JP4735484B2 - Laminated film - Google Patents

Description

  The present invention relates to a laminated film which is excellent as an optical film having excellent optical transparency, heat resistance, adhesiveness, dimensional stability, solvent resistance, chemical resistance and the like, and has bending workability.

Conventionally, in the fields of optical parts such as lenses, sealing materials, backlights, light guide plates, substrates, touch panels, etc. where inorganic glass has been used, weight reduction, miniaturization, high density, production With the demand for improved handling and improved handling properties such as being hard to break, there is a strong demand for replacement of inorganic glass with an optically transparent resin, and a part of the replacement is being promoted.
However, these resins do not have sufficient heat resistance, low water absorption, dimensional stability, and chemical resistance compared to inorganic glass, and there is a problem of dimensional stability due to the large coefficient of linear expansion of the resin, especially in substrate applications. There is a strong demand for a reduction in linear expansion coefficient.

Conventionally, as a transparent heat-resistant resin, an addition polymer of a cyclic olefin compound represented by 2-norbornene (bicyclo [2.2.1] hept-2-ene) has been proposed. Adhesion / adhesion with other members Cyclic olefin polymers having an alkoxysilyl group have been proposed for the purpose of improving the properties and obtaining a crosslinked composite by hydrolysis / condensation. A method of crosslinking a composition comprising a cyclic olefin polymer having a polyfunctional alkoxysilane, a hydrolyzate or hydrolysis condensate, an inorganic oxide selected from alumina fine particles or silica fine particles, or having an alkoxysilyl group A method of grafting alumina fine particles or silica fine particles to a cyclic olefin polymer using a specific metal compound catalyst. Are plan (see Patent Document 1 to 13).
However, in the above prior art, when the composite is formed into a film or sheet, the optical transparency is insufficient or it is easily cracked even though there is an effect on the improvement of the elastic modulus and the reduction of the linear expansion coefficient. It has problems such as being difficult to bend because it is brittle.
Japanese Patent Laid-Open No. 5-214079 JP-A-3-95230 JP-A-3-95235 Japanese Patent Laid-Open No. 3-188113 US 5,912,313 Publication US 6,031,058 US 6,455,650 gazette JP 2002-327024 A JP 2003-160620 A JP 2002-327024 A JP 2003-48918 A JP 2002-226661 A JP 2003-105214 A

  The present invention has been made in view of the above problems, and when it is used as a film or sheet, it exhibits a high elastic modulus and a small linear expansion coefficient, and further has excellent optical transparency, is resistant to cracking and exhibits high toughness. And the manufacturing method of a laminated | multilayer film is provided.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, by forming inorganic oxide layers on both sides of a transparent heat-resistant film made of a cyclic olefin polymer having a specific structure, transparency, heat resistance The present invention has been completed by finding that a laminated film having excellent properties and dimensional stability, and excellent chemical resistance, mechanical strength and low water absorption can be obtained.
That is, the laminated film of the present invention comprises a cyclic olefin polymer having a structural unit represented by the following formula (1) (hereinafter also referred to as “specific structural unit (1)”) (hereinafter referred to as “specific cyclic olefin polymer”). Or at least one selected from silica, alumina, titania, zirconia and niobium oxide on both surfaces of a polymer film layer containing a crosslinked product of the polymer (hereinafter also referred to as “specific crosslinked product”). An inorganic oxide layer having a film thickness of 500 to 10,000 nm is laminated.

[In the formula (1), A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group or a halogenated hydrocarbon. A polar group represented by a group, a hydrolyzable silyl group, or — (CH ₂ ) _k —X. A ¹ and A ² or A ¹ and A ⁴ are bonded to each other, and together with the carbon atoms to which they are bonded, an alicyclic hydrocarbon structure, aromatic hydrocarbon structure, acid anhydride structure, lactone structure or An imide structure may be formed. P is 0 or 1.
Here, X in — (CH ₂ ) _k —X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ are each independently a hydrocarbon having 1 to 10 carbon atoms. Represents a substituent containing a group, a halogenated hydrocarbon group, or an oxetanyl group, and k is an integer of 0 to 5. ]

  The specific cyclic olefin polymer comprises a structural unit having a hydrolyzable silyl group represented by the following formula (2) (hereinafter also referred to as “specific structural unit (1-1)”). It is preferable to have 0.2-30 mol% with respect to all the structural units.

[In the formula (2), B ¹ , B ² , B ³ and B ⁴ are each independently a hydrogen atom, a halogen atom, — (CH ₂ ) _m —Si (R ⁴ ) _a (R ⁵ ) _3-a Alternatively, it is a hydrolyzable silyl group represented by the following formula (3). However, at least one of B ¹ , B ² , B ³ and B ⁴ is the hydrolyzable silyl group. Q is 0 or 1.
Here, R ⁴ represents an alkoxyl group, an aryloxyl group or a halogen atom, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, m represents 0 or 1, and a represents 1 to 3. ]

[In the formula (3), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y represents a divalent hydrocarbon of an aliphatic diol, alicyclic diol or aromatic diol having 2 to 20 carbon atoms. Indicates a residue, n is 0 or 1. ]

  The specific cyclic olefin-based polymer includes at least a structural unit having an oxetanyl group represented by any of the following formulas (4) or (5) (hereinafter also referred to as “specific structural unit (1-2)”). 1 type is included and it is preferable that the content rate of this structural unit (1-2) is 0.2-30 mol% with respect to all the structural units.

[In formula (4) and formula (5), the definitions of A ¹ , A ² and A ³ are the same as those in formula (1). X _{^{is, - (CR 12 R 13)}} r - or _{^{- (CR 14 R 15) s}} -T- (CR 16 R 17) t - indicates, where T is -O -, - C (O) -, -OC (O) -, - C (O) O- or ^-SiR 18 ^{R 19} - shows a, r, s and t are an integer of 0 to 6. R ^{7 to} R ¹⁹ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group, and p represents 0 or 1. ]

Furthermore, the polymer film layer is preferably a film containing a specific crosslinked product obtained by crosslinking reaction of a group selected from a hydrolyzable silyl group and an oxetanyl group in the cyclic olefin polymer.
The inorganic oxide layer is preferably a single layer containing at least one selected from silica, alumina, titania, zirconia and niobium oxide or a laminated structure of different inorganic oxide layers.

  According to the present invention, there is provided a laminated film having a particularly low linear expansion coefficient and excellent dimensional stability while satisfying excellent transparency, heat resistance, chemical resistance, mechanical strength, and low water absorption at a high level. Can do.

Hereinafter, embodiments of the present invention will be described in detail.
The laminated film of the present invention is formed by integrally laminating an inorganic oxide layer on both sides of a transparent heat-resistant resin layer, and specifically, a laminated film having the following constitution (a) or (b): is there.
(A) A laminated film in which inorganic oxide layers are laminated on both sides of a polymer film layer made of a specific cyclic olefin-based polymer (hereinafter also referred to as “first laminated film”).
(B) A laminated film in which inorganic oxide layers are laminated on both sides of a polymer film layer made of a specific crosslinked body (hereinafter also referred to as “second laminated film”).

<< First laminated film >>
A 1st laminated | multilayer film is a laminated | multilayer film which formed the inorganic oxide layer on both surfaces of the polymer film layer which consists of a specific cyclic olefin type polymer which has a specific structural unit (1).

<Specific cyclic olefin polymer>
Specific monomer The specific cyclic olefin polymer used in the present invention can be obtained by addition polymerization of a monomer represented by the following formula (6) (hereinafter also referred to as “specific monomer”). The specific monomer forms the specific structural unit (1) by addition polymerization.

Wherein ^{(6), A 1, A} 2, A 3, A 4 and p definition is the same as defined in the above formula (1). ]

  Examples of the specific monomer (1) include a monomer having a hydrolyzable silyl group represented by the following formula (7) (hereinafter also referred to as “specific monomer (1-1)”), A monomer having an oxetanyl group represented by (8) or (9) (hereinafter also referred to as “specific monomer (1-2)”) is particularly preferable.

Wherein ^{(7), B 1, B} 2, B 3, the definition of ^{B 4} and q are as defined in the above formula (2). ]

[In Formula (8) and Formula (9), the definitions of A ¹ , A ² , A ³ , R ^{7 to} R ¹¹ and p are the same as the definitions in Formulas (4) and (5) above. ]

The specific monomer (1-1) forms the specific structural unit (1-1) by addition polymerization, and the specific monomer (1-2) has the specific structural unit (1) formed by addition polymerization. -2). The specific cyclic olefin-based polymer obtained using these monomers can be made into a specific cross-linked product by cross-linking hydrolyzable silyl groups and oxetanyl groups present in the polymer.
Here, the hydrolyzable silyl group forms a siloxane bond structure by hydrolysis / condensation reaction in the presence of water, and this hydrolysis / condensation reaction is accelerated by a catalyst such as acid, alkali or metal salt compound. It is what is done.
Oxetanyl groups form cationic crosslinks in the presence of a cationic polymerization catalyst such as an acid. These crosslinks improve the heat resistance, solvent resistance, and chemical resistance of the polymer and reduce the linear expansion coefficient. It is done.

  The specific cyclic olefin-based polymer has 0.2 to 30 mol% of at least one crosslinkable structural unit selected from the specific structural units (1-1) and (1-2) with respect to the total structural units. Is preferred. When the content ratio of the crosslinkable structural unit is less than 0.5 mol%, the heat resistance, solvent resistance, chemical resistance and low linear expansion coefficient of the specific cyclic olefin polymer may not be sufficient. On the other hand, when the content ratio of the crosslinkable structural unit exceeds 30 mol%, the toughness of the obtained laminated film is lowered, and the bending workability of the laminated film may not be sufficient.

Specific examples of the specific monomer (1-1) include the following compounds, but the present invention is not limited to these specific examples.
5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-trimethoxysilylmethyl-bicyclo [2.2.1] hept-2-ene,
5-trimethoxysilylethyl-bicyclo [2.2.1] hept-2-ene,
5-trimethoxysilylpropyl-bicyclo [2.2.1] hept-2-ene,
5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-triethoxysilylmethyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilylpropyl-bicyclo [2.2.1] hept-2-ene,
5-methyldiethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-dimethylmethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-ethyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-cyclohexyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-chlorodimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-phenyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-trimethoxysilylmethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,

5- [1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-ethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3′-dimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-3 ′, 4′-dimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-ethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] methyl-bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-spiro-cyclohexyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-3′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 7′-dioxa-1′-silacycloheptyl] -bicyclo [2.2.1] hept-2-ene,
9- [1′-Methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9- [1′-Methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
Etc.
Among these specific monomers (1-1), a cyclic olefin compound having a methoxysilyl group or an ethoxysilyl group is preferable from the viewpoint of the crosslinking reactivity of the cyclic olefin polymerization of the present invention described later.

Among the specific monomers (1-2), examples of the compound represented by the formula (8) include 5- (3-oxetanyl) bicyclo [2.2.1] hept-2-ene, 5- (3-methyl-3-oxetanyl) bicyclo [2.2.1] hept-2-ene, 5- (3-ethyl-3-oxetanyl) bicyclo [2.2.1] hept-2-ene, 5- [(3-Oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene, A group in which an oxetanyl group such as 5-[(3-ethyl-3-oxetanyl) methyl] bicyclo [2.2.1] hept-2-ene is bonded to a cyclic olefin via a carbon chain;
2-[(3-Oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, 2-[(3-methyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5- Ene, 2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene, 5-[(3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept 2-ene, 5-[(3-methyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methoxyethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) Methoxyethyl] bicyclo 2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) methoxyethyl] bicyclo [2.2.1] hept-2-ene, 8-[(3-oxetanyl) methoxy ] Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-methyl-3-oxetanyl) methoxy] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-ethyl-3-oxetanyl) methoxy] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-oxetanyl) methoxymethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-methyl-3-oxetanyl) methoxymethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-[(3-ethyl-3-oxetanyl) methoxymethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5,6-bis [(3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5,6-bis [(3-methyl- 3-Oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2-ene, 5,6-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-2 -Bonded by an ether bond such as ene, etc.
5-[(3-Oxetanyl) methylcarbonyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methylcarbonyl] bicyclo [2.2.1] hept- 2-ene, 5-[(3-ethyl-3-oxetanyl) methylcarbonyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methylcarbonylmethyl] bicyclo [2.2 .1] hept-2-ene, 5-[(3-methyl-3-oxetanyl) methylcarbonylmethyl] bicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) ) Methylcarbonylmethyl] bicyclo [2.2.1] hept-2-ene and the like bonded by a carbonyl group,
Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-methyl-3- Oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl, 2-methylbicyclo [2.2.1] hept-5-ene- 2-Carboxylic acid (3-oxetanyl) methyl, 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-methyl-3-oxetanyl) methyl, 2-methylbicyclo [2. 2.1] Hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-oxetanyl) methoxymethyl], tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-methyl-3-oxetanyl) methoxymethyl], tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-ethyl-3-oxetanyl) methoxymethyl], 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-oxetanyl) methoxymethyl], 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-methyl-3-oxetanyl) methoxymethyl], 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-carboxylic acid (3-ethyl-3-oxetanyl) methoxymethyl], bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (3 -Oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (3-methyl-3-oxetanyl) methyl, bicyclo [2.2.1] hept-5-ene- 1,3-dicarboxylic acid (3-ethyl-3-oxetanyl) methyl, and the like bonded by an ester bond,
5- (3-oxetanyl) dimethylsilylbicyclo [2.2.1] hept-2-ene, 5- (3-methyl-3-oxetanyl) dimethylsilylbicyclo [2.2.1] hept-2-ene, 5- (3-ethyl-3-oxetanyl) dimethylsilylbicyclo [2.2.1] hept-2-ene, 5-[(3-oxetanyl) methyl] dimethylsilylbicyclo [2.2.1] hept-2 -Ene, 5-[(3-methyl-3-oxetanyl) methyl] dimethylsilylbicyclo [2.2.1] hept-2-ene, 5-[(3-ethyl-3-oxetanyl) methyl] dimethylsilylbicyclo [2.2.1] Those bonded by a silyl group such as hept-2-ene are preferably used, but are not limited thereto.

Examples of the compound represented by the above formula (9) include spiro-oxetane-5,3′-bicyclo [2.2.1] hept-2-ene, spiro-oxetane-8,3′-tetracyclo. [4.4.0.1 ^2,5 . Cyclic olefins in which an oxetane ring is bonded by a spiro structure, such as ^{17, 10} ] dodec-3-ene, are desirably used.

As the specific monomer (1-1) and the other specific monomer (1) used by being copolymerized with the specific monomer (1-2), A ¹ , A ² in the above formula (6), A compound in which A ³ and A ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group is preferred. For example,
Bicyclo [2.2.1] hept-2-ene,
5-methyl-bicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-dienetetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene,
9-methyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene,
9-ethyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene,
A compound selected from one or more of these is preferred, and bicyclo [2.2.1] hept-2-ene is particularly preferred.
Further, the specific monomer (1) in which at least one of A ¹ , A ² , A ³ and A ^{4 in} the formula (6) is a polar group represented by — (CH ₂ ) _k —X By using it at a ratio of 10 mol% or less, preferably 7 mol% or less, the solubility of the specific cyclic olefin polymer to be obtained in a solvent, substrate adhesion, flexibility, etc. are improved. be able to. However, if the proportion of these monomers used is too high, there is a risk of increasing water absorption and deteriorating the linear expansion coefficient. Examples of the specific monomer (1) having a polar group include methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate and 8-carboxymethyltetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Production Method of Specific Cyclic Olefin Polymer The specific cyclic olefin polymer is obtained by addition polymerization of the above-mentioned specific monomer in the presence of a polymerization catalyst. As preferable polymerization catalysts used in the present invention, the following (1) to (3) can be used.
(1) Nickel-based multi-component catalyst comprising a nickel compound, a compound selected from super strong acids, Lewis acids and ionic boron compounds and an organoaluminum compound (2) having at least one sigma bond connecting between nickel and carbon A nickel-based single-component catalyst comprising a nickel complex having a super strong acid anion as a counter anion (3) a palladium compound, a phosphine compound and / or a phosphonium compound, an ionic boron compound, and an organoaluminum compound or an organolithium compound as required Among these catalysts, it is preferable to use (3) a palladium-based multicomponent catalyst because the resulting polymer has a small linear expansion coefficient.
It is considered that the microstructure of the specific cyclic olefin polymer greatly influences the difference in the linear expansion coefficient caused by the selection of the catalyst. That is, a cyclic olefin copolymer polymerized by a palladium catalyst system has a polymer chain bond mode (2,3-bond / 2,7-bond) and / or stereoregularity (compared with a nickel catalyst system). (Atactic / erythro-disyndiotactic / erythro-diisotactic, etc.) are well controlled, and as a result, it is presumed that the molecular chain becomes stiffer and the packing property is improved.

Specific examples of the palladium compound include β-diketonate compounds such as palladium bisacetylacetonate, palladium acetate, palladium propionate, palladium 2-ethylhexanoate, palladium naphthenate, palladium neodecanoate and the like, and these Examples thereof include strong Bronsted acid-modified compounds such as tetrafluoroboric acid, hexafluorophosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and hexafluoroantimonic acid. Furthermore, [tetrakis (acetonitrile) palladium] tetrafluoroborate, [tetrakis (benzonitrile) palladium] tetrafluoroborate, bis (triphenylphosphine) palladium dichloride, [1,2-bis (diphenylphosphino) ethane] Palladium dichloride, [1,2-bis (diphenylphosphino) ethane] palladium methyl chloride, di-μ-chlorobis (η ³ -allyl palladium), (η ³ -allyl) (triphenylphosphine) palladium chloride, (1, 5-cyclooctadiene) palladium dichloride, (methyl) (1,5-cyclooctadiene) palladium chloride, [(η ³ -allyl) (1,5-cyclooctadiene) palladium] hexafluorophosphate, [(η ³ -Crotyl) (1,5-cyclooctadiene) palladium] hexafluorophosphate, di-μ-chlorobis (6-methoxynorbornen-2-yl-5-palladium), [6-methoxynorbornen-2-yl-5 - palladium (cyclooctadiene)] hexafluorophosphate such as eta ³ - allyl, diene, triene complex compounds, palladium - compound having carbon bond.
These palladium compounds may be used as a single component catalyst, but are more preferably used as a multicomponent catalyst system in combination with the following promoter component. As a promoter component, (i) a phosphine compound and / or a phosphonium compound (ii) a compound that reacts with a palladium compound to form an ionic complex, and optionally (iii) a combination with organoaluminums or organolithiums it can.

  Examples of the phosphine compound shown in (i) include trimethylphosphine, triethylphosphine, tri-t-butylphosphine, triphenylphosphine, tri (methylphenyl) phosphine, tricyclohexylphosphine, trioctylphosphine, trimethylphosphite, tributylphosphite. And triphenyl phosphite. Examples of phosphonium compounds include trimethylphosphonium, triethylphosphonium, tri-t-butylphosphonium, triphenylphosphonium, tri (methylphenyl) phosphonium, tricyclohexylphosphonium, and trioctylphosphonium. Fluorophosphate, hexafluoroantimonate, tetrafluoroborate, p-toluenesulfonate, trifluoromethanesulfonate, acetate, 2-ethylhexanoate, tetrakis (pentafluorophenyl) borate, etc. Used as

As the compound that reacts with the palladium compound shown in (ii) to form an ionic complex, for example, an ionic compound represented by [L] ⁺ [CA] ⁻ is used.
[Wherein [L] ⁺ represents a Lewis acid, ammonium, phosphonium, or metal atom cation, and [CA] ⁻ represents BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , B (C ₆ F ₅ ). ₄ ⁻ represents a non-coordinating or weakly coordinating anion selected from B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄ ^— . ]
Specific examples include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, dimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, triphenyltetraborate Phenylmethyl, ferrocenium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Methyldibutylammonium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentaful) Rophenyl) methylpyridinium borate, tetrakis (pentafluorophenyl) triphenylmethylborate, ferrocenium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis [3,5-di (trifluoromethyl) phenyl] dimethylanilinium borate, tetrakis [3,5-di (trifluoromethyl) phenyl] triphenylmethyl borate, tetrakis [3,5-di (trifluoromethyl) ) Phenyl] lithium borate, tetrakis [3,5-di (trifluoromethyl) phenyl] sodium borate, silver tetraphenylborate, silver tetrafluoroborate, silver hexafluorophosphate, hexafluoroantimony Silver hexafluorophosphate thallium, but like ammonium hexafluorophosphate and the like, but is not limited thereto.

  The optionally added (iii) organoaluminum compounds or organolithium compounds include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum hydride, alkylaluminoxane, methyllithium, butyllithium, phenyllithium. Etc. Of these, trialkylaluminum such as triethylaluminum and triisobutylaluminum, and alkyllithium such as butyllithium are preferably used, and trialkylaluminum is more preferably used.

For example, β-diketonate compounds such as palladium bisacetylacetonate, carboxylates such as palladium acetate and palladium 2-ethylhexanoate, (1,5-cyclooctadiene) palladium dichloride, tricyclohexylphosphine and triphenylphosphine High polymerization activity is obtained and obtained by using in a four-component system in combination with phosphine compounds such as triethylaluminum and ionic compounds such as triphenylmethyl tetrakis (pentafluorophenyl) borate. It is preferable because the physical properties of the cyclic olefin copolymer are excellent. Further, a combination of tetrakis (pentafluorophenyl) borate dimethylanilinium instead of tetrakis (pentafluorophenyl) borate triphenylmethyl can be used. Di-μ-chlorobis (6-methoxynorbornene-2-yl-5-palladium) and di-μ-chlorobis (η ³ -allyl palladium) are phosphine compounds such as triphenylphosphine and tricyclohexylphosphine, and hexa It can be used in a three-component system in combination with silver fluoroantimonate. The (methyl) (1,5-cyclooctadiene) palladium chloride is preferably a three-component system of a phosphine compound such as triphenylphosphine and sodium tetrakis [3,5-di (trifluoromethyl) phenyl] borate. It is done.

  Among these, in particular, β-diketonate compounds such as palladium bisacetylacetonate, carboxylates such as palladium acetate, phosphine compounds such as tricyclohexylphosphine and trioctylphosphine, and triphenylmethyl tetrakis (pentafluorophenyl) borate. A catalyst system in which an ionic compound such as the above and an organoaluminum compound are combined are preferable because of high polymerization activity, excellent dimensional stability of the resulting crosslinked product, and high availability of each component constituting the catalyst system.

  Solvents used for the polymerization reaction of the specific cyclic olefin polymer include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane, toluene, Aromatic hydrocarbon solvents such as benzene and xylene, halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorocyclohexane, chlorobenzene and o-dichlorobenzene, Choose from polar solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol dimethyl ether, nitromethane, N-methylpyrrolidone, pyridine, N, N'-dimethylimidazolidinone, dimethylformamide, acetamide, etc. Solvent is used in combination singly or two or more.

The polymerization reaction is performed in a range of −20 ° C. to 150 ° C. in a nitrogen or argon atmosphere. The polymerization operation can be carried out either batchwise or continuously, and the specific monomers (A) and (B), if necessary, other monomers and a solvent are added, if necessary, a molecular weight regulator is added, The polymerization catalyst is added to initiate polymerization.
Here, in carrying out the polymerization reaction in a batch system, the composition of the monomer in the polymerization system varies greatly throughout the polymerization process as described above in order to make the polymer substantially have no composition distribution. It is necessary to control so that it does not. On the other hand, in carrying out the polymerization reaction in a continuous manner, all the monomers, solvent, polymerization catalyst, and if necessary, a molecular weight regulator are introduced into the reaction vessel at a constant rate, so that The composition can be kept constant, and the resulting copolymer can be substantially free of composition distribution.

  The polymerization is stopped by adding a compound selected from water, alcohol, organic acid, carbon dioxide, aldehyde, phosphine compound, phosphite compound and the like. Alternatively, the metal-carbon bond may be cleaved by adding a reducing agent such as excess hydrogen or sodium tetrahydroborate. If necessary, the polymerization catalyst residue from the polymerization reaction mixture may be separated and removed, and a known method may be appropriately used. For example, after adding an acid such as hydrochloric acid, nitric acid, sulfuric acid, maleic acid or fumaric acid, the polymerization reaction mixture is washed with a solution of water or alcohol, or a method using an adsorbent such as diatomaceous earth, alumina, silica or activated carbon, It can be removed by filtration using a filter or the like. The cyclic olefin copolymer is isolated, for example, by coagulating the polymerization reaction mixture in a poor solvent such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, and drying under reduced pressure. When the catalyst residue is sufficiently small, the copolymer solution obtained after polymerization may be processed into a crosslinkable composition described later without purification.

Performance of Specific Cyclic Olefin Polymer The specific cyclic olefin polymer has a glass transition temperature usually in the range of 150 to 450 ° C, and preferably 200 to 400 ° C.
When the glass transition temperature is less than 150 ° C., there is a possibility that problems such as thermal deformation of the heat-resistant resin layer in the specific laminate obtained may occur. On the other hand, when the glass transition temperature exceeds 450 ° C., the specific cyclic olefin-based polymer becomes rigid, so that the heat-resistant resin layer in the specific laminate obtained is easily broken and has low toughness.
Here, the glass transition temperature of the specific cyclic olefin polymer is Tan δ measured by dynamic viscoelasticity (ratio of storage elastic modulus E ′ and loss elastic modulus E ″ Tan δ = E ″ / E ') Measured at the peak temperature of temperature dispersion.

  The molecular weight of the cyclic olefin copolymer in the present invention is measured at 120 ° C. by gel permeation chromatography using o-dichlorobenzene as a solvent, and has a polystyrene-equivalent number average molecular weight (Mn) of 30,000 to 500, The weight average molecular weight (Mw) is 50,000 to 1,000,000, preferably the number average molecular weight is 40,000 to 200,000, and the weight average molecular weight is 80,000 to 600,000. When the number average molecular weight is less than 30,000 and the weight average molecular weight is less than 50,000, the breaking strength and elongation of the thin film, film and sheet are often insufficient and the film tends to break. On the other hand, when the number average molecular weight exceeds 500,000 and the weight average molecular weight exceeds 1,000,000, general-purpose hydrocarbon solvents such as toluene and cyclohexane, or components insoluble in these mixed solvents are formed, or the solution viscosity is Since it becomes too high, it may be difficult to form a film by the solution casting method.

The molecular weight of the specific cyclic olefin copolymer is controlled by adding a molecular weight regulator such as α-olefin compound, aromatic vinyl compound, cyclic non-conjugated polyene, hydrogen, adjustment of the amount of polymerization catalyst, adjustment of polymerization temperature. An appropriate method can be appropriately selected from a control method by adjusting the conversion rate to a copolymer or a combination of these methods.
The specific cyclic olefin polymer preferably has a linear expansion coefficient in the range of 70 ppm / ° C. or less, more preferably 60 ppm / ° C. or less, and particularly preferably 50 ppm / ° C. or less.
When the linear expansion coefficient exceeds 70 ppm / ° C., the polymer film layer in the obtained laminated film may be deformed under a use environment having a large temperature change.

<Polymer film layer>
The polymer film layer used in the present invention can be obtained by forming the specific cyclic olefin polymer into a film. As the method, the polymer is dissolved in an appropriate solvent and cast on a metal belt, a metal drum, a carrier film, a silicon wafer, a glass plate, or the like by a method such as coating, spraying, screen printing, spin coating or dipping. Then, a solution casting method in which a drying process is performed, a method of mixing a polymer with a small amount of solvent, and evaporating the solvent using a melt extruder, injection molding, blow molding, press molding, extrusion molding, etc. are used. . Among these, molding by the solution cast method is desirable from the viewpoint of the quality of the surface of the molded body and the reduction of birefringence.
As a solvent used in the solution casting method, halogenated hydrocarbon solvents such as chlorobenzene and o-cyclobenzene are not desirable because they may cause adverse effects on the human body and the environment. Since the cyclic olefin copolymer of the present invention exhibits good solubility in a hydrocarbon solvent, it is a hydrocarbon solvent, particularly an aromatic hydrocarbon solvent such as toluene, xylene, ethylbenzene, mesitylene, cyclopentane, An alicyclic hydrocarbon solvent such as cyclohexane, methylcyclohexane and ethylcyclohexane, and a mixed solvent composed of two or more selected from these are preferably used.
Moreover, antioxidant can be further added to the polymer film used by this invention, and oxidation stability can be improved.
Antioxidants include 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis- (6-t-butyl-3-methylphenol), 1,1′-bis (4- Hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, pentaerythrityltetrakis [3- (3,5-di-t- Phenolic, hydroquinone antioxidants such as butyl-4-hydroxyphenyl) propionate and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, and tris (4-methoxy-3, Examples thereof include phosphorus-based antioxidants such as 5-diphenyl) phosphite and tris (nonylphenyl) phosphite. The antioxidant is preferably added in the range of 0.05 to 5.0 parts by weight per 100 parts by weight of the specific cyclic olefin polymer.
The thickness of the polymer film layer is 50 to 500 μm, preferably 50 to 200 μm.

<Laminated film>
The first laminated film of the present invention has a structure in which an inorganic oxide layer containing at least one selected from silica, alumina, titania, zirconia and niobium oxide is laminated on both surfaces of the polymer film layer described above. .
The inorganic oxide layer is formed by sputtering, vapor deposition, or the like. Preferably, the polymer film is formed by sputtering or vapor deposition on both surfaces of the polymer film at one time or in two steps of an upper surface and a lower surface.
As the formation conditions of the inorganic oxide layer, the inorganic oxide layer is formed on the film at 80 to 270 ° C., preferably 100 to 200 ° C. under vacuum.
The film thickness of the obtained inorganic oxide layer is 500 to 10000 nm, preferably 500 to 5000 nm. When the film thickness is less than 500 nm, a laminated film having a sufficiently low linear expansion coefficient may not be obtained, and when it exceeds 10,000 nm, the toughness and strength of the obtained laminated film may be insufficient.
The linear expansion coefficient of the laminated film of the present invention is preferably 60 ppm / ° C. or less, particularly preferably 50 ppm / ° C. or less, and further preferably 20 to 40 ppm / ° C. When the linear expansion coefficient exceeds 60 ppm / ° C., for example, the dimensional stability in the liquid crystal module laminating step is poor, and troubles such as warping or peeling occur, which is not preferable.
Moreover, the light transmittance of the laminated film of the present invention is 80% or more, preferably 85% or more. If it is less than 80%, for example, the liquid crystal display is not preferable because it becomes dark or the image accuracy is lowered.
The breaking strength of the laminated film of the present invention is preferably 30 MPa or more, more preferably 40 MPa or more, and the elongation at break is preferably 5% or more, more preferably,
5 to 100%.
Furthermore, the flexural modulus of the laminated film of the present invention is preferably 3 GPa or more, more preferably 3 to 10 GPa.

<< Second laminated film >>
A 2nd laminated | multilayer film is a laminated | multilayer film which formed the inorganic oxide layer on both surfaces of the polymer film layer containing a specific crosslinked body.
<Specific crosslinked body>
The specific crosslinked product is obtained by crosslinking reaction of the crosslinkable group in the specific cyclic olefin polymer described above. Therefore, the specific cyclic olefin system used for the formation of the specific cross-linked body has a cross-linkable group in its side chain, specifically, at least one cross-link selected from a hydrolyzable silyl group and an oxetanyl group. It is a polymer having a functional group. Preferably, a polymer having at least one structural unit selected from the specific structural units (1-1) and (1-2) described above is used.
The second laminated film is more preferable for the purpose of the present invention because it can provide better heat resistance, solvent resistance, chemical resistance, and a low linear expansion coefficient compared to the first laminated film.
The linear expansion coefficient of the laminated film of the present invention is preferably 60 ppm / ° C. or less, particularly preferably 50 ppm / ° C. or less, and further preferably 20 to 40 ppm / ° C. When the linear expansion coefficient exceeds 60 ppm / ° C., for example, the dimensional stability in the liquid crystal module laminating step is poor, and troubles such as warping or peeling occur, which is not preferable.
Moreover, the light transmittance of the laminated film of the present invention is 80% or more, preferably 85% or more. If it is less than 80%, for example, the liquid crystal display is not preferable because it becomes dark or the image accuracy is lowered.
The breaking strength of the laminated film of the present invention is preferably 30 MPa or more, more preferably 40 MPa or more, and the elongation at break is preferably 5% or more, more preferably,
5 to 100%.
Furthermore, the flexural modulus of the laminated film of the present invention is preferably 3 GPa or more, more preferably 3 to 10 GPa.

Manufacturing method of specific crosslinked body The specific crosslinked body is obtained by forming a polymer film having the specific cyclic olefin-based polymer having the crosslinkable group and crosslinking the polymer in the polymer film. Specifically, a specific cyclic olefin-based polymer and, if necessary, a crosslinking catalyst are dissolved in a solvent, a polymer film is formed by the above-described solution casting method, the polymer film is crosslinked, and then the remaining solvent By removing, a specific crosslinked body is formed.

  In the present invention, a method of producing a specific crosslinked product by forming a polymer film using an acid generator as a crosslinking catalyst and crosslinking the polymer in the polymer film is suitably carried out. For example, as a method for crosslinking a polymer having a hydrolyzable silyl group, a method of heating, a method of adding as a hydrolysis / condensation catalyst such as an acid, a base, or a metal salt compound are known. However, when crosslinked only by heating, the progress of crosslinking is slow and insufficient compared to the presence of a catalyst, and a crosslinked product having poor dimensional stability and mechanical strength can be obtained, or the crosslinking can proceed sufficiently. Therefore, the polymer may be deteriorated by performing a treatment at a high temperature for a long time. On the other hand, when the above catalyst is used, the crosslinking proceeds rapidly at a relatively low temperature, but the crosslinking proceeds before or during the molding of the polymer film, which may make it difficult to mold the polymer film. When an acid generator is used, the crosslinking reaction does not proceed during the molding of the polymer film, and the crosslinking can proceed quickly by generating an acid after molding, so that excellent optical properties are maintained and high heat resistance is achieved. It is possible to obtain a cross-linked product that is particularly excellent in dimensional stability while satisfying properties, low water absorption, solvent resistance and chemical resistance at high levels.

Here, as a specific example of the acid generator, a compound that generates acid by decomposition or hydrolysis by heat of 110 to 200 ° C. or active energy rays such as ultraviolet rays in the presence or absence of water or water vapor, That is,
a) Trialkyl phosphites, dialkyl phosphites, monoalkyl phosphites, secondary or tertiary alcohol esters of organic carboxylic acids, hemiacetal esters of organic carboxylic acids, trialkylsilyl of organic carboxylic acids Compounds that act as acids by heating in the presence of water or water vapor, such as esters, aromatic or alicyclic sulfonic acids or ester compounds of sulfinic acids,
b) Aromatic sulfonium salts, aromatic ammonium salts, aromatic pyridinium salts, aromatic phosphonium salts having a counter anion selected from BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , B (C ₆ F ₅ ) _{4 and the} like A thermal acid generator that acts as an acid by heating, such as aromatic iodonium salt, hydrazinium salt, ferrocenium salt,
c) Diazonium salts, ammonium salts, iodonium salts, sulfonium salts that generate Bronsted acid or Lewis acid by irradiation with light rays such as g-line, h-line, i-line, ultraviolet ray, far-ultraviolet ray, X-ray, electron beam, Onium salts such as phosphonium salts, arsenium salts, and oxonium salts, halogenated organic compounds such as halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, and halogen-containing benzophenone compounds, quinonediazide compounds, α, α-bis ( Photoacid generators such as sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfonyl compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds,
And so on. These can be used alone or in combination of two or more.
Among these, in the crosslinking reaction of the polymer having the structural unit (1-1), the compound represented by the above a) is preferable, and p-toluenesulfonic acid-cyclohexyl ester has particularly good solubility in an organic solvent. It is preferably used because of its high effect in the crosslinking reaction. In the crosslinking reaction of the polymer having the structural unit (1-2), the photoacid generator represented by c) is preferably used. Two or more acid generators may be used in combination.

  In the composition used for forming the polymer film, the acid generator is usually 0.0001 to 20 parts by weight, preferably 0.001 to 100 parts by weight per 100 parts by weight of the specific cyclic olefin polymer, although depending on the type. It is used in the range of 10 parts by weight, preferably 0.1 to 10 parts by weight. If the amount is less than 0.0001 parts by weight, the crosslinking reaction does not proceed sufficiently, so that the required chemical resistance, solvent resistance, and dimensional stability cannot be obtained. Mechanical strength, electrical properties, transparency, etc. may decrease.

Depending on the type of crosslinkable group and acid generator, the crosslinking reaction of the polymer film may be carried out by bringing the acid into contact with water, hot water, water vapor or a water-containing liquid composition, or by irradiating active energy rays. Generate and do.
The step of bringing into contact with water, hot water, water vapor or a water-containing liquid composition is performed under conditions of 100 to 240 ° C. and 30 to 120 minutes. Here, the water-containing liquid composition has a boiling point of 100 ° C. or higher under a pressure of 0.1 MPa, can form a homogeneous liquid phase with water at the treatment temperature, and dissolves the specific cyclic olefin polymer. And a composition of water and no compound. Specifically, a composition of a polyol compound and / or a mono- or diol compound containing an ether bond and water is preferably used. The water content in the hydrated liquid composition is 500 ppm to 50% by weight, preferably 1 to 30% by weight.
Moreover, as a process of irradiating an active energy ray, it is performed on the conditions of 0-150 degreeC and 0.1-100 minutes. Here, although there is no restriction | limiting in particular in the source of the active energy ray used, Light with a wavelength of 200 nm-450 nm is used preferably. For example, it is desirable to irradiate the entire molded body using a high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, excimer lamp, etc., and also irradiate laser light or convergent light using lenses, mirrors, etc. Can do. Furthermore, it can also irradiate through the photomask which has the light transmissive part of a predetermined pattern.

  In addition, before and / or after the crosslinking reaction, pre-baking, post-baking, and heat curing can be performed as necessary. Moreover, you may mix | blend a photosensitizer with the polymer film containing a photo-acid generator as needed. Here, the function of the photosensitizer is to absorb active energy rays and improve the sensitivity of the photoacid generator. Examples of the photosensitizer include benzoquinone, naphthoquinones, anthraquinones, thioxanthones, anthracene derivatives, benzophenone derivatives, chloranil and the like. The amount of addition is not particularly limited, but it is preferably used in the range of 0.01 to 300 parts by weight, preferably 0.1 to 100 parts by weight per 100 parts by weight of the photoacid generator. More preferably, the range of 0.5 to 50 parts by weight is most preferable. If the addition amount is less than 0.01 parts by weight, the effect cannot be sufficiently obtained, while if it exceeds 300 parts by weight, the weather resistance is lowered.

Furthermore, in order to obtain a crosslinked product exhibiting excellent dimensional stability and mechanical strength, the residual solvent is preferably less than 1.0% by weight, preferably less than 0.5% by weight, more preferably after the crosslinking reaction. It is necessary to remove to less than 0.3% by weight.
Examples of the method for removing the residual solvent include a method of heating under normal pressure or reduced pressure, a method of treating with water or an organic solvent, a vapor thereof, or a method combining these. Here, as the organic solvent used for removing the residual solvent, a solvent that dissolves the cyclic olefin copolymer little or not at all and is uniformly mixed with the solvent to be removed is preferably used. Examples include dichloromethane, 1,2-dichloroethane, hexane, heptane, methanol, ethanol, acetone, diethyl ether and the like. The solvent used for the removal of these residual solvents can be reduced to the level required by treatment with superheated steam at 100 to 280 ° C. or by exposing the crosslinked product to the above-mentioned organic solvent atmosphere.

The specific crosslinked product preferably has a linear expansion coefficient in the range of 70 ppm / ° C. or less, more preferably 60 ppm / ° C. or less, and particularly preferably 50 ppm / ° C. or less.
When the linear expansion coefficient exceeds 70 ppm / ° C., the polymer film layer in the obtained laminated film may be deformed under a use environment having a large temperature change.

<Laminated film>
The second laminated film of the present invention is an inorganic oxide containing at least one selected from silica, alumina, titania, zirconia and niobium oxide on both surfaces of a crosslinked polymer film in the same manner as the first laminated film. It has a structure in which physical layers are stacked.
The film thickness of the obtained inorganic oxide layer is 500 to 10000 nm, preferably 500 to 5000 nm. When the film thickness is less than 500 nm, a laminated film having a sufficiently low linear expansion coefficient may not be obtained, and when it exceeds 10,000 nm, the toughness and bending elastic modulus of the obtained laminated film may be insufficient.
The linear expansion coefficient of the laminated film of the present invention is preferably 60 ppm / ° C. or less, particularly preferably 50 ppm / ° C. or less, and further preferably 20 to 40 ppm / ° C. When the linear expansion coefficient exceeds 60 ppm / ° C., for example, the dimensional stability in the liquid crystal module laminating step is poor, and troubles such as warping or peeling occur, which is not preferable.
In addition, the preferable value of the light transmittance, breaking strength, breaking elongation, and bending elastic modulus of the 2nd laminated film of this invention is the same as that of the 1st laminated film mentioned above.

  The laminated film of the present invention is useful for optical parts, among them, display device substrates such as LCD, PDP or electronic paper, optical recording substrates such as light guide plates, retardation films, touch panels, CDs, MDs and DVDs, Used for solar cell plastic substrates.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified. The copolymer composition, molecular weight, glass transition temperature, residual solvent amount, light transmittance, linear expansion coefficient, and mechanical properties were measured by the following methods.

(1) Copolymer composition Unless otherwise specified, the copolymer composition was measured by the following method.
A part of the polymerization reaction solution was collected, and the copolymer was coagulated with excess isopropyl alcohol. The obtained copolymer was dried in a vacuum dryer at 100 ° C. for 8 hours, and then deuterated benzene (benzene-d ₆ ) or deuterated benzene (benzene-d ₆ ) and deuterated o-dichlorobenzene. It is dissolved using a mixture (volume ratio 2/1 to ^1/2 ) with (o-dichlorobenzene-d ₄ ), heated to 80 ° C. as necessary, and 270 MHz ¹ H-NMR (JEOL Ltd.) It was measured by the company's EX-270) and determined from the proton absorption ratio.
(2) Molecular weight (weight average molecular weight, number average molecular weight):
Using an H-type column manufactured by Tosoh Corporation with a 150C gel permeation chromatography (GPC) apparatus manufactured by WATERS, the measurement was performed at 120 ° C. using o-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene equivalent value.
(3) Glass transition temperature:
The glass transition temperature was measured at the peak temperature of temperature dispersion of Tan δ measured by dynamic viscoelasticity (ratio of storage elastic modulus E ′ and loss elastic modulus E ″ Tan δ = E ″ / E ′). Measurement of dynamic viscoelasticity using Leo Vibron DDV-01FP (manufactured by Orientec), measuring frequency 10Hz, heating rate 4 ° C / min, excitation mode single waveform, excitation amplitude 2.5μm Was used to measure the peak temperature of Tan δ.
(4) Light transmittance:
The light transmittance at a wavelength of 550 nm was measured for a 100 μt film using a visible / ultraviolet spectrophotometer (U-2010 Spectro Photo Meter manufactured by Hitachi).
(5) Linear expansion coefficient:
Using TMA (Thermal Mechanical Analysis) SS6100 (manufactured by Seiko Instruments Inc.), a film piece having a sample shape of 100 μm in thickness, 10 mm in length and 10 mm in width was fixed upright, and a load of 1 g was applied by a probe. . In order to remove the thermal history of the film, the temperature was once raised from room temperature to 200 ° C. at 5 ° C./min, and then again raised from room temperature at a rate of 5 ° C./min. The linear expansion coefficient was determined from the slope of elongation.
(6) Residual solvent amount Finely cut 1 gram of crosslinked film is dissolved or swollen in toluene or cyclohexane to extract the residual solvent in the film, and used as a column in the HP-5890 gas chromatograph (manufactured by Hewlett-Packard). PoraplotQ (manufactured by Hewlett Packard) was attached and analyzed, and the amount of residual solvent in the film was quantified.
(7) Mechanical property 1 (breaking strength and breaking elongation)
According to JIS K7113, the test speed is 5 mm / min. Measured with
(8) Mechanical properties 2 (flexural modulus)
According to JIS K7113, the test speed is 5 mm / min. Measured with

[Production Example 1] (Polymerization of alkoxysilyl group-containing cyclic olefin copolymer A)
32.2 ml of bicyclo [2.2.1] hept-2-ene at a concentration of 7.0 mol / liter in dry toluene in a glass 300 ml pressure-resistant container sufficiently dried and replaced with nitrogen (225 mmol), 5-trimethoxytoxylsilylbicyclo [2.2.1] hept-2-ene (25 mmol), and 187 ml of dry toluene were charged. Further, 0.25 ml (2.5 μmol) of tricyclohexylphosphine prepared in toluene at 0.01 mol / liter was added, the container was sealed with a septum seal, and ethylene was further fed at a rate of 120 ml / min. And the temperature of the system was adjusted to 75 ° C. Subsequently, palladium acetate prepared at 0.01 mol / liter in toluene was dissolved in 0.25 ml of a small amount of methylene chloride and toluene to make 0.01 mol / liter of triphenylcarbenium tetrakis (penta Polymerization was initiated with 0.3 ml of fluorophenyl) borate. After reacting for 3 hours after the initiation of polymerization, about 0.5 ml of trioctylamine was added to terminate the polymerization. Diluted with about 100 milliliters of toluene, coagulated with about 2 liters of acetone, and dried under vacuum at 90 ° C. for 24 hours to obtain a cyclic olefin copolymer A in a yield of 97%. Copolymer A had a weight average molecular weight (Mw) of 187,000, a number average molecular weight (Mn) of 69,000, and a glass transition temperature of 365 ° C. Copolymer A ¹ H-NMR [(JEOL) 270 MHz H-NMR (Proton Nuclear Magnetic Resonance) (solvent: C ₆ D ₆ ) measured with 3.5 ppm absorption (SiOCH ₃ CH ₃ ) To determine the content of alkoxysilyl groups in the resulting copolymer. As a result of analysis by the method described above, the proportion of structural units derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene was 9.8 mol%.

[Production Example 2] (Polymerization of Oxetanyl Group-Containing Cyclic Olefin Copolymer B)
A well-dried, nitrogen-substituted glass 100 ml pressure vessel was charged with 12.9 ml of bicyclo [2.2.1] hept-2-ene at a concentration of 7.0 mol / l in dry toluene (90 ml). Mmol), bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyloxetane-3-yl) methyl (10 mmol), dry toluene 25 ml, dry cyclohexane 27 ml. The container was sealed with a septum seal, and ethylene was blown in at a rate of 60 ml / min for 0.3 minutes to adjust the system temperature to 80 ° C.
Subsequently, 0.2 ml of palladium acetate prepared at 0.005 mol / liter in toluene, 0.5 ml of tricyclohexylphosphine prepared at 0.002 mol / liter in toluene, and 0. Polymerization was started by sequentially adding 0.5 ml of triphenylcarbenium tetrakis (pentafluorophenyl) borate prepared to 002 mol / liter. After reacting for 24 hours after the start of polymerization, 0.5 ml of trioctylamine prepared to 0.01 mol / liter in toluene was added to terminate the polymerization. Diluted with 100 ml of cyclohexane, coagulated with about 500 ml of 2-propanol, and dried under vacuum at 90 ° C. for 24 hours to obtain an oxetanyl group-containing cyclic olefin copolymer in a yield of 98%. The copolymer had a weight average molecular weight (Mw) of 179,000 and a number average molecular weight (Mn) of 62,000. Copolymer ¹ H-NMR [(JEOL) 270 MHz ¹ H-NMR (proton nuclear magnetic resonance) (solvent: C ₆ D ₆ ) measured by 4.3 ppm, 4.5 ppm absorption The oxetanyl group content of the polymer was determined. As a result, the ratio of structural units derived from bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyloxetane-3-yl) methyl was 9.8 mol%. .

[Example 1]
100 parts of copolymer A is dissolved in 450 parts of toluene, and pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-dithiol) are used as antioxidants. -T-Butylphenyl) phosphite was added in an amount of 0.6 parts, respectively, and 1.5 parts of p-toluenesulfonic acid-cyclohexyl ester was further added. This solution was filtered through a membrane filter having a pore size of 10 μm, cast on a smooth polyethylene terephthalate film at 25 ° C., and the solvent was evaporated while gradually raising the temperature to 50 ° C. to obtain a polymer film.
This film was cross-linked by exposing it to pressurized steam at 180 ° C. and 0.48 MPa for 2 hours at 120 ° C. to obtain a crosslinked film A-1 having a thickness of 100 μm.
Furthermore, using this crosslinked product film, silica was subjected to double-sided vapor deposition with a thickness of 2000 nm on one side by an ion assist method using an Optran vacuum vapor deposition apparatus F1800 to obtain a double-sided silica film B-1.
This silica double-sided vapor-deposited film B-1 had excellent transparency and flexural modulus as shown in Table 1, and had a low linear expansion coefficient.

[Example 2]
Similarly to Example 1, both surfaces of the crosslinked film A-1 were subjected to double-sided vapor deposition at a thickness of 3000 nm on one side of the silica using a vacuum vapor deposition apparatus to obtain a double-sided silica film B-2.
This silica double-sided vapor-deposited film B-2, as shown in Table 2, had excellent transparency and bending elastic modulus as in B-1, and had a low linear expansion coefficient.
[Example 3]
100 parts of the copolymer A was dissolved in 450 parts of toluene, and pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4) were used as antioxidants. -Di-t-butylphenyl) phosphite was added in an amount of 0.6 parts, respectively, and 1.5 parts of p-toluenesulfonic acid-cyclohexyl ester was further added. Using the solution obtained by filtering this solution through a membrane filter having a pore diameter of 10 μm, a crosslinked film A-2 having a thickness of 60 μm was obtained in the same manner as in Example 1.
Furthermore, both surfaces of this crosslinked body film A-2 were subjected to double-sided vapor deposition at a thickness of 2000 nm on one side of the silica using a vacuum vapor deposition apparatus in the same manner as in Example 1 to obtain a double-sided silica film B-3.
As shown in Table 2, this silica double-sided vapor-deposited film B-3 had excellent transparency and bending elastic modulus, and had a low coefficient of linear expansion, as in B-1.

[Example 4]
100 parts of copolymer B is dissolved in 450 parts of toluene, and pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-acid) are used as antioxidants. -T-Butylphenyl) phosphite was added in an amount of 0.6 parts, respectively, and 1.5 parts of p-toluenesulfonic acid-cyclohexyl ester was further added. This solution was filtered through a membrane filter having a pore size of 10 μm, cast on a smooth polyethylene terephthalate film at 25 ° C., and the solvent was evaporated while gradually raising the temperature to 50 ° C. to obtain a crosslinkable composition film.
This film was dried and crosslinked at 120 ° C. for 2 hours and 180 ° C. for 2 hours to obtain a crosslinked film C-1 having a thickness of 100 μm.
Furthermore, using this cross-linked film, double-sided vapor deposition was performed with a thickness of 2000 nm on one side using an ion-assisted method using an Optran vacuum vapor deposition apparatus F1800 to obtain a double-sided silica film D-1.
This silica double-sided vapor-deposited film D-1 had excellent transparency and flexural modulus as shown in Table 1, and had a low linear expansion coefficient.
[Comparative Example 1]
The crosslinked film A-1 of Example 1 was used as it was.
Compared to Examples 1 to 3, the linear expansion coefficient was large, and the bending elastic modulus was inferior.

The laminated film of the present invention is excellent in optical transparency, heat resistance, adhesiveness, dimensional stability, solvent resistance, chemical resistance and the like, and can satisfy liquid crystal resistance when liquid crystal is injected. It is useful for parts such as substrates for flat displays such as display elements and electroluminescence display elements. Among them, display device substrates such as LCD, PDP or electronic paper, light guide plates, retardation films, touch panels, CD, MD It is particularly useful for optical recording substrates such as DVDs and solar cell plastic substrates.
Furthermore, since the laminated film of the present invention is excellent in bending workability, it is also suitable for roll-to-roll processing of these substrates, and thus is excellent in industrial productivity.

Claims (5)

At least selected from silica, alumina, titania, zirconia and niobium oxide on both surfaces of a cyclic olefin polymer having a structural unit represented by the following formula (1) or a polymer film layer containing a crosslinked product of the polymer. A laminated film comprising an inorganic oxide layer having a thickness of 500 to 10,000 nm containing one kind.

[In the formula (1), A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group or a halogenated hydrocarbon. A polar group represented by a group, a hydrolyzable silyl group, or — (CH ₂ ) _k —X. A ¹ and A ² or A ¹ and A ⁴ are bonded to each other, and together with the carbon atoms to which they are bonded, an alicyclic hydrocarbon structure, aromatic hydrocarbon structure, acid anhydride structure, lactone structure or An imide structure may be formed. P is 0 or 1.
Here, X in — (CH ₂ ) _k —X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ are each independently a hydrocarbon having 1 to 10 carbon atoms. Represents a substituent containing a group, a halogenated hydrocarbon group, or an oxetanyl group, and k is an integer of 0 to 5. ] The cyclic olefin-based polymer has a structural unit having a hydrolyzable silyl group represented by the following formula (2), in an amount of 0.2 to 30 mol% with respect to all the structural units constituting the polymer. The laminated film according to claim 1.

[In the formula (2), B ¹ , B ² , B ³ and B ⁴ are each independently a hydrogen atom, a halogen atom, — (CH ₂ ) _m —Si (R ⁴ ) _a (R ⁵ ) _3-a Alternatively, it is a hydrolyzable silyl group represented by the following formula (3). However, at least one of B ¹ , B ² , B ³ and B ⁴ is the hydrolyzable silyl group. Q is 0 or 1.
Here, R ⁴ represents an alkoxyl group, an aryloxyl group or a halogen atom, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, m represents 0 or 1, and a represents 1 to 3. ]

[In the formula (3), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y represents a divalent hydrocarbon of an aliphatic diol, alicyclic diol or aromatic diol having 2 to 20 carbon atoms. Indicates a residue, n is 0 or 1. ] The cyclic olefin polymer includes at least one structural unit having an oxetanyl group represented by any of the following formulas (4) or (5), and the content ratio of the structural unit having the oxetanyl group is the total structural unit. It is 0.2-30 mol% with respect to a laminated film of Claim 1 characterized by the above-mentioned.

[In formula (4) and formula (5), the definitions of A ¹ , A ² and A ³ are the same as those in formula (1). X _{^{is, - (CR 12 R 13)}} r - or _{^{- (CR 14 R 15) s}} -T- (CR 16 R 17) t - indicates, where T is -O -, - C (O) -, -OC (O) -, - C (O) O- or ^-SiR 18 ^{R 19} - shows a, r, s and t are an integer of 0 to 6. R ^{7 to} R ¹⁹ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group, and p represents 0 or 1. ] The laminate according to any one of claims 2 to 3, wherein the polymer film layer is a film containing a crosslinked product obtained by crosslinking reaction of a group selected from a hydrolyzable silyl group and an oxetanyl group in the cyclic olefin polymer. the film.   2. The laminated film according to claim 1, wherein the inorganic oxide layer is a single layer containing at least one selected from silica, alumina, titania, zirconia and niobium oxide or a laminated structure of different inorganic oxide layers.