JP2010089458A - Laminated film, laminated film with inorganic vapor deposition layer, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film of excellent heat resistance without impairing a characteristic such as transparency of a cyclic olefin resin film, a laminated film with an inorganic vapor deposition layer excellent in tightness and strength, and a method for manufacturing the same. <P>SOLUTION: This laminated film (I) includes a cured layer (B) formed on at least one face of the cyclic olefin resin film (A), using a curable composition containing (a) a compound having a tri-functional or more functional polymerizable unsaturated group, (b) a compound having a mono-functional or more functional polymerizable unsaturated group and alicyclic structure, and (c) a compound having an acidic group and a mono-functional or more functional polymerizable unsaturated group, at a predetermined ratio. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated film having a cured layer on a cyclic olefin-based resin film, a laminated film having an inorganic vapor-deposited layer on the laminated film, and a method for producing a laminated film having an inorganic vapor-deposited layer.

  A film made of a cyclic olefin resin has low birefringence, excellent transparency, relatively high heat resistance, and low hygroscopicity, and thus is suitably used for various optical applications. It is used for applications such as a phase difference film, a light guide film, a light diffusion film, a transparent conductive film having a conductive layer formed on its surface, and an optical film having a layer for cutting off a specific wavelength.

  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. In particular, when a metal or metal oxide layer is formed by vapor deposition, if the vapor deposition temperature is low, the strength of the metal or metal oxide becomes low, and cracks are likely to occur in the metal or metal oxide layer during production or use. Therefore, 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 made of a cyclic olefin resin is not known, and the appearance of a film made of a cyclic olefin resin that is superior in shape stability at high temperatures has been desired.
JP 2000-273272 A

  This invention makes it a subject to provide the laminated | multilayer film which was further excellent in heat resistance, without impairing the characteristics, such as the outstanding transparency which a cyclic olefin resin film has. Moreover, this invention makes it the subject to provide the laminated film which has the inorganic vapor deposition layer excellent in adhesiveness and intensity | strength, and its manufacturing method.

The laminated film (I) of the present invention is
On at least one side of the cyclic olefin-based resin film (A),
(a) a compound having a tri- or higher functional polymerizable unsaturated group,
(b) a compound having a monofunctional or higher polymerizable unsaturated group and an alicyclic structure, and
(c) (a) 85 to 20 parts by weight, (b) 10 to 50 parts by weight, (c) 5 to 30 parts by weight (provided (a) a compound having an acidic group and one or more polymerizable unsaturated groups ), (B), and (c) in a ratio of 100 parts by weight), and is characterized by having a cured layer (B) formed using a curable composition.

In such a laminated film (I) of the present invention, the cured layer (B) preferably has a thickness of 0.1 to 20 with respect to a thickness 100 of the cyclic olefin resin film (A).
In the laminated film (I) of the present invention, the curable composition comprises (d) an active energy polymerization initiator in an amount of 1 to 20 weights per 100 weight parts in total of (a), (b) and (c). It is preferable to contain a part.

The laminated film (II) having an inorganic vapor deposition layer of the present invention is characterized by having at least one inorganic vapor deposition layer on the cured layer (B) of the laminated film (I) of the present invention.
In the laminated film (II) having the inorganic vapor deposition layer of the present invention, the inorganic vapor deposition layer is Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, It is preferable that at least one element selected from Ge, Br, Sr, Zr, Nb, Mo, In, and Sn is included, and the inorganic vapor deposition layer includes Mg, Al, Si, Ca, Sc, Ti, and V. , Cr, Mn, Fe, Cu, Zn, Ga, Ge, Br, Sr, Zr, Nb, Mo, In, Sn, and at least one element selected from N, O, and F It is also preferable to include a compound with an element.

  The manufacturing method of laminated film (II) which has an inorganic vapor deposition layer of this invention uses the patterning layer formed with the photosensitive resin composition on the cured layer (B) of the laminated film (I) of the said invention. An inorganic vapor deposition layer is formed by vapor deposition.

  In such a method for producing a laminated film (II) having an inorganic vapor deposition layer of the present invention, the vapor deposition temperature of the inorganic vapor deposition layer is from (Tg-30) ° C. to (Tg + 40) ° C. of the cyclic olefin resin film (A). Preferably there is.

  The laminated film (II) having the inorganic deposited layer of the present invention is preferably obtained by the method for producing a laminated film having the inorganic deposited layer of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated film which has high heat resistance and can form a vapor deposition film at high temperature can be provided, without impairing the characteristics, such as the outstanding transparency which a cyclic olefin resin film has. In addition, according to the present invention, it has an inorganic vapor deposition layer with excellent adhesion and strength, excellent heat resistance stability, cracking due to secondary processing such as punching and cutting, and temperature change during manufacturing and use. Can be provided, and a laminated film having an inorganic vapor deposition layer and a method for producing the same can be provided.

Hereinafter, the present invention will be specifically described.
<Laminated film (I)>
The laminated film (I) of the present invention has a cured layer (B) formed using a curable composition on at least one surface of the cyclic olefin-based resin film (A).

Cyclic olefin resin film (A)
The cyclic olefin resin film (A), which is the base film of the laminated film (I) of the present invention, is not particularly limited as long as it is a film formed from a cyclic olefin resin or a resin composition containing a cyclic olefin resin. However, it is preferable that the resin mainly contains a cyclic olefin resin, and it is particularly preferable that the resin component constituting the film (A) is only the cyclic olefin resin.

In the present invention, the cyclic olefin-based resin is a polymer obtained by polymerizing or copolymerizing a cyclic olefin-based 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 above-mentioned (1), (2) and (3) are preferable as the cyclic olefin-based resin according to the present invention, and the above (3) is more preferable.
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 may be used alone or in combination of two or more.
Preferred cyclic olefin-based resins according to the present invention include those having a structural unit (1) represented by the following formula (1). Such a cyclic olefin-based resin may be a resin containing only the following formula (1) as the cyclic olefin-based structural unit, but preferably together with the structural unit (1) represented by the following formula (1) It is desirable to have a structural unit (2) represented by the following formula (2). The cyclic olefin resin according to the present invention may further have other structural units as necessary.

(In Formula (1) and Formula (2), 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 - with a group represented,
R ^{1 to} R ⁴ each independently represents one represented by the following (i) to (v), or (vi) or (vii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
(Iv) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
(V) a polar group,
(Vi) R ¹ and R ² , or R ³ and R ⁴ represent an alkylidene group formed by bonding to each other, and R ^{1 to} R ⁴ not participating in the bonding are independent of each other from (i) to (i) (V) represents one selected from
(Vii) An aromatic ring or a non-aromatic monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by combining R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ with each other And R ^{1 to} R ⁴ not involved in the bond are independently selected from the above (i) to (v). )
In such structural units (1) and (2), in the above formulas (1) and (2), R ¹ and R ³ are hydrogen atoms or carbon atoms of 1 to 10, more preferably 1 to 4, particularly Preferably, it is a hydrocarbon group of 1-2, R ² and R ⁴ are hydrogen atoms or monovalent organic groups, and at least one of R ² and R ⁴ has a polarity other than hydrogen atoms and hydrocarbon groups A polar group having m
Is an integer of 0-3, p is an integer of 0-3, more preferably m + p = 0-4, more preferably 0-2, particularly preferably m = 0, p = 0. Cyclic olefin-based resins having such structural units (1) and (2) are preferred in that the resin has a high glass transition temperature and excellent mechanical strength.

  In the above formulas (1) and (2), 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, and these polar groups are methylene groups. And may be bonded via a linking group such as 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 formulas (1) and (2), 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 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 formula — (CH ₂ ) _n COOR is bonded. This is preferable in that the hygroscopicity of the cyclic olefin resin can be lowered.

  When the cyclic olefin resin used in the present invention has the structural unit (1) and, if necessary, the structural unit (2), the structural unit (1) is 100 to 50% by weight and the structural unit (2) is 0 to 50% by weight. %, More preferably 100 to 80% by weight of the structural unit (1) and 0 to 20% by weight of the structural unit (2).

  When the cyclic olefin resin 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, cycloheptene. And cycloolefins such as 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 resin 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, Al)
Etc.), 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 is formed. A catalyst comprising a combination with at least one selected from those possessed. 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 alkanes such as pentane, hexane, heptane, octane, nonane and decane. , Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene Halogenated alkanes such as chloroform and tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane; Ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, it can be used singly 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 resin 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 resin 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 to 25
Those in the range of 0,000, particularly preferably 40,000 to 200,000 are suitable.

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

  The glass transition temperature (Tg) of the cyclic olefin resin 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.

The cyclic olefin-based resin forming the cyclic olefin-based resin film (A) or a resin composition containing the cyclic olefin-based resin film includes a known antioxidant such as 2,6-di-t-butyl-4-methylphenol, 2,2 '-Dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane; UV Stabilization can be achieved by adding absorbents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. Further, additives such as a lubricant can be added for the purpose of improving processability.

  The film (A) according to the present invention is obtained by molding a cyclic olefin resin 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). Can do.

  Although the thickness of a film (A) can be suitably selected according to a use and is not specifically limited, Usually, 1-500 micrometers, Preferably it is 1-300 micrometers, More preferably, it is about 10-200 micrometers, More preferably, it is about 50-200 micrometers. It is desirable that

  The film (A) according to the present invention has a thickness distribution within ± 20%, preferably within ± 10%, more preferably within ± 5%, and 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 (A), a commercially available product may be used, and specifically, a product name “Arton” manufactured by JSR Corporation may be used.
The film (A) 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.

Hardened layer (B) formed using curable composition
The cured layer (B) formed using the curable composition according to the present invention (hereinafter also simply referred to as a cured layer (B)) is obtained from a specific curable composition.

The curable composition (B) that forms the cured layer (B) is:
(A) a compound having a tri- or higher functional polymerizable unsaturated group,
(B) a compound having a monofunctional or higher polymerizable unsaturated group and an alicyclic structure, and (c) a compound having an acidic group and a monofunctional or higher polymerizable unsaturated group.

(A) The compound having a trifunctional or higher functional unsaturated group is a compound other than the compound (b) having a monofunctional or higher polymerizable unsaturated group and an alicyclic structure, which will be described later. Any compound having a polymerizable unsaturated group can be used without limitation, and examples thereof include polyfunctional (meth) acrylic esters and polyfunctional urethane acrylic esters. Of these, polyfunctional (meth) acrylic esters are preferred.

Such a compound (a) is effective in improving heat resistance.
Hereinafter, specific examples of the compound (a) used in the present invention include (meth) acrylic esters such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth)
Acrylates and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoesters (meth) acrylates having 3 or more (meth) acryloyl groups in the molecule, oligoether (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 the polyfunctional urethane acrylic esters include a polyfunctional urethane (meth) acrylate having a (meth) acrylo group having three or more functions obtained by reacting a polyol compound, a diisocyanate compound, and a compound having a (meth) acryloyloxy group. .

  Examples of the polyol compound include diethylene glycol, dipropylene glycol, butanediol, hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol, hexamethylene glycol, 2-ethylhexylene glycol, 1,1,1-tril Examples thereof include methylolmethane, 1,1,1-trimethylolpropane, cyclohexyltriol, phenyltriol, and triazinetriol. Among them, triols having a cyclic structure such as cyclohexyltriol, phenyltriol, and triazinetriol are preferable.

  Examples of the diisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, Trimethylhexamethylene diisocyanate, norbornene diisocyanate and the like can be used, among which tolylene diisocyanate and isophorone diisocyanate are preferable.

  Examples of the compound having a (meth) acryloyloxy group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyphenoxypropyl (meth) acrylate, (meth) acryloyloxyethyl hydroxyethylphthalic acid, hydroxybutyl (meth) Acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly [epsilon] -caprolactone mono (meth) acrylate, hydroxybutyl (meth) acrylate, [epsilon] -caprolactone mono (meth) acrylate and the like can be used. Of these, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate are preferable.

  Examples of such commercially available compounds (a) include EBECRYL 220, 1290, 1290K, 5129, 8201, 8210, 8301, KRM 7804, 8452, U15HA manufactured by Daicel Cytec Co., Ltd. U53H, Shin Nakamura Chemical Co., Ltd. NK ester A-9550, and the like.

(B) As the compound having a monofunctional or higher polymerizable unsaturated group and an alicyclic structure, (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. Although the compound (b) should just have a monofunctional or more polymerizable unsaturated group, it is more preferable to have a monofunctional or a bifunctional or more polymerizable unsaturated group.

Such a compound (b) is effective in securing strong adhesion to the surface of the cyclic olefin resin film (A).
Specific examples of the alicyclic structure-containing (meth) acrylic acid 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 compound (b) are dicyclopentanyl (meth) acrylate, tricyclodecanediyl di (meth) acrylate, tetratricyclodecanediyl di (meth) acrylate and the like.

  (C) Acid-modified (meth) acrylic acid esters and acid-modified urethane acrylic esters are preferably used as the compound having an acidic group and one or more polymerizable unsaturated groups. As the acidic group possessed by the compound (c), phosphoric acid, carboxylic acid, phthalic acid, succinic acid, maleic acid and the like are preferable, and the compound (c) may have two or more acidic groups.

Such a compound (c) is effective in ensuring adhesion with a metal oxide vapor deposition film.
Specific examples of the compound (c) preferably used include methacryloyloxyethylphthalic acid, methacryloyloxypropylhexahydrophthalic acid, trisacryloyloxymethylphthalic acid, trisacryloyloxymethylsuccinic acid, phosphoric acid (meth) Examples thereof include acrylate, methacryloxyethyl phosphate, and carboxylic acid polyester acrylate.

  As a commercial item of such a compound (c), for example, Daicel Cytec Co., Ltd. EBECRYL 168, 770, Shin-Nakamura Chemical Co., Ltd. NK ester CB-1, CB-23, CBX-1N, CBX-0 etc. can be mentioned.

  In the curable composition used in the present invention, the above compounds (a), (b) and (c) are mixed with (a) 85 to 20 parts by weight, (b) 10 to 50 parts by weight, and (c) 5 to 30 parts by weight. Parts, preferably (a) 60 to 85 parts by weight, (b) 10 to 30 parts by weight, (c) 5 to 10 parts by weight (however, (a), (b ), (C) is 100 parts by weight).

  In the curable composition according to the present invention, a polymerization initiator may be added to shorten the curing time, and (d) the active energy polymerization initiator is added to the above-mentioned (a), (b) and (c). (D) The active energy polymerization initiator is preferably contained in an amount of 1 to 20 parts by weight, more preferably 1 to 10 parts by weight.

  Examples of the active energy polymerization initiator (d) include those commonly used such as a compound that generates an active radical species thermally and a compound that generates an active radical species by irradiation.

In the present invention, it is preferable to use a radiation polymerization initiator as the polymerization initiator (d), and among them, both aryl ketones having a 1-hydroxycyclohexyl group and aryl ketones having an N-morpholino group, or a combination thereof. 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 curable composition of the present invention can further contain oxide particles, surface-modified oxide particles, sensitizers, various additives, solvents and the like.
Examples of the oxide particles include particles of oxides of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, and calcium. Specifically, for example, silica And aluminum oxide, titania, zirconia, zinc oxide, magnesium oxide, iron oxide, potassium oxide and calcium oxide. The oxide particles are preferably powdery or solvent-dispersed 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.

  As the surface-modified oxide particles, for example, oxide particles of at least one element selected from silicon, aluminum, titanium, zirconium, zinc, magnesium, iron, potassium, calcium, and an organic compound containing a polymerizable unsaturated group And surface-modified oxide particles obtained by combining

A cured product obtained from a curable resin composition containing such oxide particles or surface-modified oxide particles is preferable because it easily exhibits colorlessness.
Examples of sensitizers that can be incorporated into the curable composition include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Examples thereof include ethyl 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.

Additives that can be blended in the curable composition include, for example, antioxidants, ultraviolet absorbers, light stabilizers, organometallic agents such as coupling agents such as organic silane and organic titanium, anti-aging agents, and thermal polymerization inhibitors. , Colorants, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like.

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.

  It is preferable that the curable composition used by this invention contains the organic solvent in the quantity used as a moderate 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 organic solvent 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, and γ-butyrolactone. Esters 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 it can. 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 cured layer (B) according to the present invention is formed on at least one side of the cyclic olefin resin film (A) using the curable composition.
The cured layer (B) can usually be formed by coating (coating) a curable composition on the cyclic olefin resin film (A) by a known method, and drying and curing.

Coating methods include, for example, dipping coat, spray coating, flow coating, shower coating, roll coating, spin coating, gravure coating, micro gravure coating, comma roll coating, Mayer bar coating, slot-by coating, and air knife coating. Commonly used coating methods such as lip coating, kiss coating and brush coating 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.

The curable composition according to the present invention can be cured by curing with heat and / or radiation.
“Radiation” in the curing treatment 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. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as Co ^60. For gamma rays, a vacuum tube that collides accelerated electrons 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.

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.
. 1-2 J / cm ² . Moreover, as for the preferable irradiation conditions of an electron beam, a pressurization voltage is 10-30.
0 KV, electron density is 0.02 to 0.30 mA / cm ² , electron beam dose is 1 to 10 M
rad.

  Further, as a post-treatment after curing and drying, the cured layer may be annealed at a temperature equal to or lower than Tg of the cyclic olefin-based resin film (A) before forming the vapor deposition layer. For the annealing treatment, a device that can generally apply heat, such as a hot air dryer or a vacuum dryer, can be used.

  In the present invention, the cured layer (B) can be formed in this manner. When the cured layer (B) is provided on both sides of the cyclic olefin resin film (A), the cured layer (B) may be formed on both sides simultaneously or sequentially on each side.

Laminated film (I)
The laminated film (I) of the present invention has the above-mentioned cured layer (B) on at least one side of the above-mentioned cyclic olefin resin film (A). The thickness of the cured layer (B) is preferably 0.1 to 20, more preferably 1 to 10 with respect to the thickness 100 of the cyclic olefin resin film (A). In addition, the thickness of the hardened layer (B) here means the thickness per one side, when the hardened layer (B) is provided on both surfaces of the cyclic olefin resin film (A).

The cured layer (B) in the laminated film (I) of the present invention is formed from a specific curable composition, thereby imparting excellent heat resistance to the surface of the cyclic olefin-based resin film (A),
Excellent adhesion to the cyclic olefin-based resin film (A), hardly causing peeling, and when an inorganic vapor deposition layer is further formed on the surface of the cured layer (B), adhesion to the inorganic vapor deposition layer to be formed Furthermore, since the strength and rigidity are improved, damage during manufacturing, processing, or use can be suppressed. In addition, when the laminated film (I) of the present invention has a cured layer (B) on both sides, particularly when the thickness and the degree of curing of the cured layer (B) formed on both sides are equivalent, processing is performed. At the time of use or at the time of use, it is possible to suitably prevent deformation such as a change in film dimensions and curling.

  The laminated film (I) of the present invention can be suitably used for applications such as optical components and liquid crystal elements. In addition, the 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. as necessary. Functionality such as prevention, contamination prevention, anti-condensation, water repellency, oil repellency, electromagnetic wave shielding, ultraviolet shielding, heat ray absorption, conductivity, insulation, flame retardancy, antibacterial properties, etc. it can. Moreover, the laminated film of the present invention can be suitably used for applications in which a deposited film is applied at a high temperature by being excellent in heat resistance and strength.

<Laminated film (II) having an inorganic vapor deposition layer>
The laminated film (II) having an inorganic vapor deposition layer of the present invention has at least one inorganic vapor deposition layer on the cured layer (B) of the above-mentioned laminated film (I). An inorganic vapor deposition layer may be provided in the single side | surface of laminated | multilayer film (I), and may be provided in both surfaces.

  The inorganic vapor deposition layer constituting the laminated film (II) of the present invention is not particularly limited as long as it is one or more inorganic element layers or inorganic compound layers formed by vapor deposition. For example, a metal simple substance or a metal oxide, nitride, fluoride, etc. are mentioned.

  Preferably, the inorganic vapor deposition layer constituting the laminated film (II) is Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Br, Sr, Zr, It is preferable to include at least one element selected from Nb, Mo, In, and Sn. Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Br , Sr, Zr, Nb, Mo, In, and Sn and more preferably a compound of at least one element selected from N, O, and F.

Specific materials for the inorganic vapor deposition layer include, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, aluminum hexafluoride sodium, and the like suitable for forming a low refractive index layer;
Such as titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as a main component and a small amount of titanium oxide, tin oxide, cerium oxide, etc. Suitable for forming a high refractive index layer;
In addition to metal oxides such as indium oxide containing tin oxide and tin oxide containing antimony, such as gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, cobalt, tin or alloys thereof, The thing suitable for formation of an electroconductive layer is mentioned.

Examples of the method for forming the inorganic vapor deposition layer include a vacuum vapor deposition method, a sputtering method, and a CDV method.
In the present invention, the inorganic vapor deposition layer may be provided on the entire surface of the cured layer (B) of the laminated film (I), or may be partially provided via a mask or the like. When providing an inorganic vapor deposition layer partially, forming an inorganic vapor deposition layer by vapor deposition using the patterning layer formed with the photosensitive resin composition on the cured layer (B) of laminated film (I). Is preferred. Such a method is particularly preferably employed when the inorganic vapor deposition layer is a conductive pattern.

  The temperature of vapor deposition is not particularly limited as long as it is a temperature at which an inorganic vapor deposition layer can be formed, but in the present invention, the laminated film (I) has higher heat resistance due to the cured layer (B). The inorganic vapor deposition layer can be formed by performing vapor deposition at a higher temperature than when the inorganic vapor deposition layer is directly provided on the cyclic olefin-based resin film. In the present invention, the vapor deposition temperature of the inorganic vapor deposition layer is preferably (Tg-30) ° C. to (Tg + 40) ° C. of the cyclic olefin resin film (A), more preferably (Tg−) of the cyclic olefin resin film (A). 30) ° C. to (Tg + 20) ° C. Here, the Tg of the cyclic olefin resin film (A) means Tg (glass transition temperature) of the cyclic olefin resin constituting the cyclic olefin resin film (A). As described above, in the present invention, the inorganic vapor deposition layer is formed without causing deformation of the laminated film (I) even at a high temperature in the vicinity of Tg of the cyclic olefin resin constituting the cyclic olefin resin film or at a temperature higher than Tg. Can do. When the vapor deposition temperature is high, the adhesion between the inorganic vapor deposition layer to be formed and the laminated film (I) will be strong, and peeling will not easily occur, and the strength of the inorganic vapor deposition layer itself to be formed should be large. Can do.

  In the laminated film (II) having an inorganic vapor deposition layer of the present invention, when the inorganic vapor deposition layer is composed of a plurality of layers, a method of sequentially forming and laminating desired inorganic vapor deposition layers can be adopted without limitation.

  For example, when forming a dielectric multilayer film in which a low dielectric constant dielectric layer and a high refractive index dielectric layer are sequentially laminated as the inorganic vapor deposition layer, each dielectric layer material is cured of the laminated film (I). It can carry out by vapor-depositing alternately on a layer (B) and laminating | stacking.

  The laminated film (II) having an inorganic vapor-deposited layer of the present invention can be used for all purposes of the laminated film having a vapor-deposited layer, for example, a conductive film having a conductive inorganic vapor-deposited layer such as ITO, metal oxide, etc. Optical films such as near-infrared cut filters with multiple vapor deposition layers, antireflection films with metal oxide film vapor deposition layers, gas barrier films, (films for thin film transistors, films for organic EL, electronic paper, film antennas, solar (Various film base materials provided with photo patterning such as a battery film) and the like, and can be suitably used for applications requiring heat resistance, dimensional stability, and heat dimensional stability at the time of production and use.

  The laminated film (II) having an inorganic vapor deposition layer of the present invention has excellent heat resistance and strength as a laminated film (I), which is a base film for vapor deposition. It can be set as the laminated film which has the inorganic vapor deposition layer excellent in property and intensity | strength.

  For this reason, the laminated film having the inorganic vapor deposition layer of the present invention is not susceptible to cracking or peeling of the inorganic vapor deposition film due to temperature change or stress during secondary processing such as manufacturing, punching, cutting, mounting, etc. Etc. can be highly suppressed.

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

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

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

<Crack>
About the film which has the inorganic vapor deposition film cut out to 30x30mm, after heating for 30 minutes at 150 degreeC with a hot-air oven, the presence or absence of the crack (crack) of the surface was visually confirmed under the halogen light source. (Heat-resistant crack)
Moreover, about the film which has an inorganic vapor deposition film | membrane, after winding around a 20 mm diameter cylinder, the presence or absence of the crack (crack) of the surface was confirmed visually under the halogen light source. (Bending crack)
A sample having no crack in the inorganic deposited film was evaluated as “A”, and a sample having a crack in the inorganic deposited film was evaluated as “B”.

<Adhesion>
For a film having a dielectric multilayer film, in accordance with JIS-K5600-5-6 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion (Crosscut Method)” A peeling test was conducted, and regarding the peeling of the cured layer (base material adhesion) and the peeling of the inorganic vapor deposition layer (vapor deposition layer adhesion), those having no peeling were evaluated as “A”, and those having peeling were evaluated as “B”.

[Components of curable composition]
In the examples and comparative examples, the following components were used for the preparation of the curable compositions.
(A) Compound (a-1) having a tri- or higher functional polymerizable unsaturated group : Dipentaerythritol hexaacrylate (hexafunctional, HEXIA), manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A-DPH”
(A-2): Trimethylolpropane triacrylate (trifunctional), manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A-TMPT”
(A-3): Pentaerythritol tetraacrylate (tetrafunctional), manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A-TMMT”
(A-4): Urethane acrylate (hexafunctional), number average molecular weight 1000, manufactured by Daicel Cytec, trade name “EBECRYL 1290K”
(A-5): Urethane acrylate (9 functional), manufactured by Daicel Cytec, trade name “KRM7804”
(A-6): Urethane acrylate (10 functional), manufactured by Daicel Cytec, trade name “KRM8452”
(A-7): Urethane acrylate (15 functional), number average molecular weight 2300, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “U15HA”
(B) Compound (b-1) having a monofunctional or higher polymerizable unsaturated group and an alicyclic structure : Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A-DCP”
(B-2): dicyclopentanyl acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “FANCRYL FA-513AS”
(B-3): Dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “FANCRYL FA-513M”
(B-4): Isobornyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A
-IB "
(B-5): Tricyclodecane dimethanol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester DCP”
(B-6): Isobornyl methacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK ester
IB "
(C) Compound (c-1) having acidic group and one or more polymerizable unsaturated group : Carboxylic acid polyester acrylate / 2 hydroxyethyl methacrylate (HEMA) = 60/40, manufactured by Daicel Cytec Co., Ltd., trade name “EBECRYL 770 "
(C-2): Phosphoric acid methacrylate (1-2 functional), manufactured by Daicel Cytec, trade name “EB”
ECRYL 168 "
(D) Active energy polymerization initiator (d-1): 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba, trade name “Irgacure 184”
(D-2): 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, manufactured by Ciba, trade name “Irgacure907”
[Example 1]
(A) a compound having a tri- or higher functional polymerizable unsaturated group, (b) a mono- or higher functional polymerizable unsaturated group and a compound having an alicyclic structure, (c) an acidic group and a mono- or higher functional polymerizable unsaturated group. About the compound which has group, and (d) active energy polymerization initiator, each component shown in Table 1 is mixed in the ratio shown in Table 1, and it diluted so that solid content concentration may become 45 weight% with methyl ethyl ketone. A curable composition was prepared.

A transparent cyclic olefin resin, Arton (registered trademark) manufactured by JSR Corporation (glass transition point: 165 ° C., total light transmittance at 93 μm thickness: 93%, grade: G7810) with a film thickness of 100 μm Olefin-based resin film is cut into A4 size, and the curable composition prepared above is used on both sides so that the coater bar has a predetermined thickness using a lab coater (Automatic film applicator manufactured by Yasuda Seiki Seisakusho, Model No. 542-AB) Applied.

Using an inert oven (Inert oven DN410I manufactured by Yamato Kagaku), drying at 80 ° C. for 3 minutes, and then UV conveyor (eye ultraviolet curing device manufactured by Eye Graphics, model US)
2-X0405 60 Hz) was used and UV cured at a metal halide lamp illuminance of 270 mW / cm ² and an integrated light quantity of 500 mJ / cm ² to obtain a laminated film in which a transparent cured layer having a thickness of 3 μm was formed on each surface. The obtained laminated film had a good appearance with no foreign matter, unevenness or repellency observed by visual observation.

The obtained laminated film was cut out to 110 × 260 mm, placed on a jig, and SiO ₂ was deposited at a deposition temperature of 130 ° C. to form a ₂ μm thick SiO ₂ deposited film on each surface.
About the laminated film which has the obtained vapor deposition film, each characteristic was evaluated by the above-mentioned method. The results are shown in Table 1.

[Examples 2 to 17, Comparative Examples 1 to 3]
In Example 1, a laminated film was produced in the same manner as in Example 1 except that each component shown in Table 1 was used in the ratio shown in Table 1 for the preparation of the curable composition. Using the laminated film, a laminated film having a vapor deposition film was produced in the same manner as in Example 1, and each characteristic was evaluated by the method described above. The results are shown in Table 1.

[Example 18]
In Example 2, a laminated film was produced in the same manner as in Example 2 except that the thickness of the cured layer on each surface was 20 μm, and the laminated film thus obtained was used as in Example 2. Then, a laminated film having a vapor deposition film was produced, and each characteristic was evaluated by the method described above. The results are shown in Table 1.

[Comparative Example 4]
A transparent cyclic olefin resin, Arton (registered trademark) manufactured by JSR Corporation (glass transition point: 165 ° C., total light transmittance at 93 μm thickness: 93%, grade: G7810) with a film thickness of 100 μm The olefin resin film was cut out to 110 × 260 mm, placed on a jig, and SiO ₂ was deposited at a deposition temperature of 130 ° C. to form a ₂ μm thick SiO ₂ deposited film on each surface.

  About the laminated film which has the obtained vapor deposition film, each characteristic was evaluated by the above-mentioned method. The results are shown in Table 1.

  The laminated film (I) according to the present invention can be suitably used as those imparting heat resistance and strength to various optical film applications to which a conventional cyclic olefin-based resin film can be applied. It can be used suitably for the use which forms.

  The laminated film (II) having an inorganic vapor deposition layer according to the present invention includes a near-infrared cut filter, an antireflection film, a gas barrier film, a thin film transistor film, an organic EL film, electronic paper, a film antenna, a solar cell film, and the like. Various film base materials provided with photo patterning can be suitably used for manufacturing processes and applications requiring heat resistance, dimensional stability, and heat dimensional stability at the time of use. These laminated films (II) are, for example, heat ray cut filters for glass for automobiles and buildings; digital cameras; applications for correcting visual sensitivity of image sensors such as digital video; electronic displays such as mobile phones, PDAs, personal computers and televisions. It can be suitably used for applications such as a flexible substrate having a fine patterning step using a photoresist such as near-infrared cut and antireflection of surface; solar cell; thin film transistor; light guide film.

FIG. 1 shows an example of the structure of a laminated film having an inorganic vapor deposition layer of the present invention.

Claims (9)

On at least one side of the cyclic olefin-based resin film (A),
(A) a compound having a tri- or higher functional polymerizable unsaturated group,
(B) a compound having a monofunctional or higher polymerizable unsaturated group and an alicyclic structure, and (c) an acidic group and a compound having a monofunctional or higher polymerizable unsaturated group (a) 85 to 20 parts by weight, ( b) A curable composition containing 10 to 50 parts by weight and (c) 5 to 30 parts by weight (provided that the total of (a), (b) and (c) is 100 parts by weight) is used. A laminated film (I) having a cured layer (B) formed by   The laminated film (I) according to claim 1, wherein the cured layer (B) has a thickness of 0.1 to 20 with respect to a thickness 100 of the cyclic olefin resin film (A).   The said curable composition contains 1-20 weight part of (d) active energy polymerization initiator with respect to a total of 100 weight part of (a), (b), and (c). The laminated film (I) according to 1 or 2.   A laminated film (II) having an inorganic vapor-deposited layer, comprising at least one inorganic vapor-deposited layer on the cured layer (B) of the laminated film (I) according to any one of claims 1 to 3.   The inorganic vapor deposition layer is selected from Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Br, Sr, Zr, Nb, Mo, In, and Sn. The laminated film (II) having an inorganic vapor deposition layer according to claim 4, comprising at least one element.   The inorganic vapor deposition layer is selected from Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Br, Sr, Zr, Nb, Mo, In, and Sn. The laminated film (II) having an inorganic vapor deposition layer according to claim 4, comprising a compound of at least one element and at least one element selected from N, O, and F.   Forming an inorganic vapor deposition layer by vapor deposition on the cured layer (B) of the laminated film (I) according to any one of claims 1 to 3, using a patterning layer formed of a photosensitive resin composition. The manufacturing method of laminated film (II) which has the inorganic vapor deposition layer characterized.   The laminated film (II) having an inorganic vapor deposition layer according to claim 7, wherein the vapor deposition temperature of the inorganic vapor deposition layer is (Tg-30) ° C to (Tg + 40) ° C of the cyclic olefin resin film (A). ) Manufacturing method.   A laminated film (II) having an inorganic vapor-deposited layer obtained by the production method according to claim 7 or 8.

Images