KR20080073168A - Cyclic oleffin-based resin film, and method for manufacturing the same - Google Patents

Abstract

A cyclic olefin-based resin film is provided to be superior in mechanical properties and thermal stability, and to remove a breaking phenomenon because the film is prepared by cross-linking cyclic olefin-based addition polymer. A cyclic olefin-based resin film is prepared by adding an acid or base crosslinking agent to a cyclic olefin-based addition polymer comprising a cyclic olefin-based monomer capable of being cross-linked by the acid or base crosslinking agent. The cyclic olefin-based monomer is a monomer represented by the following formula 1. The acid crosslinking agent and the base crosslinking agent are contained in amounts of 1-10wt% and 1-30wt% based on the cyclic olefin-based addition polymer, respectively.

Description

Cyclic olefin resin film and its manufacturing method {CYCLIC OLEFFIN-BASED RESIN FILM, AND METHOD FOR MANUFACTURING THE SAME}

1 is a graph showing the differential scanning calorimetry (DSC) results of Preparation Example 1. FIG.

2 is a graph showing the DSC results of Preparation Example 5.

3 is a graph showing the DSC results of Preparation Example 7.

4 is a graph showing the DSC results of Preparation Example 10.

The present invention relates to a cyclic olefin resin film having excellent mechanical properties and thermal stability, and a method of manufacturing the same.

A film formed of a conventional cyclic olefin resin is basically less flexible and easily broken or broken. In addition, thermally unstable, there are many problems in the use of a plastic substrate, a matrix, an optically anisotropic film in the coefficient of thermal expansion (CTE).

The present invention is to solve this problem, an object of the present invention is to provide a cyclic olefin resin film having excellent mechanical properties and thermal stability, a method for manufacturing the same, a plastic substrate and an electronic device comprising the cyclic olefin resin film. have.

In order to achieve the above object, the present invention provides a cyclic olefin resin film formed by crosslinking by adding an acid or a base crosslinking agent to a cyclic olefin addition polymer comprising a cyclic olefin monomer crosslinkable by an acid or base crosslinking agent.

In addition, the present invention provides a film comprising the steps of a) adding an acid or base crosslinking agent to a cyclic olefin based addition polymer comprising a cyclic olefinic monomer crosslinkable by an acid or base crosslinking agent, and b) converting the mixture obtained in step a) into a film. It provides a method for producing a cyclic olefin resin film comprising the step of molding.

The present invention also provides a plastic substrate or electronic device comprising the cyclic olefin resin film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The cyclic olefin resin film according to the present invention is prepared by using an cyclic olefin additive polymer containing a cyclic olefin monomer crosslinkable by an acid or base crosslinking agent, and adding an acid or base crosslinking agent to the polymer.

The cyclic olefin resin film according to the present invention is not only eliminates the phenomenon of breaking basically, because the polymer chains in the film are intertwined with each other, there is an advantage that can be excellent in flexibility, and also provide stability to thermally. . Therefore, the cyclic olefin resin film according to the present invention is cheaper and has excellent physical properties, and thus may be used as a plastic substrate, a compensation film, a protective film, an optically anisotropic film, and the like, and may be applied to a display such as an LCD or a PDP.

In an embodiment of the present invention, the cyclic olefin monomer crosslinkable by the acid or base crosslinking agent is preferably a monomer represented by the following formula (1).

In Chemical Formula 1,

p is an integer from 0 to 4,

R ¹ , R ² , R ³ and R ⁴ are the same as or different from each other, -epoxy group, -acryl group, -silane group, hydrogen atom, C ₁ ~ C ₁₂ alkyl group, C ₄ ~ C ₈ cyclo alkyl group , A halogen group and a substituent group including a compound represented by Formulas 1a to 1d below, at least one selected from -epoxy group, -acryl group, and -silane group,

In Chemical Formulas 1a, 1b, 1c, and 1d,

A is linear or branched alkyl of 1 to 20 carbon atoms; Carbonyl; Carboxy; And arylene or haloarylene having 6 to 40 carbon atoms unsubstituted or substituted with at least one substituent selected from linear or branched alkyl having 1 to 20 carbon atoms, carbonyl and carboxy; One selected from the group consisting of;

B is oxygen or nitrogen;

X is oxygen or sulfur;

R ¹⁵ is a direct bond; Linear or branched alkylene or halo alkylene having 1 to 20 carbon atoms; Linear or branched alkenylene or haloalkenylene having 2 to 20 carbon atoms; Cycloalkylene or halocycloalkylene having 5 to 12 carbon atoms unsubstituted or substituted with a hydrocarbon; Arylene or haloarylene having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon; Aralkylene or haloaralkylene having 7 to 15 carbon atoms unsubstituted or substituted with hydrocarbon; Alkynylene or haloalkynylene having 3 to 20 carbon atoms;

R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ Each independently represent alkyl having 1 to 20 carbon atoms or haloalkyl; Alkoxy or haloalkoxy; Aryloxy or haloaryloxy; Aryl or haloaryl of 6 to 40 carbon atoms unsubstituted or substituted with cyano or nitro.

Substituents including the -epoxy, -acryl or -silane-based functional group include -NCO, -R ₅ NCO, -CN, -R ₅ CN, -R ₅ C (O) OCH = CH ₂ , -R ₅ OC ( O) R ₅ CH = CH ₂ , -R ₅ C (O) OC (R ₆ ) = CH (R ₇ ), -R ₅ OC (O) R ₅ C (R ₆ ) = CH (R ₇ ),

등을 포함할 수 있으나, 반드시 이에 한정되는 것은 아니다.

And the like, but are not necessarily limited thereto.

Wherein R ₅ of each of the functional groups is halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyl Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from oxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkyl chelene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxyylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy;

Each of R ₆ , R ₇ , and R ₈ Are the same as or different from each other, and each hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy.

In the present invention, the cyclic olefin-based addition polymer may further include a cyclic olefin monomer represented by the following formula (2) in addition to the cyclic olefin monomer crosslinkable by an acid or base crosslinking agent.

In Chemical Formula 2,

m and n are each independently an integer of 0 to 2,

R ^{1 ”} and R ^2” are Each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched haloalkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched haloalkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched haloalkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, halo alkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Halocycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Haloarylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Haloaralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; And a non-hydrocarbon polar group including at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.

When R ^{1 ″} and R ^{2 ″} are each independently a polar functional group, R ^{1 ″} and R ^{2 ″} are each independently linked to an alkylidene group having 1 to 10 carbon atoms, a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or having 6 to 6 carbon atoms. It may be formed of 24 aromatic ring compounds.

The non-hydrocarbon polar group is -R ⁹ OR ¹⁰ , -OR ¹⁰ , -OC (O) OR ¹⁰ , -R ⁹ OC (O) OR ¹⁰ , -C (O) R ¹⁰ , -R ⁹ C (O) OR ¹⁰ _, -C (O) OR ¹⁰ , -R ⁹ C (O) R ¹⁰ , -OC (O) R ¹⁰ , -R ⁹ OC (O) R ¹⁰ ,-(R ⁹ O) _k -OR ¹⁰ (k is Integer from 1 to 10),-(OR ⁹ ) _k -OR ¹⁰ (k is an integer from 1 to 10), -C (O) -OC (O) R ¹⁰ , -R ⁹ C (O) -O- C (O) R ¹⁰ , -SR ¹⁰ , -R ⁹ SR ¹⁰ , -SSR ¹⁰ , -R ⁹ SSR ¹⁰ , -S (= O) R ¹⁰ , -R ⁹ S (= O) R ¹⁰ , -R ⁹ C (= S) R ¹⁰ , -R ⁹ C (= S) SR ¹⁰ , -R ⁹ SO ₃ R ¹⁰ , -SO ₃ R ¹⁰ , -R ⁹ N = C = S, -N = C = S, -NCO , -R ⁹ -NCO, -CN, -R ⁹ CN, -NNC (= S) R ¹⁰ , -R ⁹ NNC (= S) R ¹⁰ , -NO ₂ , -R ⁹ NO ₂ ,

, 또는

, or

이며;

Is;

Wherein R ⁹ and R ¹¹ are the same as or different from each other, and are each halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxyylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; When two or more R ⁹ or R ¹¹ are present, they are the same as or different from each other;

R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ are the same as or different from each other, and are each hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; When two or more R ^{12 's} are present, they are the same or different from each other.

Alkenyl in the present invention includes vinyl and allyl.

In the present invention, the cyclic olefin based addition polymer may be prepared by a method known in the art.

When the cyclic olefin addition polymer of the present invention includes the monomer of Chemical Formula 2, it is preferable that 0.1 to 90 mol% of the monomer represented by Chemical Formula 2 and 1 to 50 mol% of the monomer represented by Chemical Formula 1 are preferable. .

For example, the cyclic olefin-based addition polymer including the polymer of the double-cyclic compound polymerized by including the monomer of Formula 1 and Formula 2 as a monomer in the main chain may be represented by the following formula (3).

In Chemical Formula 3,

s and t are each independently an integer from 50 to 5,000,

n, m, p, R ¹ , R ² , R ³ , R ⁴ , R ¹ and R ^{2 ″ are} the same as defined in Chemical Formulas 1 and 2 above.

The acid or base crosslinking agent for crosslinking the cyclic olefin addition polymer containing a cyclic olefin monomer which can be crosslinked by an acid or base crosslinking agent according to the present invention is not particularly limited as long as it can crosslink the polymer.

As said acid crosslinking agent, For example, Organic or an inorganic acid; Substances which act as acids at 50 ° C .; Substances which act as an acid in the presence of water or steam, and the like, which are preferably included in an amount of 1 to 10% by weight based on the addition polymer of the present invention.

The organic or inorganic acid may be hydrochloric acid, sulfuric acid, hydrofluoric acid, tetrafluoroboric acid, phosphorous acid, organic carboxylic acid. , Organic sulfonic acid, organic sulfinic acid, organic phosphoric acid, and the like.

Examples of the material that act as an acid at 50 ° C. include aromatic sulfonium salt, aromatic ammonium salt, aromatic pyridinuim salt, aromatic phosphonium salt, aromatic iodine It can be selected from the group consisting of aromatic iodonium salt, hydrazinium salt, iron salt of metallocene, and these include counter anions, BF ₄ -and PF. _6- , AsF _6- , SbF _6- , B (C ₆ F ₅ ) ₄ -and the like can be used as an acid.

Substances which act as acids in the presence of water or steam include trialkylphosphite, triarylphosphite, dialkylphosphite, monoalkylphosphite, hypophosphite, and hypophosphite. ), Esters of organic carboxylic acids, secondary or tertiary alcohols, trialkylsilyl esters of organic carboxylic acids, and the like. It may be selected from the group consisting of.

As the base crosslinking agent, for example, it may be selected from the group consisting of primary amine, secondary amine, tertiary amine and the like. Primary amines include R ²¹ -NH ₂ , NH ₂ -R ²¹ -NH ₂ , C ₆ H ₅ -R ²¹ -NH ₂ , R ^{21 '} R ²¹ -NH ₂ , Si (R ²¹ ) ₃ -NH _2, etc. As the secondary amine, R ²¹ -NHR ²² , NHR ²² -R ²¹ -NH ₂ , C ₆ H ₅ -R ²¹ -NHR ²² , R ^{21 '} R ²¹ -NHR ²² , Si (R ²¹ ) _3- NHR ²² , Si (R ²¹ ) ₃ -NH-Si (R ²² ) ₃ , and the like, and tertiary amines include DBU, DBN, TMG, alkyl imidazoles, DABCO, NAMs, and the like. R ²¹ and R ²² are hydrocarbons having 1 to 8 carbon atoms, and R ^{21 '} is a cyclic hydrocarbon. Specifically, R ²¹ and R ²² are-(CH ₂ ) n-(n is an integer between 1 and 8), R ^{21 '} is And cyclopentyl-, cyclohexyl-, cycloheptyl-, and cyclooctyl-, and these base crosslinkers are preferably included in an amount of 1 to 30% by weight based on the additive polymer of the present invention.

The cyclic olefin resin film according to the present invention is formed by adding an acid or base crosslinking agent to a cyclic olefin addition polymer comprising a cyclic olefin monomer crosslinkable by the acid or base crosslinking agent. Specifically, an acid or base crosslinking agent is added to the cyclic olefin based addition polymer, and then it is molded into a film. The method of forming into the film may use a technique known in the art, for example, by coating and drying a mixture of the cyclic olefin-based addition polymer and an acid or base crosslinking agent on a substrate to prepare a cyclic olefin resin film. have.

The cyclic olefin resin film may be made by a solution casting method, wherein the solvent may be toluene, dichloromethane, xylene, ethyl acetate and the like. The polymer is adjusted to a concentration of 10 to 20wt% of the total solution, coated on a glass plate and dried at room temperature for 1 to 3 hours. During this process, it is desirable to adjust the environment so that the humidity is maintained at 50 ± 5% and the temperature is 20 ~ 23 ℃. And it is preferable to further dry at 100-150 degreeC for 1-3 hours.

The cyclic olefin resin film according to the present invention may be used as an LCD substrate and a flexible substrate as a plastic substrate. In addition, it can be used as a compensation film, a protective film, an electromagnetic shielding filter and the like in electronic devices such as a display device such as LCD and PDP.

Hereinafter, the present invention will be described in detail through embodiments of the present invention. However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

 <Manufacture example 1>

2.72 g (20 mmol) of 2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane and oxirane-2-yl-bicyclo [2.2.1] hept-5-en-2- The carboxylate 27.4g (180mmol) was put in toluene (147ml) and the temperature was raised while stirring. When the temperature reached 90 ° C, a solution of 4.5 mg (0.02 mmol) of palladium acetate and 40 mg (0.042 mol) of tris (cyclohexyl) phosphonium tetrakis (pentafluorophenyl) borate salt in 2 ml of MC was added thereto. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 60%. The weight average molecular weight of the polymer was 205k (PDI = 2.3).

<Manufacture example 2>

8.17 g (60 mmol) of 2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane and oxirane-2-yl-bicyclo [2.2.1] hept-5-en-2- 21.2 g (140 mmol) of carboxylate was added to toluene (147 mL), followed by stirring while raising the temperature. When the temperature reached 90 ° C, a solution of 4.5 mg (0.02 mmol) of palladium acetate and 40 mg (0.042 mol) of tris (cyclohexyl) phosphonium tetrakis (pentafluorophenyl) borate salt in 2 ml of MC was added thereto. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 60%. The weight average molecular weight of the polymer was 188k (PDI = 2.5).

<Manufacture example 3>

13.62 g (100 mmol) of 2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane and oxirane-2-yl-bicyclo [2.2.1] hept-5-en-2- 15.22 g (100 mmol) of carboxylate was added to toluene (147 mL), followed by stirring at elevated temperature. When the temperature reached 90 ° C, a solution of 4.5 mg (0.02 mmol) of palladium acetate and 40 mg (0.042 mol) of tris (cyclohexyl) phosphonium tetrakis (pentafluorophenyl) borate salt in 2 ml of MC was added thereto. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 60%. The weight average molecular weight of the polymer was 180k (PDI = 2.1).

<Manufacture example 4>

19.07 g (140 mmol) of 2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane and oxirane-2-yl-bicyclo [2.2.1] hept-5-en-2- 9.13 g (60 mmol) of carboxylate was added to toluene (147 mL), followed by stirring while raising the temperature. When the temperature reached 90 ° C, a solution of 4.5 mg (0.02 mmol) of palladium acetate and 40 mg (0.042 mol) of tris (cyclohexyl) phosphonium tetrakis (pentafluorophenyl) borate salt in 2 ml of MC was added thereto. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 60%. The weight average molecular weight of the polymer was 163k (PDI = 2.4).

Production Example 5

24.5 g (180 mmol) of 2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane and oxirane-2-yl-bicyclo [2.2.1] hept-5-en-2- 3.04 g (20 mmol) of carboxylate was added to toluene (147 mL), followed by stirring while raising the temperature. When the temperature reached 90 ° C, a solution of 4.5 mg (0.02 mmol) of palladium acetate and 40 mg (0.042 mol) of tris (cyclohexyl) phosphonium tetrakis (pentafluorophenyl) borate salt in 2 ml of MC was added thereto. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 60%. The weight average molecular weight of the polymer was 155k (PDI = 2.5).

<Manufacture example 6>

5-norbornene-2-triethoxysilane (1 g, 3.9 mmol) and norbornene carboxylic acid methyl ester (5.34 g, 35.1 mmol) were mixed with toluene (63 mL) and stirred for 30 minutes under nitrogen atmosphere. . After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 27%. The weight average molecular weight of the polymer was 93k (PDI = 1.81).

<Manufacture example 7>

5-norbornene-2-triethoxysilane (3 g, 11.7 mmol) and norbornene carboxylic acid methyl ester (4.15 g, 27.3 mmol) were mixed with toluene (72 mL) and stirred for 30 minutes under nitrogen atmosphere. . After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 44%. The weight average molecular weight of the polymer was 176k (PDI = 2.01).

<Manufacture example 8>

5-norbornene-2-triethoxysilane (5 g, 19.5 mmol) and norbornene carboxylic acid methyl ester (2.97 g, 19.5 mmol) were mixed with toluene (80 mL) and stirred for 30 minutes under nitrogen atmosphere. . After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 54%. The weight average molecular weight of the polymer was 283k (PDI = 2.79).

<Manufacture example 9>

5-norbornene-2-triethoxysilane (7 g, 27.3 mmol) and norbornene carboxylic acid methyl ester (1.78 g, 11.7 mmol) were mixed with toluene (88 mL) and stirred for 30 minutes under nitrogen atmosphere. . After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 86%. The weight average molecular weight of the polymer was 502k (PDI = 3.18).

Production Example 10

5-norbornene-2-triethoxysilane (8 g, 31.2 mmol) and norbornene carboxylic acid methyl ester (1.19 g, 7.8 mmol) were mixed with toluene (92 mL) and stirred for 30 minutes under nitrogen atmosphere. . After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 60%. The weight average molecular weight of the polymer was 863k (PDI = 2.31).

Production Example 11

5-norbornene-2-triethoxysilane (1 g, 3.9 mmol) and norbornene methyl acetate (5.83 g, 35.1 mmol, endo / exo = 55/45) were mixed with toluene (48 mL) under nitrogen atmosphere. Stirred for 30 minutes. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 56%. The weight average molecular weight of the polymer was 623k (PDI = 2.2).

Production Example 12

5-norbornene-2-triethoxysilane (2 g, 7.8 mmol) and norbornene methyl acetate (5.2 g, 31.2 mmol, endo / exo = 55/45) were mixed with toluene (50 mL) under nitrogen atmosphere. Stirred for 30 minutes. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. Yield of the obtained polymer was 58%. The weight average molecular weight of the polymer was 523k (PDI = 2.58).

Production Example 13

5-norbornene-2-triethoxysilane (3 g, 11.7 mmol) and norbornenemethyl acetate (4.53 g, 27.3 mmol, endo / exo = 55/45) were mixed with toluene (53 mL) under nitrogen atmosphere. Stirred for 30 minutes. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 81%. The weight average molecular weight of the polymer was 401k (PDI = 4.15).

Production Example 14

5-norbornene-2-triethoxysilane (5 g, 19.5 mmol) and norbornenemethyl acetate (3.24 g, 19.5 mmol, endo / exo = 55/45) were mixed with toluene (58 mL) under nitrogen atmosphere. Stirred for 30 minutes. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 73%. The weight average molecular weight of the polymer was 408k (PDI = 2.39).

Production Example 15

2-vinyl-5-norbornene (0.47 g, 3.9 mmol) and 2-butyl-5-norbornene (5.27 g, 35.1 mmol) were mixed in toluene (29 mL) and stirred for 30 minutes under nitrogen atmosphere. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 81%. The average molecular weight of the polymer was 250k (PDI = 2.11).

Production Example 16

2-vinyl-5-norbornene (1.41 g, 11.7 mmol) and 2-butyl-5-norbornene (4.1 g, 27.3 mmol) were mixed with toluene (28 mL) and stirred for 30 minutes under nitrogen atmosphere. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 78%. The weight average molecular weight of the polymer was 248k (PDI = 2.32).

Production Example 17

2-vinyl-5-norbornene (2.34 g, 19.5 mmol) and 2-butyl-5-norbornene (2.93 g, 19.5 mmol) were mixed with toluene (28 mL) and stirred for 30 minutes under nitrogen atmosphere. After stirring, the temperature was raised to 90 ° C., palladium acetate (0.87 mg, 3.9 μmol) and tris (cyclohexane) phosphonium-tetrakis (pentafluorophenyl) borate salt (7.9 mg) dissolved in MC (1 mL). , 81.9 μmol) was added to the reaction solution. After 18 hours, the solution was slowly added dropwise to methanol to stop the polymerization. The polymer precipitated in methanol was obtained through a filter. The polymer was washed two more times with methanol, and the obtained polymer was dried at 60 ° C. using a vacuum oven. The yield of the obtained polymer was 78%. The weight average molecular weight of the polymer was 193k (PDI = 2.44).

<Example 1>

The polymer obtained in Preparation Example 1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 10wt%, and PGMEA solution containing 5wt% of acetic acid was slowly dropped therein, and shaking was performed for 10 minutes. . The solution was well sprayed with about 5 ml on a clean glass plate, and then pushed out with a blade placed 100 μm above the glass plate. The polymer film coated on the surface was aged at room temperature for about 1 hour and then dried in an oven at 100 ° C. for 1 hour. After drying, the film was removed from the glass plate to obtain a transparent polymer film.

 <Example 2>

 Except for using the polymer of Preparation Example 2 instead of the polymer of Preparation Example 1 in Example 1, the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 3>

Except for using the polymer of Preparation Example 3 instead of the polymer of Preparation Example 1 in Example 1, the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 4>

Except for using the polymer of Preparation Example 4 instead of the polymer of Preparation Example 1 in Example 1 to perform the same experiment to obtain a transparent polymer film.

<Example 5>

Except for using the polymer of Preparation Example 5 instead of the polymer of Preparation Example 1 in Example 1, the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 6>

The polymer obtained in Preparation Example 6 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 10wt%, to which PGMEA solution in which 5wt% nitric acid was dissolved was slowly dropped and shaken for 10 minutes. . The solution was well sprayed with about 5 ml on a clean glass plate, and then pushed out with a blade placed 100 μm above the glass plate. The polymer film coated on the surface was aged at room temperature for about 1 hour and then dried in an oven at 100 ° C. for 1 hour. After drying, the film was removed from the glass plate to obtain a transparent polymer film.

<Example 7>

Except for using the polymer of Preparation Example 7 instead of the polymer of Preparation Example 6 in Example 6 and the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 8>

Except for using the polymer of Preparation Example 8 instead of the polymer of Preparation Example 6 in Example 6 to perform the same experiment to obtain a transparent polymer film.

Example 9

Except for using the polymer of Preparation Example 9 instead of the polymer of Preparation Example 6 in Example 6 to perform the same experiment to obtain a transparent polymer film.

<Example 10>

Except for using the polymer of Preparation Example 10 instead of the polymer of Preparation Example 6 in Example 6 to perform the same experiment to obtain a transparent polymer film.

<Example 11>

Except for using the polymer of Preparation Example 11 instead of the polymer of Preparation Example 6 in Example 6 and the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 12>

Except for using the polymer of Preparation Example 12 instead of the polymer of Preparation Example 6 in Example 6 to perform the same experiment to obtain a transparent polymer film.

Example 13

Except for using the polymer of Preparation Example 13 instead of the polymer of Preparation Example 6 in Example 6, the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 14>

Except for using the polymer of Preparation Example 14 instead of the polymer of Preparation Example 6 in Example 6 to perform the same experiment to obtain a transparent polymer film.

<Example 15>

Except for using the polymer of Preparation Example 15 instead of the polymer of Preparation Example 6 in Example 6 and the experiment was carried out in the same manner to obtain a transparent polymer film.

<Example 16>

 The polymer obtained in Preparation Example 14 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 10wt%, and the PGMEA solution in which 5wt% of triphenylphosphine was dissolved was slowly dropped and shaken for 10 minutes. ) Was added. The solution was well sprayed with about 5 ml on a clean glass plate, and then pushed out with a blade placed 100 μm above the glass plate. The polymer film coated on the surface was aged at room temperature for about 1 hour and then dried in an oven at 100 ° C. for 1 hour. After drying, the film was removed from the glass plate to obtain a transparent polymer film.

<Example 17>

 The polymer obtained in Preparation Example 15 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 10 wt%, and 0.1 wt% of azobisisobutyronitrile and 30 wt% of dipentaerythritol hexaacrylate were dissolved therein. The PGMEA solution was slowly dropped and shaken for 10 minutes. The solution was well sprayed with about 5 ml on a clean glass plate, and then pushed out with a blade placed 100 μm above the glass plate. The polymer film coated on the surface was aged at room temperature for about 1 hour, and then dried in an oven at 100 ° C. for 3 hours. After drying, the film was removed from the glass plate to obtain a transparent polymer film.

Example 18

 The polymer obtained in Preparation Example 16 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 10 wt%, and 0.1 wt% of azobisisobutyronitrile and 20 wt% of dipentaerythritol hexaacrylate were dissolved therein. The PGMEA solution was slowly dropped and shaken for 10 minutes. The solution was well sprayed with about 5 ml on a clean glass plate, and then pushed out with a blade placed 100 μm above the glass plate. The polymer film coated on the surface was aged at room temperature for about 1 hour and then dried in an oven at 100 ° C. for 3 hours. After drying, the film was removed from the glass plate to obtain a transparent polymer film.

Example 19

 The polymer obtained in Preparation Example 17 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 10 wt%, and 0.1 wt% of azobisisobutyronitrile and 10 wt% of dipentaerythritol hexaacrylate were dissolved therein. The PGMEA solution was slowly dropped and shaken for 10 minutes. The solution was well sprayed with about 5 ml on a clean glass plate, and then pushed out with a blade placed 100 μm above the glass plate. The polymer film coated on the surface was aged at room temperature for about 1 hour, and then dried in an oven at 100 ° C. for 3 hours. After drying, the film was removed from the glass plate to obtain a transparent polymer film.

Experimental Example 1

In order to measure the thermal behavior of the polymers obtained in Preparation Examples 1, 5, 7 and 10, the coefficient of thermal expansion (CTE) was measured in a range of 60 ° C to 380 ° C through differential scanning calorimetry (DSC). Measured. This is shown in FIGS. 1 to 4, respectively.

Experimental Example 2

In order to measure the coefficient of thermal expansion (CTE) of the polymer films obtained in Preparation Examples 1 to 17 and Examples 1 to 19, each film was cut to a size of 2 cm × 5 cm and thermomechanical analysis (TMA, Thermomechanical) CTE was measured at 170 ppm / ° C. through Analysis) and is shown in Table 1 below.

As the cyclic olefin resin film according to the present invention is produced by crosslinking a cyclic olefin addition polymer, not only the phenomenon of breaking can be removed, but also thermal stability can be provided, which is cheaper and excellent in physical properties. Therefore, by using such a cyclic olefin resin film, it can be used in electronic devices such as plastic substrates or display devices such as LCDs and PDPs.

Claims (15)

A cyclic olefin resin film prepared by adding an acid or a base crosslinking agent to a cyclic olefin addition polymer containing a cyclic olefin monomer crosslinkable by an acid or base crosslinking agent. The cyclic olefin resin film of claim 1, wherein the cyclic olefin monomer is a monomer represented by Formula 1 below: [Formula 1]

In Chemical Formula 1, p is an integer from 0 to 4, R ¹ , R ² , R ³ , and R ⁴ are the same as or different from each other, -epoxy group, -acryl group, -silane group, hydrogen atom, C ₁ -C ₁₂ alkyl group, C ₄ -C ₈ cycloalkyl A group, a halogen group, and a substituent group including a compound represented by Formulas 1a to 1d below, at least one selected from -epoxy group, -acryl group, and -silane group, [Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

In Chemical Formulas 1a, 1b, 1c, and 1d, A is linear or branched alkyl of 1 to 20 carbon atoms; Carbonyl; Carboxy; And arylene or haloarylene having 6 to 40 carbon atoms unsubstituted or substituted with at least one substituent selected from linear or branched alkyl having 1 to 20 carbon atoms, carbonyl and carboxy; B is oxygen or nitrogen; X is oxygen or sulfur; R ¹⁵ is a bond; Linear or branched alkylene or halo alkylene having 1 to 20 carbon atoms; Linear or branched alkenylene or haloalkenylene having 2 to 20 carbon atoms; Cycloalkylene or halocycloalkylene having 5 to 12 carbon atoms unsubstituted or substituted with a hydrocarbon; Arylene or haloarylene having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon; Aralkylene or haloaralkylene having 7 to 15 carbon atoms unsubstituted or substituted with hydrocarbon; Alkynylene or haloalkynylene having 3 to 20 carbon atoms; R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ Each independently represent alkyl having 1 to 20 carbon atoms or haloalkyl; Alkoxy or haloalkoxy; Aryloxy or haloaryloxy; Aryl or haloaryl of 6 to 40 carbon atoms unsubstituted or substituted with cyano or nitro, Substituents including the -epoxy, -acryl and -silane-based functional groups are -NCO, -R ₅ NCO, -CN, -R ₅ CN, -R ₅ C (O) OCH = CH ₂ , -R ₅ OC (O ) R ₅ CH = CH ₂ , -R ₅ C (O) OC (R ₆ ) = CH (R ₇ ), -R ₅ OC (O) R ₅ C (R ₆ ) = CH (R ₇ ),

And

Including, R ₅ of each of the above functional groups is halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halo Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxyylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Each of R ₆ , R ₇ , and R ₈ Are the same as or different from each other, and each hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy. The cyclic olefin resin film of claim 1, wherein the cyclic olefin addition polymer further comprises a monomer represented by Formula 2 below: [Formula 2]

In Chemical Formula 2, m and n are each independently an integer of 0 to 2, R ^{1 ”} and R ^2” are Each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched haloalkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched haloalkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched haloalkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Halocycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Haloarylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Haloaralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; And a non-hydrocarbon polar group including at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron. When R ^{1 ″} and R ^{2 ″} are each independently a polar functional group, R ^{1 ″} and R ^{2 ″} are each independently linked to an alkylidene group having 1 to 10 carbon atoms, a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or having 6 to 6 carbon atoms. 24 aromatic ring compounds. The method of claim 3, wherein the non-hydrocarbon polar group is -R ⁹ OR ¹⁰ , -OR ¹⁰ , -OC (O) OR ¹⁰ , -R ⁹ OC (O) OR ¹⁰ , -C (O) R ¹⁰ , -R ⁹ C (O) OR ¹⁰ _, -C (O) OR ¹⁰ , -R ⁹ C (O) R ¹⁰ , -OC (O) R ¹⁰ , -R ⁹ OC (O) R ¹⁰ ,-(R ⁹ O) _k- OR ¹⁰ (k is an integer from 1 to 10),-(OR ⁹ ) _k -OR ¹⁰ (k is an integer from 1 to 10), -C (O) -OC (O) R ¹⁰ , -R ⁹ C (O ) -OC (O) R ¹⁰ , -SR ¹⁰ , -R ⁹ SR ¹⁰ , -SSR ¹⁰ , -R ⁹ SSR ¹⁰ , -S (= O) R ¹⁰ , -R ⁹ S (= O) R ¹⁰ ,- R ⁹ C (= S) R ¹⁰ , -R ⁹ C (= S) SR ¹⁰ , -R ⁹ SO ₃ R ¹⁰ , -SO ₃ R ¹⁰ , -R ⁹ N = C = S, -N = C = S , -NCO, -R ⁹ -NCO, -CN, -R ⁹ CN, -NNC (= S) R ¹⁰ , -R ⁹ NNC (= S) R ¹⁰ , -NO ₂ , -R ⁹ NO ₂ ,

, or

Is; Wherein R ⁹ and R ¹¹ are the same as or different from each other, and are each halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, halo aralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkylene having 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxyylene unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; When two or more R ⁹ or R ¹¹ are present, they are the same as or different from each other; R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ are the same as or different from each other, and are each hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aralkyl of 7 to 15 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Carbonyloxy unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; When two or more R ^{12 's} are present, they are the same or different from each other. The cyclic olefin resin film according to claim 3, wherein the cyclic olefin addition polymer is an addition polymer synthesized from 1 to 50 mol% of the monomer represented by the formula (1) and 0.1 to 99 mol% of the monomer represented by the formula (2). The method of claim 1, wherein the acid is an organic or inorganic acid; Substances which act as acids at 50 ° C .; And a cyclic olefin resin film selected from the group consisting of a substance which acts as an acid in the presence of water or steam. The method of claim 6, wherein the organic or inorganic acid is hydrochloric acid, sulfuric acid, hydrofluoric acid, tetrafluoroboric acid, phosphoric acid, phosphoric acid, organic carboxylic acid ( A cyclic olefin resin film selected from the group consisting of organic carboxylic acid, organic sulfonic acid, organic sulfinic acid, and organic phosphoric acid. The method of claim 6, wherein the material that acts as an acid at 50 ° C is aromatic sulfonium salt (aromatic sulfonium salt), aromatic ammonium salt (aromatic ammonium salt), aromatic pyridinuim salt (aromatic pyridinuim salt), aromatic phosphonium salt ), Aromatic iodonium salt, hydrazinium salt and iron salt of metallocene, which are the counter anions BF _4- , PF _6- , AsF _6- , SbF ₆ -and B (C ₆ F ₅ ) ₄ -It is a cyclic olefin resin film which is used as an acid using at least one selected from. The method according to claim 6, wherein the substance which acts as an acid in the presence of water or steam is trialkylphosphite, triarylphosphite, dialkylphosphite, monoalkylphosphite, hypoalkylphosphite, hypo Phosphites, esters of an organic carboxylic acid, secondary or tertiary alcohols and trialkylsilyl esters of organic carboxylic acids acid) is selected from the group consisting of cyclic olefin resin film. The cyclic olefin resin film of claim 1, wherein the acid crosslinking agent is included in an amount of 1 to 10 wt% based on the cyclic olefin addition polymer. The method according to claim 1, wherein the base crosslinking agent R ²¹ -NH ₂ , NH ₂ -R ²¹ -NH ₂ , C ₆ H ₅ -R ²¹ -NH ₂ , R ^{21 '} R ²¹ -NH ₂ , Si (R ²¹ ) ₃ -NH ₂ , R ²¹ -NHR ²² , NHR ²² -R ²¹ -NH ₂ , C ₆ H ₅ -R ²¹ -NHR ²² , R ^{21 '} R ²¹ -NHR ²² , Si (R ²¹ ) ₃ -NHR ²² , Si Comprising a base represented by (R ²¹ ) ₃ -NH-Si (R ²² ) _3, DBU, DBN, TMG, alkyl imidazoles, DABCO, and NAMs, wherein R ²¹ and R ²² Is a C1-C8 hydrocarbon, R21 ^' is a cyclic hydrocarbon resin film. The cyclic olefin resin film of claim 1, wherein the base crosslinking agent is included in an amount of 1 to 30 wt% based on the cyclic olefin additive polymer. a) adding an acid or base crosslinking agent to a cyclic olefin based addition polymer comprising a cyclic olefinic monomer crosslinkable by an acid or base crosslinking agent, and b) molding the mixture obtained in step a) into a film The manufacturing method of the cyclic olefin resin film containing. The plastic substrate containing the cyclic olefin resin film of any one of Claims 1-12. An electronic device comprising the cyclic olefin resin film of claim 1.

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