and wound into a long roll.
Next, the long roll-shaped material is continuously unwound, a low refractive index layer and a near-infrared absorbing layer are formed on the high refractive index layer in the same procedure as in Example 1, and the same evaluation as in Example 1 is performed. Went. The results are shown in Table 3.

(Hardcoat layer forming composition G)
・ Ionizing radiation curable resin 100 parts by mass Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. 6-functional acrylic UV curable resin, solid content 100%)
-Polymer having an unsaturated double bond copolymerizable at the terminal 20 parts by mass
(9 mass parts solid content)
(Macromonomer AA-6 manufactured by Toa Gosei Co., Ltd.
Terminal methacrylate polymethyl methacrylate, molecular weight 6000,
(45% solid content, diluted with toluene)
・ 7 parts by weight of photopolymerization initiator (Irgacure (IR) 184, manufactured by Ciba Specialty Chemicals)
-Photopolymerization initiator 1 part by mass (Irgacure (IR) 907 manufactured by Ciba Specialty Chemicals)
・ Solvent 120 parts by mass (methyl ethyl ketone (MEK) / propylene glycol monomethyl ether (PGM))

(Composition F for forming a high refractive index layer)
・ Matrix component 100 parts by mass Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. 6-functional acrylic UV curable resin, solid content 100%)
・ 400 parts by mass of zinc antimonate
(Solid content 240 parts by weight)
(Nissan Chemical, Celnax CX-Z603M-F2, solid content 60%,
Refractive index 1.7)
・ 20 parts by mass of photopolymerization initiator (Irgacure (IR) 184 manufactured by Ciba Specialty Chemicals)
・ Dispersant 4 parts by mass
(Solid content 0.8 parts by mass)
(Nippon Lubrizol Corporation, Solsperse 20000,
Alkylamine EO / PO adduct, solid content 20%)

Comparative Example 5
In Example 2, after forming the low refractive index layer, Example 2 was repeated except that the sheet was once wound up and the sheet was wound up again to form a near-infrared absorbing layer.

Comparative Example 6
In Comparative Example 5, the graft copolymer was omitted from the low refractive index layer forming composition A to form a low refractive index layer forming composition D, and the composition D was used as the low refractive index layer forming composition. Except for the above, Comparative Example 5 was repeated.

Comparative Example 7
On the biaxial PET (1), a hard coat layer and a high refractive index layer were formed in the same manner as in Example 2, and after winding into a long roll, the long roll was continuously wound. The composition C for forming a near-infrared absorbing layer used in Example 1 was continuously applied to the side opposite to the surface on which the hard coat layer was formed so as to have a dry film thickness of 1.5 μm, and passed through a drying furnace at 80 ° C. The near-infrared absorbing layer was formed and wound into a long roll. Subsequently, the long roll-shaped material is continuously unwound again, and the low refractive index layer forming composition A used in Example 2 is applied onto the high refractive index layer so as to have a dry film thickness of 70 nm. A low-refractive index layer was formed by passing through a drying oven at 0 ° C. The first coater and the second coater used in Comparative Example 7 are the same as those in Example 2.

Comparative Example 8
In Comparative Example 7, the diimonium dye (1) and the cyanine dye (1) were omitted from the composition C for forming a near-infrared absorbing layer. 200 parts by weight of a solid content) and 6 boride compound fine particles (a dispersion of hexaboride fine particles having a concentration of 1.85% dispersed in toluene, an average particle size of 0.02 μm (manufactured by Sumitomo Metal Mining Co., Ltd., “KHF -7A ")) was used as 2 parts by weight of solid content to make composition E for forming a near infrared absorption layer, and Comparative Example 7 was repeated except that the composition E was used as a composition for forming a near infrared absorption layer. It was.

  The results of Comparative Examples 5 to 8 are shown in Table 4.

From the results of Tables 1 to 4, the following matters are derived.
In Example 1, a hard coat layer is provided on one surface of the transparent base film (A), and a low refractive index layer-forming composition having a specific composition is applied thereon with a first coater, followed by heating and drying. After forming the low refractive index layer (B), the composition for forming a near-infrared absorbing layer having a specific composition is applied to the other surface of the transparent base film (A) with a second coater without winding the sheet. And it heat-drys and forms the near-infrared absorption layer (C). Thereby, after forming a low refractive index layer (B), since the near-infrared absorption layer (C) is formed without winding up a sheet | seat, the component of the composition for low refractive index layer formation is a transparent base film. There is no transfer to the other surface of (A), and coating unevenness of the near-infrared absorbing layer (C) does not occur. Moreover, the high temperature drying necessary for forming the low refractive index layer (B) does not adversely affect the near infrared absorbing dye contained in the near infrared absorbing layer (C), and the dye does not change color. Furthermore, since the composition for forming a low refractive index layer and the composition for forming a near-infrared absorbing layer having a specific composition are used, it is excellent in alkali resistance, stain resistance, average visible light transmittance, and near-infrared absorption.
In contrast, in Comparative Example 1, since the sheet is wound into a roll after the formation of the low refractive index layer (B), the component of the low refractive index layer forming composition is the transparent base film (A). Transfer to the other surface caused uneven coating of the near-infrared absorbing layer (C).
In Comparative Example 2, since the specific graft copolymer was omitted from the composition for forming a low refractive index layer, the coating unevenness of the laminated sheet did not occur, but the alkali resistance and stain resistance were evaluated as x. .
In Comparative Example 3, since the low refractive index layer (B) is formed after the formation of the near-infrared absorbing layer (C) and dried at a high temperature, the dye contained in the near-infrared absorbing layer (C) is discolored by heat. The discoloration of the laminated sheet was evaluated as x.
Comparative Example 4 is an example in which, in the production method of Comparative Example 3, the dye of the near infrared absorption layer (C) is changed to ATO fine particles and hexaboride compound fine particles which are inorganic near infrared absorbers, and a laminated sheet Although there was no problem with discoloration, the average visible light transmittance deteriorated.

In Example 2, a hard coat layer and a high refractive index layer are provided on one surface of the transparent substrate film (A), and a composition for forming a low refractive index layer having a specific composition is formed on the high refractive index layer as the first. After coating with a coater, heating and drying to form the low refractive index layer (B), the near-infrared absorbing layer having a specific composition is formed on the other surface of the transparent base film (A) without winding up the sheet. The composition is applied with a second coater and dried by heating to form a near-infrared absorbing layer (C). Thereby, after forming a low refractive index layer (B), since the near-infrared absorption layer (C) is formed without winding up a sheet | seat, the component of the composition for low refractive index layer formation is a transparent base film. There is no transfer to the other surface of (A), and coating unevenness of the near-infrared absorbing layer (C) does not occur. Moreover, the high temperature drying necessary for forming the low refractive index layer (B) does not adversely affect the near infrared absorbing dye contained in the near infrared absorbing layer (C), and the dye does not change color. Furthermore, since the composition for forming a low refractive index layer and the composition for forming a near-infrared absorbing layer having a specific composition are used, it is excellent in alkali resistance, stain resistance, average visible light transmittance, and near-infrared absorption.
In contrast, in Comparative Example 5, since the sheet is wound into a roll after the formation of the low refractive index layer (B), the component of the low refractive index layer forming composition is the transparent base film (A). Transfer to the other surface caused uneven coating of the near-infrared absorbing layer (C).
In Comparative Example 6, since the specific graft copolymer was omitted from the composition for forming a low refractive index layer, the coating unevenness of the laminated sheet did not occur, but the alkali resistance and stain resistance were evaluated as x. .
In Comparative Example 7, since the low refractive index layer (B) is formed after the near infrared absorption layer (C) is formed and dried at a high temperature, the dye contained in the near infrared absorption layer (C) is discolored by heat. The discoloration of the laminated sheet was evaluated as x.
Comparative Example 8 is an example in which the dye of the near infrared absorption layer (C) is changed to ATO fine particles and hexaboride compound fine particles, which are inorganic near infrared absorbers, in the production method of Comparative Example 7, and a laminated sheet Although there was no problem with discoloration, the average visible light transmittance deteriorated.

  According to the production method of the present invention, there is no coating unevenness, discoloration, and it is possible to produce a laminated sheet excellent in alkali resistance, stain resistance, average visible light transmittance, and near infrared absorptivity. In particular, it is suitably used for a plasma display panel.

Claims (7)

Forming a low refractive index layer (B) on one surface of the transparent substrate film (A), forming a near infrared absorbing layer (C) on the other surface of the transparent substrate film (A), and A method for producing a laminated sheet comprising:
The following composition for forming a low refractive index layer is applied to one surface of the transparent substrate film (A) with a first coater and dried by heating to form the low refractive index layer (B). Without winding, the following composition for forming a near-infrared absorbing layer is applied to the other surface of the transparent substrate film (A) with a second coater, followed by drying by heating to form the near-infrared absorbing layer (C). A method for producing a laminated sheet, comprising:
Low refractive index layer forming composition: Contains a graft copolymer having a repeating unit formed using a radical polymerizable monomer as a trunk and silicone as a branch.
Near-infrared absorbing layer forming composition: containing an acrylic resin binder and a near-infrared absorbing dye, and containing 5-50 parts by weight of the near-infrared absorbing dye with respect to 100 parts by weight of the acrylic resin binder.   The low refractive index layer forming composition is a matrix component mainly composed of a disilane compound having a divalent organic group containing one or more fluorine atoms or a (partial) hydrolyzate thereof; hollow silica particles; and It contains a graft copolymer and contains 20 to 120 parts by mass of the hollow silica particles and 5 to 40 parts by mass of the graft copolymer with respect to 100 parts by mass of the matrix component. The manufacturing method of the lamination sheet of description.   The method for producing a laminated sheet according to claim 1 or 2, wherein two or more kinds of the near infrared absorbing dyes are used.   The method for producing a laminated sheet according to claim 3, wherein the near-infrared absorbing dye is at least two kinds selected from a diimonium dye, a cyanine dye, and a phthalocyanine dye.   The method for producing a laminated sheet according to claim 1, wherein the acrylic resin is a polymethyl methacrylate resin.   The said transparent base film (A) is a biaxially-stretched polyethylene terephthalate film, The manufacturing method of the laminated sheet of Claim 1 characterized by the above-mentioned.   2. The method according to claim 1, further comprising forming a pressure-sensitive adhesive layer (D) on the surface of the near infrared absorbing layer (C) opposite to the surface on the transparent base film (A) side. A method for producing a laminated sheet.