JP5540477B2 - Manufacturing method of near infrared cut filter and near infrared cut filter obtained by the method - Google Patents

Description

The present invention relates to a method for producing an optical laminated film having a dielectric multilayer film, and an optical laminated film obtained by the production method. Specifically, the present invention can form a dielectric multilayer film having high heat resistance and improved crack resistance, a near-infrared cut filter, a visibility correction filter for a solid-state imaging device such as a CCD, a CMOS, and the like. The present invention relates to a method for producing an optical laminated film that can be suitably used as an antireflection film for electronic displays such as telephones, PDAs, personal computers, and TVs, and an optical laminated film obtained by the production method.

  In recent years, televisions equipped with a plasma display panel (PDP) have been commercialized and have come to be widely used in ordinary homes. This PDP is a display that operates using plasma discharge, but it is known that near infrared rays (wavelength: 800 to 1000 nm) are generated during plasma discharge.

  On the other hand, in homes, near-infrared rays are often used for remote control of home appliances such as TVs, stereos and air conditioners, and also for personal computer information exchange. It has always been pointed out that there is a high possibility of causing malfunctions. There is also a problem that it is difficult to see an image due to the high surface reflection of the screen.

Therefore, many of the commercially available PDPs are provided with a filter function for cutting near infrared rays emitted from the front plate.
In addition, CCDs and CMOS image sensors, which are solid-state image pickup devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, etc., and these solid-state image pickup devices are sensitive to near-infrared light at their light receiving parts. Therefore, it is necessary to perform visibility correction, and a near-infrared cut filter is often used.

  As the near-infrared cut filter, those manufactured by various methods are conventionally used. For example, a metal such as silver deposited on the surface of a transparent substrate such as glass to reflect near infrared rays, or a transparent substrate such as glass, acrylic resin, or polycarbonate resin with a near infrared absorbing dye added Etc. are provided for practical use.

  However, the near-infrared cut filter in which a metal is vapor-deposited on a glass base material has a problem that not only the manufacturing cost is high, but also a glass piece of the base material is mixed as a foreign substance during cutting.

  Also, near-infrared cut filters and antireflection films produced by vacuum deposition and the like have already been widely put into practical use, but their heat resistance is not high, and even if the temperature is 100 ° C. or less, the film is cracked. There was a case that the trouble to enter occurred.

Further, as a near-infrared cut filter in which a near-infrared absorber is dispersed in a transparent substrate, a filter in which a copper compound having a near-infrared absorbing ability is dispersed in phosphate glass is known. Polishing is necessary for the production, and the manufacturing cost is high. Further, when used as a near-infrared cut filter for a solid-state imaging device, phosphate glass has a relatively high hygroscopic property, and may have an adverse effect on the solid-state imaging device.
Furthermore, when an inorganic material is used as a base material, there has been a limit to cope with the recent thinning and downsizing of solid-state imaging devices.

  On the other hand, a near-infrared cut filter using a transparent resin as a substrate and containing a near-infrared absorbing dye in the transparent resin is also known (see, for example, Patent Document 1). However, the near-infrared cut filter using a transparent resin as a base material may not always have sufficient near-infrared absorbing ability as compared with the near-infrared cut filter based on phosphate glass.

  In order to solve such a problem, the present inventor specified a near-infrared reflective film made of a dielectric multilayer film on both surfaces of a thermoplastic resin transparent substrate having a specific glass transition point and a thermal expansion coefficient. The near-infrared cut filter which has the structure is proposed (see Patent Document 2).

However, a near-infrared cut filter that has excellent heat resistance characteristics, is less likely to cause curling and cracking during soldering of filter parts, and is less likely to cause optical distortion due to curling even at high temperatures after being incorporated into a product. The appearance of an optical laminated film useful for applications such as an antireflection film has been desired.
JP-A-6-200113 JP 2006-30944 A

  An object of the present invention is to provide a method for producing an optical laminated film having a dielectric multilayer film, high heat resistance, and improved crack resistance, and an optical laminated film. In addition, the present invention has excellent near-infrared cutting ability, low hygroscopicity, less foreign matter and warping, excellent heat resistance, and can be used particularly for correcting the visibility of solid-state imaging devices such as CCDs and CMOSs. It is an object to provide an optical laminated film suitable for a cut filter and a method for producing the same. Furthermore, this invention makes it a subject to provide the optical laminated | multilayer film suitable for the antireflection film excellent in heat resistance and improved crack resistance, and its manufacturing method.

  The method for producing an optical laminated film of the present invention is based on a base film containing a transparent resin having a glass transition temperature (Tg) of 110 to 500 ° C. and a total light transmittance of 80 to 94% at a thickness of 100 μm. Further, the dielectric layer A and the dielectric layer B having a refractive index higher than that of the dielectric layer A are deposited at a temperature of 100 ° C. or higher and 10 ° C. or lower than the Tg of the transparent resin. And a dielectric multilayer film is formed.

In such a method for producing an optical laminated film of the present invention, the dielectric multilayer film is preferably formed on both surfaces of the base film.
In the manufacturing method of the optical laminated film of this invention, it is preferable that the said transparent resin is cyclic olefin resin which has the structural unit (1) represented by following formula (1).

(In the formula, m represents an integer of 0 or more, p represents an integer of 0 or more,
X independently represents a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —.
R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Or a polar group, and R ¹ and R ² and / or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group,
R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring, and the carbocyclic or heterocyclic ring may be a monocyclic structure or a polycyclic structure. However, at least one group of R ^{1 to} R ⁴ includes atoms other than carbon atoms and hydrogen atoms. )
In the method for producing an optical laminated film of the present invention, the dielectric layer A and / or the dielectric layer B includes Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg, Ca, Zn, Sr. , Ba, V, Nb, Mo, W, preferably, and contains Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg, Ca, Zn It is also preferable to contain an oxide of at least one element selected from Sr, Ba, V, Nb, Mo, and W.

  In the method for producing an optical laminated film of the present invention, the base film is a transparent resin having a glass transition temperature (Tg) of 110 to 500 ° C. and a total light transmittance of 80 to 94% at a thickness of 100 μm. A film formed by forming a cured layer obtained by photocuring the active energy ray-curable resin composition on at least one surface of the film, and with respect to the thickness 100 of the film made of a transparent resin, The total thickness of the hardened layer is preferably in the range of 0.2-40. Here, the active energy ray-curable resin composition preferably contains a polyfunctional monomer having 3 or more acryloyl groups. In this case, the active energy ray-curable resin composition further comprises a polyfunctional urethane acrylate. It is more preferable to contain.

The optical laminated film of the present invention is obtained by the method for producing an optical laminated film of the present invention.
The optical laminated film of the present invention is preferably an infrared cut filter, and is preferably an antireflection film.

According to the present invention, a method and a method for producing an optical laminated film having a dielectric multilayer film, having excellent adhesion between the base film and the dielectric multilayer film, high heat resistance, and improved crack resistance, and An optical laminated film obtained by the method can be provided. When the optical laminated film of the present invention is a near-infrared cut filter, it has excellent near-infrared cut ability, low hygroscopicity, little foreign matter and warpage, excellent heat resistance, and suitable for assembly or use at high temperatures In particular, it can be suitably used for correcting the visibility of a solid-state imaging device such as a CCD or CMOS. In addition, when the optical laminated film of the present invention is an antireflection film, it has an excellent antireflection function, has excellent heat resistance, is unlikely to be distorted or cracked, and is an electronic display for mobile phones, PDAs, personal computers, TVs, etc. It can be suitably used as a surface antireflection film.

Hereinafter, the present invention will be specifically described.
The method for producing an optical laminated film of the present invention is based on a base film containing a transparent resin having a glass transition temperature (Tg) of 110 to 500 ° C. and a total light transmittance of 80 to 94% at a thickness of 100 μm. In addition, the dielectric layer A and the dielectric layer B having a refractive index higher than that of the dielectric layer A are alternated at a deposition temperature of 100 ° C. or higher and 10 ° C. or lower than the Tg of the transparent resin. And depositing and laminating to form a dielectric multilayer film.

Base film The base film which comprises the optical laminated film of this invention contains the specific transparent resin mentioned later. A base film may be formed only from specific transparent resin, may be formed from the resin composition containing transparent resin, and may have a hardened layer in at least one surface.

<Transparent resin>
As the transparent resin used in the present invention, a resin having a glass transition temperature (Tg) of 110 to 500 ° C. and a total light transmittance of 80 to 94% at a thickness of 100 μm does not impair the effects of the present invention. As long as it is a thing, it can use without a restriction | limiting especially.

<Physical properties of transparent resin>
As a transparent resin used in the present invention, the glass transition temperature (Tg) ensures thermal stability and moldability to a film, and forms a dielectric multilayer film by high-temperature deposition at a deposition temperature of 100 ° C. or higher. In order to obtain a film that can be obtained, it is usually 110 to 300 ° C, preferably 110 to 200 ° C, more preferably 120 to 180 ° C. In addition, when the glass transition temperature of the transparent resin is 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. or higher, a film capable of forming a dielectric multilayer film at a higher temperature can be obtained. .

  The total light transmittance at a thickness of 100 μm is usually 80 to 94%, preferably 83 to 93%, and more preferably 85 to 92%. When the total light transmittance is within such a range, the base film obtained from the transparent resin exhibits good transparency as an optical film.

  Examples of such transparent resin include (modified) acrylic resin, polycarbonate (PC), polyethersulfone (PES), polyethylene naphthalate (PEN), polyimide, organic-inorganic nanohybrid material, and cyclic olefin resin. be able to.

-Cyclic olefin resin When the transparent resin is a cyclic olefin resin, as the cyclic olefin resin, a cyclic olefin monomer having a norbornene skeleton is polymerized or copolymerized with a copolymerizable monomer as necessary. Polymers or copolymers (hereinafter also referred to as (co) polymers) obtained by the above, or hydrogenated ones can be used. Addition (co) polymers, ring-opening (co) polymers In the present invention, the transparent resin is preferably a cyclic olefin resin having a structural unit (1) represented by the following formula (1).

(In the formula (1), m represents an integer of 0 or more, preferably an integer of 0 to 5, particularly preferably 0, and p is an integer of 0 or more, preferably an integer of 0 to 5, particularly preferably. Represents 1.
X independently represents a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —.
R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Or a polar group, and R ¹ and R ² and / or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group,
R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring, and the carbocyclic or heterocyclic ring may be a monocyclic structure or a polycyclic structure. However, at least one group of R ^{1 to} R ⁴ includes atoms other than carbon atoms and hydrogen atoms. )
The cyclic olefin-based resin may be a resin containing only the structural unit (1) represented by the above formula (1) as the cyclic olefin-based structural unit, but preferably the structure represented by the above formula (1). It is desirable to have the structural unit (2) represented by the following formula (2) together with the unit (1). Furthermore, you may have another structural unit as needed.

(In formula (2), Y is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —, and R ^{5 to} R ⁸ are each independently hydrogen. A halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing oxygen, nitrogen, sulfur or silicon; or a polar group, R ⁵ and R ⁶ And / or R ⁷ and R ⁸ may be combined to form a divalent hydrocarbon group, and R ⁵ or R ⁶ and R ⁷ or R ⁸ are bonded to each other to form a carbocyclic or heterocyclic ring. And the carbocycle or heterocycle may be monocyclic or polycyclic.)
The cyclic olefin-based resin having the structural unit (1) and, if necessary, the structural unit (2) is, for example, one or more monomers (1m) represented by the following formula (1m) and, if necessary, the following: It is obtained by ring-opening copolymerization with one or more monomers (2m) represented by the formula (2m) and hydrogenating as necessary. In the ring-opening copolymerization, a copolymerizable monomer may be used together with the monomer (1m) and optionally (2m).

(In formula (1m), the definitions of m, p, R ¹ , R ² , R ³ and R ⁴ are as defined in formula (1).)

(In formula (2m), definitions of R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined in formula (2).)
In the formulas (1), (2), (1m) and (2m), R ^{1 to} R ⁸ are each a hydrogen atom; a halogen atom; a substituent optionally having a linking group containing oxygen, nitrogen, sulfur or silicon Or an unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group. The above atoms and groups will be described below.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group. Group and the like.

The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 10)); Linking groups containing oxygen, nitrogen, sulfur or silicon (for example, carbonyl group (—CO—), oxycarbonyl group (—O (CO) —), sulfone group (—SO ₂ —), ether bond (—O—) , Thioether bond (-S-), imino group (-NH-)
, Amide bond (—NHCO—, —CONH—), siloxane bond (—OSi (R ₂ ) — (
In the formula, R is an alkyl group such as methyl or ethyl)), and the like, and may be a linking group containing a plurality of these.

Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide ring-containing group, a triorganosiloxy group, a triorganosilyl group, and an amino group. , An acyl group, an alkoxysilyl group, a sulfonyl-containing group, a carboxyl group, and the like. More specifically, examples of the alkoxy group include methoxy group and ethoxy group; examples of the alkoxycarbonyl group include methoxycarbonyl group and ethoxycarbonyl group; examples of the aryloxycarbonyl group include A phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, a biphenylyloxycarbonyl group, and the like; examples of the triorganosiloxy group include a trimethylsiloxy group, a triethylsiloxy group, and the like; Includes a trimethylsilyl group, a triethylsilyl group and the like; examples of the amino group include a primary amino group; examples of the alkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.

More specific examples of the cyclic olefin resin used in the present invention include copolymers shown in the following <1> to <3>. Of these, the copolymer shown in <3> is particularly preferred because of excellent thermal stability and excellent optical properties.
<1> A ring-opening copolymer of the monomer (1m) and, if necessary, the monomer (2m).
<2> A ring-opening copolymer of the monomer (1m) and, if necessary, the monomer (2m) and other copolymerizable monomers.
<3> A hydrogenated product of the ring-opening copolymer of <1> and <2>.

<Monomer (1m)>
The structural unit (1) is usually derived from the monomer (1m) represented by the above formula (1m). Specific examples of the monomer (1m) are given below, but the present invention is not limited to these specific examples. Moreover, you may use a monomer (1m) combining 2 or more types.

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene,

8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [1 ^2,5 . 1 ^7,10 ]
-3-dodecene,

8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.

The monomer (1m) is a group in which at least one of R ^{1 to} R ⁴ in the formula (1m) includes an atom other than a carbon atom and a hydrogen atom, but includes an atom other than a carbon atom and a hydrogen atom. The group is preferably a polar group. That is, in the above formula (1m), R ¹ and R ³ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ⁴ represent a hydrogen atom or a monovalent organic group, When at least one of R ² and R ⁴ contains a monomer (1m) representing a polar group other than a hydrogen atom and a hydrocarbon group, it is preferable because adhesion and adhesion to other materials are improved.

  Ratio of structural unit (1) having at least one polar group in all structural units (1), that is, inclusion of a monomer having at least one polar group in the molecule in the total amount of monomer (1m) The ratio is determined by a desired function and the like, and is not particularly limited, but is usually 50 mol% or more in order to improve adhesion and adhesion with a dielectric layer (dielectric multilayer film) or a cured layer. , Preferably 70 mol% or more, more preferably 80 mol% or more. All of the structural units (1) may have a polar group.

In the above formula (1m), when R ² and / or R ⁴ represents a polar group represented by the following formula (3), the monomer (1) having the polar group is obtained from the copolymer obtained It is preferable in that the glass transition temperature [Tg] and water absorption can be easily controlled.

^{_{- (CH 2) p COOR 9}} ... (3)
(In formula (3), p represents an integer of 0 to 5, and R ⁹ represents a monovalent organic group.)
In the above formula (3), examples of the “monovalent organic group” represented by R ⁹ include alkyl groups such as methyl group, ethyl group, and propyl group; phenyl group, naphthyl group, anthracenyl group, biphenylyl group, etc. In addition to these, monovalent groups having an aromatic ring such as fluorenes such as diphenylsulfone and tetrahydrofluorene, and a heterocyclic ring such as a furan ring and an imide ring are also included.

  In the above formula (3), p preferably represents an integer of 0 to 2, more preferably 0. The smaller the integer p is, the higher the glass transition temperature [Tg] of the resulting copolymer is, and the monomer (1m) in which p is 0 is particularly preferred because of its ease of synthesis.

  In the above formula (1m), the alkyl group is further bonded to the carbon atom to which the polar group represented by the above formula (3) is bonded. It is preferable in order to balance this. The number of carbon atoms of the “alkyl group” is preferably 1 to 5, more preferably 1 to 2, and particularly preferably 1.

In the above formula (1m), the monomer (1m) in which m is 1 and n is 0 is preferable in that a copolymer having a high glass transition temperature [Tg] can be obtained.
As the monomer (1m), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is the glass transition temperature [Tg] of the copolymer obtained.
It is preferable because it can maintain the water absorption to such an extent that the adhesiveness and adhesiveness with other materials are good, and is hardly affected by the adverse effects such as deformation due to water absorption.

<Monomer (2m)>
The structural unit (2) contained in the cyclic olefin-based resin according to the present invention as needed is usually derived from the monomer (2m) represented by the above formula (2m). Specific examples of the monomer (2m) are shown below, but the present invention is not limited to these specific examples. Moreover, you may use a monomer (2m) combining 2 or more types.

Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5- (2-naphthyl) bicyclo [2.2.1] hept-2-ene (including both α and β types),
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
5- (4-phenylphenyl) bicyclo [2.2.1] hept-2-ene,
4- (bicyclo [2.2.1] hept-5-en-2-yl) phenylsulfonylbenzene and the like can be mentioned.

Among these, in the above formula (2m), R ^{5 to} R ⁸ are all hydrogen atoms; or any one of R ^{5 to} R ⁸ is a hydrocarbon group having 1 to 30 carbon atoms, and the remaining three are hydrogen. The monomer (2m) representing an atom is preferable because it has a large effect of improving the toughness of the laminate having the obtained dielectric multilayer film. In particular, R ^{5 to} R ⁸ are all hydrogen atoms; or R ^{5 to} R A monomer in which any one of ⁸ represents a methyl group, an ethyl group, or a phenyl group and the remaining three all represent hydrogen atoms is also preferable from the viewpoint of heat resistance. Furthermore, when the monomer (2m) is bicyclo [2.2.1] hept-2-ene or 5-phenylbicyclo [2.2.1] hept-2-ene, its synthesis is easy. This is preferable in terms of improving the toughness of the resin, adjusting the glass transition temperature [Tg], and being excellent in coextrusion moldability.

  In the present invention, when the monomer (2m) is used in combination with the monomer (1m), the weight ratio to be used is set so that the total weight of the monomer (1m) and the monomer (2m) is 100. In general, monomer (1m): monomer (2m) = 95: 5 to 5:95, preferably 95: 5 to 60:40, more preferably 95: 5 to 70:30, still more preferably It is desirable that it is 95: 5-75: 25. If the monomer (1m) weight ratio is larger than the above range, the effect of improving toughness may not be expected. If the monomer (1m) weight ratio is smaller than the above range, the glass transition temperature [Tg] will be low. There may be a problem with heat resistance.

<Other copolymerizable monomers>
Examples of the monomer (1m) and other copolymerizable monomers that can be copolymerized with the monomer (2m) include, for example, cyclobutene, cyclopentene, cycloheptene, cyclooctene, and tricyclo [5.2.1. And cycloolefins such as 0 ^2,6 ] -3-decene and dicyclopentadiene. The number of carbon atoms in the cycloolefin is preferably 4-20, and more preferably 5-12. Examples of the cycloolefin other than the monomer (1m) and the monomer (2m) that can be used as the copolymerizable monomer include, for example, any ^one of R ^{1 to} R ⁴ in the above formula (1m) is hydrogen. Examples thereof include monomers that are hydrocarbon groups having no atoms or heteroatoms. These copolymerizable monomers are useful for resin modification such as improvement in retardation, Tg adjustment, and improvement in moldability.

  Further, as the “other copolymerizable monomer”, an unsaturated double bond-containing compound such as an unsaturated hydrocarbon polymer having an olefinically unsaturated bond is also suitable. In particular, the presence of monomer (1) and optionally monomer (2) in the main chain of polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene, etc. Below, a copolymer obtained by copolymerizing an “unsaturated double bond-containing compound” is preferable because impact resistance is improved.

  In order to obtain a ring-opening copolymer containing a structural unit derived from “another copolymerizable monomer”, in the ring-opening polymerization step, a specific monomer and a copolymerizable monomer are subjected to ring-opening copolymerization. In addition, conjugated diene compounds such as polybutadiene and polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene and the like have 2 carbon-carbon double bonds in the main chain. The monomer (1) and, if necessary, the hand monomer (2) may be subjected to ring-opening polymerization in the presence of an unsaturated hydrocarbon polymer or the like containing two or more.

  Monomer (1) and, optionally, monomer (2) and “other copolymerizable monomer” (copolymerizable cyclic monomer and / or unsaturated double bond-containing compound) When the total weight of [monomer (1) + monomer (2)] and “other copolymerizable monomer” is 100, the weight ratio used is [monomer (1) + Monomer (2)]: “Other copolymerizable monomer” = 100: 0 to 50:50 is preferable, 100: 0 to 60:40 is more preferable, and 100: 0 to 70:30 is more preferable. .

<Ring-opening polymerization catalyst>
The ring-opening (co) polymerization reaction of these monomers is performed in the presence of a metathesis catalyst. The metathesis catalyst includes at least one metal compound selected from a tungsten compound, a molybdenum compound, and a rhenium compound (hereinafter referred to as “component (a)”), and a Group 1 element (for example, Li, Na, K) of the periodic table. Etc.), Group 2 elements (eg Mg, Ca etc.), Group 12 elements (eg Zn, Cd, Hg etc.), Group 13 elements (eg B, Al etc.), Group 4 elements (eg Ti, Zr etc.) Or at least one compound selected from those having at least one element-carbon bond or the element-hydrogen bond (hereinafter referred to as a compound of a Group 14 element (for example, Si, Sn, Pb, etc.)). And “(b) component”), and may contain an additive (hereinafter referred to as “(c) component”) in order to enhance the catalytic activity. There.

Specific examples of suitable metal compounds constituting the component (a) include metal compounds described in JP-A-1-240517 such as WCl ₆ , MoCl ₅ , and ReOCl ₃ .

Specific examples of the compound constituting the component (b) include n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ A
l, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylaluminoxane, LiH and the like, the compounds described in JP-A-1-240517 are listed. Can do.

  As the component (c), alcohols, aldehydes, ketones, amines and the like can be preferably used, but other compounds shown in JP-A-1-240517 can be used.

In addition, as a metathesis catalyst other than the components (a), (b), and (c), a known ruthenium compound can be used as a Grubbs catalyst.
<Solvent for polymerization reaction>
The ring-opening polymerization reaction is preferably performed in the presence of a solvent. Examples of the solvent used (solvent constituting the molecular weight regulator solution, solvent for the specific monomer and / or metathesis catalyst) include, for example, alkanes, cyclohexane Alkanes; aromatic hydrocarbons; halogenated alkanes, halogenated aryls; saturated carboxylic acid esters; ethers and the like.

<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted depending on the polymerization temperature, the type of catalyst, and the type of solvent, but it is preferable to adjust the molecular weight regulator by coexisting in the reaction system.

    The ring-opening (co) polymer obtained as described above can be used as it is, but the above-mentioned obtained by hydrogenating an olefinically unsaturated bond in the molecule of the ring-opening (co) polymer. The hydrogenated product <3> is preferable because it is excellent in heat-resistant coloring and light resistance and can improve the durability of the obtained near-infrared cut filter and antireflection filter.

<Hydrogenation catalyst>
For the hydrogenation reaction of the ring-opening (co) polymer, a method of hydrogenating a normal olefinically unsaturated bond can be applied. As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used.

The hydrogenation rate of the hydrogenated (co) polymer is 500 MHz and the value measured by ¹ H-NMR is 5
It is 0% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more. The higher the hydrogenation rate, the better the stability against heat and light, and when a near-infrared cut filter or antireflection film having the dielectric multilayer film of the present invention is produced, stable characteristics can be obtained over a long period of time. it can.

  In addition, when the ring-opening (co) polymer molecule has an aromatic group, the aromatic group is less likely to deteriorate the heat resistance coloring property and light resistance, and conversely, optical characteristics such as refractive index and wavelength dispersion. The optical properties such as the above or heat resistance may be brought about, and hydrogenation is not necessarily required.

  The ring-opening (co) polymer obtained as described above can be stabilized by adding a known antioxidant, an ultraviolet absorber, and the like. Further, additives such as a lubricant can be added for the purpose of improving processability.

  The hydrogenated (co) polymer of a cyclic olefin resin that can be used as a transparent resin in the present invention has a gel content of 5% by weight or less contained in the hydrogenated (co) polymer. More preferably, it is particularly preferably 1% by weight or less.

  In addition, as the cyclic olefin resin used in the present invention, <4>: the ring-opening (co) polymer of the above <1> or <2> was cyclized by Friedel-Craft reaction and then hydrogenated (co) Polymers can also be used.

<Physical properties of cyclic olefin resin>
The cyclic olefin-based resin is preferably hydrogenated (the above hydrogenated product <3>), and the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more. More preferably, it is 97% or more, particularly preferably 99% or more.

  The cyclic olefin-based resin preferably has a logarithmic viscosity measured using an Ubbelohde viscometer in chloroform at 30 ° C. (sample concentration: 0.5 g / dl), more preferably from 0.2 to 5.0 dl / g. It is desirable to be 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g.

  The average molecular weight when the transparent resin of the present invention is the cyclic olefin resin is 8,000 to 100,000 in terms of polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) is preferably from 20,000 to 300,000, more preferably from 30,000 to 250,000, particularly preferably from 40,000 to 200,000. . The molecular weight distribution (Mw / Mn) is preferably in the range of 1 to 5.

  The cyclic olefin-based resin may be a resin composition containing the cyclic olefin-based resin as described above. In addition to the cyclic olefin resin, the resin composition includes an antioxidant, a heat stabilizer, a light stabilizer, a phase difference adjusting agent, an ultraviolet absorber, an antistatic agent, a dispersant, and a processability improver as necessary. , Chlorine scavengers, flame retardants, crystallization nucleating agents, antiblocking agents, antifogging agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, contamination Known additives such as an inhibitor, an antibacterial agent, other resins, and a thermoplastic elastomer can be added as long as the effects of the invention are not impaired.

・ Film containing cyclic olefin-based resin The film containing cyclic olefin-based resin is produced in the form of a film or sheet by a known method such as melt molding method or solution casting method (solvent casting method). Can be used. Of these, the solvent casting method is preferred from the viewpoint of good film thickness uniformity and surface smoothness. From the viewpoint of production cost, the melt molding method is preferable.

The thickness of the film containing the cyclic olefin resin used in the present invention is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, and particularly preferably 50 to 200 μm. If it is such thickness, while being able to ensure favorable handling, winding to a roll shape is easy.

  The thickness distribution of the film containing the cyclic olefin-based resin is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, and particularly preferably within ± 3% with respect to the average value. The thickness variation per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less. By performing such thickness control, unevenness in the surface of the obtained optical laminated film can be prevented.

As a film containing the said cyclic olefin resin, what was extended | stretched as needed may be used.
Specifically as a film containing the said cyclic olefin, the product name "Arton" by JSR Co., Ltd., etc. are mentioned.

  When the base film is formed from a transparent resin other than the cyclic olefin-based resin, the method for forming the film is not particularly limited, and can be appropriately selected and employed depending on the type of resin and the desired film thickness. . The thickness of the film formed from the transparent resin is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, and particularly preferably 50 to 200 μm, as in the case of a film containing a cyclic olefin resin. is there. If it is such thickness, while being able to ensure favorable handling, winding to a roll shape is easy. The thickness distribution of the film formed from the transparent resin is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% with respect to the average value. The thickness variation per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less.

Moreover, the film containing transparent resin may have the hardened layer obtained by photocuring an active energy ray curable resin composition on the single side | surface or both surfaces.
-Cured layer The base film used in the present invention may be a film formed only of a transparent resin such as a cyclic olefin resin, but a cured layer is further formed on at least one surface of the film made of the transparent resin. It may be. In the present invention, the cured layer is a layer obtained by photocuring the active energy ray-curable resin composition.

  In the present invention, active energy ray curability is applied to one or both sides of a film made of a transparent resin for the purpose of further improving the adhesion between the dielectric multilayer film and the base film and improving the heat resistance of the optical laminated film. A cured film can be formed using the resin composition. In the present invention, the surface on which the cured film is formed is preferably the surface on which the dielectric multilayer film is formed.

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition is preferably (A) a polyfunctional monomer having a surface tension of 37 mN / m or less and having 3 or more acryloyl groups (hereinafter referred to as component (A)), (B) glycidyl (meta ) Addition reaction of acrylic acid to acrylate polymer (hereinafter referred to as “component (B)”) and (C) optionally other acrylic oligomer (hereinafter referred to as “component (C)”) in a specific amount. It becomes. In particular, the component (A) is a component that can impart the hardness of a protective layer obtained from the active energy ray-curable resin composition, adhesion to a transparent film, and the like. The component (B) is a component that can impart further improvement in the hardness of the protective layer, curability, reduction in curling during curing, and the like. By blending the component (B), the component (B) has a high molecular weight and has many hydroxyl groups in the molecule, so the compatibility with the highly hydrophobic component (A) decreases. (B) It is thought that it is because it transfers to the surface of the surface protective film from which a component is obtained. (C) component is an arbitrary component which can provide toughness etc.

  The surface tension of the component (A) is suitably in the range of 37 mN / m or less, more preferably 30 mN / m or more, from the viewpoint that sufficient hardness and adhesion can be obtained. The surface tension is measured by a vertical plate method (wilhemy method) using a Kyowa CBVP surface tension meter.

  Specific examples of the component (A) include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, triacrylate of glycerin propylene glycol adduct, triacrylate of trimethylolpropane propylene glycol adduct, and the like. Is high in hardness, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate are preferable.

  The compounding amount of the component (A) in the active energy ray-curable resin composition is 40 to 60% by weight (however, the total of the components (A), (B), and (C) is 100% by weight). It is appropriate that it is 50 to 60% by weight.

  As described above, the component (B) is a polymer acrylate obtained by adding acrylic acid to a glycidyl (meth) acrylate polymer. The addition amount of acrylic acid to the epoxy group is suitably about 1: 1 to 1: 0.8 because unreacted epoxy adversely affects the stability of the composition, and 1: 1 to 1: 0.9. The degree is preferred.

  Examples of the glycidyl (meth) acrylate polymer include homopolymers of glycidyl (meth) acrylate, copolymers of glycidyl (meth) acrylate and various α, β-unsaturated monomers not containing a carboxyl group, and the like. It is done. Examples of the α, β-unsaturated monomer not containing the carboxyl group include various (meth) acrylic acid esters, styrene, vinyl acetate, acrylonitrile and the like. When glycidyl (meth) acrylate and an α, β-unsaturated monomer not containing a carboxyl group are copolymerized to obtain a glycidyl (meth) acrylate polymer, crosslinking occurs during the reaction. Therefore, high viscosity and gelation can be effectively prevented. The molecular weight of the glycidyl (meth) acrylate polymer is a weight average molecular weight of about 5,000 to 100,000 and 10,000 to 50 from the viewpoint of curling reduction during curing and prevention of gelation during the acrylic addition reaction. About 1,000 is preferable. (B) 70 weight% or more is suitable for the usage-amount of the glycidyl (meth) acrylate in a component in consideration of the hardness of a protective layer, the transferability of a polymer, etc., and 75 weight% or more is preferable.

  A known copolymerization method can be applied to the production of the component (B). The production of the glycidyl (meth) acrylate polymer is carried out by charging this monomer, a polymerization initiator, and, if necessary, a chain transfer agent and a solvent into a reaction vessel, under a nitrogen stream at 80 to 90 ° C. for about 3 to 6 hours. It is appropriate to do in The resulting glycidyl (meth) acrylate polymer and acrylic acid can be subjected to a ring-opening esterification reaction to obtain the component (B). Usually, in order to prevent polymerization of acrylic acid itself, The reaction temperature is suitably 100 to 120 ° C., and the reaction time is suitably about 5 to 8 hours.

  The blending amount of the component (B) in the active energy ray-curable resin composition is 10 to 60% by weight (provided that the total of the components (A), (B), and (C) is 100% by weight). It is suitable and 20 to 50% by weight is preferred.

Specific examples of the component (C) include polyfunctional polyester acrylate, polyfunctional urethane acrylate, and epoxy acrylate. Of these, polyfunctional urethane acrylates are preferred from the viewpoints of scratch resistance and toughness of the cured coating film. For example, (a) a urethane reaction product of (meth) acrylate having a hydroxyl group and an isocyanate compound having two or more isocyanate groups in the molecule, and (b) an isocyanate compound having two or more isocyanate groups in the molecule. Examples include a reaction product obtained by reacting a polyol, polyester or polyamide-based diol to synthesize an adduct, and then adding a (meth) acrylate having a hydroxyl group to the remaining isocyanate group (for example, JP-A-2002-275392). Issue).

  The polyfunctional urethane acrylate is a urethane reaction product composed of a (meth) acrylate having a hydroxyl group and a polyvalent isocyanate compound having two or more isocyanate groups. As the (meth) acrylate having a hydroxyl group, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

The blending amount of the component (C) in the active energy ray-curable resin composition is 0 to 50% by weight (however, the sum of the components (A), (B) and (C) is 100% by weight). Is suitable.
An organic solvent can be blended with the active energy ray-curable resin composition in order to adjust its viscosity. As the organic solvent, those which do not dissolve the cyclic olefin resin film, which is a transparent film, are suitable. For example, ester solvents, alcohol solvents, and ketone solvents are preferable.

  Examples of the active energy ray used for curing the active energy ray-curable resin composition include light such as ultraviolet rays. In the case of curing with ultraviolet rays, usually about 1 to 15 parts by weight of a photopolymerization initiator can be contained with respect to 100 parts by weight of the resin composition. As the photopolymerization initiator, various known materials such as Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 754 (all manufactured by Ciba Specialty Chemicals), benzophenone, and the like can be used. If necessary, various additives other than those described above, for example, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, an antistatic agent, a light stabilizer, a solvent, an antifoaming agent, and a leveling agent may be blended.

<Formation of cured layer>
In the present invention, the cured layer can be formed by photocuring the active energy ray-curable resin composition on both surfaces of a film containing a transparent resin.

  The cured layer can be formed by applying / drying the above-described active energy ray-curable resin composition on the surface of a film containing a transparent resin and irradiating with light. Formation of a coating film by application / drying and light irradiation may be performed simultaneously on both surfaces of a film containing a transparent resin, or may be performed sequentially on each side.

  As the coating method of the active energy ray-curable resin composition, bar coater coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, Various methods such as offset printing, flexographic printing, and screen printing can be employed. The irradiation of the active energy ray (light) is not particularly limited, and is a method known in the art depending on the composition of the active energy ray-curable resin composition used, the type of active energy ray pair, the thickness of the resin composition, and the like. Can be adjusted appropriately.

  The thickness of the cured layer formed is 0.2 to 40, preferably 0.5, as the total thickness of the cured layers formed on one or both sides with respect to the film thickness 100 of the transparent resin. It is -30, More preferably, it is the range of 1-20. When the cured layer is formed on both sides, the thickness of the cured layer may be the same on both sides or may be different, but if the thickness is equivalent on both sides, the resulting infrared cut filter, etc. The optical laminated film is particularly preferable because it hardly causes warpage.

  In the base film with the cured layer formed in this way, the surface smoothness is improved by forming the cured layer, compared with the film made of only the transparent resin. An optical laminated film such as a film can be produced, which is preferable. In addition, the base film with a hardened layer is more rigid than a film made of only transparent resin, can prevent scratches in the manufacturing process, has improved heat resistance, and can receive heat. Dimensional changes, curls, cracks, etc. are unlikely to occur. In order to improve the heat resistance of the base film on which the cured layer is formed, the deposition lamination of the dielectric multilayer film described later is performed at a high temperature close to the Tg of the transparent resin such as Tg-10 ° C. of the transparent resin. Even when carried out at a speed, an optical laminated film can be produced efficiently without causing an adverse effect on the substrate film. Moreover, since the heat resistance of the obtained optical laminated film is also improved, an optical laminated film suitable for use at high temperatures can be obtained.

Dielectric multilayer film The dielectric multilayer film is formed by laminating a dielectric layer A and a dielectric layer B having a refractive index higher than that of the dielectric layer A. In the present invention, by forming such a dielectric multilayer film on at least one surface of the base film, a near-infrared cut filter excellent in the ability to reflect near-infrared rays, or an anti-reflection film excellent in anti-reflection characteristics An optical laminated film such as can be produced. The dielectric multilayer film is preferably formed on both surfaces of the base film.

<Dielectric layers>
As a material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be normally used, and a material having a refractive index range of 1.2 to 1.6 is preferably selected. Examples of these materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

  As a material constituting the dielectric layer B, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is preferably selected. These materials include, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as the main component, titanium oxide, tin oxide, cerium oxide, etc. The thing etc. which were made to contain a small amount are mentioned.

  In the present invention, the dielectric layer A and / or the dielectric layer B is made of Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg, Ca, Zn, Sr, Ba, V, Nb, Mo. The dielectric layer A and / or the dielectric layer B preferably contains at least one element selected from W, W, Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg More preferably, it contains an oxide of at least one element selected from Ca, Zn, Sr, Ba, V, Nb, Mo, and W.

  More preferably, both of the dielectric layer A and the dielectric layer B are respectively Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg, Ca, Zn, Sr, Ba, V, It contains at least one element selected from Nb, Mo, and W. More preferably, each of the dielectric layer A and the dielectric layer B contains Si, Ti, Ge, Zr, Sn, Al, Sc, respectively. And an oxide of at least one element selected from Ga, In, Mg, Ca, Zn, Sr, Ba, V, Nb, Mo, and W. The dielectric layer A and the dielectric layer B may contain different elements or oxides of the elements.

<Vapor deposition of dielectric layer>
The dielectric layer A and the dielectric layer B may be laminated to form a dielectric multilayer film as long as the above-described dielectric layer material is sequentially laminated on the base film by vapor deposition. Specifically, the dielectric multilayer film can be formed by alternately laminating the dielectric layers A and the dielectric layers B by, for example, a CVD method, a sputtering method, a vacuum deposition method, or the like. Vapor deposition is usually performed at a deposition temperature in the range of 100 ° C. or more and 10 ° C. or more lower than the Tg of the transparent resin film, preferably 100 ° C. or more and 20 ° C. or more lower than the Tg of the transparent resin film. . It is preferable to perform vapor deposition under such temperature conditions because a dielectric multilayer film having excellent adhesion can be formed without excessive heating of the substrate film. In addition, the deposition temperature of the dielectric layers A and B is preferably 110 ° C. or more, more preferably for the purpose of further improving the adhesion, heat resistance, crack resistance, etc. of the formed dielectric multilayer film to the base film. The temperature can be 115 ° C. or higher, more preferably 120 ° C. or higher.

  In this invention, since the base film containing the transparent resin which has a high glass transition temperature (Tg) of 110-500 degreeC is used, dielectric multilayer film formation by vapor deposition at higher temperature than usual can be performed. When the dielectric multilayer film is formed by vapor deposition at a high temperature, the adhesion of the dielectric multilayer film is improved, and the strength of the dielectric multilayer film as the deposited film is increased. The heat resistance and scratch resistance of the laminate are also improved.

  When a dielectric multilayer film is formed on a base film having a cured layer, dimensional changes, curls and cracks are further increased than when a dielectric multilayer film is formed directly on a base film made only of a transparent resin. Generation | occurrence | production can be suppressed suitably, it is hard to produce thermal deformation, and the dielectric multilayer film formation by vapor deposition at high temperature can be performed.

  The thickness of each of the dielectric layer A and the dielectric layer B is not particularly limited, but when used for the production of a near-infrared cut filter, the near-infrared wavelength λ (nm) to be blocked. Of 0.1λ to 0.5λ. When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection and refraction are different. The relationship is broken, and control for blocking / transmitting a specific wavelength tends to be impossible.

  When the dielectric layers A and B have a dielectric multilayer film only on one surface of the base film, the number is usually in the range of 2 to 80 layers, preferably in the range of 4 to 50 layers. On the other hand, when it has a dielectric multilayer film on both surfaces of a base film, the number of laminated layers of the dielectric layers is usually in the range of 4 to 80 layers, preferably 8 to 50 layers as the whole number of laminated layers on both sides of the laminated film. Range.

  Further, when the obtained optical laminated film is used for a near-infrared cut filter, when the near-infrared absorber is contained in the base film, the dielectric multilayer film is formed only on one surface of the base film. In the case of having the dielectric multilayer film, the number of laminated layers in the dielectric multilayer film can be 2 to 40 layers, preferably 4 to 30 layers. The number of laminated body layers can be 4 to 40 layers, preferably 8 to 30 layers, as a whole of the number of laminated layers on both sides of the substrate. In the production of an optical laminated film used as a near-infrared cut filter, when a film containing a near-infrared absorber is used as a base film, productivity can be further increased and the dielectric multilayer film can be made difficult to break.

-Functional film The optical laminated film of the present invention may further have at least one functional film selected from an equivalent refractive index film, an antireflection functional film, and a hard coat film on the surface thereof. The optical laminated film of the present invention may have a structure in which these functional films are formed on a dielectric multilayer film, but the dielectric multilayer film is provided on one surface of the base film and the other surface. A structure in which a functional film is formed is preferable. When the optical laminated film of the present invention has a structure in which a dielectric multilayer film is formed on one side of the base film and a functional film is formed on the other side, the step of providing the functional film forms the dielectric multilayer film It may be performed after this, or may be performed prior to the formation of the dielectric multilayer film.

<Equivalent refractive index film>
The equivalent refractive index film used in the present invention is a film having substantially the same equivalent refractive index as the film containing the transparent resin. Examples of these equivalent refractive index films include a symmetrical three-layer film centered on an alumina layer composed of three layers of silica layer / alumina layer / silica layer. When the symmetric three-layer film is used as an equivalent refractive index film, the refractive index can be made substantially the same as that of a film containing a transparent resin by adjusting the film thickness of each layer.

<Anti-reflective function film>
The antireflection functional film used in the present invention means that, for example, when the optical laminated film according to the present invention is used as a near-infrared cut filter, the transmittance is improved by preventing the reflection of incident light, and the incident light is efficiently A film having a function of utilizing. Examples of materials that can be used as the antireflection functional film include zirconium oxide, alumina, and magnesium fluoride. Examples of the antireflection functional film include a single layer made of any one of these materials, or a multilayer film in which a plurality of layers made of these materials are combined.

<Hard coat film>
The hard coat film used in the present invention is a film having a high hardness and having a function of improving the scratch resistance of the near infrared cut filter according to the present invention.

  Examples of materials that can be used for the hard coat film include organic hard coat materials, acrylate hard coat materials, oxetane hard coat materials, and the like as organic materials. Examples of the inorganic material include a water-based silicate hard coat material and a water-based alumina hard coat material. In addition, organic-inorganic hybrid hard coat materials and the like, such as combinations of the above materials, can also be mentioned.

<Method for forming functional film>
The method for forming these functional films is not particularly limited as long as the functional film is formed. For example, a raw material is formed by a CVD method, a sputtering method, a vacuum deposition method, or a liquid composition containing the raw material. It can be formed by coating an object and drying it to form a film. Moreover, you may form by sticking the functional film formed into a film beforehand through an adhesive agent or an adhesive.

When the functional film is obtained from a liquid composition containing a raw material, it can be obtained, for example, by directly applying the liquid composition on a transparent substrate and drying it.
Moreover, when it has the said functional film in one surface of a base film, the functional film may be 1 type, but you may laminate | stack a multiple types of functional film. When a plurality of types of functional films are stacked, for example, a plurality of types of functional films can be stacked by the above-described film forming method.

Thus, by producing the optical laminated film according to the present invention, an optical laminated film with less warping and cracking of the dielectric multilayer film can be obtained.
And when the optical laminated film obtained in this way is used as a near infrared cut filter, when irradiated with laser light having a wavelength of 633 nm, Newton's ring generated in a region having a diameter of 60 mm from the irradiation center of the laser light. The maximum number is usually 8 or less, preferably 5 or less, and is excellent in surface smoothness and uniformity. Therefore, it can be suitably used particularly for correcting the visibility of a solid-state image sensor.

-Use of optical laminated film The optical laminated film of the present invention is not particularly limited, but can be suitably used as a near-infrared cut filter or an antireflection film.

  The near-infrared cut filter according to the present invention has an excellent near-infrared cut ability, has excellent heat resistance, and is less likely to cause distortion or cracking. Therefore, it is useful not only as a heat ray cut filter mounted on glass of automobiles and buildings, but also particularly useful for correcting the visibility of solid-state image sensors such as CCDs and CMOSs in digital still cameras and mobile phone cameras. Therefore, it can be suitably used for applications that require high-temperature adhesion during product incorporation, use in a high-temperature region, and the like.

The antireflection film according to the present invention has an excellent antireflection function, is excellent in heat resistance, and is less likely to cause distortion or cracking. Therefore, it is useful for preventing surface reflection of electronic displays such as mobile phones, PDAs, personal computers and TVs.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. “Parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

Each physical property value was measured or evaluated by the following method.
<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Inc., the temperature was increased at a rate of 10 ° C. per minute under a nitrogen stream.

<Appearance of laminated film>
The film was evaluated as “A” when there was no foreign matter, unevenness, or repellency, and “B” when the film was observed visually as having foreign matter, unevenness, or repellency.

<Deformation (Curl, Uneri)>
For a film having a dielectric multilayer film after vapor deposition, the curl is 100 mm wide, the amount of warpage is less than 20 mm, and the undulation is 100 × 260 mm square and less than 5 mm. The case where the curl was 100 mm wide, the amount of warpage was 20 mm or more, and / or the undulation (waving) was 100 × 260 mm square and 5 mm or more was evaluated as “B”.

<Crack>
Regarding a film having a dielectric multilayer film, visually, “A” indicates that the dielectric multilayer film layer (deposition layer) has no cracks, and “B” indicates that the dielectric multilayer film layer (deposition layer) has cracks. evaluated.

<Appearance of film having dielectric multilayer film>
Regarding the film having a dielectric multilayer film, the film having no foreign matter, unevenness, and repellency was visually evaluated as “A”, and the film having foreign matter, unevenness, and repellency was evaluated as “B”.

<Adhesion>
For a film having a dielectric multilayer film, in accordance with JIS-K5600-5-6 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion (Crosscut Method)” A peel test was conducted, and the case where the coat layer (cured layer and dielectric multilayer film) was not peeled was evaluated as “A”, and the case where peel was present was evaluated as “B”.

<Heating test>
A film cut out to 30 × 30 mm was placed on a hot plate at a predetermined temperature ± 5 ° C., and a sample after heating for 120 seconds at 120 ° C. ± 5 ° C. The presence or absence of cracks was visually confirmed, and at each heating temperature, no cracks were evaluated as “A”, and cracks were evaluated as “B”.

  In addition, the comprehensive evaluation of the heating test is “A”, 120 ° C. or 160 ° C. from the evaluation results of the heating test at 120 ° C. and 160 ° C. Any one of the heating tests in which cracking occurred was designated as “B”, and in any heating test at 120 ° C. and 160 ° C., cracking was designated as “C”.

[Example 1]
[Preparation example] Hard coat agent UV curable resin composition (Desolite Z-7524 manufactured by JSR Corporation: composition is shown in Table 1. Solid content concentration is 53.2%) is solidified with methyl ethyl ketone. It diluted so that a density | concentration might be 45 weight%, and obtained the ultraviolet curable resin composition.

A transparent film having a film thickness of 100 μm made of JSR Co., Ltd. cyclic olefin resin, Arton (registered trademark) (glass transition point: 165 ° C., total light transmittance at 93 μm thickness: 93%, grade: G7810) Use the UV curable resin composition prepared above on a transparent film cut out to A4 size using a lab coater (Automatic film applicator manufactured by Yasuda Seiki Seisakusho, Model No. 542-AB), with a coater bar to obtain a predetermined thickness. It was applied to both sides.

After drying using an inert oven (Inert oven DN410I manufactured by Yamato Scientific Co., Ltd.) at 80 ° C. for 3 minutes, UV conveyor (eye ultraviolet curing device manufactured by Eye Graphics, model US2-X)
0405 60 Hz), UV curing was performed at a metal halide lamp illuminance of 270 mW / cm ² and an integrated light quantity of 500 mJ / cm ² to obtain a base film having a transparent cured layer having a thickness of 1.0 μm formed on each surface. The obtained base film had a good appearance with no foreign matter, unevenness or repellency observed by visual observation.

The obtained base film is cut out to 110 × 260 mm, placed on a jig, and SiO ₂ layers and TiO ₂ layers are alternately laminated and deposited at a deposition temperature of 130 ° C., and a dielectric multilayer film is formed on both sides. Thus, a laminated film with a dielectric multilayer film was obtained. The dielectric multilayer film layer formed on the base film had a layer structure of one layer of 110 to 120 nm and 17 layers on one side (the outermost layer was a SiO ₂ layer).

About the obtained laminated | multilayer film with a dielectric multilayer film, each characteristic was evaluated by the above-mentioned method. The results are shown in Table 2.
[ Reference Example 2, Comparative Examples 1-2]
A film with a dielectric multilayer film was obtained in the same manner as in Example 1 except that the presence or absence of the cured layer and the deposition temperature of the SiO ₂ layer and the TiO ₂ layer were set to the conditions shown in Table 2.

Each characteristic of the obtained film with a dielectric multilayer film was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[Example 3]
In the same manner as in Example 1, a laminated film in which a transparent cured layer having a thickness of 1.0 μm was formed on each surface was cut out to 110 × 260 mm, placed in a jig, an Al ₂ O ₃ layer, a SiO ₂ layer, and TiO ₂ layers were laminated and deposited in order at a deposition temperature of 130 ° C., and a dielectric multilayer film was formed on both sides to obtain a film with a dielectric multilayer film. The dielectric multilayer film layer formed on the laminated film had a layer structure in which one layer was 70 to 110 nm and one side was three layers (the outermost layer was an SiO ₂ layer).

Each characteristic was evaluated by the above-mentioned method about the obtained film with a dielectric multilayer film. The results are shown in Table 3.
[ Reference Example 4, Comparative Examples 3 to 4]
Dielectric multilayer film in the same manner as in Example 3, except that the presence or absence of the hardened layer and the deposition temperature of the Al ₂ O ₃ layer, the SiO ₂ layer, and the TiO ₂ layer were set to the conditions shown in Table 3. An attached film was obtained.
Each characteristic of the obtained film with a dielectric multilayer film was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 5]
A film with a dielectric multilayer film was obtained in the same manner as in Example 1 except that the deposition temperatures of the SiO ₂ layer and the TiO ₂ layer were changed to the conditions shown in Table 3.

  Each characteristic of the obtained film with a dielectric multilayer film was evaluated in the same manner as in Example 1. The results are shown in Table 3.

The optical laminated film of the present invention can be suitably used as a near infrared cut filter or an antireflection film.
The near-infrared cut filter according to the present invention has excellent near-infrared cut ability, is excellent in heat resistance, and is less likely to be distorted or cracked. Not only is it useful, but it is particularly useful for correcting the visibility of solid-state imaging devices such as CCDs and CMOSs such as digital still cameras and mobile phone cameras.

In addition, the antireflection film according to the present invention has an excellent antireflection function, is excellent in heat resistance, and is less likely to be distorted or cracked. Therefore, it is used for antireflection on the surface of electronic displays such as mobile phones, PDAs, personal computers and TVs Useful as.

FIG. 1 is a schematic diagram of curl and undulation (waving) that can be evaluated as “A” (good) in evaluating deformation of a film (near infrared cut filter) on which a dielectric multilayer film is deposited.

Claims (8)

An active energy ray-curable resin composition is applied to both surfaces of a transparent resin film having a glass transition temperature (Tg) of 110 to 500 ° C. and a total light transmittance of 80 to 94% at a thickness of 100 μm. On the base film in which the total thickness of the cured layer is in the range of 0.2 to 40 with respect to the thickness 100 of the film made of a transparent resin, formed by forming a cured layer obtained by photocuring,
The dielectric layer A and the dielectric layer B having a refractive index higher than that of the dielectric layer A are deposited at a temperature of 100 ° C. or higher and 10 ° C. or lower than the Tg of the transparent resin. And a method for producing a near-infrared cut filter, wherein a dielectric multilayer film is formed.   The method for producing a near-infrared cut filter according to claim 1, wherein the dielectric multilayer film is formed on both surfaces of the base film. The said transparent resin is cyclic olefin resin which has a structural unit (1) represented by following formula (1), The manufacturing method of the near-infrared cut filter of Claim 1 or 2 characterized by the above-mentioned.

(In the formula, m represents an integer of 0 or more, p represents an integer of 0 or more,
X independently represents a group represented by the formula: —CH═CH— or a group represented by the formula: —CH ₂ CH ₂ —.
R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Or a polar group, and R ¹ and R ² and / or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group,
R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a carbocyclic or heterocyclic ring, and the carbocyclic or heterocyclic ring may be a monocyclic structure or a polycyclic structure. However, at least one group of R ^{1 to} R ⁴ includes atoms other than carbon atoms and hydrogen atoms. )   The dielectric layer A and / or the dielectric layer B is made of Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg, Ca, Zn, Sr, Ba, V, Nb, Mo, and W. The method for producing a near-infrared cut filter according to claim 1, comprising at least one element selected.   The dielectric layer A and / or the dielectric layer B is made of Si, Ti, Ge, Zr, Sn, Al, Sc, Ga, In, Mg, Ca, Zn, Sr, Ba, V, Nb, Mo, and W. The method for producing a near-infrared cut filter according to claim 1, comprising an oxide of at least one selected element.   The said active energy ray curable resin composition contains the polyfunctional monomer which has 3 or more acryloyl groups, The manufacturing method of the near-infrared cut filter in any one of Claims 1-5 characterized by the above-mentioned.   The said active energy ray-curable resin composition contains polyfunctional urethane acrylate further, The manufacturing method of the near-infrared cut filter in any one of Claims 1-6 characterized by the above-mentioned.   A near-infrared cut filter obtained by the production method according to claim 1.

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