JPH11274792A - Electromagnetic wave shielding reflection suppressing material and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart electromagnetic wave shielding performance by applying an oxidizing coating liquid, where a polymer of specified multifunctional acrylate ester containing fluorine and a photopolymerization starting agent are mixed at a specified ratio, to a basic material having electromagnetic wave shielding function and then curing it to obtain a reflecting member. SOLUTION: A substrate 1 having electromagnetic wave shielding function is produced by forming a transparent indium tin film on the surface of a transparent resin, clamping a metal mesh between transparent resin plates and depositing an inorganic conductive material on the surface thereof. A polymer 3 can be synthesized easily by radical polymerization, or the like. Any polymerization starting agent starting polymerization through irradiation with UV-ray may be mixed with a specified curing coating liquid containing fluorine. Preferably, the coating liquid contains 80-99 wt.% of multifunctional acrylate ester 1 and 20-1 wt.% of polymer 3. mixing ratio of a solvent containing fluorine and a non-fluorine based curing coating liquid is preferably set at 3-100 weight times of the total quantity of curing components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electromagnetic wave-shielding anti-reflective material having a high surface hardness, a low refractive index and excellent visibility, which can be used as a component of a display device, and a method for producing the same. About.

[0002]

2. Description of the Related Art In recent years, TVs, OA equipment, cathode ray tubes (CRs)
T) It has become a problem that electromagnetic waves generated from an electronic image display device such as a display and a plasma display (PDP) adversely affect the human body and surrounding electronic devices. In order to solve the problem of the electromagnetic wave, an electromagnetic wave shielding substrate is used on the front surface of the device. For example, the following technology is known as a method for providing an electromagnetic wave shielding function. (1) A method in which a stainless steel or copper mesh is attached to the front of a transparent substrate (also called a panel).
0-3687), (2) a method of forming a conductive substance such as ITO (indium tin oxide) by sputtering or the like (JP-A-5-134102);
(3) A method in which a metal is formed on a fiber or the like by an electroless plating method to form a mesh, and the mesh is incorporated into a transparent substrate (Japanese Patent Application Laid-Open No. 8-183132). On the other hand, when a transparent substrate is used for shielding these electromagnetic waves, for example, the background fluorescent lamp is reflected and the visibility is deteriorated, and when used for a long time, there is a problem that eyes are tired.

On the other hand, the following techniques are already known as antireflective materials and antireflective materials. That is, when an antireflection film made of a substance having a lower refractive index than that of the substrate is formed on the outermost layer of the film with a film thickness of about ｎｍ of the visible light wavelength (about 100 nm), the surface reflection is reduced by the interference effect, and the transmission It is known that the rate improves. Such a principle is applied to a reflection-reducing film, a reflection-reducing sheet, and the like in a field such as a liquid crystal display device in which surface reflection is required to be reduced.

In order to produce the anti-reflection film and the anti-reflection sheet, for example, (i) magnesium fluoride or the like is deposited,
A method of performing sputtering, (ii) a method of applying and drying a solution in which a resin such as a fluoropolymer having a low refractive index is dissolved, and the like are performed (Japanese Patent Application Laid-Open No. 6-115023). However, the former method (i) of vapor deposition-sputtering is performed under vacuum conditions, so that the productivity is poor and it is difficult to increase the area, and the latter method (ii) of solution / coating / drying has a high productivity. Although it is possible to increase the area, the fluorine-containing polymer has a drawback that the hardness is low and the wear resistance is inferior.

Further, there has been proposed a method in which a fluorine-containing monomer is formed into a solution as required, coated on a film, and polymerized by irradiation with active energy rays, heating or the like. As the fluorine-containing monomer for carrying out this method, for example, monofunctional fluorine-containing alkyl acrylates and monofunctional fluorine-containing methacrylic alkyl esters are known. However, the fluorine-containing polymer obtained by polymerizing and curing them has the disadvantage that it has low hardness and poor abrasion resistance, similarly to the resin used in the method (ii).

On the other hand, recently, the size and weight have been reduced, such as large-sized PDPs and wall-mounted TVs. There is a demand for productivity that enables mass production. Conventionally, a method of individually preparing an electromagnetic wave shielding material and an anti-reflection material in advance and bonding an anti-reflection film to the electromagnetic wave shielding material has been conventionally performed (Japanese Patent Laid-Open No. 9-2475).
No. 82). Due to the above-mentioned increase in size, weight reduction, productivity, and the like, integration of a material having an electromagnetic wave shielding function and a material having an antireflection function has been demanded. For example, Japanese Patent Application Laid-Open No. 5-283889 discloses a method of forming a transparent thin film layer made of a compound having a low refractive index on an electromagnetic wave shielding material formed on a transparent substrate by electroless plating. An integrated light-transmitting electromagnetic wave shielding material that improves the visibility of a display by reducing the number of such elements is disclosed. However, the method of forming this transparent thin film layer is a method of applying a fluoropolymer, for example, a Teflon resin or an amorphous fluoropolymer by dip coating and drying,
There are problems with the adhesion to the substrate and the surface hardness.

[0007]

A first object of the present invention is to provide a specific composite material having (a) an electromagnetic wave shielding function and (b) an antireflection function, wherein the antireflection function specifies a specific component. An object of the present invention is to provide an electromagnetic wave shielding and anti-reflective material having an anti-reflection layer formed by curing a curable coating liquid containing the same in a proportion.
A second object of the present invention is to provide a method for producing the above-mentioned electromagnetic wave shielding / reducing material with good productivity.

[0008]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that the polymerization of a specific fluorine-containing polyfunctional (meth) acrylic ester and a specific fluorine-containing (meth) acrylic ester has been considered. After applying a curable coating solution containing a coalescence and a photopolymerization initiator to a substrate having an electromagnetic wave shielding function, it was found that when cured by irradiation with ultraviolet light, it became an excellent electromagnetic wave shielding / reflecting material, and completed the present invention. did. That is, the present invention includes the following (1) to (6).

(1) (a) Electromagnetic wave shielding function and (b)
A composite material having an anti-reflection function,
70 to 100% by weight of a fluorinated polyfunctional (meth) acrylate as the A component and a fluorinated polymer 3 as the B component
An electromagnetic wave-shielding anti-reflective material comprising a anti-reflection layer obtained by curing a curable coating solution containing 0 to 0% by weight. (2) An electromagnetic wave-shielding anti-reflective material comprising a substrate having an electromagnetic wave-shielding function and an anti-reflection layer formed on one or both surfaces of the substrate, wherein the anti-reflection layer is a fluorine-containing polyfunctional (meth) acrylate of component A And a cured layer of a curable coating solution containing a fluorine-containing polymer of the component B, wherein the component A is represented by the following general formula [1]

Embedded image [Wherein X ¹ and X ² are the same or different groups,
Y ¹ represents a hydrogen atom or a methyl group;
Pieces organic bivalent to octavalent fluorine atoms having two or more fluoroalkylene group having 1 to 14 carbon atoms, fluoro cycloalkylene group or -C having 3 to 14 carbon atoms and having a fluorine atom 4 or more (Y ²⁾ HCH ₂ -group, wherein Y ² is a fluoroalkyl group having 1 to 14 carbon atoms having 3 or more fluorine atoms, and a 3 to 14 carbon atoms having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. ) Or the following general formula [2]

Embedded image (Where Y ³ has 1 to 3 carbon atoms having 3 or more fluorine atoms)
14 fluoroalkyl groups, Z is a hydrogen atom or carbon atom 1
To 3 alkyl groups. ), M,
n is a number of 1 or 2. A bifunctional to tetrafunctional fluorinated (meth) acrylate represented by the following general formula [3]:

Embedded image (Wherein X ³ represents a hydrogen atom or a methyl group, and Y ⁴ represents a C 2-14 fluoroalkyl group having 3 or more fluorine atoms or a C 4-14 carbon atom having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. The above-mentioned electromagnetic wave-shielding anti-reflective material which is a polymer containing 50% by weight or more as a constituent unit based on a monofunctional fluorine-containing (meth) acrylate represented by the formula (1).

(3) The refractive index of the antireflection layer is smaller than the refractive index of the substrate, and the refractive index of the antireflection layer is 1.5 or less;
The above-mentioned electromagnetic wave shielding / reducing material having a thickness of 70 to 150 nm. (4) The electromagnetic wave shielding / reflecting material according to the above, wherein the electromagnetic wave shielding function is at least one selected from the group consisting of a conductive mesh layer, an ITO (indium tin oxide) deposited layer, and an Ag deposited layer.

(5) The method for producing an electromagnetic wave shielding / reflecting material according to the above, wherein one or both surfaces of a substrate having an electromagnetic wave shielding function are coated with the following curable coating solution and cured by ultraviolet rays to reduce reflection. A method for producing an electromagnetic wave shielding antireflective material for forming a layer. The curable coating liquid contains 70 to 100% by weight of a fluorinated polyfunctional (meth) acrylate as the A component, 30 to 0% by weight of a fluorinated polymer as the B component, and a necessary amount of a photopolymerization initiator as the C component. It is a curable coating liquid. (6) The fluorine-containing polyfunctional (meth) acrylate of the component A is represented by the following general formula [1]

Embedded image [Wherein X ¹ and X ² are the same or different groups,
Y ¹ represents a hydrogen atom or a methyl group;
Pieces organic bivalent to octavalent fluorine atoms having two or more fluoroalkylene group having 1 to 14 carbon atoms, fluoro cycloalkylene group or -C having 3 to 14 carbon atoms and having a fluorine atom 4 or more (Y ²⁾ HCH ₂ -group, wherein Y ² is a fluoroalkyl group having 1 to 14 carbon atoms having 3 or more fluorine atoms, and a 3 to 14 carbon atoms having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. ) Or the following general formula [2]

Embedded image (Where Y ³ has 1 to 3 carbon atoms having 3 or more fluorine atoms)
14 fluoroalkyl groups, Z is a hydrogen atom or carbon atom 1
To 3 alkyl groups. ), M,
n is a number of 1 or 2. A bifunctional or tetrafunctional fluorinated (meth) acrylate represented by the following general formula [3]:

Embedded image (Wherein X ³ represents a hydrogen atom or a methyl group, Y ³ represents a C 2-14 fluoroalkyl group having 3 or more fluorine atoms or a C 4-14 carbon atom having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. A) a polymer containing 50% by weight or more as a structural unit based on a monofunctional fluorine-containing (meth) acrylate represented by the formula (1), wherein the ultraviolet curing is polymerization curing by ultraviolet light performed in an inert gas atmosphere. Method for producing an anti-reflective material.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The "substrate having an electromagnetic wave shielding function" used in the present invention may be a conventionally used substrate, and examples thereof include the following. [A] A transparent resin surface on which a transparent ITO (indium tin oxide) film is formed. [B] A metal mesh sandwiched between transparent resin plates. [C] An inorganic conductive substance deposited on the surface of a transparent resin plate.

The material of the substrate having an electromagnetic wave shielding function (hereinafter, referred to as an electromagnetic wave shielding substrate) is not particularly limited. For example, polyethylene terephthalate (PET), polycarbonate (P)
C), polymethyl methacrylate (PMMA), triacetyl cellulose (TAC), polyolefin (PO),
Polyamide (PA), polyvinyl chloride (PVC) and the like can be preferably mentioned. Furthermore, as a substrate,
Those having antiglare treatment or transparent coloring on the surface may also be used.

The anti-reflective material for electromagnetic wave shielding produced according to the present invention comprises an anti-reflection layer obtained by polymerizing and curing a curable coating solution containing a specific fluorine-containing polyfunctional (meth) acrylic ester. It is formed on one or both sides of a conductive substrate.

The specific fluorinated curable coating liquid contains a fluorinated polyfunctional (meth) acrylic acid ester. In particular, the bifunctional to quaternary to quaternary compound represented by the general formula [1] is used as the component A. Functional fluorinated (meth) acrylic acid ester {hereinafter referred to as (meth) acrylic acid ester 1} and monofunctional (meth) acrylic acid ester represented by the general formula [2] as B component {hereinafter, referred to as (meth) A coating liquid containing a polymer (hereinafter referred to as polymer 3) containing 50% by weight or more as an acrylic acid ester 2 as a constituent component and a photopolymerization initiator as a C component. A three-dimensional network structure, and a cured film can be obtained. In the general formulas [1] and [3], when Y ¹ and Y ⁴ have 15 or more carbon atoms, production is difficult.

The polyfunctional fluorine-containing (meth) acrylate is preferably a bifunctional to tetrafunctional fluorine-containing (meth) acrylate. Among them, examples of the bifunctional fluorine-containing (meth) acrylic acid ester include di (meth) acrylic acid-2,2,2-trifluoroethylethylene glycol and di (meth) acrylic acid-2,2,3 , 3,3-pentafluoropropylethylene glycol, di (meth) acrylic acid-2,2
3,3,4,4,4-heptafluorobutylethylene glycol, di (meth) acrylic acid-2,2,3,3
4,4,5,5,5-nonafluoropentylethylene glycol, di (meth) acrylic acid-2,2,3,3
4,4,5,5,6,6,6-undecafluorohexylethylene glycol, di (meth) acrylic acid-2,
2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4 5,5
6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di (meth) acrylic acid-3,
3,4,4,5,5,6,6,7,7,8,8,8,8-tridecafluorooctylethylene glycol, di (meth) acrylic acid-2,2,3,3,4,4 5,5
6,6,7,7,8,8,9,9,10,10,10-
Nonadecafluorodecylethylene glycol, di (meth) acrylic acid-3,3,4,4,5,5,6,6
7,7,8,8,9,9,10,10,10-heptadecafluorodecylethylene glycol, 2-trifluoromethyl-3,3,3-trifluoropropylethylene glycol di (meth) acrylate, 3-trifluoromethyl-4,4,4-trifluorobutylethylene glycol di (meth) acrylate, 1-methyl-2,2,3,3,3-pentafluoropropylethylene di (meth) acrylate Glycol, di (meth) acrylic acid-1
-Methyl-2,2,3,3,4,4,4-heptafluorobutylethylene glycol, di (meth) acrylic acid-
2,2,3,3-tetrafluorobutanediol, di (meth) acrylic acid-2,2,3,3,4,4-hexafluoropentanediol, di (meth) acrylic acid-
2,2,3,3,4,4,5,5-octafluorohexanediol, di (meth) acrylic acid-2,2,3
3,4,4,5,5,6,6-decafluoroheptanediol, di (meth) acrylic acid-2,2,3,3,4
4,5,5,6,6,7,7-dodecafluorooctanediol, di (meth) acrylic acid-2,2,3,3
4,4,5,5,6,6,7,7,8,8-tetradecafluorononanediol, di (meth) acrylic acid-2,
2,3,3,4,4,5,5,6,6,7,7,8,
8,9,9-hexadecafluorodecanediol, di (meth) acrylic acid-2,2,3,3,4,4,5
5,6,6,7,7,8,8,9,9,10,10-octadecafluoroundecanediol, di (meth) acrylic acid-2,2,3,3,4,4,5,5 , 6,6,
7, 7, 8, 8, 9, 9, 10, 10, 11, 11,-
Eicosafluorododecanediol and the like can be preferably mentioned. These di (meth) acrylates can be used alone or as a mixture when used.

Furthermore, examples of the fluorine-containing polyfunctional (meth) acrylate other than the diester include trifunctional and tetrafunctional fluorine-containing polyfunctional (meth) acrylates. The trifunctional fluorine-containing polyfunctional (meth)
Specific examples of the acrylate include, for example, 3-perfluorobutyl-2- (meth) acryloyloxypropyl-2,2-bis {(meth) acryloyloxymethyl} propionate and 3-perfluorohexyl-2-
(Meth) acryloyloxypropyl-2,2-bis {(meth) acryloyloxymethyl} propionate, 3-perfluorooctyl-2- (meth) acryloyloxypropyl-2,2-bis} (meth) acryloyloxymethyl {Propionate, 3-perfluorocyclopentylmethyl-2- (meth) acryloyloxypropyl-2,2-bis} (meth) acryloyloxymethyl} propionate, 3-perfluorocyclohexylmethyl-2- (meth) acryloyloxypropyl-
2,2-bis {(meth) acryloyloxymethyl} propionate, 3-perfluorocyclobutylmethyl-
2- (meth) acryloyloxypropyl-2,2-bis {(meth) acryloyloxymethyl} propionate, and further, 2-perfluorobutyl- {1- (meth)
Acroyloxymethyl {ethyl-2,2-bis} (meth) acryloyloxymethyl} propionate, 2-
Perfluorohexyl- {1- (meth) acryloyloxymethyl} ethyl-2,2-bis {(meth) acryloyloxymethyl} propionate, 2-perfluorooctyl- {1- (meth) acryloyloxymethyl} ethyl-2 , 2-bis {(meth) acryloyloxymethyl} propionate, 2-perfluorocyclopentylmethyl- {1- (meth) acryloyloxymethyl} ethyl-2,2-bis {(meth) acryloyloxymethyl} propionate, 2- Perfluorocyclohexylmethyl- {1- (meth) acryloyloxymethyl} ethyl-2,2-bis {(meth) acryloyloxymethyl} propionate, 2-perfluorocyclobutylmethyl- {1- (meth) acryloyloxymethyl} Ethyl-2,2-bis ｛(meta Acryloyloxymethyl}
And propionate.

Specific examples of tetrafunctional fluorine-containing polyfunctional (meth) acrylates include, for example, tetra (meth) acrylic acid-4,4,5,5-tetrafluorooctane-1,2 , 7,8-Tetraol, tetra (meth) acrylic acid-4,4,5,5,6,6-hexafluorononane-1,2,8,9-tetraol, tetra (meth) acrylic acid-4 , 4,5,5,6,6,7,
7,8,8-decafluoroundecane-1,2,10,
11-tetraol, tetra (meth) acrylic acid-4,
4,5,5,6,6,7,7,8,8,9, -dodecafluorododecane-1,2,11,12-tetraol can be preferably exemplified. In use, the above-mentioned fluorine-containing polyfunctional (meth) acrylate can be used alone or as a mixture.

The polyfunctional (meth) acrylic acid ester can be easily prepared, for example, by a usual ring-opening reaction between the corresponding fluorine-containing epoxy compound and (meth) acrylic acid. A method of subjecting a hydroxy (meth) acrylic acid ester and (meth) acrylic acid to a normal esterification reaction, a method of subjecting the corresponding fluorinated 1,2-diol and (meth) acrylic acid to a normal esterification reaction,
Alternatively, it can be easily obtained by a usual esterification reaction of the corresponding fluorine-containing diol with (meth) acrylic acid.

The polymer 3 is a polymer containing the monofunctional fluorinated (meth) acrylate 2 as a constituent unit, preferably at least 50% by weight, more preferably at least 70% by weight. It may also contain less than 50% by weight of constituent units composed of other copolymerizable monomers, and each constituent unit may be random or block. At this time, if the constituent unit composed of (meth) acrylic acid ester 2 is less than 50% by weight, the compatibility with (meth) acrylic acid ester 1 becomes poor, and a uniform coating film cannot be obtained.

Examples of the (meth) acrylate 2 which can be a constituent unit of the polymer 3 include, for example, 2,2,2-trifluoroethyl (meth) acrylate,
(Meth) acrylic acid-2,2,3,3-pentafluoropropyl, (meth) acrylic acid-2,2,3,3
4,4,4-heptafluorobutyl, (meth) acrylic acid-2,2,3,3,4,4,5,5,5-nonafluoropentyl, (meth) acrylic acid-2,2,3, 3,
4,4,5,5,6,6,6-undecafluorohexyl, (meth) acrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,7-tridecafluoroheptyl, (meth) acrylic acid-2,2,3,3,4,4
5,5,6,6,7,7,8,8,8-pentadecafluorooctyl, (meth) acrylic acid-3,3,4,4
5,5,6,6,7,7,8,8,8-tridecafluorooctyl, (meth) acrylic acid-2,2,3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,10-nonadecafluorodecyl, (meth) acrylic acid-3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,10-heptadecafluorodecyl, 2-trifluoromethyl-3,3,3-trifluoropropyl (meth) acrylate, -3-tri (meth) acrylate Fluoromethyl-4,4,4-trifluorobutyl, 1-methyl-2 (meth) acrylate,
2,3,3,3-pentafluoropropyl, 1-methyl-2,2,3,3,4,4,4- (meth) acrylate
Heptafluorobutyl and the like can be preferably mentioned,
When used, they can be used alone or as a mixture.

Further, in the polymer 3, the other copolymerizable monomer which can be a constituent unit as required includes, for example, olefins such as ethylene and propylene; acrylic acid, methacrylic acid, methyl acrylate, acrylic Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid 2
(Meth) acrylic acids such as ethylhexyl and their alkyl esters; vinyl acetate, vinyl propionate,
Vinyl esters of fatty acids such as vinyl stearate and vinyl pivalate; styrenes such as styrene and α-methylstyrene; vinyl halides such as vinyl chloride; vinylidene halides such as vinylidene chloride; vinyl alkyl ethers such as vinyl butyl ether; Vinyl alkyl ketones such as methyl ketone and vinyl ethyl ketone; unsaturated hydrocarbons such as isobutylene and 1,3-butadiene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; further, fumaric acid, maleic acid, citraconic acid, Preferable examples include unsaturated polybasic acids such as mesaconic acid, itaconic acid and tetrahydrophthalic acid, and their alkyl esters; vinylcarbazole, aryl acetate and the like. More preferably, an alkyl (meth) acrylate can be mentioned.

The polymer 3 can be easily synthesized by a generally used radical polymerization method or the like. Specifically, for example, azo radial polymerization initiators such as azobisisobutyronitrile, dimethyl azobisisobutyrate, azobiscyclohexanecarbonitrile, azobisvaleronitrile; benzoyl peroxide, tert-butyl hydroperoxide, cumene peroxide Radical polymerization initiators such as organic peroxides such as acetic acid, diacyl peroxide; inorganic radical polymerization initiators such as ammonium persulfate and potassium persulfate; various radical polymerizations such as redox initiators such as hydrogen peroxide-sodium hydroxide Using an initiator system, it can be obtained by a known radical polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or radiation polymerization. At this time, the reaction temperature is preferably 10 to 100 ° C., and the reaction time is preferably 1 to 100 hours. The number average molecular weight of the polymer 3 thus obtained is desirably 1,000 to 300,000. The number average molecular weight of the polymer 3 is 1000
When the number average molecular weight of the polymer 3 is more than 300,000, it is not preferable because the viscosity of the compound becomes high.

The photopolymerization initiator to be added to the above-mentioned specific fluorine-containing curable coating liquid may be any one having a polymerization initiation ability by irradiation with ultraviolet rays. Specifically, for example, acetophenones such as benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane Initiator; benzophenone-based initiator such as benzophenone, bis 4-dimethylaminophenyl ketone, phenylbenzoyl ketone; thioxanthone-based initiator such as 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone; Acid S-phenyl initiator, oxime ketone initiator, acylphosphine oxide initiator,
Examples include acylphosphonate initiators, titanocene initiators, and the like. These can be used alone or as a mixture. Depending on the type of the polymerization initiator, a method in which a reaction accelerator such as a tertiary amine such as p-dimethylaminobenzoate is added may be used. The mixing ratio of the polymerization initiator is desirably 0.001 to 20 parts by weight based on the total amount of the curable components in the fluorine-containing curable coating liquid. If the amount of the initiator is less than 0.001 part by weight, the surface hardness after curing decreases, and if it exceeds 20 parts by weight, the refractive index increases upon polymerization and curing, and a desired antireflection film cannot be formed. It is not preferable.

In the specific fluorine-containing curable coating liquid,
For adjusting the viscosity of the coating liquid and leveling the surface after coating,
A solvent may be contained as long as the reaction is not inhibited. Specific examples of the solvent include trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane, octafluorodecalin, Fluorinated solvents such as 1,2-trichloro-1,2,2-trifluoromethylethane, commercially available products such as "Asacycline (AK225)" (trade name, manufactured by Asahi Glass Co., Ltd.); isopropanol; Alcohol solvents such as butanol and isobutanol; ester solvents such as ethyl acetate, propyl acetate and isobutyl acetate; and non-fluorinated solvents such as ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. In the selection of the above-mentioned solvent, (a) drying after application is easy,
(B) From the viewpoint of not inhibiting the ultraviolet curing reaction and (c) minimizing environmental pollution, trifluoromethylbenzene is particularly preferred.

In the specific fluorine-containing curable coating liquid,
The polyfunctional (meth) acrylate 1 is 10 to 1
Polymer 3 is 90% by weight, preferably 70 to 99.9% by weight, more preferably 80 to 99% by weight.
０0% by weight, preferably 30 to 0.1% by weight, more preferably 20 to 1% by weight. If the blending amount of the polymer 3 exceeds 90% by weight, the surface hardness after curing decreases, which is not preferable. The compounding of the polymer 3 can improve the thin film coating property, so that it is preferable to use the polymer 3 in combination. The mixing ratio of the fluorinated solvent or the non-fluorinated solvent is not particularly limited, but is preferably 3 to 100 times by weight based on the total amount of the curable components in the fluorinated curable coating liquid. In particular, when the above-mentioned fluoropolymer is used in combination and the viscosity of the liquid becomes high, it is desirable to blend a fluorinated solvent or a non-fluorinated solvent for the effects such as leveling after coating.

In the above-mentioned specific fluorine-containing curable coating liquid, an energy ray-curable resin or the like generally used as another curable component can be blended if necessary. For example, a polyfunctional monomer having two or more polymerizable unsaturated groups, specifically, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, di (meth) acrylate
Neopentyl glycol acrylate, tricyclodecane dimethanol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (acryloxy) ethyl)
Preferred examples include isocyanurate, divinylben, diethylene glycol di (meth) acrylate, and the like. The addition of the above-mentioned polyfunctional monomer can improve the surface hardness and the like. The mixing ratio of the other curable component is 100% of the polyfunctional (meth) acrylate 1
It is preferably 100 parts by weight or less, particularly preferably 50 parts by weight or less based on parts by weight. If the mixing ratio of the curing component exceeds 100 parts by weight, the refractive index increases upon polymerization and curing, and a desired anti-reflection film cannot be formed, which is not preferable.

The anti-reflection film is obtained by polymerizing and curing the fluorine-containing curable coating liquid, and has a refractive index smaller than that of the substrate, preferably 1.5 or less, particularly preferably 1 or less. .45 or less, and the film thickness is preferably 70 to
It is 150 nm, particularly preferably 90 to 110 nm.

In the method for producing an electromagnetic wave shielding antireflection material of the present invention, the fluorine-containing curable coating solution is applied to the electromagnetic wave shielding substrate and polymerized and cured by irradiation with ultraviolet light in an inert gas atmosphere. This is a method of forming an antireflection film on one or both surfaces. In the case of a coating liquid containing the solvent, after application, the solvent is evaporated by drying or the like, and then polymerized and cured by irradiation with ultraviolet rays to form an anti-reflection film (layer).

The coating can be performed by a commonly used coating method. Specific examples include a roll coating method, a gravure coating method, a dip coating method, and a spin coating method. Coating is performed by these methods so that the film thickness when dried is preferably 70 to 150 nm.

The type of the ultraviolet lamp used for ultraviolet irradiation is not particularly limited as long as it is generally used, and examples thereof include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a xenon lamp. As a condition of the ultraviolet irradiation, the irradiation dose is preferably 10 mJ or more,
100 mJ or more is more preferable. An irradiation dose of less than 10 mJ is not preferable because sufficient surface hardness cannot be obtained after polymerization and curing. After the polymerization and curing, post-curing by ultraviolet irradiation may be further performed once or more. The oxygen concentration at the time of ultraviolet irradiation, nitrogen during polymerization curing and post-curing,
By blowing an inert gas such as argon, 100
It is preferable to keep the content at 0 ppm or less, more preferably at 500 ppm or less.

Further, one or more layers may be provided between the substrate and the antireflection film made of the cured product of the fluorine-containing curable coating liquid. The layer between these layers can be made of an inorganic substance, an organic substance, or a mixture thereof, and has a thickness of 0.01 to 2.
0 nm is preferred. The method for forming the layer is not particularly limited, and for example, a method such as vapor deposition, sputtering, or wet coating can be used. In addition, one or more functions such as high refractive index, antistatic, antifogging, antiglare, improvement of hardness, and blocking of light of a specific wavelength can be imparted to this layer. Particularly preferably, another antireflection effect can be improved by providing at least one other layer having a high refractive index between the substrate and the antireflection film made of the cured product of the fluorine-containing curable coating liquid. In this case, a layer having a high refractive index preferably has a thickness of about 80 to 120 nm.

Further, if necessary, an anti-reflection layer is first formed on one surface of the transparent film, and then an inorganic conductive material is sputtered on the opposite surface of the substrate film as described above, or the inorganic conductive powder is formed. May be applied later to provide electromagnetic wave shielding.

Since the anti-reflective material for electromagnetic wave shielding of the present invention has been subjected to direct anti-reflection treatment on a usual electromagnetic wave shielding substrate, it can be applied to a TV, particularly a flat large screen PDP (plasma display) or a liquid crystal display screen. The installation can reduce reflection of, for example, a fluorescent light coming from the background. Therefore, visibility is significantly improved, and eye fatigue and the like can be reduced. Further, in the manufacturing method of the present invention, since a coating liquid containing a fluorine-containing polyfunctional (meth) acrylate is applied directly to the electromagnetic wave shielding substrate and cured, the weight is reduced and the work is reduced as compared with the conventional bonding method. Can be improved. In addition, since an integrated functional material having an electromagnetic wave shielding function and an anti-reflection function can be obtained, handling can be simplified. Further, the obtained electromagnetic wave shielding / reflecting material can be installed on the front surface of a PDP or CRT to exhibit an electromagnetic wave shielding function and an anti-reflection function. FIG.
Shows an example of a mesh type electromagnetic wave shielding / reducing material. FIG. 2 shows an example of an electromagnetic wave shielding / reducing material made of ITO. FIG. 3 shows an example of the electromagnetic wave shielding / reducing material by Ag vapor deposition. FIG. 4 shows an example of a case where the electromagnetic wave-shielding anti-reflection material is used for an LCD or PDP. FIG. 5 shows an example of the case where the electromagnetic wave shielding and anti-reflection material is used for a CRT.

[0035]

According to the present invention, the electromagnetic wave-shielding anti-reflective material is
Since it has both the electromagnetic wave shielding function and the anti-reflection function, it is expected that lightness, productivity and workability will be improved as compared with conventional ones. In addition, the method for producing an electromagnetic wave shielding antireflective material of the present invention is a method of polymerizing and curing a fluorinated curable coating solution containing the fluorinated polyfunctional (meth) acrylate, a polymer and a photopolymerization initiator as curing components. The anti-reflection film obtained by this is formed on one surface or both surfaces, whereby external light reflection can be reduced and light transmittance can be improved. Further, since the surface hardness is high, the abrasion resistance is excellent and the refractive index is low, so that a reflection-reducing material useful for components of a display device or the like can be manufactured. In addition, the method for producing the anti-reflection material does not require a large apparatus, and can efficiently and continuously produce the workability as compared with the electron beam irradiation method.

[0036]

The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In addition, about various measuring methods, it performed according to the following method.

(1) Measurement of Electromagnetic Shielding Property: Using the prepared sample, an Anritsu Electromagnetic Shielding Tester (MA8602B) was used as an apparatus with an Advantest Spectroanalyzer (TR-4173) at a frequency of 300 MHz. The attenuation rate of the electromagnetic wave was determined.

(2) Spectral reflectance (%): Measured by a UV spectrum (trade name “U-best 50”, manufactured by JASCO Corporation) equipped with a 5 ° regular reflection measuring device, and a wavelength of 550 n.
The spectral reflectance at m was examined. However, the coated surface was used as a measurement surface, and the back surface was roughened with sandpaper to block reflection, and the surface was measured as single-sided spectral reflectance.

(3) Pencil hardness: JIS K 5400.
Measured according to 8.4.2.

(4) Adhesion; cross-cut peel test was conducted according to JIS
Performed according to K5400.8.5.2.

(5) Refractive index of the anti-reflection layer: A film obtained by applying a coating solution on glass so that the thickness after drying becomes about 500 μm, and irradiating with 1 J using an ultraviolet irradiator to cure. Was separated from the glass, and the refractive index of the sample was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).

(6) Weather resistance of substrate: temperature 80 ° C., humidity 9
After being placed in a 0% constant temperature / humidity chamber for 1000 hours, the state of the substrate was visually observed. The evaluation was based on ○: no change, ×: peeling or discoloration change.

Example 1-1; <Preparation of coating liquid> Diacrylic acid-2,2,3,3,4,4,5,5,6
6,7,7,8,8,9,9,9-heptadecafluorononyl ethylene glycol (hereinafter abbreviated as F17EDA)
10 parts by weight, poly (acrylic acid-3,3,4,4,5,
5,6,6,7,7,8,8,9,9,10,10,1
1 part by weight of 0-heptadecafluorodecyl), 87 parts by weight of trifluoromethylbenzene as a solvent, and Irgacure 184 (IRGACURE18) as a photopolymerization initiator.
4, 2 parts by weight of Ciba-Geigy Co., Ltd.) were mixed to prepare a fluorine-containing curable coating liquid (composition 1).

Example 1-2 <Preparation of Electromagnetic Wave Shielding Substrate> On the other hand, a silicone-treated PET release film (25 μm
Acrylic adhesive (Sankyo Chemical Industry Co., Ltd.)
AR-825) was applied by a gravure coating method and dried at 80 ° C. to form a transparent adhesive layer having a thickness of about 25 μm, thereby producing an adhesive-treated PET. This PET film and another PE
Stainless steel mesh between T films (Abel;
By laminating while sandwiching (φ30 μm, 150 mesh), a mesh type electromagnetic wave shielding substrate was obtained.

Example 1-3: <Anti-reflection treatment> Next, using a microgravure coater (manufactured by Yasui Seiki), one side of the electromagnetic wave shielding substrate produced above was dried to a thickness of about 100 nm. Was coated with a coating liquid of the above composition 1 under an atmosphere of nitrogen (oxygen concentration 500 ppm or less) with an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.).
A 0 W high-pressure mercury lamp was used to irradiate and cure with 400 mJ of ultraviolet light to prepare an anti-reflection film (layer) to obtain a material on one side of the electromagnetic wave shielding substrate which was subjected to anti-reflection treatment. The electromagnetic shielding properties, spectral reflectance, pencil hardness, adhesion, refractive index of the anti-reflection layer, and weather resistance of the material obtained by performing the single-sided anti-reflection treatment on the obtained electromagnetic shielding substrate were measured by the above-described methods.

Comparative Example 1-1 The performance was tested in the same manner as described above using only the electromagnetic wave shielding substrate prepared in Example 1-2.

Comparative Example 1-2 In place of the anti-reflection coating liquid (composition 1) prepared in Example 1-1, a fluoropolymer coating liquid (composition 2)
(Asahi Glass Co., Ltd.) was subjected to performance tests in the same manner as described above, except that a layer having a thickness of about 100 nm was formed by dip coating an electromagnetic wave shielding substrate.

COMPARATIVE EXAMPLE 1-3 The anti-reflection coating solution (composition 1) prepared in Example 1-1 was applied to a PET (100 μm thick) film and the anti-reflection layer was formed in the same manner as described above. A hardened antireflection film was prepared on the surface. Instead of using the above-mentioned coating liquid (composition 1) in Example 1-3, the anti-reflection film prepared above was bonded using an adhesive. Performance was similarly tested according to the method described above.

Example 2-1; <Hard coat treatment> 45 parts by weight of dipentaerythritol hexaacrylate (manufactured by Hitachi Chemical Co., Ltd.) and 30 parts by weight of polyethylene glycol diacrylate (trade name "A-400", manufactured by Shin-Nakamura Chemical Co., Ltd.) Parts, Irgacure 184 (trade name, manufactured by Ciba Geigy) as a photopolymerization initiator, 5 parts by weight of isopropyl alcohol as a solvent, and a TAC film (thickness; (80 μm) so as to have a thickness of 5 μm.
800 with UV irradiator (manufactured by Eye Graphics)
A hard coat film is formed by irradiating ultraviolet rays of mJ / cm ² to form a hard coat film, and a hard coat film forming TAC (hereinafter referred to as HC-T
AC).

Example 2-2: <Preparation of coating liquid, treatment with high refractive layer> Next, a 30% zinc oxide fine particle toluene dispersion (trade name "Z
S-300, 240 parts by weight, manufactured by Sumitomo Osaka Cement Co., Ltd., trimethylolpropane triacrylate (hereinafter TMPT)
A) 28 parts by weight, 1 part by weight of Darocure (“DAROCUR1116” (trade name, acetophenone-based compound manufactured by Merck) (hereinafter simply abbreviated as Darocure 1116)) as a photopolymerization initiator, and toluene 400 as a solvent
The parts by weight were mixed to prepare a coating liquid (composition 3). Next, the coating liquid of the composition 3 was coated with H using a microgravure coater.
It was applied to a C-TAC film so that the film thickness after drying was about 100 nm. 1000mJ /
A high refractive index material-forming TAC (hereinafter abbreviated as HR-TAC) film having a high refractive index material formed thereon was produced by irradiating ultraviolet rays of cm ² and curing.

Example 2-3: F17 (OH) DA (see below), F8DTA (see below), "XBA-ST silica sol" (trade name, manufactured by Nissan Chemical Industries, Inc., colloidal silica 30)
%: Xylene 45%: n-butanol 25%) and Darocure 1116 (manufactured by Merck, trade name DAROCUR)
R1116) was mixed at the mixing ratio shown in Composition 4 below to obtain a fluorine-containing monomer mixture (Composition 4). Trifluoromethylbenzene 40 was used as a solvent in each of the obtained compositions.
0 parts by weight were mixed to prepare two kinds of coating liquids. Then, using a microgravure coater, the film thickness after drying was about 10 on the HR-TAC film prepared in Example 2-2.
It was applied so as to have a thickness of 0 nm. 10 with UV irradiator
Irradiation of ultraviolet rays of 00 mJ / cm ² three times and curing to reduce reflection TAC in which a low refractive index material and a high refractive index material are laminated.
A film was prepared. One side of the unreflective TAC film, which had not been treated, was subjected to Ag vapor deposition by a conventional method to impart an electromagnetic wave shielding property, thereby obtaining an electromagnetic wave shielding / reflecting material. The performance of this sample was measured as described above. F17 (OH) DA is a mixture of the following compounds.

Embedded image Is a mixture of F ₈ DTA is an abbreviation for tetraacrylic acid-4,4,5,5, -6,6,7,7-octafluorodecane-1,2,9,10-tetraol. Composition 4; F17 (OH) DA; 10 parts by weight F8DTA; 50 parts by weight XBA-ST silica sol; 133 parts by weight Curing agent (D.1116); 1 part by weight

Comparative Example 2-1 The untreated TAC film for anti-reflection used in Example 2-1 was subjected to only the Ag vapor deposition treatment in the same manner as in Example 2-3 to give only the electromagnetic wave shielding property. A TAC film was prepared. This sample was measured similarly.

Comparative Example 2-2 A fluorinated polymer coating solution (CYTOP manufactured by Asahi Glass Co., Ltd.) was applied to the TAC film provided with the electromagnetic wave shielding property prepared in Comparative Example 2-1 by a dip coating method. The coating was applied so that the film thickness after drying was about 100 nm, to form a reflection reducing layer. The measurement was performed in the same manner as in the above sample.

Comparative Example 2-3 A treatment for forming an anti-reflection layer using a coating solution of composition 4 on one surface of a TAC film as a substrate film was performed in the same manner as in Example 2-1. On one side of the unreflective TAC film, which has not been treated, prepare a TAC film having an electromagnetic wave shielding property by previously applying Ag vapor deposition to the TAC film, and then bonding the TAC film with an adhesive to reduce the electromagnetic wave shielding property. A reflector was obtained. The physical properties of this sample were measured as described above.

[0055]

[Table 1]

[0056]

[Table 2]

From the above results, in Tables 1 and 2,
Examples 1-1 and 2-1 of the present invention are comparative examples 1-1 to 1-1.
-3, 2-1 to 2-3, the electromagnetic wave shielding property, the anti-reflection property (spectral reflectance), the pencil hardness, the adhesion, and the weather resistance are all balanced.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of an electromagnetic wave shielding / reducing material.

FIG. 2 is a cross-sectional view showing another example of the electromagnetic wave shielding and anti-reflection material.

FIG. 3 is a cross-sectional view showing another example of the electromagnetic wave shielding anti-reflection material.

FIG. 4 is a cross-sectional view showing an example of a case where an electromagnetic wave-shielding anti-reflective material is used for a PDP.

FIG. 5 is a cross-sectional view showing an example of a case where an electromagnetic wave shielding / reflecting material is used for a CRT.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C09D 4/06 G02B 1/10 Z

Claims (6)

[Claims] 1. A composite material having (a) an electromagnetic wave shielding function and (b) an anti-reflection function, wherein the anti-reflection function has a fluorine-containing polyfunctional (meth) acrylate 10 as an A component.
To 100% by weight and a fluorine-containing polymer 90 to 0 as a B component
% By weight of an anti-reflection layer formed by curing a curable coating solution containing 1% by weight. 2. An electromagnetic wave-shielding anti-reflective material comprising a substrate having an electromagnetic wave shielding function and an anti-reflection layer formed on one or both surfaces of the substrate, wherein the anti-reflection layer is a fluorine-containing polyfunctional (meth) acrylic resin of component A. This is a layer obtained by curing a curable coating solution containing an acid ester and a fluorine-containing polymer of component B, wherein the component A is represented by the following general formula [1] [Wherein X ¹ and X ² are the same or different groups,
Y ¹ represents a hydrogen atom or a methyl group;
Pieces organic bivalent to octavalent fluorine atoms having two or more fluoroalkylene group having 1 to 14 carbon atoms, fluoro cycloalkylene group or -C having 3 to 14 carbon atoms and having a fluorine atom 4 or more (Y ²⁾ HCH ₂ -group, wherein Y ² is a fluoroalkyl group having 1 to 14 carbon atoms having 3 or more fluorine atoms, and a 3 to 14 carbon atoms having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. ) Or the following general formula [2]: (Where Y ³ has 1 to 3 carbon atoms having 3 or more fluorine atoms)
14 fluoroalkyl groups, Z is a hydrogen atom or carbon atom 1
To 3 alkyl groups. ), M,
n is a number of 1 or 2. A bifunctional to tetrafunctional fluorinated (meth) acrylic acid ester represented by the following general formula [3]: (Wherein X ³ represents a hydrogen atom or a methyl group, and Y ⁴ represents a C 2-14 fluoroalkyl group having 3 or more fluorine atoms or a C 4-14 carbon atom having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. 2. The anti-reflective material for electromagnetic wave shielding according to claim 1, which is a polymer containing 50% by weight or more as a structural unit based on a monofunctional fluorine-containing (meth) acrylate represented by the formula (1). 3. The anti-reflection layer has a refractive index smaller than that of the substrate, the anti-reflection layer has a refractive index of 1.5 or less, and has a thickness of 70 to 150 nm. 2. The electromagnetic wave shielding / reflecting material according to item 1. 4. The electromagnetic wave shielding function according to claim 1, wherein the electromagnetic wave shielding function is at least one selected from the group consisting of a conductive mesh layer, an ITO (indium tin oxide) deposited layer, and an Ag deposited layer. Item 7. The electromagnetic wave shielding anti-reflective material according to Item. 5. The method for producing an electromagnetic wave shielding anti-reflective material according to claim 1, wherein:
On one or both sides of the substrate having the electromagnetic wave shielding function,
A method for producing an electromagnetic wave-shielding anti-reflection material for forming the anti-reflection layer by applying the following curable coating liquid and curing it with ultraviolet rays.
The curable coating liquid contains 70 to 100% by weight of a fluorinated polyfunctional (meth) acrylate as the A component, 30 to 0% by weight of a fluorinated polymer as the B component, and a necessary amount of a photopolymerization initiator as the C component. It is a curable coating liquid. 6. The fluorine-containing polyfunctional (meth) acrylate of the component A is represented by the following general formula [1]: [Wherein X ¹ and X ² are the same or different groups,
Y ¹ represents a hydrogen atom or a methyl group;
Pieces organic bivalent to octavalent fluorine atoms having two or more fluoroalkylene group having 1 to 14 carbon atoms, fluoro cycloalkylene group or -C having 3 to 14 carbon atoms and having a fluorine atom 4 or more (Y ²⁾ HCH ₂ -group, wherein Y ² is a fluoroalkyl group having 1 to 14 carbon atoms having 3 or more fluorine atoms, and a 3 to 14 carbon atoms having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. ) Or the following general formula [2]: (Where Y ³ has 1 to 3 carbon atoms having 3 or more fluorine atoms)
14 fluoroalkyl groups, Z is a hydrogen atom or carbon atom 1
To 3 alkyl groups. ), M,
n is a number of 1 or 2. A bifunctional or tetrafunctional fluorinated (meth) acrylic acid ester represented by the following general formula [3]: (Wherein X ³ represents a hydrogen atom or a methyl group, and Y ⁴ represents a C 2-14 fluoroalkyl group having 3 or more fluorine atoms or a C 4-14 carbon atom having 4 or more fluorine atoms.
Represents a fluorocycloalkyl group. 6. A polymer containing 50% by weight or more as a constituent unit based on a monofunctional fluorine-containing (meth) acrylate represented by the formula (1), and the ultraviolet curing is polymerization curing by ultraviolet light performed in an inert gas atmosphere. Method for producing an electromagnetic wave shielding anti-reflective material of the present invention.