KR20160002402A - Surface modified silica particles and polyimide film comprising the same - Google Patents
Surface modified silica particles and polyimide film comprising the same Download PDFInfo
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Abstract
Description
The present invention relates to a surface-modified composite silica particle and a polyimide film comprising the same, and more particularly to a surface-modified composite silica particle having a surface-modified composite silica particle having maximized compatibility and dispersibility with an organic polymer, Lt; / RTI >
In general, polyimide (PI) resin is an insoluble and infusible ultra-high temperature resistant resin, and has excellent heat resistant oxidizing property, heat resistance property, radiation resistance property, low temperature property and chemical resistance, It is widely used in electronic materials such as high-tech materials and insulating coatings, insulating films, semiconductors, and electrode protective films of TFT-LCDs.
In the case of such a polyimide, a polyamic acid derivative is prepared by combining an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate in solution, and then dehydrating and cyclizing at a high temperature to imidize the polyamic acid derivative. (PMDA) or biphenyltetracarboxylic acid dianhydride (BPDA) or the like is used as an aromatic dianhydride component, and examples of the aromatic diamine component include oxydianiline (ODA), p (P-PDA), m-phenylenediamine (m-PDA), methylene dianiline (MDA), and bisaminophenylhexafluoropropane (HFDA).
Generally, polyimide has a high aromatic ring density and is colored with a brown or dazzling color, thereby imparting transparency to brown and yellow polyimide for application in high-tech materials such as displays and semiconductors. For this purpose, a linkage group (-O-, -SO2-, -CO-, -CF3CCF3-, etc.) or a side chain having a relatively large free volume is introduced into the main chain to minimize transparency by intermolecular and intramolecular charge transfer complexes do.
However, in the case of a film imparted with transparency to polyimide, there is a problem that heat resistance is decreased due to the introduced functional groups. As a result, there is a limit to the application of the material processing process such as a display requiring a high process temperature, and when the mechanical properties are low, the display production process tears and the yield of the product is lowered.
In order to overcome the disadvantages of such transparent polyimide, it is necessary to include a substance other than a polymer. As a representative example, a Si-based inorganic substance may be mentioned. When a film made of such an inorganic filler is included in the production of the film, the film may improve the running property or increase the hardness, deformation of the optical properties, and heat resistance.
Conventional references related to a technique of introducing silica into polyimide include Korean Patent Registration No. 0652863, "Precursor Solution for Polyimide / Silica Composite Material, Manufacturing Method Thereof " And Korean Patent Registration No. 1246116 disclosing a polyimide / silica composite material having a low volume shrinkage ratio and a polyimide siloxane solution composition disclosed in WO2005-080505.
However, in case of using most of the inorganic substances, there is a difference in the size depending on the particle size and the manufacturing method of the particles when a large amount is used, but the limitation of the haze due to the aggregation of the inorganic substance in the production of the film is revealed. In addition, the inorganic substance itself is poor in compatibility with the polymer and its dispersibility is poor. Therefore, it is physically dispersed through a mill, a mixer, a high-speed stirrer homogenizer, and an ultrasonic disperser in order to prevent the dispersion. Accordingly, a technique capable of further improving the compatibility with a polymer is steadily required.
Accordingly, the present invention aims to improve the compatibility and dispersibility of the organic polymer by surface modification of the silica particles, and further to improve the heat resistance, transparency and surface hardness of the polyimide film by including the surface-modified silica particles.
One embodiment of the present invention is a silica particle modified with a polysiloxane having a surface modified with a polysiloxane, which is a polymer of a compound represented by the following formula (1) or a compound represented by the following formula (2) Lt; RTI ID = 0.0 > modified silica. ≪ / RTI >
[Chemical Formula 1]
(2)
In the general formula (1) or (2), R is the same or different from each other selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and combinations thereof. R 1 is a single bond in which a carbon atom of the benzene ring is directly bonded to silicon, an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 3 to 12 carbon atoms, a haloalkenylene group having 3 to 12 carbon atoms, 8 < / RTI > alkynylene groups, and combinations thereof.
In a preferred embodiment, the polysiloxane may be a polymer of a mixture of the compound represented by Formula 1 and the compound represented by Formula 2 in a weight ratio of 1: 1 to 1: 5.
The polysiloxane according to an embodiment of the present invention may have a weight average molecular weight of 1,000 to 10,000.
The surface-modified composite silica according to an embodiment of the present invention may have an average particle diameter of 0.1 to 50 μm.
The content of the polysiloxane according to one embodiment of the present invention may be 0.1 to 10 parts by weight based on 100 parts by weight of the silica particles.
In another embodiment of the present invention, the surface-modified complex silica particle comprising a polyimide resin and silica particles, wherein the silica particle is modified with a polysiloxane, and the polysiloxane is a compound represented by the following formula (1) And a phenyl group in a side chain thereof. The polyimide film according to claim 1,
[Chemical Formula 1]
(2)
In the general formula (1) or (2), R is the same or different from each other selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and combinations thereof. R 1 is a single bond in which a carbon atom of the benzene ring is directly bonded to silicon, an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 3 to 12 carbon atoms, a haloalkenylene group having 3 to 12 carbon atoms, 8 < / RTI > alkynylene groups, and combinations thereof.
In the film according to an embodiment of the present invention, the polysiloxane may be a polymer of a mixture of the compound represented by Formula 1 and the compound represented by Formula 2 at a weight ratio of 1: 1 to 1: 5.
In the film according to an embodiment of the present invention, the polysiloxane may have a weight average molecular weight of 1,000 to 10,000.
In the film according to an embodiment of the present invention, the surface-modified complex silica may have an average particle diameter of 0.1 to 50 μm.
In the film according to an embodiment of the present invention, the surface-modified complex silica may contain 0.1 to 10 parts by weight of polysiloxane based on 100 parts by weight of silica particles.
The film according to an embodiment of the present invention may contain 1 to 10 parts by weight of the surface-modified composite silica particles per 100 parts by weight of the polyimide resin.
The film according to an embodiment of the present invention may have a haze value of 0.5 to 2.0 as measured according to ASTM D1003. Further, the surface hardness may satisfy 2H to 3H on the basis of pencil hardness measurement (load speed of 1 kg load: 180 mm / min).
The surface-modified silica particles according to the present invention have polysulfone-bonded polysiloxane bonded to the surface of silica particles and have very similar molecular behavior to a polymer having many aromatic rings such as polyimide, The dispersibility is improved and at the same time, the improvement of the physical properties by the inorganic material is maximized, and accordingly, the polymer composite, particularly the polyimide film, having excellent surface strength characteristics can be produced.
According to one aspect of the present invention, there is provided a silica particle modified with a polysiloxane surface thereof, wherein the polysiloxane is a polymer of a compound represented by the following formula (1) or a compound represented by the following formula (2) Lt; RTI ID = 0.0 > modified silica. ≪ / RTI >
[Chemical Formula 1]
(2)
In the general formula (1) or (2), R is the same or different from each other selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and combinations thereof. R 1 is a single bond in which a carbon atom of the benzene ring is directly bonded to silicon, an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 3 to 12 carbon atoms, a haloalkenylene group having 3 to 12 carbon atoms, 8 < / RTI > alkynylene groups, and combinations thereof.
The polysiloxane having a phenyl group in its side chain as a polymeric compound of the compound represented by the formula (1) alone or a mixture of the compound represented by the formula (2) reacts with the -OH group present on the surface of the silica through reaction with the silica particles to form a bond Can be formed. Particularly, as the polysiloxane having a phenyl group is bonded to the surface of the silica particles, compatibility with a polymer containing a large number of aromatic rings and dispersibility can be improved.
The compound represented by the above formula (1) is not limited, but examples thereof include diphenylsilanediol (DPSD) Diphenyldiethoxysilanediol, diphenyldibuthoxysilanediol, and the like can be given.
The compound represented by the above formula (2) is not limited thereto. For example, the compound selected from the group consisting of phenyl trimethoxysilane (PTMS), phenyl triethoxysilane (PTES), and mixtures thereof It may be more preferable that any one is selected.
According to a preferred embodiment, the polysiloxane which modifies the surface of the silica particles is a polymer of a mixture of the compound represented by the formula (1) and the compound represented by the formula (2) in a weight ratio of 1: 1 to 1: 5 The degree of packing / packing between the silica mixtures is more advantageous, which makes it possible to obtain better surface hardness.
It is predicted that the compound represented by the formula (1) may lower the yellowing degree by increasing the spacing of the main chain, and the compound represented by the formula (2) may increase the packing between the silica to increase the surface hardness have.
Meanwhile, the polysiloxane preferably has a weight average molecular weight of 1,000 to 10,000. In the present invention, the weight average molecular weight may be measured by using a device capable of measuring the molecular weight of a polymer such as MALDS (Matrix-Assisted Laser Desorption Ionization Mass Spectrometer) or GPC . When the weight average molecular weight of the polysiloxane is within the above-mentioned range, polymerization can be sufficiently carried out to exhibit an effect of improving hardness, and it is preferable from the viewpoint of preventing clouding due to entanglement with polymers.
According to a preferred embodiment of the present invention, the surface-modified composite silica has an average particle size of 0.1 to 50 탆, and even if the surface is modified with a polysiloxane group, the size of the polysiloxane is very small, . When the average particle diameter of the surface-modified complex silica is within the above-mentioned range, it is advantageous to exhibit an effect when applied to a film and may be advantageous in controlling when applying particles.
The polysiloxane may be contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the silica particles in terms of effective surface modification, more preferably 1 to 20 parts by weight, most preferably 5 to 10 parts by weight Lt; / RTI >
There is no limitation on the method for preparing the surface-modified complex silica as described above. For example, the compound represented by the formula (1) may be reacted with the compound represented by the formula (1) Reacting the compound at a ratio of 1: 1 to 1: 5 to produce a polysiloxane; And (b) adding the polysiloxane obtained in the step (a) to a solvent in which the silica particles are dispersed and reacting.
According to a preferred embodiment of the present invention, in the step (a), the reaction is a reaction in which a hydrolysis and condensation reaction occurs in a chain to form a polysiloxane chain and is carried out by stirring at a temperature of 70 to 90 ° C for 5 to 12 hours . If the temperature is excessively low or high, the reaction solvent and the raw material can easily be volatilized, and the reaction can sufficiently take place within the time.
At this time, hydrolysis and condensation polymerization during the reaction result in the formation of byproducts such as alcohol and water. By eliminating the alcohol and water, the reverse reaction can be reduced and the reaction can be regulated. In addition, when the reaction is completed, the alcohol and water remaining in the polysiloxane may be removed by applying a condition of 80 to 100 DEG C for 10 minutes or less under a reduced pressure, but the present invention is not limited thereto.
According to a preferred embodiment of the present invention, the polysiloxane obtained in the step (a) may have a weight average molecular weight of 1,000 to 10,000 for the reasons described above.
According to a preferred embodiment of the present invention, the silica particles in the step (b) preferably have an average particle diameter of 0.1 to 50 탆. Silica is formed through the hydrolysis and condensation reaction of alkoxysilane in the presence of water and a catalyst, and any silica particles obtained by conventional synthesis methods are possible. However, when the average particle size of the silica particles is less than 0.1 탆, the particles may be too small to coat the polysiloxane, and when the particle size exceeds 50 탆, May be used.
According to a preferred embodiment of the present invention, the solvent in which the silica particles are dispersed is water; Methanol, ethanol, propanol, isopropanol and butanol; And a mixed solvent thereof. More preferably, water or a mixed solvent of water and a lower alcohol may be used.
According to a preferred embodiment of the present invention, the addition of the polysiloxane in the step (b) in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the silica particles may be advantageous in terms of effective surface modification, more preferably 1 to 20 parts by weight, Preferably 5 to 10 parts by weight may be added.
According to a preferred embodiment of the present invention, the reaction of step (b) is a reaction in the form of condensation polymerization between the OH group and the polysiloxane on the surface of the hydrolyzed silica particles to form a network while being dispersed in a solvent, It is preferable that the reaction is carried out at room temperature for 5 to 10 hours. In addition, the stirring speed can be appropriately adjusted depending on the content of silica and water used.
Particularly, in order to further promote the reaction of step (b), according to a preferred embodiment of the present invention, barium oxide, ammonia (NH 4 OH), potassium hydroxide (KOH), sodium hydroxide (NaOH) (B) may be carried out under any one of the basic catalysts selected from the group consisting of: Although not particularly limited in the present invention, barium hydroxide or ammonia can be preferably used as a basic catalyst.
According to still another aspect of the present invention, there is provided a polyimide film including the surface-modified complex silica. The surface-modified complex silica is dispersed in a solution prepared by mixing the solid polyimide resin obtained in the process of producing polyimide with a solvent, And it can be physically dispersed by using a mill, a mixer, a high-speed stirrer, a homogenizer, and an ultrasonic dispersing machine.
According to a preferred embodiment of the present invention, the surface-modified complex silica may be contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyimide resin solid content in the production of the polyimide film. If the content of the surface-modified complex silica is less than 1 part by weight, the effect of increasing the hardness may be insufficient. If the content of the surface-modified composite silica is more than 10 parts by weight, the film may become cloudy, .
In addition, it is preferable that the polyimide film including the surface-modified composite silica ultimately has a haze value of 0.5 to 2.0 based on ASTM D1003 and a surface hardness of 2H to 3H based on pencil hardness measurement (load rate of 1 kg load: 180 mm / min). In the present invention, the haze value can be measured using a haze meter measuring instrument, and the surface hardness can be measured using a pencil hardness meter for a Mitsubishi evaluation pencil (UNI) (see Examples below). The characteristics of the polyimide film of the present invention may be due to the surface-modified complex silica contained in the polyimide film.
That is, unlike silica modified with other functional groups, the composite silica according to the present invention has good compatibility with a polymer resin including a plurality of aromatic rings as a polysiloxane having a large number of phenyl groups is present on its surface It is possible to maintain transparency even when a large amount of particles are present even when a large amount of particles are present, and since the polysiloxane between the polymers plays a role of grabbing between the surface and the polymer molecules and enhancing the hardness, the polyimide In the film, the haze value and the surface hardness of the above range can be realized.
In the above and the following descriptions, it is understood that the polyimide includes an imide bond in the repeating unit of the main chain, which includes a polyamide-imide including an acid amide bond (-CONH-) in a part of the main chain Will be.
Example
Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.
Production Example 1. Preparation of silica particles
300 g of ethanol was added to a 500 ml beaker, and 7 g of tetraethylthoxysilane (TEOS, Si (OC 2 H 5 ) 4 , Sigma-Aldrich) as a silane material was added thereto, followed by stirring at room temperature for 30 minutes. Subsequently, 25 g of NH 4 OH was slowly added to the reactor, followed by stirring at the same temperature for 6 hours. After completion of the reaction, the obtained reaction product was filtered, washed with ethanol (50 ml) three times, and then dried in an oven at 40 캜 for 5 hours under reduced pressure to prepare 5 g of silica particles [SiO 2 ] having an average particle diameter of 0.2 탆.
The shape and size of the silica particles were observed by TEM (Transmission Electron Microscopy, 200 kV, JEM-2000EX, JEOL, Japan) and the electrophoretic light scattering type Zeta sizer (ELS-8000,
Otsuka electronics, Japan).
Production Example 2. Preparation of polysiloxane
Three-necked flask was charged with diphenyl silane diol (Diphenylsilandiol, DPSD, (C 6 H 5) 2 Si (OH) 2, Sigma-Aldrich) 40g and phenyltrimethoxysilane (PTMS, C 6 H 5 Si (OCH) 3 , Sigma-Aldrich) were mixed together by stirring, and reacted at 80 ° C for 10 hours to obtain 60 g of polysiloxane having a weight average molecular weight of 5,000.
Here, the weight average molecular weight (unit: g / mol) of the polysiloxane was measured on the basis of PS standard using GPC (Gel Permeation Chromatography, ViscoTek).
Preparation Example 3. Preparation of surface-modified complex silica
After dispersing 5 g of the silica particles obtained in Preparation Example 1 in 300 ml of ethanol, 0.5 g of the polysiloxane obtained in Preparation Example 2 and 1 ml of NH 4 OH were added and reacted at room temperature for 12 hours Average particle size of 0.2 mm To prepare surface-modified composite silica particles. After completion of the reaction, the obtained reaction product was filtered and washed three times with ethanol (50 ml).
The particle size of the surface-modified complex silica was measured by the same method as that of the measurement of the average particle diameter of the silica particles.
Example 1
(0.1 wt%) was added to 100 g of N, N-dimethylacetamide (DMAc), and the dispersion was dispersed using an ultrasonic dispersing machine of Qsonica (Misonix) at 20 kHz To prepare a mixed composition.
Examples 2 and 3
The composition was prepared in the same manner as in Example 1 except that the amounts of the surface-modified composite silica particles were 0.5 g (0.5 wt%) and 1 g (1 wt%), respectively.
Comparative Examples 1 to 3
(Nippon shokubai, KE-P10, average particle size of 0.15 mu m) having a surface-OH component instead of the surface-modified complex silica obtained in Production Example 3 was added to 100 g of N, N-dimethylacetamide (DMAc) The compositions of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that 0.5 g (0.1 wt%), 0.5 g (0.5 wt%) and 1 g (1 wt%) were added.
The haze of the compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was measured and reported in Table 1 below. At this time, the haze measuring method was measured according to ASTM D1003 standard using a haze meter (HM-150 product, manufactured by Murakaml Color Research Laboratory).
As shown in Table 1, the haze values of the films of Examples 1 to 3 were higher than those of Comparative Examples 1 to 3 because of the excellent dispersibility of the surface- It was confirmed that the haze was remarkably low as compared with 1 to 3.
Example 4
716 g of N, N-dimethylacetamide (DMAc) was charged into a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the reactor, 57.64 g (0.18 mol) of TFDB (2,2 ' -bis (trifluoromethyl) biphenyl-4,4 ' -diamine) was dissolved and the solution was maintained at 25 deg. 23.99 g (0.054 mol) of 6FDA (4,4 '- (hexaflouroisopropyllidene) diphathalic anhydride) and 7.06 g (0.036 mol) of CBDA (cyclobutane-1,2,3,4-tetracarboxylic dianhydride) And dissolved and reacted. After the temperature of the solution was maintained at 15 캜, 18.27 g (0.09 mol) of terephthaloyl chloride (TPC) was added and reacted at 25 캜 for 12 hours to obtain a polyamic acid having a solid content of 13% by weight and a viscosity of 860 poise Solution.
Then, 34.17 g of pyridine and 44.12 g of acetic anhydride were added to the polyamic acid solution obtained. The mixture was stirred for 30 minutes and then stirred at 70 ° C for 1 hour. The mixture was cooled to room temperature and precipitated with 20 L of methanol. The precipitated solid was filtered Followed by drying at 100 ° C under vacuum for 6 hours to obtain 95 g of a solid powdery copolymerized polyamide-imide.
The copolymerized polyamide-imide of 95 g of the solid powder was dissolved in 768 g of N, N-dimethylacetamide (DMAc) to obtain a 11 wt% solution. Then, 0.95 g of the surface-modified complex silica obtained in Production Example 3 was added, .
The solution thus obtained was coated on a stainless steel plate, cast to 100 탆, dried by hot air at 150 캜 for 1 hour, at 200 캜 for 1 hour and at 300 캜 for 30 minutes by hot air, then slowly cooled and separated from the plate, Amide-imide film. Thereafter, the substrate was subjected to heat treatment at 300 ° C for 10 minutes as a final heat treatment process.
Example 5
A polyimide-imide film of 10 탆 was obtained in the same manner as in Example 4 except that the amount of the surface-opened composite silica particles was adjusted to 4.75 g.
Comparative Example 4
A polyimide-imide film having a thickness of 10 mu m was obtained in the same manner as in Example 4 except that no surface-modified complex silica was added at all.
Comparative Example 5
Except that 0.95 g of the filler (Nippon shokubai, KE-P10, average particle size 0.15 mu m) used in the above Comparative Example was used instead of the surface-modified composite silica particles, and 10 mu m polyamide- .
Comparative Example 6
Except that 0.95 g of the filler (Nippon shokubai, KE-P10, average particle size 0.15 mu m) used in the above Comparative Example was used instead of the surface-modified composite silica particles, and 10 mu m polyamide- .
The surface hardness of the films prepared in Examples 4 to 5 and Comparative Examples 4 to 6 was measured and described in Table 2. The surface hardness of the film was measured by using a pencil hardness tester Mitsubishi Evaluation (UNI), measuring 5 mm at a rate of 180 mm / min under a load of 1 kg, measuring the minimum pencil hardness with no scratch on the surface Respectively.
The haze of the films prepared in Examples 4 to 5 was measured and reported in Table 2 below. At this time, the haze measuring method was measured according to ASTM D1003 standard using a haze meter (HM-150 product, manufactured by Murakaml Color Research Laboratory).
As a result of the measurement of the surface hardness, as shown in Table 2, Comparative Examples 5 and 6 showed the hardness equivalent to that of Comparative Example 4 (base film) despite the addition of the filler, It was confirmed that the hardness of the film was remarkably improved due to the effect of the surface-modified composite silica particles of the present invention.
Also, it was confirmed that the haze of the film itself did not increase significantly even though the silica particles were added as a result of the haze measurement.
Claims (13)
Wherein the polysiloxane is a polymer of a compound represented by the following formula (1) alone or a mixture thereof with a compound represented by the following formula (2), wherein the side chain includes a phenyl group.
[Chemical Formula 1]
(2)
In the general formula (1) or (2), R is the same or different from each other selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and combinations thereof. R 1 is a single bond in which a carbon atom of the benzene ring is directly bonded to silicon, an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 3 to 12 carbon atoms, a haloalkenylene group having 3 to 12 carbon atoms, 8 < / RTI > alkynylene groups, and combinations thereof.
Wherein the polysiloxane is a polymer of a mixture of a compound represented by Formula 1 and a compound represented by Formula 2 in a weight ratio of 1: 1 to 1: 5.
Wherein the polysiloxane has a weight average molecular weight of 1,000 to 10,000.
The surface-modified complex silica has an average particle diameter of 0.1 to 50 탆.
Wherein the content of the polysiloxane is 0.1 to 10 parts by weight based on 100 parts by weight of the silica particles.
The silica particles are surface-modified complex silica particles whose surface is modified with polysiloxane, and the polysiloxane is a polymeric compound of a compound represented by the following formula (1) alone or a compound represented by the following formula (2) , Polyimide film.
[Chemical Formula 1]
(2)
In the general formula (1) or (2), R is the same or different from each other selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, and combinations thereof. R 1 is a single bond in which a carbon atom of the benzene ring is directly bonded to silicon, an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 3 to 12 carbon atoms, a haloalkenylene group having 3 to 12 carbon atoms, 8 < / RTI > alkynylene groups, and combinations thereof.
Wherein the polysiloxane is a polymer of a mixture of a compound represented by Formula 1 and a compound represented by Formula 2 in a weight ratio of 1: 1 to 1: 5.
Wherein the polysiloxane has a weight average molecular weight of 1,000 to 10,000.
Wherein the surface-modified complex silica has an average particle diameter of 0.1 to 50 占 퐉.
Wherein the surface-modified complex silica comprises polysiloxane in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of silica particles.
Wherein the polyimide resin comprises 1 to 10 parts by weight of the surface-modified complex silica particles per 100 parts by weight of the polyimide resin.
Wherein the polyimide film has a haze value of 0.5 to 2.0 based on ASTM D1003.
Wherein the polyimide film has a surface hardness of 2H to 3H based on pencil hardness measurement (load rate of 1 kg load: 180 mm / min).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2015/006714 WO2016003166A1 (en) | 2014-06-30 | 2015-06-30 | Surface-modified composite silica particles and polyimide film comprising same |
| TW104121192A TWI656097B (en) | 2014-06-30 | 2015-06-30 | Surface modified silica particles and polyimide film comprising the same |
| JP2016575753A JP6568121B2 (en) | 2014-06-30 | 2015-06-30 | Surface-modified composite silica particles and polyimide film containing the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140081404 | 2014-06-30 | ||
| KR1020140081404 | 2014-06-30 |
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| Publication Number | Publication Date |
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| KR20160002402A true KR20160002402A (en) | 2016-01-07 |
| KR102037699B1 KR102037699B1 (en) | 2019-10-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150092667A KR102037699B1 (en) | 2014-06-30 | 2015-06-30 | Surface modified silica particles and polyimide film comprising the same |
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| Country | Link |
|---|---|
| JP (1) | JP6568121B2 (en) |
| KR (1) | KR102037699B1 (en) |
| CN (1) | CN106661273B (en) |
| TW (1) | TWI656097B (en) |
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| KR20210026053A (en) | 2019-08-29 | 2021-03-10 | 피아이첨단소재 주식회사 | Polyimide film and manufacturing method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171577A (en) * | 2001-12-06 | 2003-06-20 | Toyo Ink Mfg Co Ltd | Highly heat resistant, water repellent and lipophilic surface treated inorganic oxide, its manufacturing method and resin composition |
| US20100178478A1 (en) * | 2009-01-13 | 2010-07-15 | Korea Advanced Institute Of Science And Technology | Transparent composite compound |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0647651B2 (en) * | 1984-01-20 | 1994-06-22 | 東レ・ダウコーニング・シリコーン 株式会社 | Method for producing transparent organopolysiloxane composition |
| JP2002309109A (en) * | 2001-04-18 | 2002-10-23 | Fuji Photo Film Co Ltd | Process for producing film with high surface hardness |
| KR100614976B1 (en) * | 2004-04-12 | 2006-08-25 | 한국과학기술원 | Inorganic/Organic Hybrid Oligomer, Nano Hybrid Polymer for Optical Devices and Displays, and Manufacturing Method thereof |
| JP4601324B2 (en) * | 2004-05-17 | 2010-12-22 | 三菱樹脂株式会社 | Thermoplastic resin composition and resin film using the same |
| JP5232445B2 (en) * | 2007-11-12 | 2013-07-10 | 株式会社日本触媒 | Particle and method for producing particle |
| EP2110414A1 (en) * | 2008-04-18 | 2009-10-21 | Nanoresins AG | Surface modified silicon dioxide particles |
| CN102086303A (en) * | 2009-12-03 | 2011-06-08 | 财团法人工业技术研究院 | Polyamic acid resin composite and polyimide film and laminated material prepared from same |
| JP2011225872A (en) * | 2010-04-02 | 2011-11-10 | Ube Industries Ltd | Polyamide resin composition for film |
| CN104411744B (en) * | 2012-06-29 | 2018-02-16 | 可隆工业株式会社 | Polyimides and the Kapton containing the polyimides |
-
2015
- 2015-06-30 CN CN201580035728.0A patent/CN106661273B/en active Active
- 2015-06-30 TW TW104121192A patent/TWI656097B/en active
- 2015-06-30 KR KR1020150092667A patent/KR102037699B1/en active IP Right Grant
- 2015-06-30 JP JP2016575753A patent/JP6568121B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171577A (en) * | 2001-12-06 | 2003-06-20 | Toyo Ink Mfg Co Ltd | Highly heat resistant, water repellent and lipophilic surface treated inorganic oxide, its manufacturing method and resin composition |
| US20100178478A1 (en) * | 2009-01-13 | 2010-07-15 | Korea Advanced Institute Of Science And Technology | Transparent composite compound |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10809421B2 (en) | 2016-10-21 | 2020-10-20 | Samsung Electronics Co., Ltd. | Stacked transparent film and window for display device and display device |
| US11198762B2 (en) | 2017-11-03 | 2021-12-14 | Samsung Electronics Co., Ltd. | Polyimide, composition for preparing polyimide, article including polyimide, and display device including the article |
| KR20190109346A (en) * | 2017-11-09 | 2019-09-25 | 스미또모 가가꾸 가부시키가이샤 | Optical film |
| KR20210026053A (en) | 2019-08-29 | 2021-03-10 | 피아이첨단소재 주식회사 | Polyimide film and manufacturing method thereof |
| KR20210055230A (en) | 2019-11-07 | 2021-05-17 | 피아이첨단소재 주식회사 | Low Dielectric Polyimide Film and Manufacturing Method Thereof |
| KR20210057942A (en) | 2019-11-13 | 2021-05-24 | 피아이첨단소재 주식회사 | High Elastic and High Heat Resistant Polyimide Film and Manufacturing Method Thereof |
| KR20220060476A (en) | 2020-11-04 | 2022-05-11 | 피아이첨단소재 주식회사 | Polyimide film WITH HIGH DIMENSIONAL STABILTY and manufacturing method thereof |
| KR20220071797A (en) | 2020-11-24 | 2022-05-31 | 피아이첨단소재 주식회사 | Polyimide film with high dimensional stability and manufacturing method thereof |
| KR20240053229A (en) | 2022-10-17 | 2024-04-24 | 피아이첨단소재 주식회사 | Polyimide film and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102037699B1 (en) | 2019-10-29 |
| TW201600462A (en) | 2016-01-01 |
| CN106661273B (en) | 2020-05-12 |
| JP6568121B2 (en) | 2019-08-28 |
| CN106661273A (en) | 2017-05-10 |
| JP2017520662A (en) | 2017-07-27 |
| TWI656097B (en) | 2019-04-11 |
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