JP2010023234A - Laminated film and process for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant laminated film which does not spoil characteristics such as outstanding transparency a cyclic olefin-based resin film has, is excellent in dimensional stability at high temperature, and does not peel from a surface material, and also to provide a method for manufacturing the same. <P>SOLUTION: The heat-resistant laminated film has: (A) a particle which is made by combining an oxide particle of at least one kind of element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium, with an organic compound containing a polymerizable unsaturated group; and (B) a particle-containing layer (II) formed by using a curable composition including a compound which has an alicyclic structure and contains two or more polymerizable unsaturated group in a molecule, in both sides of a film (I) which has a cyclic olefin-based polymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated film and a method for producing the same. In detail, this invention relates to the laminated film which has the layer formed from a curable composition on both surfaces of the film which has a cyclic olefin polymer, and its manufacturing method.

  A film made of a cyclic olefin polymer has low birefringence, excellent transparency, relatively excellent heat resistance, and low hygroscopicity, and thus is suitably used for various optical applications, for example, a protective film, It is used for applications such as a retardation film and a transparent conductive film having a conductive layer formed on the surface.

However, in recent high-temperature use, dimensional changes such as heat shrinkage may occur, and the appearance of a film excellent in heat resistance has been demanded.
On the other hand, as a technique for protecting the surface of a resin molded product, the applicants of the present application apply a resin composition containing specific particles to the surface of an article and cure it to form a composite, thereby increasing hardness, It has been proposed to improve scratch resistance (see Patent Document 1).

However, a method for imparting further heat resistance to a film composed of a cyclic olefin polymer is not known, and the appearance of a film composed of a cyclic olefin polymer superior in shape stability at high temperatures is desired. It was.
JP 2000-273272 A

  The present invention provides a heat-resistant laminated film that is excellent in dimensional stability at high temperatures and does not cause peeling from a surface material, and a method for producing the same, without impairing the properties such as excellent transparency of the cyclic olefin resin film. The challenge is to do.

The laminated film of the present invention is
On both sides of the film (I) having a cyclic olefin polymer,
(A) Surface obtained by bonding oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium and an organic compound containing a polymerizable unsaturated group Modified oxide particles, and (B) a particle-containing layer (II) formed using a curable composition containing an alicyclic structure and a compound containing two or more polymerizable unsaturated groups in the molecule. And
The total thickness in terms of oxide particles of the surface-modified oxide particles (A) in the particle-containing layer (II) formed on both surfaces is 100 film thickness of the film (I) having a cyclic olefin polymer. It is characterized by being in the range of 0.1-30.

Such a laminated film of the present invention,
For the film thickness 100 of the film (I) having a cyclic olefin polymer,
The total film thickness of the particle-containing layer (II) formed on both sides is preferably in the range of 0.5-100.

In the laminated film of the present invention, the curable composition comprises surface-modified oxide particles (A) obtained by binding oxide particles and an organic compound containing a polymerizable unsaturated group in all components except a solvent. , 5
It is preferable to contain in 90 mass%.

  In the laminated film of the present invention, the cyclic olefin polymer preferably has a structural unit represented by the following formula (1).

（式（１）中、ｍは０以上の整数、ｐは０以上の整数であり、Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ¹〜Ｒ⁴は各々独立に水素原子；ハロゲン原子；酸素、窒素、イオウ若しくはケイ素を含む連結基を有していてもよい置換または非置換の炭素原子数１〜３０の炭化水素基；または極性基を表し、Ｒ¹
とＲ²および／またはＲ³とＲ⁴は一体化して２価の炭化水素基を形成してもよく、Ｒ¹またはＲ²と、Ｒ³またはＲ⁴とは相互に結合して炭素環または複素環を形成してもよく、該炭
素環または複素環は、単環構造でも多環構造でもよい。）
本発明の積層フィルムの製造方法は、
（Ａ）珪素、アルミニウム、チタン、ジルコニウム、亜鉛、マグネシウム、鉄、カリウム、カルシウムより選ばれる少なくとも１種の元素の酸化物粒子と、重合性不飽和基を含む有機化合物とを結合させてなる表面変性酸化物粒子、
（Ｂ）脂環構造を有し、分子内に２以上の重合性不飽和基を含む化合物、および
（Ｃ）溶剤
を含む硬化性組成物を、環状オレフィン系重合体を有するフィルムの両面に塗布し、乾燥して塗膜を形成する工程と、塗膜を硬化する工程とを有することを特徴としている。

(In formula (1), m is an integer of 0 or more, p is an integer of 0 or more, and X is independently a group represented by the formula: —CH═CH— or a formula: —CH ₂ CH ₂ —. R ^{1 to} R ⁴ are each independently 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 oxygen, nitrogen, sulfur or silicon Or a polar group, R ¹
And R ² and / or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a carbocyclic ring or A heterocycle may be formed, and the carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure. )
The method for producing the laminated film of the present invention comprises:
(A) Surface obtained by bonding oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium and an organic compound containing a polymerizable unsaturated group Modified oxide particles,
(B) A curable composition containing an alicyclic structure and containing two or more polymerizable unsaturated groups in the molecule and (C) a solvent is applied to both surfaces of a film having a cyclic olefin polymer. And a step of forming a coating film by drying and a step of curing the coating film.

The conductive laminated film of the present invention is characterized by having a conductive layer on the surface of the laminated film of the present invention.
The optical film of the present invention is characterized by having a vapor-deposited layer of metal or metal oxide on the surface of the laminated film of the present invention.

The substrate film of the present invention is characterized in that it has a patterning layer formed of a photosensitive resin composition on the surface of the laminated film of the present invention.

  According to the present invention, a laminated film excellent in high-temperature heat resistance and production thereof, which does not impair the excellent transparency of a cyclic olefin polymer film, has little dimensional change even under high-temperature conditions, and does not peel or crack. A method can be provided. Moreover, according to this invention, the electroconductive laminated | multilayer film, optical film, and board | substrate film excellent in heat-resistant stability can be provided.

Hereinafter, the present invention will be specifically described.
The laminated film of the present invention has a particle-containing layer (II) on both surfaces of a film (I) containing a cyclic olefin polymer.

Film containing cyclic olefin polymer (I)
The film (I) containing a cyclic olefin polymer, which is a base film of the heat-resistant laminated film of the present invention, is a film formed from a cyclic olefin polymer or a resin composition containing a cyclic olefin polymer. Although it can be used without particular limitation as long as it is used, it is preferable that it mainly contains a cyclic olefin polymer, and it is particularly preferable that the resin component constituting the film (I) is only a cyclic olefin polymer.

In the present invention, the cyclic olefin polymer is a polymer obtained by polymerizing or copolymerizing a cyclic olefin monomer having a norbornene skeleton, and examples thereof include the following.
(1) A ring-opening polymer of a cyclic olefin monomer.
(2) A ring-opening copolymer of a cyclic olefin monomer and a copolymerizable monomer.
(3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above.
(4) A (co) polymer obtained by cyclizing the ring-opening (co) polymer of (1) or (2) by Friedel-Craft reaction and then hydrogenating it.
(5) A saturated copolymer of a cyclic olefin monomer and an unsaturated double bond-containing compound.
(6) Addition (co) polymers of cyclic olefin monomers and hydrogenated (co) polymers thereof.
(7) An alternating copolymer of a cyclic olefin monomer and an acrylate.

Of these, the cyclic olefin polymer according to the present invention is preferably the above (1), (2), (3), and more preferably (3).
As the cyclic olefin monomer, a compound having a norbornene skeleton can be used without particular limitation. For example, the following compounds can be used.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene,
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-cyanobicyclo [2.2.1] hept-2-ene,
8 methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [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-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3
-Dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8 ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
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,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-fluoro-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [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-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-tetracyclo [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- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [ 4.4.0.1 ^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-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-trifluoromethoxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [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-heptafluoro-iso- propyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [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-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene.

These can be used alone or in combination of two or more.
Preferred cyclic olefin polymers according to the present invention include those having a structural unit (1) represented by the following formula (1).

（式（１）中、ｍは０以上の整数、ｐは０以上の整数であり、Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ₂ＣＨ₂−で表される基であり、Ｒ¹〜Ｒ⁴は各々独立に水素原子；ハロゲン原子；酸素、窒素、イオウ若しくはケイ素を含む連結基を有していてもよい置換または非置換の炭素原子数１〜３０の炭化水素基；または極性基を表し、Ｒ¹
とＲ²および／またはＲ³とＲ⁴は一体化して２価の炭化水素基を形成してもよく、Ｒ¹またはＲ²と、Ｒ³またはＲ⁴とは相互に結合して炭素環または複素環を形成してもよく、該炭
素環または複素環は、単環構造でも多環構造でもよい。）
このような構造単位（１）においては、上記式（１）中、Ｒ¹ 及びＲ³が水素原子又は
炭素数１〜１０、さらに好ましくは１〜４、特に好ましくは１〜２の炭化水素基であり、Ｒ² 及びＲ⁴ が水素原子又は一価の有機基であって、Ｒ² 及びＲ⁴の少なくとも一つは水
素原子及び炭化水素基以外の極性を有する極性基を示し、ｍは０〜３の整数、ｐは０〜３の整数であり、より好ましくはｍ＋ｐ＝０〜４、さらに好ましくは０〜２、特に好ましくはｍ＝０、ｐ＝０であるものである。このような構造単位（１）を有する環状オレフィン系重合体は、樹脂のガラス転移温度が高く、かつ機械的強度も優れたものとなる点で好ましい。

(In the formula (1), m is an integer of 0 or more, p is an integer of 0 or more, X is independently a formula: or a group represented by the formula represented by _{-CH = CH-: -CH 2 CH 2} - Table R ^{1 to} R ⁴ are each independently 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 oxygen, nitrogen, sulfur or silicon Or a polar group, R ¹
And R ² and / or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a carbocyclic ring or A heterocycle may be formed, and the carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure. )
In such a structural unit (1), in the above formula (1), R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 10, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms. R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group, and m is 0 An integer of ˜3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, more preferably 0 to 2, and particularly preferably m = 0 and p = 0. The cyclic olefin polymer having such a structural unit (1) is preferable in that the glass transition temperature of the resin is high and the mechanical strength is excellent.

  In the above formula (1), examples of the polar group include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups have a linking group such as a methylene group. It may be bonded via. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is obtained by using a cyclic olefin-based resin having a high glass transition temperature, a low hygroscopic property, and various materials. It is preferable at the point from which it has the outstanding adhesiveness. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer having n of 0 is It is preferable in that the synthesis is easy.

In the above formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group. In particular, it is obtained that the alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the above formula — (CH ₂ ) _n COOR is bonded. This is preferable in that the hygroscopicity can be lowered.

  When the cyclic olefin polymer is a copolymer of a cyclic olefin monomer and a copolymerizable monomer or a hydrogenated product thereof, specific examples of the copolymerizable monomer include cyclobutene, cyclopentene, Mention may be made of cycloolefins such as cycloheptene, cyclooctene and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.

The preferred use range of the cyclic olefin monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.
When the cyclic olefin polymer is a ring-opening (co) polymer of a monomer containing a cyclic olefin monomer, the ring-opening polymerization reaction is performed in the presence of a metathesis catalyst. This metathesis catalyst includes (a) at least one selected from W, Mo and Re compounds, (b) Deming periodic table group IA elements (for example, Li, Na, K, etc.), IIA group elements (for example, , Mg, Ca, etc.), group IIB elements (eg, Zn, Cd, Hg, etc.), group IIIA elements (eg, B, A, etc.)
l), a group IVA element (for example, Si, Sn, Pb, etc.), or a compound of a group IVB element (for example, Ti, Zr, etc.), wherein at least one of the element-carbon bond or the element-hydrogen bond A catalyst comprising a combination with at least one selected from those having the following. In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added.

(A) Representative examples of suitable W, the compounds of Mo or Re as a component, WCl _6,
The compounds described in JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right column, line 17 such as MoCl ₆ and ReOCl _{3 can be} exemplified. Specific examples of the component (b) include n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like, the compounds described in JP-A-1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3 can be mentioned. As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further, JP-A-1-132626, page 8, lower right column, The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

The amount of the metathesis catalyst used is a range in which “(a) component: specific monomer” is usually 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. , Preferably 1
The range may be 1,000 to 1: 10,000. The ratio of the component (a) to the component (b) is such that (a) :( b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atomic ratio. The ratio of the component (a) to the component (c) is such that the molar ratio (c) :( a) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. be able to.

Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include, for example, pentane, hexane, heptane,
Alkanes such as octane, nonane, decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride Halogenated alkanes such as dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, dimethoxyethane; Examples thereof include ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred.

The amount of the solvent used is such that “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. it can.
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. Suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene. Of these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in admixture of two or more.

  The molecular weight regulator is used in an amount of 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, based on 1 mol of the cyclic olefin monomer used for the ring-opening (co) polymerization reaction. can do.

  In order to obtain a ring-opening copolymer, in the ring-opening polymerization step, a cyclic olefin monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization. Furthermore, conjugates such as polybutadiene and polyisoprene may be used. Cyclic in the presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain such as diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, and polynorbornene. The olefin monomer may be subjected to ring-opening polymerization.

  The ring-opening (co) polymer obtained as described above can be used as it is, but the hydrogenation obtained by hydrogenating an olefinically unsaturated bond in the molecule of this (co) polymer ( The (co) polymer is preferred because it is excellent in heat-resistant coloring and light resistance and can improve the durability of the film (I) as a substrate.

  For the hydrogenation reaction, a method of hydrogenating a normal olefinically unsaturated bond can be applied. That is, a hydrogenation catalyst is added to a ring-opening polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is allowed to act at 0 to 200 ° C., preferably 20 to 180 ° C. be able to.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. In addition, homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts can be used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.
The hydrogenation rate of the hydrogenated (co) polymer is 500 MHz and the value measured by ¹ H-NMR is 5
Desirably, 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 to heat and light, and the resulting film exhibits stable characteristics over a long period of time.

  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 cyclic olefin polymer used in the present invention preferably has a gel content of 5% by weight or less, more preferably 1% by weight or less.
The preferred molecular weight of the cyclic olefin polymer used in the present invention is an intrinsic viscosity [η] _inh. 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g, and the number in terms of polystyrene measured by gel permeation chromatography (GPC). The average molecular weight (Mn) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is 20,000 to 300. 30,000, more preferably 30,000-2
50,000, particularly preferably in the range of 40,000 to 200,000 is suitable.

Inherent viscosity [η] _inh , number average molecular weight and weight average molecular weight are in the above ranges, so that the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin polymer and optical properties when used as a film Good balance with stability of characteristics.

  The glass transition temperature (Tg) of the cyclic olefin polymer used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. . Within such a range, it is possible to stabilize the change in optical properties of the obtained film and prevent thermal deterioration during processing.

For the cyclic olefin polymer forming the film (I) or the resin composition containing the same, known antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2′-
Dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
Methane; UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-
It can be stabilized by adding 4-methoxybenzophenone or the like. Further, additives such as a lubricant can be added for the purpose of improving processability.

  The film (I) according to the present invention is obtained by molding a cyclic olefin polymer or a resin composition containing the same into a film by a known method such as a melt molding method or a solution casting method (solvent casting method). be able to.

  The thickness of the film (I) can be appropriately selected depending on the application and is not particularly limited, but is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 200 μm, and still more preferably about 50 to 200 μm. It is desirable that

  The film (I) according to the present invention has a thickness distribution within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% with respect to the average value. desirable. 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. When the thickness distribution satisfies such a range, there is little unevenness in the optical characteristics in the film surface, which is preferable because it can be suitably used for optical applications.

As the film (I), a commercially available product may be used, and specifically, a product name “Arton” manufactured by JSR Corporation may be used.
The film (I) according to the present invention may be as it is formed, or may be stretched. As the stretching method, it can be produced by a known uniaxial stretching method or biaxial stretching method. That is, a horizontal uniaxial stretching method by a tenter method, a compression stretching method between rolls, a longitudinal uniaxial stretching method using rolls with different circumferences, a biaxial stretching method in which horizontal uniaxial and longitudinal uniaxial are combined, a stretching method by an inflation method, etc. Can be used.

Particle-containing layer (II)
The particle-containing layer (II) constituting the heat-resistant laminated film of the present invention is formed using a curable composition.

<Curable composition>
The curable composition for forming the particle-containing layer (II) is:
(A) Surface obtained by bonding oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium and an organic compound containing a polymerizable unsaturated group Modified oxide particles, and
(B) A compound having an alicyclic structure and containing two or more polymerizable unsaturated groups in the molecule is contained as an essential component, and usually (C) a solvent.

・ Surface modified oxide particles (A)
The surface-modified oxide particles (A) constituting the curable composition are particles formed by bonding oxide particles and an organic compound containing a polymerizable unsaturated group.

  The oxide particles are oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium. Use of such oxide particles is preferable because a layer obtained from the curable composition tends to exhibit colorlessness.

Examples of these oxides include silica, aluminum oxide, titania, zirconia, zinc oxide, magnesium oxide, iron oxide, potassium oxide, and calcium oxide. The oxide may be a synthetic product or a purified product of mineral. Among these, silica, aluminum oxide, and zirconia are preferable from the viewpoint of high hardness. These can be used singly or in combination of two or more. Furthermore, the oxide particles of such elements are preferably in the form of powder or solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propyl acetate, ethyl lactate, Esters such as γ-butyrolactone; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Can be mentioned. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred. More preferred are methyl ethyl ketone and methyl isobutyl ketone.

  The number average particle diameter of the oxide particles is preferably 0.001 μm to 2 μm, more preferably 0.001 μm to 0.2 μm, and particularly preferably 0.001 μm to 0.1 μm. If the number average particle diameter exceeds 2 μm, the transparency when cured is reduced, or the surface state when coated is likely to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

Examples of products commercially available as silicon oxide particles (for example, silica particles) include, for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., product names: methanol silica sol, I
PA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST- 50, ST-OL and the like. Moreover, as a powder silica, Nippon Aerosil Co., Ltd. product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT
600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Trade name: Sildex H31, H32,
H51, H52, H121, H122, manufactured by Nippon Silica Industry Co., Ltd. Trade name: E220A,
E220, Fuji Silysia Co., Ltd. trade name: SYLYSIA470, Nippon Sheet Glass Co., Ltd. trade name: SG Flakes, etc.

As an aqueous dispersion of alumina, product name: Alumina Sol-1 manufactured by Nissan Chemical Industries, Ltd.
00, -200, -520; As an aqueous dispersion of zinc antimonate powder, Nissan Chemical Industries (
Product name: Celnax; As powder and solvent dispersions such as alumina, titanium oxide, zinc oxide, etc., trade name: Nanotech, etc., manufactured by CI Kasei Co., Ltd. can be mentioned. The oxide particles have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of oxide particles (by BET method using nitrogen) is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g. These oxide particles can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured product.

  The organic compound containing a polymerizable unsaturated group that forms the surface-modified oxide particles (A) is not particularly limited. For example, the polymerizable unsaturated group may be an acryloyl group, a methacryloyl group, a vinyl group, Organic compounds containing groups such as a propenyl group, a butadienyl group, a styryl group, an ethynyl group, a cinnamoyl group, a maleate group, and an acrylamide group are preferred. This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

The organic compound containing such a polymerizable unsaturated group is preferably further [-XC (= Y) -NH-] (A1) in the molecule.
(In the formula, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S).
It is preferable to have a group represented by: As such a group (A1), specifically, [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (= O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [—S—C (═S) —NH—] Can be mentioned. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups. The group represented by the formula (A1) generates moderate cohesive force due to hydrogen bonding between molecules, and when cured, has excellent mechanical strength, adhesion to a substrate, and properties such as heat resistance. It is thought to be granted.

  The organic compound containing a polymerizable unsaturated group is preferably a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “a silanol group-containing compound”). It may also be referred to as a “silanol group-generating compound”. Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable. The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

  Preferable specific examples of the organic compound containing a polymerizable unsaturated group that forms the surface-modified oxide particles (A) include a compound represented by the following formula (A2).

式（Ａ２）中において、Ｒ⁵、Ｒ⁶は同一でも異なっていてもよいが、水素原子又はＣ₁
からＣ₈のアルキル基若しくはアリール基であり、例えば、メチル、エチル、プロピル、
ブチル、オクチル、フェニル、キシリル基等を挙げることができる。ここでｍは１、２又は３である。

In formula ^{(A2), R 5, R} 6 may be the same or different, but the hydrogen atom or a C ₁
To C ₈ alkyl or aryl groups such as methyl, ethyl, propyl,
Examples thereof include butyl, octyl, phenyl and xylyl groups. Here, m is 1, 2 or 3.

In the formula (A2), examples of the group represented by [(R ⁵ O) _m R ⁶ _3-m Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, Examples thereof include a dimethylmethoxysilyl group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ⁷ is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

R ⁸ is a divalent organic group and usually has a molecular weight of 14 to 10,000, preferably a molecular weight of 7
It is selected from 6 to 500 divalent organic groups. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. In addition, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (A1). Can also be included.

R ⁹ is an (n + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

  For the synthesis of the organic compound containing a polymerizable unsaturated group used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. (B) The reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

  In order to synthesize the compound represented by the formula (A2), among these methods (i) is preferably used. More specifically, for example, method (a); first, a mercaptoalkoxysilane and a polyisocyanate compound are reacted so that an alkoxysilyl group, a [—S—C (═O) —NH—] group and an isocyanate are present in the molecule. An intermediate containing a group is formed, and then the isocyanate remaining in the intermediate is reacted with a hydroxy group-containing polymerizable unsaturated compound to convert the unsaturated compound to [—O—C (═O) —NH. -] A method of bonding via a group, method (b); first, a polyisocyanate compound and a hydroxy group-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, [—O—C (= An intermediate containing an O) -NH-] group and an isocyanate group is formed, and this is reacted with mercaptoalkoxysilane to convert the mercaptoalkoxysilane to [—S—C (═O) —NH. How attached via a group, and the like. Further, among them, the method (a) is preferable in that there is no decrease in polymerizable unsaturated groups due to the Michael addition reaction.

  In the synthesis of the compound represented by the formula (A2), examples of the alkoxysilane that can form a [—S—C (═O) —NH—] group by reaction with an isocyanate group include an alkoxysilyl group. And compounds having at least one mercapto group in the molecule. Examples of such mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxy silane, mercapto Mention may be made of propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Moreover, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan and an addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

  The polyisocyanate compound used for synthesizing the organic compound containing a polymerizable unsaturated group used in the present invention is a polyisocyanate compound composed of a chain saturated hydrocarbon, a cyclic saturated hydrocarbon, or an aromatic hydrocarbon. You can choose from.

Examples of such polyisocyanate compounds include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4. -Xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4, 4'-diphenylmethane diisocyanate, 3,
3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate,
1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl- 1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethyl Examples include xylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, and the like are preferable. These can be used alone or in combination of two or more.

Examples of active hydrogen-containing polymerizable unsaturated compounds that can be bonded to the polyisocyanate compound via an [—O—C (═O) —NH—] group in the synthesis of an organic compound containing a polymerizable unsaturated group In the molecule, it has at least one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with an isocyanate group and one polymerizable unsaturated group. The compound containing above can be mentioned. Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythr Litholtri (meth) acrylate, dipentaerythritol penta Data) acrylate - door, and the like can be given. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable. These compounds can be used individually by 1 type or in mixture of 2 or more types.

  The surface-modified oxide particles (A) according to the present invention can be produced using the above-described oxide particles and an organic compound containing a polymerizable unsaturated group. For example, the above-described oxide particles and polymerization are performed. It can be produced by reacting with an organic compound containing a polymerizable unsaturated group. Oxide particles are known to contain moisture as adsorbed water on the particle surface under normal storage conditions, and at least the components that react with silanol group-generating compounds such as hydroxides and hydrates are present on the surface. It is estimated to be. Therefore, at the time of producing the surface-modified oxide particles (A), an organic compound containing a polymerizable unsaturated group such as a silanol group-generating compound and the oxide particles are mixed, heated and stirred. Is possible. Note that the reaction is preferably performed in the presence of water in order to efficiently combine the silanol group generation site of the organic compound containing a polymerizable unsaturated group with the oxide particles. However, when the organic compound containing a polymerizable unsaturated group has a silanol group, there is no need for water. Therefore, the surface-modified oxide particles (A) can be produced by a method including an operation of mixing at least the oxide particles and an organic compound containing a polymerizable unsaturated group.

Hereinafter, the example of the manufacturing method of surface modified oxide particle (A) is demonstrated in detail. The binding amount of the organic compound containing a polymerizable unsaturated group to the oxide particle is 100% by weight of the surface-modified oxide particle (A) (the total of the organic compound containing the oxide particle and the polymerizable unsaturated group), Preferably it is 0.01 weight% or more, More preferably, it is 0.1 weight% or more, Most preferably, it is 1 weight% or more. When the binding amount of the organic compound containing a polymerizable unsaturated group bonded to the oxide particles is less than 0.01% by weight, the dispersibility of the surface-modified oxide particles (A) in the composition is not sufficient, and thus obtained. The cured product obtained may not have sufficient transparency and scratch resistance. Moreover, the compounding ratio of the oxide particles in the raw material during the production of the surface-modified oxide particles (A) is preferably 5 to 99% by weight, and more preferably 10 to 98% by weight.

  Hereinafter, as an example of using an alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (A2) as an organic compound containing a polymerizable unsaturated group, a method for producing the surface-modified oxide particles (A) is further described. This will be described in detail. The amount of water consumed by hydrolysis of the alkoxysilane compound during the production of the surface-modified oxide particles (A) may be an amount that hydrolyzes at least one of the alkoxy groups on silicon in one molecule. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the oxide particles under completely moisture-free conditions is a product in which the alkoxysilane compound is physically adsorbed on the surface of the oxide particles and is composed of such components. In the cured product of the composition containing the surface-modified oxide particles (A), the effect of developing high hardness and scratch resistance is low.

  During the production of the surface-modified oxide particles (A), the alkoxysilane compound is separately subjected to a hydrolysis operation, and then mixed with powdered oxide particles or a solvent-dispersed sol of oxide particles, and heated and stirred. Or a method of hydrolyzing the alkoxysilane compound in the presence of oxide particles; a method of performing surface treatment of the oxide particles in the presence of other components such as a polymerization initiator, etc. Can be selected. In this, the method of hydrolyzing the said alkoxysilane compound in presence of an oxide particle is preferable. During the production of the surface-modified oxide particles (A), the temperature is preferably 0 ° C. or higher and 150 ° C. or lower, and more preferably 20 ° C. or higher and 100 ° C. or lower. The processing time is usually in the range of 5 minutes to 24 hours.

  In the production of the surface-modified oxide particles (A), when using powdered oxide powder, an organic solvent is added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. Also good. As such an organic solvent, the same solvent as that used as the dispersion medium of the solvent dispersion sol of the oxide particles can be used. The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

  When a solvent-dispersed sol is used as a raw material for the surface-modified oxide particles (A), it can be produced by mixing at least a solvent-dispersed sol and an organic compound containing a polymerizable unsaturated group. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

Moreover, in order to accelerate | stimulate reaction at the time of manufacture of surface modification oxide particle (A), you may add an acid, a salt, or a base as a catalyst. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, and itacone An unsaturated organic acid such as an acid, as a salt, for example, an ammonium salt such as tetramethylammonium hydrochloride or tetrabutylammonium hydrochloride, and as a base, for example, aqueous ammonia, diethylamine, triethylamine, dibutylamine, Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide Etc. Among these, preferred examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amine or quaternary ammonium hydroxide. The amount of these acids, salts or bases added is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound. It is. In order to accelerate the reaction, it is also preferable to add a dehydrating agent. As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable. The amount of the alkoxysilane compound bonded to the surface-modified oxide particles (A) is usually from 110 ° C. in the air as a constant value of weight loss% when the dry powder is completely burned in the air. It can be determined by thermogravimetric analysis up to 800 ° C.

  The blending amount of the surface-modified oxide particles (A) in the curable composition is preferably 5 to 90% by weight, with the total of the blending components excluding the solvent of the curable composition being 100% by weight, More preferred is 70% by weight. If it is less than 5% by weight, the hardness of the cured product may be insufficient, and if it exceeds 90% by weight, it may not be cured (not form a film). The amount of the surface-modified oxide particles (A) means a solid content, and when the surface-modified oxide particles (A) are used in the form of a solvent-dispersed sol, the blending amount does not include the amount of the solvent. .

-Compound (B) having an alicyclic structure and containing two or more polymerizable unsaturated groups in the molecule
The compound (B) according to the present invention is a compound having an alicyclic structure and containing two or more polymerizable unsaturated groups in the molecule. As such a compound (B), (meth) acrylic acid esters having an alicyclic structure are preferably used.

The alicyclic structure-containing (meth) acrylic acid ester used as the compound (B) is not particularly limited as long as it is a (meth) acrylic acid ester having a cyclic structure with a saturated hydrocarbon in the ester substituent. For example, (meth) acrylic acid esters having a cyclohexane ring, (meth) acrylic acid esters having a bicyclo [2.2.1] heptane ring, tricyclo [5.2.1.0 ^2,6 ] (Meth) acrylic acid esters having a decane ring, tetracyclo [6.2.1.0 ^2,7 . 1 ^3,6] having a dodecane ring (meth) acrylate and the like. Among these, (meth) acrylic acid esters having a bicyclo [2.2.1] heptane ring, and having a tricyclo [5.2.1.0 ^2,6 ] decane ring (
(Meth) acrylic acid esters, tetracyclo [6.2.1.0 ^2,7 . 1 ^3,6 ] At least one selected from the group consisting of (meth) acrylic acid esters having a dodecane ring is preferred. Such a compound (B) is indispensable for ensuring strong adhesion to the surface of the film (I) containing the cyclic olefin polymer.

Specific examples of the alicyclic structure-containing (meth) acrylic esters suitably used as the compound (B) include cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanediyl di (meth) acrylate, tetratricyclodecanediyl dimetadi (meth) acrylate, Examples thereof include polymerizable monomers such as (meth) acrylate modified with ethylene glycol or propylene glycol. In addition, an oligomer of a cyclic olefin monomer, an intermediate or monomer having an unsaturated double bond before hydrogenation, and the same synthesis as (meth) acrylates such as dicyclopentanyl (meth) acrylate It may be a photopolymerizable oligomer having a (meth) acryloyl group modified by a method. Preferred as the alicyclic structure-containing (meth) acrylic acid esters (B) are dicyclopentanyl (meth) acrylate, tricyclodecanediyl di (meth) acrylate, tetratricyclodecanediyl di (meth) acrylate, and the like. is there.

-Other components In the curable composition concerning this invention, the compound (C) which contains two or more polymerizable unsaturated groups in a molecule | numerator other than a compound (B), and a polymerization initiator (D) as needed. ), A sensitizer, a solvent, oxide particles other than the particles (A), various additives, and the like.

The compound (C) containing two or more polymerizable unsaturated groups in the molecule other than the compound (B) is not particularly limited, and examples thereof include (meth) acrylic esters and vinyl compounds. . Of these, (meth) acrylic esters are preferred. Specific examples of the compound (C) used in the present invention are listed below. (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene Glucol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (
(Meth) acrylates, poly (meth) acrylates of adducts of ethylene oxide or propylene oxide to these starting alcohols, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers ( Mention may be made of (meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates and the like. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferable. Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

As a commercial item of such a compound (C), Toagosei Co., Ltd. product name: Aronix M-400, M-408, M-450, M-305, M-309, M-31, for example
0, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, TO-924, TO-1270, TO-1231, TO-595
, TO-756, TO-1231, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade names: KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR- 502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, HDDA, NPGDA, TPG A, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, TMPTA, THE-330, TPA- 320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. product name: Light acrylate PE-4A, DPE-6A, DTMP-4A, and the like. In addition to the compound (B) and the compound (C), the composition of the present invention may contain a compound having one polymerizable unsaturated group in the molecule, if necessary.

  When the curable composition which concerns on this invention contains the said compound (C), the compounding ratio (weight ratio) of a compound (B) and a compound (C) is (B) :( C) = 5. : 95 to 90:10, and (B) :( C) = 10: 90 to 80:20 is preferable. When the compounding ratio of the compound (B) to the compound (C) is less than 5/95, adhesion, particularly adhesion to a norbornene-based resin, may be insufficient.

  The curable composition according to the present invention preferably contains a polymerization initiator (D). Here, the hardening method of a curable composition is demonstrated including that the curable composition concerning this invention uses a polymerization initiator (D).

The curable composition according to the present invention is cured by heat and / or radiation. In the present invention, “radiation” means infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like. When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation, the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. Examples of the infrared radiation source include a lamp, a resistance heating plate, Lasers, etc., visible light sources such as sunlight, lamps, fluorescent lamps, lasers, etc. Ultraviolet ray sources such as mercury lamps, halide lamps, lasers, etc. Examples of the radiation source include a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which a metal is generated through a high voltage pulse, and a collision between an ionized gaseous molecule and a metal electrode 2. A secondary electron system using secondary electrons can be mentioned. As a source of alpha rays, solid rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited. For gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations may be irradiated alone or in combination of two or more, or one or more kinds of radiation may be irradiated after a certain period.

  In order to shorten the curing time, a polymerization initiator (D) may be added to the curable composition of the present invention. Examples of such a polymerization initiator (D) include thermally active radical species. Commonly used compounds such as a compound to be generated and a compound to generate an active radical species by irradiation are exemplified.

  In the present invention, it is preferable to use a radiation polymerization initiator as the polymerization initiator (D). Among them, both aryl ketones having a 1-hydroxycyclohexyl group and aryl ketones having an N-morpholino group, or their It is more preferable to use a radiation polymerization initiator containing any of them. When only aryl ketones having a 1-hydroxycyclohexyl group are added, a cured product with little coloring can be formed in a short time. On the other hand, when only aryl ketones having an N-morpholino group are added, a cured product having a high surface hardness can be formed in a short time. When both are used in combination, a cured product having a high surface hardness and little coloring can be formed in a short time.

The aryl ketones having a 1-hydroxycyclohexyl group are not particularly limited, and examples thereof include 1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl isopropyl phenyl ketone, 1-hydroxycyclohexyl dodecyl phenyl ketone, and the like. The aryl ketones having an N-morpholino group used in the present invention are not particularly limited. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2 -Methyl-1- [4- (methoxy) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- (2-hydroxyethoxy) phenyl] -2-morpholinopropanone-1,2- Methyl-1- [4- (dimethylamino) phenyl] -2-morpholinopropanone-1,2-methyl-1- [4- (diphenylamino) phenyl] -2-morpholinopropanone-1,2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1
Examples include 3,6-bis (2-methyl-2-morpholinopropionyl) -9-N-octylcarbazole. These radiation polymerization initiators may be used singly or in combination of two or more, but when cured, in order to improve the curing rate and hardness of both the surface portion and the interior It is preferable to use a combination of an aryl ketone having a 1-hydroxycyclohexyl group and an aryl ketone having an N-morpholino group. Examples of such commercially available radiation polymerization initiators include trade names: Irgacure 184, 907 manufactured by Ciba Specialty Chemicals Co., Ltd.

  The polymerization initiator (D) blended in the curable composition according to the present invention as necessary is 0.01 to 20 when the total of the blending components of the curable composition excluding the solvent is 100% by weight. It is preferable to mix | blend a weight part, and 0.1-10 weight part is further more preferable. If it is less than 0.01 part by weight, the hardness when it is a cured product may be insufficient, and if it exceeds 20 parts by weight, the inside (lower layer) may not be cured when it is a cured product.

  In addition, when the aryl ketone having a 1-hydroxycyclohexyl group and the aryl ketone having an N-morpholino group are used in combination, the mixing ratio of both is preferably 10:90 to 90:10, and 40:60 ~ 80: 20 is more preferred.

  Examples of sensitizers that can be incorporated into the curable composition of the present invention include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4- Examples thereof include ethyl dimethylaminobenzoate and isoamyl 4-dimethylaminobenzoate. Examples of commercially available products of this sensitizer include Nippon Kayaku Co., Ltd. trade name: KAYACURE DMBI, EPA, and the like.

  In addition to the dispersion solvent, a solvent can be added to the curable composition according to the present invention after preparing the composition for improving coating properties, adjusting viscosity, adjusting solid content concentration, and the like. As the solvent, the same solvent as that used as the dispersion solvent can be used.

  It is preferable that the curable composition used by this invention contains a solvent in the quantity used as an appropriate viscosity from the surface of workability | operativity. The viscosity of the curable composition is, for example, 0.1 to 50,000 mPa · s / 25 ° C., and preferably 0.5 to 10,000 mPa · s / 25 ° C.

  Examples of the oxide particles other than the surface-modified oxide particles (A) that can be blended in the curable composition include metal oxide particles used as a raw material for the surface-modified oxide particles (A). Can do.

  Examples of additives that can be incorporated into the curable composition include antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, anti-aging agents, thermal polymerization inhibitors, colorants, leveling agents, surfactants, Examples include storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, and coating surface improvers.

Examples of commercially available antioxidants include trade names manufactured by Ciba Specialty Chemicals Co., Ltd .: Irganox 1010, 1035, 1076, 1222, and the like. Examples of ultraviolet absorbers include Ciba Specialty Chemicals Co., Ltd. Product name: Tinuvin P, 23
4, 320, 326, 327, 328, 213, 400, manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400, etc. As commercial products of light stabilizers, Ciba Specialty Chemicals Co., Ltd. trade names: Tinuvin 292, 144, 622LD, Sankyo Chemical Industries Co., Ltd. trade names: Sanol LS-770, 765, 292, 2626, 1114, 744 and the like, and examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Commercially available products include Toray Dow Corning Silicone Co., Ltd. Product name: SH 062, SZ6030, manufactured by Shin-Etsu Silicone Co., Ltd. Trade names: KBE903, KBM803, etc., and commercial products of anti-aging agents are trade names manufactured by Sumitomo Chemical Co., Ltd. Trade names: Antigen W, S, P, 3C 6C, RD-G, FR, AW and the like.

  Additives other than the above include epoxy resin, polyamide, polyimide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer, styrene / ethylene / butene / Examples thereof include polymers or oligomers such as styrene block copolymers, styrene / isoprene / styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers.

<Formation method of particle content layer (II)>
The particle-containing layer (II) according to the present invention is formed on the film (I) having a cyclic olefin polymer by using the curable composition described above. The particle-containing layer (II) can be usually formed by coating (coating) a curable composition on the film (I) by a known method, and drying and curing. That is, the heat-resistant laminated film of the present invention is produced by coating the curable composition on the film (I) having a cyclic olefin polymer, and drying and curing to form the particle-containing layer (II). can do.

  Coating methods include, for example, dipping coat, spray coat, flow coat, shower coat, roll coat, spin coat, gravure coat, micro gravure coat, comma roll coat Commonly used coating methods such as Mayer bar coat, slot-by coat, air knife coat, lip coat, kiss coat, and brush coat can be used. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

  Although drying of the coated curable composition is not specifically limited, Preferably it can carry out by removing a volatile component at 0-200 degreeC. Drying may be performed prior to curing or may be performed simultaneously with curing.

Curing can be performed by subjecting the coating film of the curable composition to a curing treatment with heat and / or radiation. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Further, preferable electron beam irradiation conditions are:
The applied voltage is 10 to 300 KV, the electron density is 0.02 to 0.30 mA / cm ² , and the electron beam irradiation amount is 1 to 10 Mrad.

  In the present invention, the particle-containing layer (II) can be formed in this manner. The formation of the particle-containing layer (II) on the film (I) may be performed simultaneously on both sides or sequentially on each side.

  The formed particle-containing layer (II) is particularly excellent in adhesiveness with the film (I) having a cyclic olefin polymer and hardly causes peeling. The particle-containing layer (II) is also excellent in hardness, scratch resistance, and transparency.

  The laminated film of the present application is converted to oxide particles of the surface-modified oxide particles (A) in the particle-containing layer (II) formed on both sides with respect to the film thickness 100 of the film (I) having a cyclic olefin polymer. Is generally in the range of 0.1 to 30, preferably in the range of 0.1 to 20, and more preferably in the range of 0.3 to 15. When the thickness of the oxide particles is within the above range, dimensional changes due to heating can be suppressed.

  The thickness in terms of oxide particles of the surface-modified oxide particles (A) is the total film thickness on both surfaces of the particle-containing layer, the density of the oxide particles, the density of the particle-containing layer (II), and the particle-containing layer (II). The specific thickness obtained by calculating the volume ratio between the particle-containing layer and the oxide particles using the concentration by mass of the oxide particles in the particle.

Heat-resistant laminated film The heat-resistant laminated film of the present invention has excellent hardness, scratch resistance, and transparency as well as excellent heat stability by having the particle-containing layer (II) on both sides of the film (I). Show. In the heat-resistant laminated film of the present invention, when the thickness and the degree of curing of the particle-containing layer (II) formed on both sides of the film (I) are equivalent, changes in film dimensions during processing or use at high temperatures And curling can be particularly preferably prevented. In such a heat-resistant laminated film of the present invention, dimensional change and curl can be highly suppressed as compared with the case where the film (I) which is the base film is used as it is at a high temperature.

  The heat resistant laminated film of the present invention can be suitably used for applications such as optical components and liquid crystal elements. Further, the heat-resistant laminated film of the present invention can be used after being subjected to surface treatment such as painting, plating, physical vapor deposition, chemical vapor deposition, corona treatment, plasma treatment, etc. , Impart anti-static properties, anti-contamination properties, anti-condensation properties, water repellency, oil repellency, electromagnetic wave shielding properties, ultraviolet ray shielding properties, heat ray absorption properties, electrical conductivity, insulation properties, flame retardancy, antibacterial properties, etc. be able to.

Transparent conductive layer The conductive transparent film of the present invention is obtained by further laminating a transparent conductive layer on the above-described laminated film of the present invention.

The transparent conductive layer according to the present invention is a layer having transparency in the visible light region and having conductivity.
As a method for forming the transparent conductive layer, any of the conventionally known techniques such as vacuum deposition, sputtering, and ion plating can be used. From the viewpoint of film uniformity and adhesion of the thin film to the transparent substrate. The thin film formation by sputtering is preferred. Further, the thin film material to be used is not particularly limited. For example, in addition to metal oxides such as indium oxide containing tin oxide and tin oxide containing antimony, gold, silver, platinum, palladium, copper, aluminum, Nickel, chromium, titanium, cobalt, tin, or alloys thereof are preferably used. The thickness of the conductive thin film needs to be 30 angstroms or more, and if it is thinner than this, it is difficult to form a continuous film having good conductivity with a surface resistance of 1000 Ω / □ or less. On the other hand, if the thickness is too large, the transparency is lowered, and the preferred thickness is about 50 to 2000 angstroms.

Optical Film The optical film of the present invention has a metal or metal oxide deposited layer on the surface of the above-described laminated film of the present invention. The vapor deposition layer may be a single layer or a multilayer.

  When the optical film of the present invention has a multilayer vapor deposition layer, the multilayer vapor deposition film is preferably a reflection film having a predetermined wavelength band composed of a dielectric multilayer film. In such a case, the optical film is an optical film. It can be suitably used as a filter film, and in particular, an optical filter film that reflects and cuts near-infrared (wavelength: 800 nm to 1000 nm) and acts as a near-infrared cut filter is desirable.

  When the optical film of the present invention has a multilayer vapor deposition layer, the multilayer vapor deposition film alternately includes dielectric layers A and dielectric layers B having a refractive index higher than that of the dielectric layer A. It is preferable to have a near-infrared reflective film made of a laminated dielectric multilayer film.

By having such a dielectric multilayer film on at least one surface of the transparent substrate, a near-infrared cut filter having an excellent ability to reflect near-infrared light can be obtained.
<Dielectric layer A>
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.

<Dielectric layer B>
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. Examples of these materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as a main component, and small amounts of titanium oxide, tin oxide, cerium oxide, and the like. The thing etc. which were made to contain are mentioned.

  The dielectric layer A and the dielectric layer B are formed by alternately depositing the metal or metal oxide constituting the dielectric layer A and the dielectric layer B by vapor deposition, for example, by CVD, sputtering, vacuum deposition, or the like. It can be formed by stacking. The thicknesses of the dielectric layer A and the dielectric layer B are usually 0.1λ to 0.5λ of the near infrared wavelength λ (nm) to be blocked. When the thickness is out of the above range, the product (n × d) of the refractive index (n) and the film thickness (d) is greatly different from the optical film thickness calculated by λ / 4, and the optical reflection and refraction There is a tendency that the relationship of characteristics is broken and control for blocking / transmitting a specific wavelength cannot be performed. When the dielectric multilayer film is provided only on one surface of the transparent substrate, the number of laminated dielectric multilayer films is usually in the range of 10 to 80 layers, and preferably in the range of 25 to 50 layers. On the other hand, in the case where the dielectric layer film is provided on both surfaces of the transparent substrate, the number of stacked layers of the dielectric layers is generally in the range of 10 to 80 layers, preferably 25 to 50 layers as the entire number of stacked layers on both surfaces of the substrate. It is a range. Moreover, when using the thermoplastic resin containing a near-infrared absorber as a transparent substrate, when the dielectric multilayer film is provided only on one surface of the transparent substrate, the number of laminated layers in the dielectric multilayer film is 5 to 5. 40 layers, preferably 10 to 30 layers, and when the dielectric layer film is provided on both sides of the transparent substrate, the number of laminated layers of the dielectric layers is 5 to 40 as the whole number of laminated layers on both sides of the substrate. There can be 10 to 30 layers, preferably 10 to 30 layers. When a thermoplastic resin containing a near infrared absorber is used as a transparent substrate, productivity can be further improved and the dielectric multilayer film can be made difficult to break. In the optical film of the present invention that functions as a near-infrared cut filter, at least one functional film selected from an equivalent refractive index film, an antireflection film, and a hard coat film may be used.

Substrate film substrate film present invention comprises a patterned layer in the laminated film, formed by further photosensitive resin composition of the present invention described above. That is, the substrate film of the present invention may have a pattern of a cured product of the photosensitive resin composition, and also has an inorganic (metal) thin film pattern formed using the photosensitive composition. Also good. In such a substrate film, the formed pattern is preferably an electrode pattern.

  As an electrode pattern manufacturing method, an inorganic thin film is formed on the above-described laminated film of the present invention by sputtering or vapor deposition, and a photosensitive resin composition is applied, exposed and developed, and then an inorganic thin film pattern is formed with an etching solution. An etching method, a film of a photosensitive inorganic powder-containing resin composition is formed on a substrate, and this film is irradiated with ultraviolet rays through a photomask and developed to leave a pattern on the substrate. Examples include a photolithography method for firing. All of these methods involve heating during pattern formation, but since the laminated film of the present invention is excellent in heat resistance, pattern formation can be suitably performed without causing deformation, shrinkage, etc. It can also be suitably used for precision applications.

  The substrate film of the present invention is an electrode for manufacturing a plasma display panel (PDP), a liquid crystal display element (LCD), an organic EL element, a printed circuit board, a multilayer circuit board, a solar cell board, a multichip module, and an LSI. It can use suitably for manufacture. Since the substrate film of the present invention has flexibility, a display that is more flexible than the case of using a conventional substrate in which electrodes are formed in a rigid inorganic material such as glass or silicone wafer can be produced.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following, parts and% respectively represent parts by weight and% by weight unless otherwise specified. Further, in the present invention, the “solid content” means a portion obtained by removing volatile components such as a solvent from the composition, and specifically obtained by drying the composition on a hot plate at 120 ° C. for 1 hour. It means a residue (nonvolatile component).

Evaluation Method In the following examples and comparative examples, the properties of the laminated film were measured or evaluated by the following methods.

(Film appearance)
The following criteria were used for visual evaluation.
○: There is no foreign matter, unevenness, or repellency on the film.
X: The film has foreign matter, unevenness, and repellency.
A film having no foreign matter, unevenness, and repellency was evaluated as “◯”, and a film having foreign matter, unevenness, and repellency was evaluated as “x”.

(Peeling)
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 of the coating layer was conducted. Evaluated by criteria.
○: No peeling of the coat layer.
X: There exists peeling of a coating layer.

(crack)
Using a constant temperature dryer (model: DV402) manufactured by Yamato Scientific Co., Ltd., the film surface temperature reached 140 ° C. and heated for 2 minutes. This was visually evaluated according to the following criteria.
○: No cracking in the coating layer.
X: There is a crack in the coating layer.

(Heating dimensional change)
Using a 250 mm x 250 mm size film and using a constant temperature dryer (model: DV402) manufactured by Yamato Scientific Co., Ltd., the film surface temperature reached a predetermined temperature (140 ° C and 200 ° C) and heated for 30 minutes. The dimensional change RT (ppm) of the film before and after heating was measured, and the rate of change was calculated. The film dimensions were measured using calipers for each of the TD direction and MD direction of the film. This result was evaluated according to the following criteria. A: The dimensional change rate before and after heating is reduced by 10% or more with respect to an uncoated film (film of Comparative Example 1).
X: The dimensional change rate before and after heating is a reduction of less than 10% with respect to an uncoated film.

(Thickness of oxide particles)
The volume ratio is obtained from the density of the oxide particles and the density of the coating film after curing and drying of the coating liquid excluding the oxide particles, and the dry film thickness of the laminated film is measured with an ultraviolet-visible spectrometer. The specific film thickness in terms of particles was calculated.

[Preparation Example 1] (Preparation of surface-modified silica particles)
1,3-bis (isocyanatomethyl) cyclohexane 22 with respect to a solution comprising 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air
The mixture was added dropwise at 50 ° C. over 1 hour while stirring 3 parts, and then heated and stirred at 70 ° C. for 3 hours. To this was added dropwise 555 parts of pentaerythritol triacrylate at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain a silane compound. Analysis of the amount of residual isocyanate in the product was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of the mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of the raw isocyanate compound disappear, and a new urethane bond and —S (C ═O) A peak of 1660 Kaiser characteristic of the NH— group and a peak of 1720 Kaiser characteristic of acryloxy are observed, and an acryloxy group as a polymerizable unsaturated group and —S (C═O) NH—, urethane bond It was shown that an acryloxy group-modified alkoxysilane having the same structure was produced.

Under a nitrogen stream, 30 parts of the silane compound produced above, MEK-ST (manufactured by Nissan Chemical Co., Ltd., methyl ethyl ketone-dispersed colloidal silica (average particle size 0.01 to 0.015 μm, density 2.2 g / cm ³ ), silica (Concentration 30%) 233 parts, 5 parts of isopropyl alcohol and 3 parts of ion-exchanged water were stirred at 80 ° C. for 3 hours, 18 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour. As a result, a colorless and transparent silica particle dispersion was obtained.

[Preparation Example 2] (Preparation of curable composition A)
In a container shielded from ultraviolet rays under a dry air stream, 24.94 parts of dipentaerythritol hexaacrylate (DPHA), 8.27 parts of tricyclodecanediyldimethylene diacrylate (Iupimer SA1002, manufactured by Mitsubishi Chemical Corporation), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) 2.
07 parts, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholyl) -1-propanone (Irgacure 907, Ciba Specialty Chemicals) 1.24 parts, and methyl ethyl ketone 13.48 parts Was stirred at room temperature for 30 minutes to obtain a curable composition A.

The solid content in the obtained curable composition A was 73%.
[Preparation Example 3] (Preparation of curable composition B)
Under a dry air stream, 0.171 parts of dibutyltin dilaurate, 7.087 parts of 3-mercaptopropyltrimethoxysilane, 0.019 parts of 2,6-di-t-butyl-p-cresol in a container shielded from ultraviolet rays Tetramethylol methane triacrylate 69.04
8 parts, 18.678 parts of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and 4.997 parts of methyl ethyl ketone were mixed to prepare mixture a.

Next, in a container shielded from ultraviolet rays under a dry air stream, DPHA 24.94 parts, tricyclodecanediyl dimethylene diacrylate 8.27 parts, 1-hydroxycyclohexyl phenyl ketone 2.07 parts, 2-methyl-1- [ 4- (methylthio) phenyl] -2- (4-morpholyl) -1-propanone (Irgacure 907, manufactured by Ciba Specialty Chemicals) 1.24 parts, methyl ethyl ketone 13.48 parts, surface-modified silica particles obtained in Preparation Example 1 Solution (dissolved in methyl ethyl ketone at a solid content of 32%) 92.35 parts, 0.03 parts of 0.1N sulfuric acid, 8.78 parts of the mixture a, 0.01 parts of p-methoxyphenol, 0.01 parts of distilled water, orthoformic acid 1.4 parts of methyl were stirred at room temperature for 30 minutes to prepare 139.21 parts of a composition, which was And concentrated to 100 parts to obtain a curable composition B by aerator. The resulting curable composition B had a solid content of 76% and an inorganic content of 40%.

[Preparation Examples 4 to 7] (Preparation of curable compositions C, D, E, and F)
Curable compositions C, D, E and F were obtained in the same manner as in Preparation Example 3 with the formulation shown in Table 1.

［実施例１］
硬化性組成物Ａ２５部と、硬化性組成物Ｂ７５部とを混合して、シリカ粒子含有量が固形分中の１０％である硬化性組成物（ＡＢ１）を得た。

[Example 1]
25 parts of curable composition A and 75 parts of curable composition B were mixed to obtain a curable composition (AB1) having a silica particle content of 10% in the solid content.

Using the bar coater, the cured curable composition is 2 μm thick on both sides of a 100 μm thick cyclic olefin resin film (trade name: ARTON G7810, manufactured by JSR Corporation). After being applied for 3 minutes in a hot air dryer at 80 ° C., it was cured by irradiation with a light amount of 1 J / cm ² using a conveyor type mercury lamp. Each of the properties of the laminated film (1) obtained after coating, drying and curing on the other side, providing a layer of a 2 μm curable composition on each side and storing at 25 ° C. for 24 hours. Evaluated. The results are shown in Table 2.

A curable composition (1) obtained by mixing 25 parts of curable composition A and 75 parts of curable composition B was applied on a glass plate by a bar coater method, dried at 140 ° C. for 2 minutes, and then glass. It peeled from the board and the cured film (1) of 20 cm x 20 cm x 10 micrometers was obtained. The weight of the cured film was 0.36 g, the density of the resulting cured film (1) was 0.91 g / cm ^3.

  Moreover, when the film thickness of the laminated film after curing was measured with an ultraviolet-visible spectrometer, the film thickness of the layer formed from the curable composition (AB1) on the cyclic olefin resin film was 2 μm on one side and measured on both sides. It was confirmed that the thickness was 4 μm. From the density of the oxide particles and the density and thickness of the curable composition (AB1), the specific thickness of the oxide particles was 0.16 μm.

[Example 2]
In Example 1, the curable composition (AB2) obtained by mixing 50 parts of the curable composition A and 50 parts of the curable composition B and having a silica particle content of 20% of the solid content is used for coating. A laminated film (2) having a cured film on both sides was produced in the same manner as in Example 1 except that the properties were evaluated. The results are shown in Table 2.

When the density of the curable composition (2) was determined by the same method as in Example 1, it was 0.97 g / cm ³ and the specific thickness of the oxide particles was 0.35 μm.
[Example 3]
In Example 1, the curable composition (AB3) obtained by mixing 75 parts of the curable composition A and 25 parts of the curable composition B and having a silica particle content of 30% in the solid content is used for coating. A laminated film (3) having a cured film on both sides was produced in the same manner as in Example 1 except that the properties were evaluated. The results are shown in Table 2.

When the density of the curable composition (3) was determined by the same method as in Example 1, it was 1.04 g / cm ³ and the specific thickness of the oxide particles was 0.57 μm.
[Example 4]
A laminated film having a cured film on both sides in the same manner as in Example 1 except that only the curable composition B (silica particle content is 40% of the solid content) was used for coating in Example 1. (4) was manufactured and each property was evaluated. The results are shown in Table 2.

When the density of the curable composition (B1) was determined by the same method as in Example 1, it was 1.13 g / cm ³ and the specific thickness of the oxide particles was 0.82 μm.
[Example 5]
A laminated film having a cured film on both sides in the same manner as in Example 1 except that only the curable composition C (silica particle content is 60% of the solid content) was used for coating in Example 1. (5) was manufactured and each property was evaluated. The results are shown in Table 2.

When the density of the curable composition (C1) was determined in the same manner as in Example 1, 1.35 g
/ Cm ³ , and the specific thickness of the oxide particles was 1.47 μm.
[Example 6]
In Example 5, the coating thickness of the curable composition C was set to have a cured film on both sides in the same manner as in Example 5 except that the thickness after curing was 5 μm on each side. A laminated film (6) was produced, and each property was evaluated. The results are shown in Table 2.

From the film thickness of the layer formed from the cyclic olefin film and the curable composition C, the specific film thickness of the oxide particles was 3.67 μm.
[Example 7]
In Example 5, the coating thickness of the curable composition C was set to have a cured film on both sides in the same manner as in Example 5 except that the thickness after curing was 10 μm on each side. A laminated film (7) was produced and evaluated for each property. The results are shown in Table 2.

From the film thickness of the layer formed from the cyclic olefin film and the curable composition C, the specific film thickness of the oxide particles was 7.34 μm.
[Example 8]
In Example 5, the coating thickness of the curable composition C was set to have a cured film on both sides in the same manner as in Example 5 except that the thickness after curing was 15 μm on each side. A laminated film (8) was produced, and each property was evaluated. The results are shown in Table 2. The specific film thickness of the oxide particles was 11.01 μm.

[Example 9]
In Example 5, the coating thickness of the curable composition C was set to have a cured film on both sides in the same manner as in Example 5, except that the thickness after curing was 25 μm on each side. A laminated film (9) was produced and evaluated for each property. The results are shown in Table 2.

From the film thickness of the layer formed from the cyclic olefin film and the curable composition C, the specific film thickness of the oxide particles was 18.35 μm.
[Example 10]
In Example 1, the curable composition (CD1) obtained by mixing 50 parts of the curable composition C and 50 parts of the curable composition D and having a silica particle content of 80% of the solid content is used for coating. A laminated film (10) having a cured film on both sides was produced in the same manner as in Example 1 except that the properties were evaluated. The results are shown in Table 2.

The density of the curable composition (6) obtained by mixing 50 parts of the curable composition C and 50 parts of the curable composition D was measured and calculated in the same manner as in Example 1, and was 1.67 g / cm ³ . The specific thickness of the oxide particles was 2.43 μm.

[Comparative Example 1]
Each property was evaluated in the same manner as in Example 1 for an untreated cyclic olefin-based resin film (thickness: 100 μm, trade name: ARTON G7810, manufactured by JSR Co., Ltd.) that does not form a cured film with the curable composition. . The results are shown in Table 2.

[Comparative Example 2]
In Example 1, curable composition F (silica particle content is 40% of solid content. Silica particles are a surface of a compound having an alicyclic structure and having two or more polymerizable unsaturated groups in the molecule. A laminated film (11) cyclic olefin-based resin film having a cured film on both sides was produced in the same manner as in Example 1 except that the untreated) was used for coating, and each property was evaluated. The results are shown in Table 2.

When the density of the curable composition (F1) was determined by the same method as in Example 1, it was 1.13 g / cm ³ and the specific thickness of the oxide particles was 0.82 μm.
[Comparative Example 3]
In Example 1, a cyclic olefin resin film having a cured film on both sides was produced in the same manner as in Example 1 except that only the curable composition A (not containing silica particles) was used for coating. Each property was evaluated. The results are shown in Table 2.

[Comparative Example 4]
In Example 5, the coating thickness of the curable composition C was set to be a cured film on both sides in the same manner as in Example 5 except that the thickness after curing was 0.1 μm on each side. A laminated film (12) having the following properties was produced, and each property was evaluated. The results are shown in Table 2.
The specific film thickness of the oxide particles was 0.07 μm from the density of the cured film (5) and the oxide particles.

[Comparative Example 5]
In Example 5, the coating thickness of the curable composition C was set to have a cured film on both sides in the same manner as in Example 5 except that the thickness after curing was 50 μm on each side. A laminated film (13) was produced, and each property was evaluated. The results are shown in Table 2.
The specific film thickness of the oxide particles was 36.69 μm based on the density of the cured film (5) and the oxide particles.

[Comparative Example 6]
In Example 1, a curable composition (CD2) obtained by mixing curable composition C25 parts and curable composition D75 parts and having a silica particle content of 90% of the solid content was used for coating. A laminated film (14) having a cured film on both sides was produced in the same manner as in Example 1 except that the properties were evaluated. The results are shown in Table 2.

When the density of the curable composition (CD2) was determined by the same method as in Example 1, it was 1.90 g / cm ³ and the specific thickness of the oxide particles was 3.11 μm.
[Comparative Example 7]
A laminated film having a cured film on both sides in the same manner as in Example 1 except that only the curable composition E (silica particle content is 60% of the solid content) was used for coating in Example 1. (15) was manufactured, and each property was evaluated. The results are shown in Table 2.

When the density of the curable composition (E1) was determined by the same method as in Example 1, it was 1.35 g / cm ³ and the specific thickness of the surface oxide particles was 1.47 μm.

The heat resistant laminated film of the present invention can be suitably used for applications such as optical components and liquid crystal elements. In addition, the heat-resistant laminated film of the present invention has antireflection properties, antistatic properties, antifouling properties, anticondensation properties, water repellency, oil repellency, electromagnetic wave shielding properties, ultraviolet ray shielding properties, heat ray absorptive properties, conductive properties as necessary It can also be used as a film imparted with functionality such as property, insulation, flame retardancy, and antibacterial properties. The heat-resistant laminated film of the present invention is a manufacturing process and an optical filter substrate having a metal and a metal oxide vapor-deposited layer, a conductive laminated film, The base material for flexible substrates etc. which forms patterning can be formed suitably. The conductive laminated film of the present invention can be suitably used as a conductive transparent film when a touch panel is used in combination with various displays and liquid layer display devices.

Claims (8)

On both sides of the film (I) having a cyclic olefin polymer,
(A) Surface obtained by bonding oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium and an organic compound containing a polymerizable unsaturated group Modified oxide particles, and (B) a particle-containing layer (II) formed using a curable composition containing an alicyclic structure and a compound containing two or more polymerizable unsaturated groups in the molecule. And
The total thickness in terms of oxide particles of the surface-modified oxide particles (A) in the particle-containing layer (II) formed on both surfaces is 100 film thickness of the film (I) having a cyclic olefin polymer. The laminated film is characterized by being in the range of 0.1-30. For the film thickness 100 of the film (I) having a cyclic olefin polymer,
The total film thickness of the particle-containing layers (II) formed on both surfaces is in the range of 0.5 to 100, and the laminated film according to claim 1.   5 to 90% by mass of the surface-modified oxide particles (A) in which the curable composition is formed by bonding oxide particles and an organic compound containing a polymerizable unsaturated group in all components except the solvent. It contains in the range, The laminated | multilayer film of Claim 1 or 2 characterized by the above-mentioned. The said cyclic olefin polymer has a structural unit represented by following formula (1), The laminated | multilayer film in any one of Claims 1-3 characterized by the above-mentioned.

(In the formula (1), m is an integer of 0 or more, p is an integer of 0 or more, X is independently a formula: or a group represented by the formula represented by _{-CH = CH-: -CH 2 CH 2} - Table R ^{1 to} R ⁴ are each independently 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 oxygen, nitrogen, sulfur or silicon Or a polar group, R ¹
And R ² and / or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a carbocyclic ring or A heterocycle may be formed, and the carbocycle or heterocycle may be a monocyclic structure or a polycyclic structure. ) (A) Surface obtained by bonding oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium and an organic compound containing a polymerizable unsaturated group Modified oxide particles,
(B) A curable composition containing an alicyclic structure and containing two or more polymerizable unsaturated groups in the molecule and (C) a solvent is applied to both surfaces of a film having a cyclic olefin polymer. And a process for forming a coating film by drying, and a process for curing the coating film.   A conductive laminated film comprising a conductive layer on the surface of the laminated film according to claim 1.   An optical film having a metal or metal oxide vapor deposition layer on the surface of the laminated film according to claim 1.   A substrate film comprising a patterning layer formed of a photosensitive resin composition on a surface of the laminated film according to claim 1.