KR20110116540A - Cyclic olefin-based resin film and method of producting the same - Google Patents

Abstract

The present invention relates to a cyclic olefin resin film and a method for manufacturing the same, and specifically has an advantage of significantly improving the coefficient of thermal expansion of the film by improving the degree of crosslinking to an appropriate level or more.

Description

Cyclic olefin resin film and its manufacturing method {CYCLIC OLEFIN-BASED RESIN FILM AND METHOD OF PRODUCTING THE SAME}

The present invention relates to a cyclic olefin resin film and a method for producing the same.

Since the cyclic olefin polymer has a bulky substitution structure in the main chain skeleton, it is amorphous and has excellent transparency and heat resistance, and has a low photoelastic coefficient, low hygroscopicity, acid resistance, alkali resistance and high electrical insulation, so that it can be used for display applications, optical lenses, optical disks, It is known as a material which can be applied to optical fibers, transparent conductive film substrate applications and the like.

Films formed of conventional cyclic olefin polymers are basically inflexible and therefore easily broken or broken off due to their toughness. In addition, thermally unstable, there was a lot of problems to use as a plastic substrate, a matrix, an optically anisotropic film, even in the coefficient of thermal expansion (CTE).

Korean Patent Publication No. 2008-73168 discloses a technique for forming a film after adding an acid or a base crosslinking agent to a solution containing a cyclic olefin-based polymer, but in the case of a film formed by such a method, transparency and haze In addition to being unsuitable for use for optical films and flexible substrates, the film formed has difficulty in improving physical properties due to insufficient crosslinking.

The present invention provides a cyclic olefin resin film and a method for producing the same which improve the degree of crosslinking and significantly improve the physical properties including the coefficient of thermal expansion.

One embodiment of the present invention is a cyclic olefin resin film having a value of 2 or less crosslinking degree calculated by the following formula (1).

<Equation 1>

(In Formula 1, the 770cm ^-1 region represents the absorbance value by the siloxane reaction group, and the 850cm ^-1 region represents the absorbance value by the carbosilyl reaction group.)

According to another embodiment of the present invention, the cyclic olefin resin film is a cyclic olefin resin film having a linear expansion ratio of 70 ppm / ° C. or less.

Another embodiment of the present invention to dissolve a norbornene-based polymer in a solvent to prepare a polymer solution (S1); Coating the polymer solution on a substrate and then drying to prepare a film (S2); And it is a method for producing a cyclic olefin resin film comprising the step (S3) of the film acid treatment.

Another embodiment of the present invention is the drying step in the step S2 of the cyclic olefin resin film of the first drying for 1 to 24 hours at 15 to 50 ℃ and then secondary drying for 5 minutes to 1 hour at 100 to 300 ℃ It is a manufacturing method.

Another embodiment of the present invention is a method for producing a cyclic olefin resin film comprising the step (S2-1) of acid-processing the film produced after the first drying process.

According to another embodiment of the present invention, the acid treatment step is a method for producing a cyclic olefin resin film treated with an acid of 1 to 50 w / w%.

According to another embodiment of the present invention, the acid treatment process is a method for producing a cyclic olefin resin film which is performed at 10 to 50 ° C. for 1 minute to 1 hour.

According to another embodiment of the present invention, the acid used in the acid treatment is any one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphorous acid, and combinations thereof, carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, and the like. It is a manufacturing method of the cyclic olefin resin film used individually or in mixture of any organic acid selected from the group which consists of a combination.

Another embodiment of the present invention is a method of producing a cyclic olefin resin film using any one or more of the solvent in the step S1 selected from toluene, xylene, dichloromethane and tetrahydrofuran.

Another embodiment of the present invention is a norbornene-based polymer is a method for producing a cyclic olefin resin film represented by the formula (1).

<Formula 1>

Wherein R 1 to R 8 each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a polar group, a single bond or a divalent linking group having a linking group including hydrogen, oxygen, nitrogen, silicon or sulfur. Group, silane group, halogen atom,

At least one of R1 to R4 includes a silane group,

k and i are integers from 0 to 3,

n has a value of 0 to less than 1, and m + n is 1).

Another embodiment of the present invention is a method for producing a cyclic olefin resin film having a molar ratio of m: n in the general formula (1) is 1 to 100: 0 to 99.

Another embodiment of the present invention is a norbornene-based polymer is a method for producing a cyclic olefin resin film having a weight average molecular weight of 10,000 to 1,000,000.

Another embodiment of the present invention is a cyclic olefin resin film prepared by the above production method.

According to another embodiment of the present invention, the cyclic olefin resin film is a cyclic olefin resin film having a value of 2 or less in the degree of crosslinking calculated by the following Equation 1.

<Equation 1>

(In Formula 1, the 770cm ^-1 region represents the absorbance value by the siloxane reaction group, and the 850cm ^-1 region represents the absorbance value by the carbosilyl reaction group.)

According to another embodiment of the present invention, the cyclic olefin resin film is a cyclic olefin resin film having a linear expansion ratio of 70 ppm / ° C. or less.

The cyclic olefin resin film and the manufacturing method thereof according to the present invention has an advantage of significantly improving the thermal expansion coefficient of the film by improving the degree of crosslinking to an appropriate level or more.

1 is a graph showing the results measured by an FT-IR spectrophotometer of the film prepared according to Example 1.
Figure 2 is a graph showing the results measured by the FT-IR spectrophotometer of the film prepared according to Example 2.
Figure 3 is a graph showing the results measured by the FT-IR spectrophotometer of the film prepared according to Example 6.
Figure 4 is a graph showing the results measured by the FT-IR spectrophotometer of the film prepared according to Comparative Example 1.
5 is a graph showing the results measured by an FT-IR spectrophotometer of the film prepared according to Comparative Example 4.

According to one embodiment of the present invention, it is to provide a cyclic olefin resin film having a value of 2 or less crosslinking degree calculated by the following formula (1).

<Equation 1>

(In Formula 1, the 770cm ^-1 region represents the absorbance value by the siloxane reaction group, and the 850cm ^-1 region represents the absorbance value by the carbosilyl reaction group.)

The degree of crosslinking according to the present invention can be defined as a value calculated by Equation 1, and the value is 2 or less, preferably 1 or less, and the lower the degree of crosslinking, the lower the lower limit value is meaningless. When the degree of crosslinking is within the above range, the thermal expansion coefficient of the film may be reduced.

Specifically, the cyclic olefin resin film is manufactured using a polymer, but an important factor for improving physical properties of the cyclic olefin resin film is that it is important to sufficiently crosslink the reaction between the polymer chains of the cyclic olefin resin film. .

The degree of crosslinking is defined by the formula 1 are prepared by using a cyclic olefin resin-based film FT- infrared spectrophotometer (FT-IR spectrophotometer) by measuring the absorbance (Absorbance) value of 770㎝ ^-1 region and a region 850㎝ ^-1 The obtained experimental value can be obtained by substituting Equation 1 above, and the degree of crosslinking reaction can be known from the crosslinking degree.

In particular, 770㎝ ^-1 areas and it is important to measure the value of absorbance (Absorbance) Area of 850㎝ ^-1, 770cm ^-1 region represents the absorbance obtained from the siloxane reactive groups is applied to the olefin-based resin film area is 850cm ^-1 Absorption value by the carbosilyl reaction group is a value that indicates the absorbance value decreases as the content of the siloxane reaction group decreases as the crosslinking reaction progresses, while the absorbance value remains the same as the content of the carbosilyl reaction group does not change. Because you can check.

When the value of the degree of crosslinking is 2 or less, the crosslinking reaction between the polymer chains of the cyclic olefin resin film proceeds sufficiently, so that the crosslinking between the siloxane reaction groups of the polymer proceeds, and thus the fluidity of the film can be remarkably reduced even if a thermal shock is applied. Physical properties including coefficients can be significantly improved.

The cyclic olefin resin film has a linear expansion coefficient of 70 ppm / 占 폚 or less, preferably 10 to 50 ppm / 占 폚.

When the linear expansion rate is within the above range, there is no stretching of the film even when a thermal shock is applied, and there is an advantage that it can be applied to various heat-resistant materials.

According to an embodiment of the present invention, dissolving a norbornene-based polymer in a solvent to prepare a polymer solution (S1), coating the polymer solution on a substrate and drying to prepare a film (S2) and the film It is to provide a method for producing a cyclic olefin resin film comprising an acid treatment step (S3).

First, a norbornene-based polymer is dissolved in a solvent to prepare a polymer solution (S1).

The norbornene-based polymer is represented by the following formula (1).

<Formula 1>

In Formula 1, R1 to R8 each independently have a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a polar group, a single bond or a divalent linking group having a linking group including hydrogen, oxygen, nitrogen, silicon or sulfur. Selected from an aromatic group, a silane group and a halogen atom, at least one of R1 to R4 includes a silane group, k and i are integers of 0 to 3, n has a value of 0 to less than 1, and m + n is It is one.

The molar ratio of m: n is preferably 1 to 100: 0 to 99. When the molar ratio of m: n is within the above range, an appropriate crosslinking degree can be selected while changing the molar ratio, and thus there is an advantage that the desired physical properties can be selectively applied.

Examples of the linking group containing hydrogen, oxygen, nitrogen, silicon, or sulfur include a carbonyl group, an oxycarbonyl group, a sulfone group, an ether bond, a thioether bond, an imino group, an amide bond, a siloxane bond, and the like. It may be a connector.

The substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms includes any one alkyl group selected from the group consisting of methyl group, ethyl group, propyl group, and combinations thereof; Any one cycloalkane group selected from the group consisting of a cyclopentyl group, a cyclohexyl group, and a combination thereof; It is preferable to include any one or more selected from any one alkenyl group selected from the group consisting of vinyl group, aryl group, propenyl group and combinations thereof.

The substituted or unsubstituted hydrocarbon group is preferably bonded directly to the ring structure, or is bonded through a linking group.

Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcohol cicarbonyl group, a cyano group, an amide group, an imide group, an amino group, an acyl group, a sulfonyl group, and a carboxyl group. More specifically, the alkoxy group includes a methoxy group, an ethoxy group, and the like, and the carbonyloxy group includes an alkylcarbonyloxy group such as an acetoxy group and propionyloxy group, an ethoxycarbonyl group, and the like. The primary amino group is mentioned.

In the aromatic group having a single bond or a divalent linking group, the divalent linking group is an alkylene group, particularly 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, for example, methylene group, ethylene group, trimethylene group, arylene group, oxyalkyl A hetero group, such as a ethylene group, an oxy arylene group, an oxy carbonyl group, an iminocarbonyl group, a carbonyl group, an acetylene group, a ureylene group, sulfur, oxygen, an amino group, etc. are mentioned. Moreover, you may combine 2 or more of these coupling groups.

Through such a linking group, an aromatic group should be included, which includes one hydrogen leaving body of the aromatic compound.

Specific examples of the 1 hydrogen leaving body include benzene, pentarene, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoranthene, acefenanthrene, prephenylene, pyrene , Chrysene, naphthacene, flyaden, pisene, perylene, penpafen, pentacene, tetraphenylene, hexaphene, pensasene, rubisen, coronene, trinaphthylene, heptaphene, heptacene, pyracene, Any one monocyclic compound selected from the group consisting of ovaren and combinations thereof, thiophene, thianthrene, furan, pyran, isobenzofuran, chromen, xanthene, phenoxathiine, pyrrole, imidazole, pyrazole, Isothiazole, Isoxazole, Pyridine, Pyridine, Pyrimidine, Pyridinine, Indolidine, Isoindole, Indole, Indazole, Purine, Quinolidine, Isoquinone, Quinoline, Phthazazine, Naphthyridine, Keno Chisarin, cynoline, pteridine, carbazole, betacarboline, phenanthilidine, acri It is preferred to have any one heterocyclic compound selected from the group consisting of dine, perimidine, phenanthroline, phenadine, phenarzin, phenothiadine, prazan, phenocyazine, and combinations thereof and substituents thereof. .

The silane group is any one selected from the group consisting of any one alkoxysilyl group or trimethylsilyl group, triethylsiligo group and combinations thereof selected from the group consisting of trimethoxysilyl group, triethoxysilyl group and combinations thereof. It is preferable that it is a triorgano siloxy group.

Fluorine, chlorine, bromine, etc. are mentioned as said halogen atom.

The norbornene-based polymer is preferably a weight average molecular weight of 10,000 to 1,000,000 in terms of suitable for forming a film. When the value is lower than the numerical value, the film is not formed without breaking, and when the value is higher than the numerical value, there is a disadvantage in that the viscosity becomes difficult to control.

The solvent is preferably used at least one selected from toluene, xylene, dichloromethane and tetrahydrofuran.

The said polymer solution may mix | blend various additives as needed.

Examples of the additive include fillers, antioxidants, phosphors, ultraviolet light absorbers, antistatic agents, light stabilizers, near infrared absorbers, colorants such as dyes and pigments, lubricants, plasticizers, flame retardants, and crosslinking agents. Examples of the filler include metal oxides such as silicon, titanium, aluminum, and zirconium.

Subsequently, the polymer solution is coated on a substrate and then dried to prepare a film (S2).

The coating process may be generally adopted as a coating process well known in the art to which the present invention pertains, for example, bar coating, spin coating, and gravure coating.

The drying process is preferably first drying at 15 to 50 ℃ for 1 to 24 hours and then second drying at 100 to 300 ℃ for 5 minutes to 1 hour in order to improve the roughness of the film surface.

At this time, the film may be subjected to acid treatment after the first drying process (S2-1).

The acid treatment step may be carried out by immersing the produced film in acid, or may be carried out by spraying acid on the film.

The acid treatment step is preferable in terms of obtaining a sufficient degree of crosslinking by treatment with an acid of 1 to 50 w / w%. In this case, the acid is diluted with distilled water in order to control the concentration of the acid, and the content of the acid indicates the weight of the acid component in the total weight, except for the acid, which means water.

The acid may be any one organic acid selected from the group consisting of any one inorganic acid, carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, and combinations thereof selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphorous acid, and combinations thereof. Or it can mix and use.

The acid treatment step is preferably performed at 10 to 50 ° C. for 1 minute to 1 hour in order to ensure processability and obtain sufficient crosslinking degree.

At this time, the washing step after the acid treatment step may be further performed. The washing process may be performed by dipping or spraying using distilled water at 10 to 50 ° C. for 1 to 10 minutes to sufficiently wash the acid.

Subsequently, an acid treatment of the film produced after the secondary drying process is performed (S3).

The acid treatment step can be carried out in the same manner as described above.

Acid treatment process according to the present invention can be carried out after the first drying, acid treatment after the first drying, and then acid treatment again after the second drying, may be acid treatment after the first and second drying.

In addition, the acid treatment process according to the present invention can be carried out in a state attached on the substrate, a state released from the substrate or a part attached to the substrate.

In the present invention, the cyclic olefin resin film is subjected to an acid treatment after drying to increase the degree of crosslinking, thereby obtaining an effect of excellent thermal properties.

According to one embodiment of the present invention, to provide a cyclic olefin resin film prepared according to the above-described manufacturing method.

The value of the crosslinking degree computed by following formula 1 of the said cyclic olefin resin film is 2 or less, Preferably it is preferable that it is 1 or less.

<Equation 1>

(In Formula 1, the 770cm ^-1 region represents the absorbance value by the siloxane reaction group, and the 850cm ^-1 region represents the absorbance value by the carbosilyl reaction group.)

The cyclic olefin resin film having a value having a crosslinking degree of 2 or less includes the same content as described above.

The cyclic olefin resin film has a linear expansion coefficient of 70 ppm / ° C or lower, preferably 10 to 50.

The cyclic olefin resin film having a value of the linear expansion coefficient of 70 ppm / ° C. or less includes the same contents as described above.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

Synthetic example  One: Allyl acetate Of norbornene (AA-NB)  Produce

DCPD (dicyclopentadiene, Aldrich, 800 ml, 5.97 mol) and allyl acetate (Aldrich, 2,247 ml, 11.93 mol) were put into a 4L high pressure reactor, and the temperature was raised to 220 degreeC. After reacting for 2 hours with stirring at 500 rpm, the reaction mixture was cooled to room temperature by cooling the cooling water and transferred to a vacuum distillation apparatus. Distillation under reduced pressure to 1 torr using a vacuum pump to obtain the allyl acetate norbornene product at 60 ℃ (yield 44%).

Synthetic example  2: Triethoxysilyl Of norbornene (TES-NB)  Produce

DCPD (dicyclopentadiene, Aldrich, 352 mL, 3.63 mol) and vinyltriethoxysilane (Aldrich, 1,098 mL, 5.25 mol) were put into a 4L high pressure reactor, and the temperature was raised to 220 degreeC. After reacting for 2 hours with stirring at 500 rpm, the reaction mixture was cooled to room temperature by cooling the cooling water and transferred to a vacuum distillation apparatus. Distillation under reduced pressure to 1 torr using a vacuum pump to give the triethoxysilyl norbornene product at 65 ℃ (yield 35%).

Synthetic example  3: Trimethoxysilyl  profile Methacrylate Of norbornene (TMSPMA-NB)  Produce

DCPD (dicyclopentadiene, Aldrich, 462 ml, 3.45 mol) and trimethoxysilyl propyl methacrylate (across, 1,802 ml, 7.58 mol) were put into a 4 L high pressure reactor, and the temperature was raised to 200 degreeC. After reacting for 2 hours with stirring at 500 rpm, the reaction mixture was cooled to room temperature by cooling the cooling water and transferred to a vacuum distillation apparatus. Distillation under reduced pressure to 1 torr using a vacuum pump to give trimethoxysilyl propyl methacrylate norbornene product at 95 ℃ (25% yield).

Manufacturing example  One: Allyl acetate Norborneen Of Triethoxysilyl Norborneen  Addition copolymer ( P1 ) Produce

15.3 g (0.0597 mol) of allyl acetate norbornene of Synthesis Example 1 and 39.7 g of Triethoxysilyl norbornene of Synthesis Example 2 as monomers in a 1,000 ml Schlenk flask 0.239 mol) and purified toluene were added together with 161 mL as a solvent. The flask was dissolved in 5 ml of CH ₂ Cl _{2 with} 13.40 mg of palladium (II) acetate and 16.73 mg of tricyclohexyl phosphine as cocatalyst and dimethylanilinium tetra as cocatalyst. 95.62 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate was added thereto and then copolymerized with stirring at 100 ° C. for 2 hours.

After 2 hours, the reaction was terminated and the reactant was cooled to room temperature. Toluene was added to make the polymer solution uniform. Then, excess acetone and methanol were added to obtain a white copolymer powder. The powder was filtered through a filter paper and a glass funnel and dried in a vacuum oven maintained at 70 ° C. for 24 hours to obtain 51.7 g of a copolymer of allyl acetate norbornene and triethoxysilyl norbornene. %). The number average molecular weight (Mn) of this copolymer was 84,000, and the weight average molecular weight (Mw) was 345,000.

Manufacturing example  2: Allyl acetate Norborneen Of Triethoxysilyl Norborneen  Addition copolymer ( P2 ) Produce

21.9 g (0.132 mol) of allyl acetate norbornene of Synthesis Example 1 and 33.8 g of Triethoxysilyl norbornene of Synthesis Example 2 as monomers in a 1,000 ml Schlenk flask ( 0.132 mol) and purified toluene were added together with 164 mL as a solvent. The flask was dissolved in 5 ml of CH ₂ Cl _{2 with} 11.84 mg of palladium (II) acetate and 14.79 mg of tricyclohexyl phosphine as a promoter and dimethylanilinium tetra as a cocatalyst. 84.52mg of dimethylanilinium tetrakis (pentafluorophenyl) borate was added thereto, followed by copolymerization with stirring at 100 ° C for 2 hours.

After 2 hours, the reaction was terminated and the reactant was cooled to room temperature. Toluene was added to make the polymer solution uniform. Then, excess acetone and methanol were added to obtain a white copolymer powder. The powder was filtered through a filter paper and a glass funnel and dried in a vacuum oven maintained at 70 ° C. for 24 hours to obtain 49.7 g of a copolymer of allyl acetate norbornene and triethoxysilyl norbornene. %). The number average molecular weight (Mn) of this copolymer was 60,000, and the weight average molecular weight (Mw) was 328,000.

Manufacturing example  3: Triethoxysilyl Norborneen  polymer( P3 ) Produce

Into a 1,000 ml Schlenk flask, 51 g (0.199 mol) of triethoxysilyl norbornene of Synthesis Example 2 as a monomer and purified toluene were added together as a solvent to 200 ml. The flask was dissolved in 5 ml of CH ₂ Cl _{2 with} 44.65 mg of palladium (II) acetate and 55.78 mg of tricyclohexyl phosphine as cocatalyst and dimethylanilinium tetra as cocatalyst. 318.7 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate were added thereto and then polymerized with stirring at 100 ° C. for 2 hours.

After 2 hours, the reaction was terminated and the reactant was cooled to room temperature. Toluene was added to make the polymer solution uniform. Then, excess acetone and methanol were added to obtain a white copolymer powder. The powder was filtered through a filter paper and a glass funnel and dried in a vacuum oven maintained at 70 ° C. for 24 hours to obtain 32.4 g of a polymer of triethoxysilyl norbornene (64 wt% based on the total amount of monomer added). The number average molecular weight (Mn) of this copolymer was 265,000, and the weight average molecular weight (Mw) was 456,000.

Manufacturing example  4: Allyl acetate Norborneen Of Trimethoxysilyl  profile Methacrylate Norborneen  Addition copolymer ( P4 ) Produce

33.24 g (0.20 mol) of allyl acetate norbornene of Synthesis Example 1 and trimethoxysilyl propyl methacrylate norbornene (Trimethoxysilyl propyl) of Synthesis Example 3 as monomers in a 1000 ml Schlenk flask 15.6 g (0.05 mol) of methacrylate norbornene and purified toluene were added together with 142 ml as a solvent. The flask was dissolved in 5 ml of CH ₂ Cl _{2 with} 11.23 mg of palladium (II) acetate and 14.02 mg of tricyclohexyl phosphine as cocatalyst and dimethylanilinium tetra as cocatalyst. 80.12 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate was added thereto and copolymerized with stirring at 100 ° C. for 2 hours.

After 2 hours, the reaction was terminated and the reactant was cooled to room temperature. Toluene was added to make the polymer solution uniform. Then, excess acetone and methanol were added to obtain a white copolymer powder. The powder was filtered through a filter paper and a glass funnel and dried in a vacuum oven maintained at 70 ° C. for 24 hours to obtain 45.3 g of a copolymer of allyl acetate norbornene and trimethoxysilyl propyl methacrylate norbornene. 93 wt% based on total monomer). The number average molecular weight (Mn) of this copolymer was 74,000, and the weight average molecular weight (Mw) was 370,000.

Manufacturing example  5: 5- Aryl acetate -2- Norborneen ( AA - NB Polymers polymerized only with monomers P5 ) Produce

The monomer was prepared in the same manner as in Preparation Example 3, except that 51 g (0.199 mol) of aryl acetate norbornene of Synthesis Example 1 was used and the reaction time was performed for 6 hours. At this time, 44.9 g (yield 88%) of aryl acetate norbornene polymers were obtained. The number average molecular weight (Mn) of this copolymer was 223,000, and the weight average molecular weight (Mw) was 340,000.

Example  One

Dichloro using polymer (P1) in which the 5-arylacetate-2-norbornene (AA-NB) monomer and the 5-triethoxysilyl-2-norbornene (TES-NB) monomer were copolymerized at a molar ratio of 8: 2. A polymer solution was prepared at 10% by weight in methane, sprinkled on a flat glass substrate, and then pushed out with a flat blade at intervals of 1200 μm. The solvent was evaporated at room temperature for 6 hours (primary drying) and the film was released from the glass substrate. The release film was inserted into a tenter where both sides of the film were exposed, soaked in 37 w / w% hydrochloric acid solution for 10 minutes, and then vacuum dried (secondary drying) at 250 ° C. for 1 hour to obtain a transparent film.

Example  2

Except that 5-arylacetate-2-norbornene (AA-NB) monomers and 5-triethoxysilyl-2-norbornene (TES-NB) monomers were polymerized in a 5: 5 molar ratio (P2). Then, a transparent film was obtained in the same manner as in Example 1.

Example  3

A transparent film was obtained in the same manner as in Example 1 except for using the polymer (P3) polymerized with only 5-triethoxysilyl-2-norbornene (TES-NB) monomer.

Example  4

Polymer (P4) polymerized using 5-trimethoxysilylpropylmethacrylate-2-norbornene (TMSPMA-NB) monomer instead of 5-triethoxysilyl-2-norbornene (TES-NB) monomer A transparent film was obtained in the same manner as in Example 1 except that it was used.

Example  5

Dichloro by using a polymer (P2) in which the 5-arylacetate-2-norbornene (AA-NB) monomer and the 5-triethoxysilyl-2-norbornene (TES-NB) monomer were copolymerized at a molar ratio of 5: 5. A polymer solution was prepared in 10% by weight in methane, and the polymer solution was transparent in the same manner as in Example 1, except that 5% by weight of silicon oxide (Degussa Aerosil S200 product) was added and dispersed. A film was obtained.

Example  6

Dichloro by using a polymer (P2) in which the 5-arylacetate-2-norbornene (AA-NB) monomer and the 5-triethoxysilyl-2-norbornene (TES-NB) monomer were copolymerized at a molar ratio of 5: 5. Except for using a polymer solution prepared by dispersing a polymer solution at 10% by weight in methane and adding 5% by weight of a crosslinking agent (3-aminopropyltriethoxysilane, manufactured by Aldrich). A transparent film was obtained in the same manner as in 1.

Comparative example  One

A film was obtained in the same manner as in Example 2 except that the acid treatment was not performed.

Comparative example  2

Propylene using a polymer (P2) in which a 5-arylacetate-2-norbornene (AA-NB) monomer and a 5-triethoxysilyl-2-norbornene (TES-NB) monomer were copolymerized in a 5: 5 molar ratio. A solution was prepared in 10% by weight of glycol monomethyl ether acetate (PGMEA), and a solution of PGMEA in which 5% by weight of hydrochloric acid was dissolved was slowly dropped, followed by shaking for 10 minutes. The film was obtained in the same manner as.

Comparative example  3

A film was obtained in the same manner as in Example 2, except that 10w / w% hydrochloric acid was used instead of 37w / w% hydrochloric acid during acid treatment.

Comparative example  4

A transparent film was obtained in the same manner as in Example 2 except for using the polymer (P5) polymerized with only 5-aryl acetate-2-norbornene (AA-NB) monomer.

Property evaluation

The physical properties of the films prepared according to Examples 1 to 6 and Comparative Examples 1 to 4 were measured by the following measuring methods, and the results are shown in Table 1 below.

1) coefficient of thermal expansion

Using TMA (Perkin Elmer Co., Diamond TMA model), cut the film into 20mm length and 4mm length, mount it on the probe, and apply the temperature of 100mN from 30 ℃ to 300 ℃ at a heating rate of 10 ℃ / min. After the 1st temperature increase, it cools to 30 degreeC, and heats up 2nd degree from 30 degreeC to 300 degreeC at the temperature increase rate of 10 degreeC / min, and calculates the thermal expansion coefficient between 40 degreeC and 250 degreeC at the time of a secondary temperature rising in ppm / degreeC unit. .

2) Transmittance and Haze

Using a haze meter (Nippon Denshoku, NDH2000 model), the transmittance and the haze of the film were measured using a D65 light source using Method 3. The wavelength is based on 550nm.

3) IR

Absorbance value of 500 ~ 4000cm ^-1 region is measured by reflection mode (with Smart Miracle accessory) using FT-IR spectrophotometer (Avatar360 FT-IR from Thermo Nicolet).

Thickness (㎛) Permeability (%) Haze (%) Degree of crosslinking Thermal expansion coefficient (ppm / ℃) Example 1 100 ± 5 92 <1 <1 46 Example 2 100 ± 5 92 <1 <1 41 Example 3 100 ± 5 92 <1 <1 35 Example 4 100 ± 5 92 <1 <1 40 Example 5 120 ± 5 92 <1 <1 32 Example 6 110 ± 5 92 <1 <1 36 Comparative Example 1 100 ± 5 90 20 9.4 142 Comparative Example 2 80 ± 5 87 30 8.2 135 Comparative Example 3 100 ± 5 90 15 7.8 131 Comparative Example 4 100 ± 5 92 <1 - 110

The norbornene-based polymer containing a silane group was used to perform a crosslinking reaction between the polymers through acid treatment, and the degree of crosslinking was confirmed by using IR.

As shown in Table 1, Comparative Examples 1 to 3 showed a significantly higher crosslinking degree and thermal expansion coefficient than those of Examples 1 to 6, and Comparative Example 4 did not have a silane group in the 770cm- ¹ region. Absorbance value could not be obtained and crosslinking degree was unknown. Therefore, in Comparative Examples 1 to 4, the thermal expansion coefficient of the film is insignificant when the crosslinking is not performed or the degree of crosslinking is insufficient. However, Examples 1 to 6 significantly improve the thermal expansion coefficient when the crosslinking is above an appropriate level, and thus the plastic substrate or heat resistance It could apply to the required film. Such films have very good thermal properties and are optically clear.

From this, it can be seen that the cyclic olefin resin film according to the present invention can be used for various electrical applications such as an optical film, a flexible substrate, and a general substrate.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (15)

The cyclic olefin resin film whose value of the crosslinking degree computed by following formula 1 is 2 or less.
<Equation 1>

(In Formula 1, the 770cm ^-1 region represents the absorbance value by the siloxane reaction group, and the 850cm ^-1 region represents the absorbance value by the carbosilyl reaction group.)
The cyclic olefin resin film of claim 1, wherein the cyclic olefin resin film has a linear expansion coefficient of 70 ppm / ° C or less. Dissolving norbornene-based polymer in a solvent to prepare a polymer solution (S1);
Coating the polymer solution on a substrate and then drying to prepare a film (S2); And
A method of producing a cyclic olefin resin film comprising the step of acid treating the film (S3). The method of claim 3, wherein the drying step in the step S2 is first dried at 15 to 50 ° C. for 1 to 24 hours, and then secondly dried at 100 to 300 ° C. for 5 minutes to 1 hour. . The method of manufacturing a cyclic olefin resin film according to claim 4, further comprising an acid treatment (S2-1) of the produced film after performing the first drying process. The method for producing a cyclic olefin resin film according to claim 3 or 5, wherein the acid treatment step is performed using an acid of 1 to 50 w / w%. The method for producing a cyclic olefin resin film according to claim 3 or 5, wherein the acid treatment step is performed at 10 to 50 ° C for 1 minute to 1 hour. According to claim 3 or 5, wherein the acid used in the acid treatment step is any one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphorous acid and combinations thereof, carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid and A method for producing a cyclic olefin resin film used alone or in combination of any one of the organic acids selected from the group consisting of a combination of these. The method of claim 3, wherein the solvent in the step S1 using any one or more selected from toluene, xylene, dichloromethane and tetrahydrofuran. The method of claim 3, wherein the norbornene-based polymer is represented by the following formula (1).

<Formula 1>

Wherein R 1 to R 8 each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a polar group, a single bond or a divalent linking group having a linking group including hydrogen, oxygen, nitrogen, silicon or sulfur. Group, silane group, halogen atom,
At least one of R1 to R4 includes a silane group,
k and i are integers from 0 to 3,
n has a value of 0 to less than 1, and m + n is 1). The method of claim 10, wherein the molar ratio of m: n in Chemical Formula 1 is 1 to 100: 0 to 99. The method of claim 10, wherein the norbornene-based polymer has a weight average molecular weight of 10,000 to 1,000,000. The cyclic olefin resin film produced according to any one of claims 3 to 12. The cyclic olefin resin film according to claim 13, wherein the cyclic olefin resin film has a value of 2 or less in the degree of crosslinking calculated by the following formula (1).
<Equation 1>

(In Formula 1, the 770cm ^-1 region represents the absorbance value by the siloxane reaction group, and the 850cm ^-1 region represents the absorbance value by the carbosilyl reaction group.)
The cyclic olefin resin film of claim 13, wherein the cyclic olefin resin film has a linear expansion coefficient of 70 ppm / ° C or less.

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