KR101619529B1 - Cyclic olefin-based resin film and method of producting the same - Google Patents

Abstract

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

Description

TECHNICAL FIELD [0001] The present invention relates to a cyclic olefin resin film and a method for producing the same.

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

Since the cyclic olefin polymer has a bulky substitution structure in the backbone skeleton, it has amorphous, excellent transparency and heat resistance, low photoelastic coefficient, low hygroscopicity, acid resistance, alkalinity and high electrical insulation, Optical fibers, transparent conductive film substrates, and the like.

The film formed from the conventional cyclic olefin-based polymer is basically fragile due to low flexibility, and toughness is easily broken. In addition, it is thermally unstable and has many problems to be used in a plastic substrate, a matrix, and an optically anisotropic film even in a coefficient of thermal expansion (CTE).

Korean Patent Laid-Open Publication No. 2008-73168 discloses a technique for forming a film by adding an acid or a base cross-linking agent to a solution containing a cyclic olefin-based polymer. However, in the case of a film formed by such a method, transparency decreases and haze And is not suitable for use as an optical film or a flexible substrate. Further, the formed film is not sufficiently crosslinked and thus it is difficult to improve the physical properties.

An object of the present invention is to provide a cyclic olefin based resin film which improves the crosslinking degree and significantly improves the physical properties including the thermal expansion coefficient, and a method for producing the same.

One embodiment of the present invention is a cyclic olefin based resin film having a value of a degree of crosslinking of 2 or less,

<Formula 1>

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

In another embodiment of the present invention, the cyclic olefin based resin film is a cyclic olefin based resin film having a linear expansion coefficient of 70 ppm / DEG C or less.

Another embodiment of the present invention is a process for producing a polymer solution, comprising: (S1) preparing a polymer solution by dissolving a norbornene polymer in a solvent; (S2) coating the polymer solution on a substrate and drying to form a film; And acid treating the film (S3).

In another embodiment of the present invention, in the step S2, the drying step is a step of drying the mixture at a temperature of 15 to 50 DEG C for 1 to 24 hours, followed by drying at 100 to 300 DEG C for 5 minutes to 1 hour Lt; / RTI &gt;

Another embodiment of the present invention is a method for producing an annular olefin based resin film, comprising the step (S2-1) of acid-treating the film produced after the primary drying step.

Another embodiment of the present invention is a method for producing the cyclic olefin based resin film wherein the acid treatment step is carried out using an acid of 1 to 50 w / w%.

Another embodiment of the present invention is a method for producing the cyclic olefin based resin film, wherein the acid treatment is carried out at 10 to 50 DEG C for 1 minute to 1 hour.

Another embodiment of the present invention is characterized in that the acid used in the acid treatment step is any of inorganic acids selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphorous acid and combinations thereof, carboxylic acids, sulfonic acids, Is used singly or in combination with the organic acid.

Another embodiment of the present invention is a method for producing a cyclic olefin based resin film using at least one solvent selected from the group consisting of toluene, xylene, dichloromethane and tetrahydrofuran in the step S1.

In another embodiment of the present invention, the norbornene polymer is a process for producing a cyclic olefin based resin film represented by the following formula (1).

&Lt; Formula 1 >

Wherein R 1 to R 8 each independently represent a substituted or unsubstituted hydrocarbon group having a linking group containing hydrogen, oxygen, nitrogen, silicon or sulfur, a hydrocarbon group having 1 to 10 carbon atoms, a polar group, an aromatic group having a single bond or a divalent linking 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 1.)

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

In another embodiment of the present invention, the norbornene polymer is a process for producing a cyclic olefin based 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 based resin film produced by the above production method.

In another embodiment of the present invention, the cyclic olefin based resin film is a cyclic olefin based resin film having a value of a degree of crosslinking of 2 or less,

<Formula 1>

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

In another embodiment of the present invention, the cyclic olefin based resin film is a cyclic olefin based resin film having a linear expansion coefficient of 70 ppm / DEG C or less.

The cyclic olefin based resin film and the method for producing the same according to the present invention have an advantage of improving the thermal expansion coefficient of the film by improving the degree of crosslinking to an appropriate level or higher.

FIG. 1 is a graph showing the results of FT-IR spectrophotometer of a film produced according to Example 1. FIG.
2 is a graph showing the results of measurement of a film prepared according to Example 2 with an FT-infrared spectrophotometer.
3 is a graph showing the results of measurement of the film prepared according to Example 6 with an FT-infrared spectrophotometer.
4 is a graph showing the results of measurement of a film prepared according to Comparative Example 1 with an FT-infrared spectrophotometer.
5 is a graph showing the results of measurement of a film prepared according to Comparative Example 4 with an FT-infrared spectrophotometer.

According to one embodiment of the present invention, there is provided a cyclic olefin based resin film having a value of a degree of crosslinking of 2 or less,

<Formula 1>

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

The degree of crosslinking according to the present invention can be defined by the value calculated by the above formula 1. The value is preferably 2 or less, preferably 1 or less, and the lower the degree of crosslinking, the better the lower limit value. When the degree of crosslinking is within the above range, the effect of reducing the thermal expansion coefficient of the film can be obtained.

Specifically, the cyclic olefin-based resin film is produced by using a polymer. As an important factor for improving the physical properties of the cyclic olefin-based resin film, it is important to perform a sufficient cross-linking reaction between the polymer chains of the cyclic olefin based 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 Can be obtained by substituting the obtained experimental value into the above formula 1, and the degree of crosslinking reaction can be obtained from the degree of crosslinking.

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 As the value indicating the absorbance value by the carbosilyl reaction group, the content of the siloxane reaction group is decreased and the absorbance value is decreased as the crosslinking reaction progresses. However, since the content of the carbosilyl reaction group is not changed and the absorbance value is the same, the relative crosslinking reaction progress .

When the value of the degree of crosslinking is not more than 2, the crosslinking reaction between the polymer chains of the cyclic olefin based resin film proceeds sufficiently and the cross-linking between the siloxane reaction groups of the polymer progresses, so that the fluidity of the film can be remarkably reduced, The physical properties including the coefficient can be remarkably improved.

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

When the coefficient of linear expansion is within the above range, there is an advantage that the film can be applied to various heat resistant materials because the film does not stretch even if heat shock is applied.

According to an embodiment of the present invention, there is provided a method for manufacturing a polymer electrolyte membrane, comprising: (S1) preparing a polymer solution by dissolving a norbornene polymer in a solvent, (S2) coating the polymer solution on a substrate, And an acid-treating step (S3). The present invention also provides a method for producing the cyclic olefin based resin film.

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

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

&Lt; Formula 1 >

Wherein R1 to R8 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 containing hydrogen, oxygen, nitrogen, An aromatic group, a silane group and a halogen atom, at least one of R 1 to R 4 includes a silane group, k and i are an integer of 0 to 3, n has a value of 0 to less than 1, m + n is Lt; / RTI &gt;

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, it is possible to select the proper degree of crosslinking while changing the molar ratio, so that it is possible to selectively apply desired properties.

Examples of the linking group containing hydrogen, oxygen, nitrogen, silicon or sulfur include a carbonyl group, an oxycarbonyl group, a sphone group, an ether bond, a thioether bond, an imino group, an amide bond and a siloxane bond. Lt; / RTI &gt;

The substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms is any one selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a combination thereof; A cyclopentyl group, a cyclohexyl group, and a combination thereof; A vinyl group, an aryl group, a propenyl group, and a combination of any of these groups.

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

The polar group includes a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcoholic carbonyl 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, examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, an ethoxycarbonyl group and the like. Is a primary amino group.

Examples of the divalent linking group in the aromatic group having a single bond or a divalent linking group include an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, an arylene group, An arylene group, an oxyarylene group, an oxycarbonyl group, an iminocarbonyl group, a carbonyl group, an acetylene group, a ureylene group, a hetero atom such as sulfur or oxygen, and an amino group. It is also possible to combine two or more of these connecting units.

The aromatic group should include an aromatic group through such a linkage, which includes a monohydroxy leaving group of an aromatic compound.

Specific examples of the monovalent hydrogen deficiency include benzene, pentane, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoransenes, , Naphthacene, prazene, picene, perylene, phenaphene, pentacene, tetraphenylene, hexaphene, penascene, rubicene, coronene, trinaphthylene, heptapene, And one or more of the group consisting of thiophene, thianthrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxathiine, pyrrole, imidazole, pyrazole, The present invention relates to a method for producing a compound represented by the general formula (1) or a salt thereof, wherein the compound is selected from the group consisting of isothiazole, isoxazole, pyridine, pyridine, pyrimidine, pyridine, indolidine, isoindole, indole, indazole, purine, quinolidine, isoquinone, quinoline, Xylylene, cyinoline, pteridine, carbazole, betacarbonyl, phenanthyridine, acry It is preferable to have any one of heterocyclic compounds and substituents thereof selected from the group consisting of pyridine, pyrimidine, phenanthroline, phenadine, phenarazine, phenothiazine, prazine, phenoxy and combinations thereof .

The silane group may be any one selected from the group consisting of a trimethoxysilyl group, a triethoxysilyl group, and a combination thereof, or any one selected from the group consisting of a trimethylsilic group, a triethylsilyl group, It is preferably a triorganosiloxy group.

Examples of the halogen atom include fluorine, chlorine, bromine and the like.

The norbornene polymer preferably has a weight average molecular weight of 10,000 to 1,000,000 from the viewpoint of film formation. If it is lower than the above-mentioned value, the film is not formed and broken, and if it is higher than the above-mentioned value, the viscosity becomes high and it becomes difficult to control.

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

The polymer solution may optionally contain various additives.

Examples of the additive include fillers, antioxidants, phosphors, ultraviolet absorbers, antistatic agents, light stabilizers, near infrared absorbers, coloring agents 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 dried to produce a film (S2).

The coating process can be generally applied by a coating process widely known in the field of the present invention, for example, bar coating, spin coating, gravure coating and the like.

The drying process is preferably first dried at 15 to 50 ° C for 1 to 24 hours, and then secondarily dried at 100 to 300 ° C for 5 minutes to 1 hour to improve the roughness of the surface of the film.

At this time, the film produced after the primary drying step can be acid treated (S2-1).

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

The acid treatment is preferably carried out with an acid of 1 to 50 w / w% in view of obtaining a sufficient degree of crosslinking. In order to control the concentration of acid, the acid is diluted in distilled water. The content of acid means the weight of acid component in the total weight and means water other than acid.

The acid may be any organic acid 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, Or may be used in combination.

The acid treatment is preferably carried out at 10 to 50 占 폚 for 1 minute to 1 hour in order to secure fairness and obtain a sufficient degree of crosslinking.

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

Next, a step of acid-treating the film produced after the secondary drying step is performed (S3).

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

The acid treatment process according to the present invention can be carried out after the primary drying. The acid treatment after the primary drying, the acid treatment after the secondary drying, and the acid treatment after the primary and secondary drying can also be performed.

Further, the acid treatment process according to the present invention can be carried out in a state of being attached to a substrate, a state of being released from the substrate, or a state where a part thereof is attached to a substrate.

In the present invention, the cyclic olefin-based resin film is subjected to a drying process followed by an acid treatment to increase the degree of crosslinking to obtain an excellent thermal property.

According to one embodiment of the present invention, there is provided a cyclic olefin based resin film produced by the above-mentioned production method.

The value of the degree of crosslinking of the cyclic olefin based resin film calculated by the following formula 1 is preferably 2 or less, and more preferably 1 or less.

<Formula 1>

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

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

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

The cyclic olefin based resin film having a linear expansion coefficient of 70 ppm / [deg.] 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 The nobonen (AA-NB)  Produce

DCPD (dicyclopentadiene, Aldrich, 800 mL, 5.97 mol) and allyl acetate (Aldrich, 2,247 mL, 11.93 mol) were placed in a 4 L high-pressure reactor and the temperature was raised to 220 ° C. After reacting for 2 hours with stirring at 500 rpm, the reaction product was cooled to room temperature by flowing cooling water, and transferred to a vacuum distillation apparatus. Distillation was carried out at a reduced pressure of 1 torr using a vacuum pump to obtain an allyl acetate norbornene product (yield: 44%) at 60 占 폚.

Synthetic example  2: Triethoxysilyl The nobonen (TES-NB)  Produce

DCPD (dicyclopentadiene, Aldrich, 352 ml, 3.63 mol) and vinyltriethoxysilane (Aldrich, 1,098 ml, 5.25 mol) were placed in a 4 L high-pressure reactor and the temperature was raised to 220 ° C. After reacting for 2 hours with stirring at 500 rpm, the reaction product was cooled to room temperature by flowing cooling water, and transferred to a vacuum distillation apparatus. Distillation was carried out at a reduced pressure of 1 torr using a vacuum pump to obtain a triethoxysilyl norbornene product (yield 35%) at 65 deg.

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

DCPD (dicyclopentadiene, Aldrich, 462 mL, 3.45 mol) and trimethoxysilylpropyl methacrylate (ACROS, 1,802 mL, 7.58 mol) were placed in a 4 L high-pressure reactor and the temperature was raised to 200 ° C. After reacting for 2 hours with stirring at 500 rpm, the reaction product was cooled to room temperature by flowing cooling water, and transferred to a vacuum distillation apparatus. Distillation was carried out at a reduced pressure of 1 torr using a vacuum pump to obtain trimethoxysilylpropyl methacrylate norbornene product (yield: 25%) at 95 占 폚.

Manufacturing example  One: Allyl acetate Nobonen / Triethoxysilyl Nobonen  Addition copolymer ( P1 ) Produce

A 1000 ml Schlenk flask was charged with 15.3 g (0.0597 mol) of the allyl acetate norbornene of Synthesis Example 1 and 39.7 g of triethoxysilyl norbornene (Synthesis Example 2) 0.239 mol) and purified toluene were added together as a solvent in an amount of 161 ml. To this flask was added 13.40 mg of palladium (II) acetate as a catalyst dissolved in 5 ml of CH ₂ Cl ₂ , 16.73 mg of tricyclohexyl phosphine as a cocatalyst, and 0.15 g of dimethylanilinium tetra 95.62 mg of kiss (pentafluorophenyl) borate (Dimethylanilinium tetrakis (pentafluorophenyl) borate) was added and copolymerized with stirring at 100 ° C for 2 hours.

After 2 hours of the reaction, the reaction was terminated and the reaction product was cooled to room temperature. To the toluene was added so that the polymer solution became homogeneous, and excess acetone and methanol were added to obtain a white copolymer powder. The powder was filtered with 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 (yield: 94 wt% %). This copolymer had a number average molecular weight (Mn) of 84,000 and a weight average molecular weight (Mw) of 345,000.

Manufacturing example  2: Allyl acetate Nobonen / Triethoxysilyl Nobonen  Addition copolymer ( P2 ) Produce

21.9 g (0.132 mol) of the allyl acetate norbornene of Synthesis Example 1 and 33.8 g of triethoxysilyl norbornene (Synthesis Example 2) were added to a 1,000 ml Schlenk flask as a monomer 0.132 mol) and purified toluene were added as 164 ml of the solvent. To this flask was added 11.84 mg of palladium (II) acetate (catalyst) dissolved in 5 ml of CH ₂ Cl ₂ , 14.79 mg of tricyclohexyl phosphine as a cocatalyst, and 0.18 g of dimethylanilinium tetra 84.52 mg of kiss (pentafluorophenyl) borate (Dimethylanilinium tetrakis (pentafluorophenyl) borate) was added and copolymerized for 2 hours while stirring at 100 ° C.

After 2 hours of the reaction, the reaction was terminated and the reaction product was cooled to room temperature. To the toluene was added so that the polymer solution became homogeneous, and 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 (yield: 89 wt. %). This copolymer had a number average molecular weight (Mn) of 60,000 and a weight average molecular weight (Mw) of 328,000.

Manufacturing example  3: Triethoxysilyl Nobonen  polymer( P3 ) Produce

In a 1,000 ml Schlenk flask, 51 g (0.199 mol) of the triethoxysilyl norbornene of the above Synthesis Example 2 and purified toluene were added as a monomer in a volume of 200 ml as a solvent. To this flask was added 44.65 mg of palladium (II) acetate as a catalyst dissolved in 5 ml of CH ₂ Cl ₂ , 55.78 mg of tricyclohexyl phosphine as a cocatalyst, and 55.78 mg of dimethylanilinium tetra 318.7 mg of kiss (pentafluorophenyl) borate (Dimethylanilinium tetrakis (pentafluorophenyl) borate) was added and polymerization was carried out at 100 ° C for 2 hours.

After 2 hours of the reaction, the reaction was terminated and the reaction product was cooled to room temperature. To the toluene was added so that the polymer solution became homogeneous, and 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 monomers charged in the yield). This copolymer had a number average molecular weight (Mn) of 265,000 and a weight average molecular weight (Mw) of 456,000

Manufacturing example  4: Allyl acetate Nobonen / Trimethoxysilyl  profile Methacrylate Nobonen  Addition copolymer ( P4 ) Produce

A 1,000-ml Schlenk flask was charged with 33.24 g (0.20 mol) of the allyl acetate norbornene of Synthesis Example 1 with trimethoxysilyl propyl (meth) acrylate of Synthesis Example 3, methacrylate norbornene (15.0 g, 0.05 mol) and purified toluene as a solvent. To the flask was added 11.23 mg of palladium (II) acetate (catalyst) dissolved in 5 ml of CH ₂ Cl ₂ , 14.02 mg of tricyclohexyl phosphine as a cocatalyst, and 0.18 g of dimethylanilinium tetra 80.12 mg of kiss (pentafluorophenyl) borate (Dimethylanilinium tetrakis (pentafluorophenyl) borate) was added and copolymerized with stirring at 100 ° C for 2 hours.

After 2 hours of the reaction, the reaction was terminated and the reaction product was cooled to room temperature. To the toluene was added so that the polymer solution became homogeneous, and excess acetone and methanol were added to obtain a white copolymer powder. The powder was filtered through a filter paper and 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 trimethoxysilylpropyl methacrylate norbornene (yield: 93 wt% based on the total amount of monomers). This copolymer had a number average molecular weight (Mn) of 74,000 and a weight average molecular weight (Mw) of 370,000.

Manufacturing example  5: 5- Aryl acetate -2- Nobonen ( AA - NB ) Polymers Polymerized with Monomers ( P5 ) Produce

Except that 51 g (0.199 mol) of the aryl acetate norbornene of Synthesis Example 1 was used as a monomer and the reaction time was 6 hours. At this time, 44.9 g (yield 88%) of an arylacetate norbornene polymer was obtained. This copolymer had a number average molecular weight (Mn) of 223,000 and a weight average molecular weight (Mw) of 340,000.

Example  One

(P1) copolymerized at a molar ratio of 8: 2 of 5-arylacetate-2-norbornene (AA-NB) monomer and 5-triethoxysilyl-2-norbornene (TES- A 10% by weight solution of the polymer in methane was prepared, sprayed on a flat glass substrate, and pushed out with a flat blade at a distance of 1200 탆. The solvent was evaporated at room temperature for 6 hours (primary drying) and the film was released on a glass substrate. The release film was sandwiched by a tenter exposed on both sides of the film, immersed in a 37 w / w% hydrochloric acid solution for 10 minutes, taken out, and vacuum dried (secondary drying) at 250 캜 for 1 hour to obtain a transparent film.

Example  2

Except that the polymer (P2) copolymerized with 5-aryl acetate-2-norbornene (AA-NB) monomer and 5-triethoxysilyl-2-norbornene (TES- And 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 that a polymer (P3) polymerized only with 5-triethoxysilyl-2-norbornene (TES-NB) monomer was used.

Example  4

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

Example  5

(P2) copolymerized with 5-aryl acetate-2-norbornene (AA-NB) monomer and 5-triethoxysilyl-2-norbornene (TES-NB) monomer in a molar ratio of 5: A polymer solution was prepared in an amount of 10% by weight in methane, and a polymer solution in which 5% by weight of silicon oxide (manufactured by Degussa Co., Aerosil S200) was added and dispersed was used. A film was obtained.

Example  6

(P2) copolymerized with 5-aryl acetate-2-norbornene (AA-NB) monomer and 5-triethoxysilyl-2-norbornene (TES-NB) monomer in a molar ratio of 5: Except that 10% by weight of a polymer solution was prepared in methane, and a polymer solution in which 5% by weight of a crosslinking agent (3-aminopropyltriethoxysilane, manufactured by Aldrich) was added and dispersed was used. 1, a transparent film was obtained.

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

(P2) copolymerized with 5-aryl acetate-2-norbornene (AA-NB) monomer and 5-triethoxysilyl-2-norbornene (TES-NB) monomer in a molar ratio of 5: Except that a 10 wt% solution of PGMEA in glycol monomethyl ether acetate (PGMEA) was prepared, and a PGMEA solution in which 5 wt% of hydrochloric acid was dissolved was slowly dropped and shaking was performed for 10 minutes. To obtain a film.

Comparative Example  3

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

Comparative Example  4

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

Character rating

The 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) Thermal expansion coefficient

The film was cut in a width of 20 mm and a length of 4 mm using a TMA (Perkin Elmer, Diamond TMA model) and mounted on a probe. The film was heated from 30 ° C to 300 ° C at a heating rate of 10 ° C / min under a load of 100 mN After the first temperature rise, it is cooled to 30 ° C, and the temperature is elevated from 30 ° C to 300 ° C at a temperature increase rate of 10 ° C / min, and the thermal expansion coefficient between 40 ° C and 250 ° C at the second temperature increase is calculated in ppm / ° C .

2) Transmittance and haze

Using a haze meter (NDH2000 model, manufactured by Nippon Denshoku), measure the transmittance and haze of the film with a D65 light source in Method 3. At this time, the wavelength is 550 nm.

3) IR

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

Thickness (㎛) Permeability (%) Haze (%) Bridging degree Thermal Expansion Coefficient (ppm / ° C) 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 cross - linking reaction between the polymers was carried out by acid treatment using a norbornene polymer containing a silane group. The degree of crosslinking was confirmed by confirming the degree of reaction using IR.

Were Comparative Examples 1 to 3 is significantly higher than that appeared in the thermal expansion coefficient and also cross-linking Examples 1-6 As shown in Table 1, Comparative Example 4 in the 770cm ^-1 region polymers do not have silane groups The absorbance value could not be obtained and the degree of crosslinking was not known. Therefore, in Comparative Examples 1 to 4, when the crosslinking was not performed or the degree of crosslinking was insufficient, the improvement of the thermal expansion coefficient of the film was insignificant. However, in Examples 1 to 6, when the crosslinking level was over the proper level, the thermal expansion coefficient was remarkably improved, It could be applied to necessary film. Such films have excellent thermal properties and are optically transparent.

From this, it can be seen that the cyclic olefin based resin film according to the present invention can be used for various electrical uses such as optical films, flexible substrates, and general substrates.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (15)

delete delete A step S1 of dissolving the norbornene-based polymer in a solvent to prepare a polymer solution;
(S2) coating the polymer solution prepared in the step (S1) on a substrate and then drying to produce a film; And
Treating the film produced in step (S2) with an acid at an acid concentration of 10 w / w% or more and 50 w / w% or less at a concentration of 10 to 50 ° C for 1 minute to 1 hour (step S3) Based resin film.
4. The method according to claim 3, wherein the drying step in step (S2) is a first drying step at 15 to 50 DEG C for 1 to 24 hours, followed by a second drying step at 100 to 300 DEG C for 5 minutes to 1 hour. A method for producing an olefin based resin film.
5. The method according to claim 4, wherein the step (S2) further comprises a step (S2-1) of subjecting the primary dried film to acid treatment after the primary drying step A method for producing a resin film.
[6] The method according to claim 5, wherein the acid treatment in step (S2-1) uses 1 to 50 w / w% of an acid.
6. The method of producing a cyclic olefin based resin film according to claim 5, wherein the acid treatment in step (S2-1) is carried out at 10 to 50 DEG C for 1 minute to 1 hour.
6. The method according to claim 3 or 5, wherein the acid used in the acid treatment is any of inorganic acids selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphorous acid, and combinations thereof, carboxylic acids, sulfonic acids, Wherein the organic acid is selected from the group consisting of a combination of one or more organic acids.
4. The method according to claim 3, wherein the solvent in step (S1) is at least one selected from the group consisting of toluene, xylene, dichloromethane and tetrahydrofuran.
4. The process for producing a cyclic olefin based resin film according to claim 3, wherein the norbornene polymer comprises a repeating unit represented by the following formula (1).
&Lt; Formula 1 >

Wherein R 1 to R 8 each independently represent a substituted or unsubstituted hydrocarbon group having a linking group containing hydrogen, oxygen, nitrogen, silicon or sulfur, a hydrocarbon group having 1 to 10 carbon atoms, a polar group, an aromatic group having a single bond or a divalent linking 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 1.)
The method for producing an olefin resin film according to claim 10, wherein the molar ratio of m: n in the formula (1) is 1 to 100: 0 to 99. The method of producing a cyclic olefin based resin film according to claim 10, wherein the norbornene polymer has a weight average molecular weight of 10,000 to 1,000,000. delete delete delete

Images